Co-reporter:Nian Zhao, Fuxing Sun, Ning Zhang, and Guangshan Zhu
Crystal Growth & Design May 3, 2017 Volume 17(Issue 5) pp:2453-2453
Publication Date(Web):April 13, 2017
DOI:10.1021/acs.cgd.6b01864
A novel anionic metal–organic framework, JUC-138, constructed by In(III) and a pyrene-based linker, H8TIAPy (H8TIAPy = 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene), has been synthesized by solvothermal reaction successfully. In JUC-138, only four carbonyl groups in each ligand connect to In3+ ions, while the others remain uncoordinated. However, each In3+ connects to four carbonyl groups in a bidentate chelate style, resulting in the formation of 2D square sheets in JUC-138. The 2D sheets interact with adjacent layers through the O–H···O hydrogen bonds between the uncoordinated carboxyl groups, thus generating the whole 3D supramolecular structure of JUC-138. UV–vis tests show the energy gap Eg of JUC-138 is 3.34 eV, indicating the semiconductor nature of JUC-138. In addition, JUC-138 shows good photocatalytic activity in Azure B (AB) decolorization and could decompose 90% AB within 4 h. This photocatalytic property makes JUC-138 promising in environment governance.
Co-reporter:Yudi Wang, Shuhao Zhang, Jionghua Wu, Kuan Liu, Dongmei Li, Qingbo Meng, and Guangshan Zhu
ACS Applied Materials & Interfaces December 20, 2017 Volume 9(Issue 50) pp:43688-43688
Publication Date(Web):November 28, 2017
DOI:10.1021/acsami.7b14073
PAF-86 film is electropolymerized (EP) by targeted monomer M1 tethered bifunctional carbozolyl moieties which not only serve in electron donation but also provide effective electrochemical (EC) active sites. The resulting PAF-86 film possesses a fairly compact surface, remarkable stability, efficient hole extraction capacity, and hole-transporting materials (HTMs) for inverted heterojunction perovskite solar cells (PSCs). Likewise, our investigation shows that PAF-86 film based perovskite solar cells (PSCs) retained about 80% power conversion efficiency (PCE) without encapsulation in air, and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) based PSCs devices reduce to 4% under the same conditions. More impressively, the electropolymerization approach is convenient, controlled, and operated at ambient conditions which elude post heat-treatments and are appropriate for industrial application.Keywords: electropolymerization; hole transport; long-term stability; perovskite solar cells; porous aromatic framework;
Co-reporter:Nian Zhao;Ping Li;Xin Mu;Chuanfang Liu;Fuxing Sun
Faraday Discussions 2017 (Volume 201) pp:63-70
Publication Date(Web):2017/09/06
DOI:10.1039/C7FD00017K
A novel ultra-stable metal–organic framework, MCIF-1, [Cu2(DCI)2](MeCN), based on dicyanoimidazole and Cu(I), has been synthesized at room temperature successfully. MCIF-1 shows excellent water stability and can retain crystallinity after soaking in water for about one week. In addition, MCIF-1 also shows exceptional resistance under both acidic and basic conditions within a large pH range from 0 to 13.5. What is more, after modifying the synthesis procedure slightly, we can produce this material in a large scale during a very short time. Mild synthesis conditions, excellent stability and ease of large scale production give MCIF-1 great potential for practical use.
Co-reporter:Nian Zhao;Ping Li;Xin Mu;Chuanfang Liu;Fuxing Sun
Faraday Discussions 2017 (Volume 201) pp:63-70
Publication Date(Web):2017/09/06
DOI:10.1039/C7FD00017K
A novel ultra-stable metal–organic framework, MCIF-1, [Cu2(DCI)2](MeCN), based on dicyanoimidazole and Cu(I), has been synthesized at room temperature successfully. MCIF-1 shows excellent water stability and can retain crystallinity after soaking in water for about one week. In addition, MCIF-1 also shows exceptional resistance under both acidic and basic conditions within a large pH range from 0 to 13.5. What is more, after modifying the synthesis procedure slightly, we can produce this material in a large scale during a very short time. Mild synthesis conditions, excellent stability and ease of large scale production give MCIF-1 great potential for practical use.
Co-reporter:Shixing Zhang, Hongming He, Fuxing Sun, Nian Zhao, Jianshi Du, Qinhe Pan, Guangshan Zhu
Inorganic Chemistry Communications 2017 Volume 79(Volume 79) pp:
Publication Date(Web):1 May 2017
DOI:10.1016/j.inoche.2016.11.011
•A novel adenine-based MOF has been obtained by mixing ligands.•The resultant MOF retains free amino groups in the framework,•It can be used as heterogeneous catalysis for the Knoevenagel condensation reaction.Metal-organic frameworks (MOFs), as a new sort of crystalline materials, have attracted lots of interest in many applications during the past decades. Recently, many efforts have been focused on the development of MOFs as heterogeneous catalysis. In this communication, we selected adenine (ad) and tetracarboxylic acid, namely 5,5′-(1,3,6,8-tetraoxobenzo[Imn] Li et al. (1999), He et al. (2016) phenanthroline-2,7-diyl)bis-1,3-benzenedicarboxylic acid (H4L), as organic linkers to assemble with Zn(II) ions to construct a novel adenine-based porous MOF. There are three different inorganic clusters in the framework, including ZnO2N2, Zn2O2N6, and ZnO5N clusters. Interesting, the resultant porous MOF, namely [H2N(CH3)2]⋅[Zn4(L)1.5(ad)3(H2O)2]⋅ 4DMF, retains free amino groups in the framework, which can be served as Lewis basic sites to catalyse Knoevenagel condensation reaction. The catalytic study exhibits that the as-synthesized MOF with free amino groups can be used as heterogeneous catalysis with remarkable catalytic efforts and good recycle.A novel adenine-based zinc(II) MOF has been formed by mixing ligands, which can be used as base catalyst for the Knoevenagel condensation reaction.Download high-res image (138KB)Download full-size image
Co-reporter:Kun Cai;Fuxing Sun;Xiaoqiang Liang;Cong Liu;Nian Zhao;Xiaoqin Zou
Journal of Materials Chemistry A 2017 vol. 5(Issue 25) pp:12943-12950
Publication Date(Web):2017/06/27
DOI:10.1039/C7TA00169J
Use of a proton exchange membrane (PEM) is a key technique in proton exchange membrane fuel cells (PEMFCs) for clean energy applications. Recently, use of metal–organic frameworks (MOFs) as well as their composite membranes with polymers as PEM have been one research focus in this area. In this paper, the synthesis and proton conductive properties of a novel hexaphosphate ester-based MOF, JUC-200, prepared by the reaction of the inositol hexaphosphoric ligand (phytic acid) and Zn(II) is described. JUC-200 shows excellent water tolerance and acid resistance in a solution of pH = 2.0, and exhibits a proton conductivity of 1.62 × 10−3 S cm−1 at 80 °C. Furthermore, the polymer composite membranes of poly(vinyl alcohol) (PVA) and JUC-200 were fabricated for use as fillers with different mass percentages (X%, the membrane denoted as JUC-200@PVA-X). The measurement of proton conductivity of these membranes shows that JUC-200@PVA-10 has the advantage of a good proton conductivity of 1.25 × 10−3 S cm−1 at 50 °C. As far as is known, this is the first water-stable and acid-stable composite made of MOFs and polymers as proton exchange membranes. This research may make some contribution to the further development of MOFs in the field of the PEMFCs.
Co-reporter:Hongming He, Haobo Han, Hui Shi, Yuyang Tian, Fuxing Sun, Yang Song, Quanshun Li, and Guangshan Zhu
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 37) pp:24517
Publication Date(Web):August 31, 2016
DOI:10.1021/acsami.6b05538
Enhancing the activity and stability of enzymes and improving their reusability are critical challenges in the field of enzyme immobilization. Here we report a facile and efficient biomimetic mineralization to embed thermophilic lipase QLM in zeolite imidazolate framework-8 (ZIF-8). Systematic characterization indicated that the entrapment of lipase molecules was successfully achieved during the crystal growth of ZIF-8 with an enzyme loading of ∼72.2 ± 1.88 mg/g lipase@ZIF-8, and the enzymes could facilitate the construction of framework building blocks. Then the composite lipase@ZIF-8 was observed to possess favorable catalytic activity and stability in the ester hydrolysis, using the hydrolysis of p-nitrophenyl caprylate as a model. Finally, the composite was successfully applied in the kinetic resolution of (R,S)-2-octanol, with favorable catalytic activity and enantioselectivity during 10 cycle reactions. Thus, the biomimetic mineralization process can be potentially used as an effective technique for realizing the entrapment of biomacromolecules and constructing efficient catalysts for industrial biocatalysis.Keywords: biomimetic mineralization; ester hydrolysis; kinetic resolution; metal−organic frameworks; thermophilic lipase
Co-reporter:Hongming He, Fuxing Sun, Shengqian Ma, and Guangshan Zhu
Inorganic Chemistry 2016 Volume 55(Issue 17) pp:9071
Publication Date(Web):August 24, 2016
DOI:10.1021/acs.inorgchem.6b01592
We reported a series of HKUST-like MOFs based on multiple copper-containing secondary building units (SBUs). Compound 1 is constructed by two SBUs: Cu2(CO2)4 paddle-wheel SBUs and Cu2I2 dimer SBUs. Compound 2 has Cu2(CO2)4 paddle-wheel SBUs and Cu4I4 SBUs. Furthermore, compound 3 possesses Cu2(CO2)4 paddle-wheel SBUs, Cu2I2 dimer SBUs, and Cu(CO2)4 SBUs. These compounds are promising materials for CO2 capture and separation, because they all display commendable adsorption of CO2 and high selectivity for CO2 over CH4 and N2. It is worthy to note that compound 1 exhibits the highest Brunauer–Emmett–Teller surface area (ca. 901 m2 g–1) among the MOF materials based on CuxIy SBUs. In addition, compound 3 is the first case that three copper SBUs coexist in MOFs.
Co-reporter:Xiaoming Zhang, Yuyang Tian, Jiangtao Jia, Tingting Zhang, Guangshan Zhu
Journal of Molecular Structure 2016 Volume 1108() pp:560-566
Publication Date(Web):15 March 2016
DOI:10.1016/j.molstruc.2015.12.055
•Three cocrystals of deferiprone were synthesized and characterized.•The dissolution study were measured and discussed.In this paper we present three new cocrystals based on deferiprone which is the first oral medicine as iron chelator. Solitary deferiprone possesses some known problems due to its good solubility and frequent dosing side effects. For these three novel co crystals, deferiprone is the active pharmaceutical ingredient (API), p-hydroxybenzoic acid (1, C7H9NO2·C7H6O3), 2, 5-dihydroxybenzoic acid (2, C7H9NO2·C7H6O4) and maleic acid (3, C7H9NO2·C4H4O4) are used as cocrystal formers (CCFs), respectively. Their structures were characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD) analysis, thermogravimetric analyses (TGA), differential thermal analysis (DTA), elemental analysis (EA) and infrared spectral analysis (IR). Single crystal X-ray diffraction demonstrates that all three cocrystals (1–3) possess strong hydrogen-bondings assembled through hydroxyl of API and carboxylic acids of CCFs. The PXRD results indicate their high purity of as-synthesized samples. TGA, DTA, EA, IR and dissolution study of API and cocrystals were also measured and discussed, respectively. The results suggest that the cocrystals exhibit low dissolution rates comparing with solitary deferiprone, which is very advantageous for the oral medicine with frequent dosing side effects.
Co-reporter:Peng Cui, Xiao-Fei Jing, Ye Yuan, Guang-Shan Zhu
Chinese Chemical Letters 2016 Volume 27(Issue 9) pp:1479-1484
Publication Date(Web):September 2016
DOI:10.1016/j.cclet.2016.03.038
A novel porous aromatic framework, PAF-8, derived from tetraphenylsilane as basic building unit, was successfully synthesized via Friedel–Crafts alkylation reaction. This PAF material had high thermal stability as well as high surface area (785 m2 g−1) calculated from the Brunauer–Emmett–Teller (BET) model. Meanwhile, PAF-8 possessed high performances in gas sorption and especially for CO2 separation.Porous aromatic framework (PAF-8) derived from tetrahedral monomer was successfully synthesized by the Friedel–Crafts alkylation reaction. PAF-8 possessed high stability and high surface areas (785 m2 g−1), as well as good CO2 and CH4 sorption abilities. Meanwhile, PAF-8 exhibited great performance in N2–CO2 and CH4–CO2 chromatographic separation, which indicated PAF-8 a potential candidate for CO2 separation.
Co-reporter:Faheem Muhammad, Wenxiu Qi, Aifei Wang, Jingkai Gu and Guangshan Zhu
Journal of Materials Chemistry A 2015 vol. 3(Issue 28) pp:5711-5719
Publication Date(Web):01 Jun 2015
DOI:10.1039/C5TB00554J
In addition to their well-known antibacterial property, silver nanoparticles (Ag NPs) have also been highlighted as anti-leukemic agents; however, the underlying mechanism responsible for inhibiting the growth of hematopoietic cancer cells is so far poorly understood. In previous reports, Ag NP-induced oxidative stress was implicated for therapeutic efficacy but the excessive production of ROS in several hematopoietic malignant cells, which can potentially induce the dissolution of Ag NPs, was not taken into consideration. In this study we proposed Ag NP dissolution, in response to increased oxidative stress in leukemic cells, as the most probable mechanism for their anticancer activity. Hypochlorous acid-mediated dissolution of therapeutically active and ultrasmall (<5 nm) Ag NPs was also exploited to develop an oxidant responsive combinatorial drug delivery system. When Ag-capped and anticancer drug loaded pores of mesoporous silica were exposed to HOCl, the ready disintegration of Ag NPs resulted in a controlled release of drug molecules. The drug release profile and growth inhibition of myeloperoxidase positive (MOLM-13) leukemic cells support the role of the oxidant in the dissolution of Ag NPs. Besides combinational chemotherapy, the current study also provides us with an opportunity to investigate the interaction of Ag NPs with biorelevant oxidants.
Co-reporter:Faheem Muhammad, Wenxiu Qi, Aifei Wang, Jingkai Gu, Jianshi Du and Guangshan Zhu
Journal of Materials Chemistry A 2015 vol. 3(Issue 8) pp:1597-1604
Publication Date(Web):23 Dec 2014
DOI:10.1039/C4TB01709A
Inflammation is a complex and dynamic defensive cellular approach to safeguard against deleterious agents; however, an overexpression of such responses frequently results in the development of a number of devastating diseases, such as atherosclerosis, cancer, inflammatory bowel, Alzheimer's and Parkinson's diseases. At the site of the inflammation, excessive amount of reactive oxygen species (ROS) are produced, and therefore researchers are now earnestly trying to exploit ROS pathological signals to design oxidative triggered drug release systems. In this study, we report a straightforward strategy to develop an oxidative stress responsive drug release systems. Newly developed, ultra-small, and thiol stabilized zinc sulfide quantum dots (ZnS QDs) are used as nanocaps to regulate the release of anticancer drug (camptothecin) from mesoporous silica nanoparticles (MSNs) in response to oxidative environment. The exposure of capped nanocarrier to a higher concentration of H2O2 fails to open the drug loaded nanochannels; however, an addition of a minute amount of divalent iron, the most abundant transition-metal in the body, readily unseals the nanochannels at considerably lower H2O2 concentrations due to the generation of highly reactive hydroxyl radicals (˙OH). Thiol groups, which stabilize the ZnS nanolids, are actually oxidized by ˙OH and as a result unleash the loaded drug molecules from the channels of silica. In addition to the inflammation-induced drug delivery, this study also provides basic insight into the fate of thiol stabilized nanoparticles upon interaction with hydroxyl radicals.
Co-reporter:Hongming He, Yang Song, Fuxing Sun, Zheng Bian, Lianxun Gao and Guangshan Zhu
Journal of Materials Chemistry A 2015 vol. 3(Issue 32) pp:16598-16603
Publication Date(Web):13 Jul 2015
DOI:10.1039/C5TA03537F
A V-shaped aromatic ligand 1,3-di(4-carboxyphenyl)benzene (H2DCPB), retaining only one branch of the H6TDCPB ligand, was utilized. The assembly of this ligand with Zn(II) ions forms a two-fold interpenetrated porous MOF with pcu topology (JUC-135). The N2 adsorption isotherm of the activated sample at 77 K revealed type-I microporous characteristics. The BET and Langmuir surface areas are calculated to be 503.7 m2 g−1 and 718.9 m2 g−1, respectively. Notably, by the fluorescence technique, JUC-135 can be used to detect nitroaromatic explosives. In particular, it is one of the most efficient porous material-based sensors for TNP (KSV = 3.7 × 104 M−1). Furthermore, JUC-135 also can distinguish TNP (blue-shift) from NB, 1,3-DNB and 2,4-DNT (red-shift) by virtue of the shift direction of fluorescence spectra.
Co-reporter:Hongmin Su, Fuxing Sun, Jiangtao Jia, Hongming He, Aifei Wang and Guangshan Zhu
Chemical Communications 2015 vol. 51(Issue 26) pp:5774-5777
Publication Date(Web):20 Feb 2015
DOI:10.1039/C4CC10159F
A highly porous bio-MOF, medi-MOF-1, constructed from Zn and the pharmaceutical ingredient curcumin has been successfully synthesized. It can display permanent porosity with a surface area as high as ca. 3002 m2 g−1, which exhibits great potential in bioapplications. Its ibuprofen delivery ability, biodegradation and cytotoxicity were also studied.
Co-reporter:Nian Zhao; Fuxing Sun; Shixing Zhang; Hongming He; Jia Liu; Qin Li
Inorganic Chemistry 2015 Volume 54(Issue 1) pp:65-68
Publication Date(Web):December 9, 2014
DOI:10.1021/ic501560z
A new three-dimensional porous metal–organic framework, JUC-119, constructed by a pyrene-based dendritic organic linker, H8TIAPy (H8TIAPy = 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene), and Eu(III) has been synthesized successfully. JUC-119 shows unexpected stability under a wide range of basic conditions from 0 to 0.01 M NaOH. Furthermore, with two carboxyl groups uncoordinated in each ligand, the crystals of JUC-119 show deprotonation-triggered Stokes shift fluorescence under basic conditions. As the concentration of base increases from 0 to 0.01 M NaOH, the luminescence emission of JUC-119 becomes gradually red shifted from 455 to 485 nm. In addition, the Stokes shift shows a good linear relationship to −log[OH–], which makes JUC-119 promising for base sensing.
Co-reporter:Hongming He, Yang Song, Fuxing Sun, Nian Zhao, and Guangshan Zhu
Crystal Growth & Design 2015 Volume 15(Issue 4) pp:2033-2038
Publication Date(Web):March 11, 2015
DOI:10.1021/acs.cgd.5b00229
We first designed and synthesized a new semirigid tripodal ligand with tetrazole groups, 1,3,5-tri(4-(2H-tetrazol-5-yl)phenoxy)benzene (H3TTPB). Two isostructural microporous metal–organic frameworks (MOFs), namely [Cu3(TTPB)2(H2O)6]·5DMF (JUC-130) and [Cd3(TTPB)2(H2O)6]·6DMF (JUC-131) (JUC = Jilin University, China), were successfully synthesized under solvothermal reactions based on this ligand, which both possess two-dimensional (2D) frameworks based on similar trinuclear metal centers as secondary building units (SBUs). H3TTPB was designed as the organic building block, not only because it is suitable to construct functionalized microporous frameworks with numerous nitrogen atoms but also by reason for its blue luminescent emission. Gas sorption measurements indicated that they are both microporous frameworks. JUC-130 showed high stability in water and selective sorption capabilities for alcohol and water vapors, which may be further used for the separation of alcohol–water mixtures. In addition, JUC-131 exhibited interesting and important fluorescent properties, which can be used as one of the few known MOFs useful for the detection of nitroaromatics via “supramolecular wire effect”.
Co-reporter:Dr. Zhuojun Yan;Dr. Ye Yuan;Dr. Yuyang Tian; Daming Zhang; Guangshan Zhu
Angewandte Chemie 2015 Volume 127( Issue 43) pp:12924-12928
Publication Date(Web):
DOI:10.1002/ange.201503362
Abstract
The targeted synthesis of a series of novel charged porous aromatic frameworks (PAFs) is reported. The compounds PAF-23, PAF-24, and PAF-25 are built up by a tetrahedral building unit, lithium tetrakis(4-iodophenyl)borate (LTIPB), and different alkyne monomers as linkers by a Sonogashira–Hagihara coupling reaction. They possess excellent adsorption properties to organic molecules owing to their “breathing” dynamic frameworks. As these PAF materials assemble three effective sorption sites, namely the ion bond, phenyl ring, and triple bond together, they exhibit high affinity and capacity for iodine molecules. To the best of our knowledge, these PAF materials give the highest adsorption values among all porous materials (zeolites, metal–organic frameworks, and porous organic frameworks) reported to date.
Co-reporter:Dr. Zhuojun Yan;Dr. Ye Yuan;Dr. Yuyang Tian; Daming Zhang; Guangshan Zhu
Angewandte Chemie International Edition 2015 Volume 54( Issue 43) pp:12733-12737
Publication Date(Web):
DOI:10.1002/anie.201503362
Abstract
The targeted synthesis of a series of novel charged porous aromatic frameworks (PAFs) is reported. The compounds PAF-23, PAF-24, and PAF-25 are built up by a tetrahedral building unit, lithium tetrakis(4-iodophenyl)borate (LTIPB), and different alkyne monomers as linkers by a Sonogashira–Hagihara coupling reaction. They possess excellent adsorption properties to organic molecules owing to their “breathing” dynamic frameworks. As these PAF materials assemble three effective sorption sites, namely the ion bond, phenyl ring, and triple bond together, they exhibit high affinity and capacity for iodine molecules. To the best of our knowledge, these PAF materials give the highest adsorption values among all porous materials (zeolites, metal–organic frameworks, and porous organic frameworks) reported to date.
Co-reporter:Faheem Muhammad, Aifei Wang, Lu Miao, Pengyuan Wang, Qin Li, Jia Liu, Jianshi Du, and Guangshan Zhu
Langmuir 2015 Volume 31(Issue 1) pp:514-521
Publication Date(Web):December 9, 2014
DOI:10.1021/la503922j
Our immune system uses toxicity of hydrogen peroxide to kill off bacterial invaders. In this contribution, we intended to integrate ROS producing capability of immune system with oxidant-sensitive nature of antibacterial silver nanoparticles (Ag NPs) to develop an oxidant drug delivery system. Prior to execute this strategy, we have developed an efficient one-pot synthetic protocol to produce ultrasmall (5 nm), water-stable, and oxidant-prone Ag NPs. Notably, the yield of as-synthesized Ag NPs is 10-fold higher than standard citrate reduction route. The resulting therapeutically active and well-dispersed Ag NPs are used as nanolids to cap the drug loaded nanochannels of porous silica. Upon exposing to H2O2, dissolution-accompanied aggregation of Ag nanolids unleashes the encapsulated therapeutic entities from channels of nanocarrier. Combination of antibacterial and anti-inflammatory drugs in single nanocarriers can potentially augment the effectiveness of various therapies.
Co-reporter:Rongrong Yuan;Hao Ren;Hongming He;Lingchang Jiang
Science China Materials 2015 Volume 58( Issue 1) pp:38-43
Publication Date(Web):2015 January
DOI:10.1007/s40843-015-0023-8
Two porous aromatic frameworks, PAF-36 and PAF-37, containing azo moieties, were synthesized via Sonogashira-Hagihara coupling reactions. Gas sorption measurements indicated that reversible stimuli-responsive adsorption properties were triggered by ultraviolet (UV) irradiation and heat treatment, because of the presence of azo functional groups. The initial Brunauer-Emmett-Teller (BET) surface areas of PAF-36 and PAF-37 were 325 and 443 m2 g−1, respectively. After UV irradiation, the BET surface areas increased during the trans-cis isomerization process, and the micropore sizes, around 6 and 8 Å, also increased. In addition, the CO2 adsorption capacities increased slightly because of trans-cis conversion of azo groups. It is worth mentioning that the CO2 uptakes of the polymers were almost constant during multiple cycles of alternating external stimuli, displaying high switchability of the trans-cis isomerization.本文报导了通过Sonogashira-Hagihara反应制备两种骨架含有偶氮官能团的多孔芳香骨架材料, PAF-36和PAF-37, 并研究了它们的氮气及二氧化碳吸附性能. 偶氮官能团经过紫外光照射和加热可以实现顺式和反式结构变换. 它们初始BET比表面积分别是325 m2 g−1和443 m2 g−1. 经过紫外光照, 偶氮官能团发生顺反异构化, 材料的BET比表面积以及在6 Å和8 Å的孔径分布均有所增大. 另外, 紫外光照后, 材料的CO2吸附性能也有一定提高. 对样品进行了三次紫外/加热循环实验后, 样品CO2吸附量几乎保持不变, 表明材料中可以发生顺反异构化的偶氮基团具有高效的开关性能. 在多孔材料中引入光控基团, 可以有效改变材料的孔结构, 进而影响材料的气体分子吸附性能.
Co-reporter:Xue Gao;Xiaoqin Zou;Heping Ma;Shuang Meng
Advanced Materials 2014 Volume 26( Issue 22) pp:3644-3648
Publication Date(Web):
DOI:10.1002/adma.201400020
Co-reporter:Aifei Wang, Mingyi Guo, Nan Wang, Jianyun Zhao, Wenxiu Qi, Faheem Muhammad, Liang Chen, Yingjie Guo, Nam-Trung Nguyen and Guangshan Zhu
Nanoscale 2014 vol. 6(Issue 10) pp:5270-5278
Publication Date(Web):17 Feb 2014
DOI:10.1039/C3NR05687B
Manganese oxide (Mn3O4) nanoparticles have recently emerged as a promising T1 contrast agent. In this study, for the first time, we demonstrated an interaction of Mn3O4 with a biological system, and found redox sensitive behavior of these paramagnetic nanoparticles in intracellular reducing environment. Inspired by these findings, we for the first time used this interaction for some therapeutic advantages and designed a versatile mesoporous silica based nanotheranostic system to realize redox-activated enhanced magnetic resonance imaging and responsive anticancer drug delivery. Contrary to previous reports, we firstly prepared high quality amine terminated hydrophilic Mn3O4 nanolids, without using multistep ligand exchange strategies. The resulting water stable and small-sized Mn3O4 nanolids were subsequently used as nanolids to cap drug loaded nanochannels of a porous carrier. Exposure to highly prevalent intracellular reducing environment resulted in the steady-state dissolution of these nanolids and attained an intelligent drug release. Furthermore, the redox receptive dissolution of paramagnetic Mn3O4 nanolids into Mn2+ in turn increases the T1 signal to twofold, providing an added opportunity to even track the feedback of therapy. This study, in addition to simultaneously realizing drug delivery and imaging, also provides a new insight into the fate and interaction of manganese oxide nanoparticles with components of biological systems.
Co-reporter:Guangli Yu, Xiaoqin Zou, Aifei Wang, Jian Sun and Guangshan Zhu
Journal of Materials Chemistry A 2014 vol. 2(Issue 37) pp:15420-15427
Publication Date(Web):22 Jul 2014
DOI:10.1039/C4TA02565B
In the present study, a facile strategy is proposed for generating bimodal porosity in porous carbons by using a sacrificed metal–organic framework (ZIF-8) as the precursor and additional silica colloids as extra porogenes via further self-assembly. Details in the formation of hierarchical structures are studied by time-dependent XRD and TEM characterizations. As-synthesized hierarchical porous carbons possess micropores (1.0 nm) and mesopores (3–20 nm) that are verified by TEM and N2-sorption measurements. Specific information on carbon structures is supplied by XRD and Raman data. Electrochemical properties have been briefly investigated by cyclic voltammetry and impedance spectroscopy. A highest capacitance of 181 F g−1 and lowest resistance of 0.21 Ω cm2 are obtained between series of ZIF-8 derivative carbons, both of which, along with high electro-stability, show promising applications for these nanoporous carbons in supercapacitors.
Co-reporter:Shuang Meng, Heping Ma, Lingchang Jiang, Hao Ren and Guangshan Zhu
Journal of Materials Chemistry A 2014 vol. 2(Issue 35) pp:14536-14541
Publication Date(Web):30 Jun 2014
DOI:10.1039/C4TA00984C
Porous organic frameworks (POFs) have attracted a great deal of attention thanks to their high surface areas, high stability and controllable skeletons. We synthesize a series of porphyrin-based porous aromatic frameworks (PAF-40s) through a cost-effective approach. The PAF-40s exhibit high surface areas and excellent chemical and thermal stability. Specifically, these PAF materials possess high adsorption capacity of small hydrocarbons, such as methane, ethylene, ethane and propane, at room temperature. Furthermore, the PAFs have remarkably high adsorption selectivity values of C2 and C3 hydrocarbons over CH4.
Co-reporter:Lina Li, Hao Ren, Ye Yuan, Guangli Yu and Guangshan Zhu
Journal of Materials Chemistry A 2014 vol. 2(Issue 29) pp:11091-11098
Publication Date(Web):11 Apr 2014
DOI:10.1039/C4TA01252F
Currently, synthesis of most porous organic frameworks (POFs) requires noble metals as the main catalyst. Herein we report a low-cost and straightforward synthetic strategy to develop porous aromatic frameworks (PAFs). With AlCl3 as the catalyst, the Scholl coupling reaction could occur between the phenyl rings of aromatic compounds. Using 3-dimensional monomers, such as triphenylamine, tetraphenylmethane, tetraphenylsilane, and tetraphenylgermane, we successfully obtained a series of PAFs with moderate Brunauer–Emmett–Teller (BET) surface areas ranging from 515 m2 g−1 to 1119 m2 g−1. Among the obtained PAF materials, PAF-41 exhibited the best CH4 and CO2 sorption capacity with CH4 (1.04 mmol g−1) and CO2 (3.52 mmol g−1) at 273 K. In addition, PAF-43 demonstrated its comparably high isosteric heat of adsorption at 34.8 kJ mol−1 for CO2 and 29.7 kJ mol−1 for CH4. It is also worth mentioning that the developed approach also overcomes typical flaws of some classic PAFs, such as high cost and complexity of precursor preparation.
Co-reporter:Xiaoqiang Liang, Feng Zhang, Haixia Zhao, Wei Ye, Lasheng Long and Guangshan Zhu
Chemical Communications 2014 vol. 50(Issue 49) pp:6513-6516
Publication Date(Web):27 Mar 2014
DOI:10.1039/C4CC00458B
A multifunctional metal–organic framework generated from chiral tricarboxylate ligands and gadolinium ions has been successfully synthesized and characterized. It shows proton conduction, dielectric anomalous behaviour and a second-order NLO effect.
Co-reporter:Faheem Muhammad, Aifei Wang, Wenxiu Qi, Shixing Zhang, and Guangshan Zhu
ACS Applied Materials & Interfaces 2014 Volume 6(Issue 21) pp:19424
Publication Date(Web):October 14, 2014
DOI:10.1021/am5055367
Regeneratable antioxidant property of nanoceria has widely been explored to minimize the deleterious influences of reactive oxygen species. Limited information is, however, available regarding the biological interactions and subsequent fate of nanoceria in body fluids. This study demonstrates a surprising dissolution of stable and ultrasmall (4 nm) cerium oxide nanoparticles (CeO2 NPs) in response to biologically prevalent antioxidant molecules (glutathione, vitamin C). Such a redox sensitive behavior of CeO2 NPs is subsequently exploited to design a redox responsive drug delivery system for transporting anticancer drug (camptothecin). Upon exposing the CeO2 capped and drug loaded nanoconstruct to vitamin c or glutathione, dissolution-accompanied aggregation of CeO2 nanolids unleashes the drug molecules from porous silica to achieve a significant anticancer activity. Besides stimuli responsive drug delivery, immobilization of nanoceria onto the surface of mesoporous silica also facilitates us to gain a basic insight into the biotransformation of CeO2 in physiological mediums.Keywords: antioxidants; chemotherapy; controlled release; nanoceria; reactive oxygen species; redox responsive
Co-reporter:Aifei Wang, Faheem Muhammad, Wenxiu Qi, Nan Wang, Liang Chen, and Guangshan Zhu
ACS Applied Materials & Interfaces 2014 Volume 6(Issue 16) pp:14377
Publication Date(Web):July 15, 2014
DOI:10.1021/am503655z
Poor water solubility is believed one of the most critical problems of numerous promising pharmaceutical ingredients in their successful clinical utilization. Nanomedicine holds considerable promise to address this challenge, because it extends the therapeutic window of hydrophobic drugs through nanonization approach. Recently, the integration of diagnostic agents with smart therapeutic nanocarriers is also an emerging research arena to simultaneously visualize diseased tissues, achieve site specific drug release and track the impact of therapy. In this study, we have developed a biocompatible smart theranostic nanosystem which transports a highly promising hydrophobic drug (curcumin) in response to mildly acidic environment. As calcium is a main constituent of human body, hence we exploited the reversible calcium chelate formation tendency of divalent calcium to load and unload curcumin molecules. Moreover, an emerging T1 contrast agent is also tethered onto the surface of nanocarrier to realize MRI diagnosis application. In-vitro cell experiments revealed a significantly high chemotherapeutic efficiency of curcumin nanoformulation (IC50; 1.67 μg/mL), whereas free curcumin was found ineffective at the corresponding concentration (IC50; 29.72 μg/mL). MR imaging test also validated the performance of resulting system. Our strategy can be extended for the targeted delivery of other hydrophobic pharmaceutical ingredients.Keywords: controlled release; curcumin; mesoporous silica; pH responsive; theranostic
Co-reporter:Rongrong Yuan, Hao Ren, Zhuojun Yan, Aifei Wang and Guangshan Zhu
Polymer Chemistry 2014 vol. 5(Issue 7) pp:2266-2272
Publication Date(Web):25 Nov 2013
DOI:10.1039/C3PY01252B
We report here the synthesis and carbon dioxide capture of a series of porous aromatic framework (PAF) materials assembled using tri(4-ethynylphenyl)amine and various aryl halides via Sonogashira–Hagihara coupling reactions. These PAF materials show moderate surface areas ranging from 370 m2 g−1 to 953 m2 g−1. The functional groups, such as –COOH, –NH2 and –OH, are incorporated into the backbone of the PAF materials. The isosteric heats of CO2 and CO2/N2 selectivities for these PAFs are calculated based on the CO2 and N2 adsorption isotherms measured at 273 and 298 K. It is found that the –NH2 functionalized network shows the highest isosteric heat of CO2 and CO2/N2 selectivity. In addition, the –COOH functionalized network displays the highest CO2 uptake in terms of per unit areas (4.37 μmol m−2, 273 K). The results indicate the incorporation of functional groups is effective for synthesizing CO2-philic PAF networks with enhanced interaction with CO2 molecules.
Co-reporter:Heping Ma, Hao Ren, Xiaoqin Zou, Shuang Meng, Fuxing Sun and Guangshan Zhu
Polymer Chemistry 2014 vol. 5(Issue 1) pp:144-152
Publication Date(Web):24 Jul 2013
DOI:10.1039/C3PY00647F
The development of microporous materials for carbon capture, especially for carbon dioxide and methane, is a rapidly growing field based on the increasing demand for clean energy and pressing environmental concerns of global warming effected by greenhouse gases. To achieve this goal of developing carbon selective porous materials, a new porous aromatic framework featuring carboxyl-decorated pores, PAF-26-COOH, has been synthesized successfully. The modification of PAF-26 materials with representative light metals is exemplified by Li, Na, K and Mg via a post-metalation approach. The obtained PAF-26 products exhibit moderate surface area and controllable pore size at the atomic level. Gas sorption of CO2, CH4 and N2 is carried out on as-prepared PAF-26 samples at mild temperatures (273 K and 298 K). It is found that the PAF-26 materials show high adsorption capacity for CO2 and CH4 and low ability toward N2. Particularly, as-synthesized PAF-26 compounds exhibit remarkably high isosteric heats of adsorption toward CO2 and CH4, indicating high affinity for CO2 and CH4 gases. The gas selectivity for CO2–N2 and CH4–N2 mixtures is predicted by the IAST model. High selectivity of 80 for CO2 over N2 is obtained for PAF-26-COOMg. In addition, high selectivity values of CH4 over N2 are observed. The high performance including high storage capacity and selectivity makes PAF-26 materials promising for carbon capture or sequestration.
Co-reporter:Juhyon Yu, Mingyi Guo, Faheem Muhammad, Aifei Wang, Feng Zhang, Qin Li, Guangshan Zhu
Carbon 2014 Volume 69() pp:502-514
Publication Date(Web):April 2014
DOI:10.1016/j.carbon.2013.12.058
Nitrogen-containing ordered mesoporous carbon has been prepared by a soft-templating strategy, without using intricate prepolymerization and hydrothermal solidification steps. This strategy involves the use of hexamethylenetetramine, slow releasing source of formaldehyde for the self-assembly of resorcinol–urea–formaldehyde resin, to mediate the formation of nitrogen enriched carbon organic precursor, whereas ampliphilic triblock copolymer (Pluronic F127) was used as a template. Small angle X-ray diffraction, transmission electron microcopy, nitrogen sorption demonstrated that the obtained mesoporous carbon possessed a body-centered cubic Im3‾m structure with a high surface area. X-ray photoelectron spectroscopy revealed that the incorporated nitrogen was present in the form of pyridine, pyrrolyic/pyridine, quaternary and oxidized nitrogen. The presence of nitrogen groups in the resulting material significantly improved the CO2 adsorption capacity for mesoporous carbon (3.3 mmol g−1 at 0 °C, 2.6 mmol g−1 at 25 °C) and activated mesocarbon (4.9 mmol g−1 at 0 °C, 3.1 mmol g−1 at 25 °C) at 0.95 bar. This feature substantiates N-doped mesoporous carbon as a promising high-performance CO2 capture sorbent.
Co-reporter:Faheem Muhammad, Mingyi Guo, Aifei Wang, Jianyun Zhao, Wenxiu Qi, Yingjie Guo, Guangshan Zhu
Journal of Colloid and Interface Science 2014 Volume 434() pp:1-8
Publication Date(Web):15 November 2014
DOI:10.1016/j.jcis.2014.07.024
•Integration of nanotechnology with combinatorial therapy.•Significant camptothecin loading with controlled release.•pH responsive release of doxorubicin.•Sense the release of doxorubicin through fluorescent on–off states.•Excellent chemotherapeutic effect.After a substantial advancement in single drug nanocarrier, nanomedicine now demands an integration of nanotechnology with combination therapy to achieve synergistic therapeutic effects. In this respect, a smart and multiple drug shuttling nanotheranostic system is developed which transport diverse kinds of anticancer drugs to cancer cells in a controlled and responsive manner respectively. Synthetically, a significantly high dose of hydrophobic camptothecin (CPT) is first loaded into the porous structure of quantum dots (CdS) coupled mesoporous silica nanocomposite. Subsequently, fluorescent doxorubicin (DOX) molecules are exclusively anchored onto the surface of CdS; as a result, the fluorescence of both CdS and DOX is quenched. Upon exposing to mildly acidic conditions, the fluorescence of both species is recovered, such fluorescent “on–off” states provides an added opportunity to real time sense drug release. In-vitro cell experiment reveals an excellent anticancer efficacy of drug cocktail, merely 3 μg/ml concentration of multiple drugs loaded nanocarrier reduces the cell viability to 30%. Furthermore, confocal imaging indicates a successful release of both therapeutic entities. We visualize that our newly fabricated multifunctional double drug-carrying nanoparticles can be a valuable addition to next generation of materials that simultaneously deliver cocktail of drugs with imaging functionality.
Co-reporter:Hongming He, Fuxing Sun, Jiangtao Jia, Zheng Bian, Nian Zhao, Xuepeng Qiu, Lianxun Gao, and Guangshan Zhu
Crystal Growth & Design 2014 Volume 14(Issue 9) pp:4258-4261
Publication Date(Web):August 12, 2014
DOI:10.1021/cg501012e
A dendritic aromatic 12-carboxyl ligand (H12TDDPB) is assembled with Zn(II) ion. The TDDPB dimer coordinated with 12 Zn(II) ions, regarded as a dodecapus, is stabilized by metal coordination and π–π stacking. The dodecapus-based framework presents a new type of topology (hhm) with the point symbol of (6·8·10)3(63·8·10·12)3(63)7. The resulting material emits strong blue luminescence in DMF, while the maximum emission of free ligand H12TDDPB is in the ultraviolet region.
Co-reporter:Hongming He, Fuxing Sun, Tsolmon Borjigin, Nian Zhao and Guangshan Zhu
Dalton Transactions 2014 vol. 43(Issue 9) pp:3716-3721
Publication Date(Web):26 Nov 2013
DOI:10.1039/C3DT53013B
Metal–organic frameworks (MOFs) are a rapidly growing class of hybrid materials with many multifunctional properties. The permanent porosity plays a central role in the functional properties. In particular, the luminescent MOFs with a permanent porosity have wide applications in guest species recognition and adsorption. In this contribution, we aim to develop tunable colors and white-light luminescence materials by the encapsulation of Ln3+ species in microporous luminescent MOFs. A semi-rigid trivalent carboxylic acid 1,3,5-tri(4-carboxyphenoxy)benzene (H3TCPB) was selected as the organic building block, not only because it is suitable to construct microporous frameworks, but also by reason of its blue luminescent emission. Under solvothermal reactions, a microporous MOF material, [Zn3(TCPB)2(H2O)2]·2H2O·4DMF (JUC-113, JUC = Jilin University, China), was synthesized, which has a permanent porosity and emits blue light. According to three-primary colors, the guest luminescent species should be Tb3+ and Eu3+ owing to their distinctive colors (Tb3+, green; Eu3+, red). In addition, the luminescent properties of JUC-113 can be easily tuned by different combinations of the encapsulation amount of Tb3+ and Eu3+, obtaining white-light emission materials.
Co-reporter:Tingting Zhang, Yan Yang, Xiaojun Zhao, Jiangtao Jia, Hongmin Su, Hongming He, Jingkai Gu and Guangshan Zhu
CrystEngComm 2014 vol. 16(Issue 33) pp:7667-7672
Publication Date(Web):26 Jun 2014
DOI:10.1039/C4CE00784K
The pharmaceutical cocrystal approach can be used to modify the properties of paliperidone. We report here two novel cocrystals, paliperidone 4-hydroxybenzoic acid cocrystal (1, 1:1, w/w) and paliperidone 4-aminobenzoic acid cocrystal (2, 1:1, w/w), with CCDC numbers of 855981 and 948923, which were constructed using paliperidone with 4-hydroxybenzoic acid and 4-aminobenzoic acid, respectively. The experimental results of the dissolution studies revealed that both 1 and 2 showed much faster dissolution rates than the original active pharmaceutical ingredient (API) in simulated gastric fluid media (pH = 1.2). The pharmacokinetic (PK) studies of 1, 2 and the original API were conducted using beagle dogs. 1 has a slightly higher maximal serum concentration, and both of the cocrystals presented considerably faster absorption rates after a single-dose oral administration to beagle dogs compared to the original API. Observed improvements suggested their potential application to the treatment of acute schizophrenia.
Co-reporter:Hongming He, Fuxing Sun, Hongmin Su, Jiangtao Jia, Qin Li and Guangshan Zhu
CrystEngComm 2014 vol. 16(Issue 3) pp:339-343
Publication Date(Web):30 Oct 2013
DOI:10.1039/C3CE41764F
Three metal–organic frameworks (MOFs), namely [Zn2(TPIA)(OH)(H2O)]·H2O (JUC-114), [Cd2(TPIA)(OH)(H2O)2]·H2O (JUC-115), and [Co2(TPIA)(OH)(H2O)2]·H2O (JUC-116) (JUC = Jilin University China), based on a new ligand, 5-(4-(2H-tetrazol-5-yl)phenoxy)isophthalic acid (H3TPIA), were synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, TGA analysis and powder X-ray diffraction. JUC-114, JUC-115 and JUC-116 all possess 3D frameworks with (4,8)-connected fluorite (flu) topology based on similar tetranuclear metal centers as secondary building unit (SBU). Furthermore, the luminescence of the ligand H3TPIA and compounds was measured at room temperature.
Co-reporter:Nian Zhao, Fuxing Sun, Hongming He, Jiangtao Jia, and Guangshan Zhu
Crystal Growth & Design 2014 Volume 14(Issue 4) pp:1738-1743
Publication Date(Web):March 10, 2014
DOI:10.1021/cg401887b
The structure transformation of a metal–organic framework (MOF) constructed by a pyrene-based ligand 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene (H8TIAPy), [Zn4(TIAPy)·(DMSO)2·(H2O)4]·(Guest) (JUC-118), was investigated when soaked in different solvents. Single crystal X-ray diffraction revealed that JUC-118 could convert into JUC-118-1, whose lattice parameters were obviously different in ethylene glycol monomethylether (EGME). It was found that the torsion angles between the pyrene and the benenze rings of the ligand changed from 41.2 deg to 61.3 deg. Thus, the channel structure in the direction [101] had an obvious difference from a compressed rhombic shape to an expanded one. In addition, EGME could also induce complete metal exchange of Cu(II) for Zn(II) when soaking either JUC-118 or JUC-118-1 in EGME. However, no similar phenomena were found while soaking them in DMF. As the lattice parameters changed, the fluorescence had a blue shift, from 485 to 460 nm. These observations might guide us to design and synthesize materials with a fluorescence response for guest recognition.
Co-reporter:Guangli Yu, Jian Sun, Faheem Muhammad, Pengyuan Wang and Guangshan Zhu
RSC Advances 2014 vol. 4(Issue 73) pp:38804-38811
Publication Date(Web):04 Aug 2014
DOI:10.1039/C4RA03746D
Novel nitrogen–cobalt catalysts have been successfully synthesized via one-step pyrolysis of cobalt-based metal organic framework (ZIF-67) at different temperatures under an inert atmosphere. The influence of the carbonization temperature on the porous structure of the nitrogen–cobalt catalysts is comprehensively investigated through XRD, XPS and N2 adsorption techniques. Furthermore, the catalytic performance is investigated for epoxidation of styrene using air as the terminal oxidant. The prepared catalysts exhibit excellent styrene conversion (76.2–91.3%) with better epoxide selectivity (81.3–84.8%) in comparison with neat ZIF-67 (39.3%, 79.4%). Advantageously, the magnetically recoverable catalysts could be efficiently reused for 5 times without noticeable deterioration in activity and selectivity. This work provides an elegant approach for the development of cost-effective and practical catalysts for oxidation reactions.
Co-reporter:Hongming He, Fuxing Sun, Nian Zhao, Rongrong Yuan and Guangshan Zhu
RSC Advances 2014 vol. 4(Issue 41) pp:21535-21540
Publication Date(Web):02 May 2014
DOI:10.1039/C4RA02872D
Three metal–organic frameworks (MOFs), namely [Zn(BPT)H2O] (JUC-121), [Zn5(IBT)6]·8[H2N(CH3)2]·DMA (JUC-122) and [Zn(TPD)(H2O)2]·0.5H2O (JUC-123) (JUC = Jilin University, China), H2BPT = (5-bromo-1,3-phenylene)bis(tetrazole), H3IBT = 4,5-bis(tetrazol-5-yl)imidazole and H2TPD = 3,5-di(tetrazol-5-yl)pyridine, were obtained by the reactions of Zn(NO3)2·6H2O and three tetrazolate ligands, which were characterized by single crystal X-ray diffraction, thermal gravimetric analyses (TGA), Fourier-transform infrared spectra (FT-IR), elemental analysis (CHN) and powder X-ray diffraction (PXRD). From the crystal structures of these complexes and the coordination modes of the ligands, we can see that the tetrazolate ligands have multi-connectivity abilities to obtain intriguing varieties of molecular architectures. JUC-121 displays a three-dimensional (3D) network with the point symbol (4·65)2(42·84)(64·82). JUC-122 shows a two-dimensional (2D) framework with the point symbol (243)2(24)9 and JUC-123 has a 2D bimodal (3, 3)-connected net with the point symbol (4·82). The solid-state fluorescent spectra of JUC-121, JUC-122, JUC-123 and the free ligands were measured at room temperature.
Co-reporter:Wei Wang, Ye Yuan, Fu-Xing Sun, Guang-Shan Zhu
Chinese Chemical Letters 2014 Volume 25(Issue 11) pp:1407-1410
Publication Date(Web):November 2014
DOI:10.1016/j.cclet.2014.08.002
Novel porous aromatic frameworks (PAF-53 and PAF-54) have been obtained by the polymerization of amino compound (p-phenylenediamine and melamine) and cyanuric chloride. They display a certain amount of CO2 adsorption capacity and highly selective separation of CO2/CH4 and CO2/N2 as 18.1 and 83 by Henry Law respectively. They may be applied as ideal adsorbents to separate and capture CO2.Two novel porous aromatic frameworks (PAF-53 and PAF-54) have been obtained by the polymerization of amino compounds (p-phenylenediamine and melamine) and cyanuric chloride. They display high selective separation of CO2/CH4 and CO2/N2 and make a promise as ideal candidates to capture CO2.
Co-reporter:Faheem Muhammad, Jianyun Zhao, Nan Wang, Mingyi Guo, Aifei Wang, Liang Chen, Yingjie Guo, Qin Li, Guangshan Zhu
Colloids and Surfaces B: Biointerfaces 2014 Volume 123() pp:506-514
Publication Date(Web):1 November 2014
DOI:10.1016/j.colsurfb.2014.09.046
•A straightforward strategy is developed to integrate the cancer combinatorial therapy with nanotechnology.•Compared to previous studies, substantially high (29%) loading of hydrophobic camptothecin is reported.•Unconventional but FDA approved antitumor drug, arsenic trioxide (ATO) is conjugated onto the surface nanocarrier as second chemotherapeutic entity.•Double drug nanoformulation exhibits an excellent cell inhibition performance.•Presence of superparamagnetic magnetite nanocrystals empowers this system to be used as a contrast agent in magnetic resonance (MR) imaging besides drug carrier.Simultaneous delivery of multiple therapeutic agents is of great importance for effective chemotherapy due of its well-known drug synergism and suppression to chemoresistance. We report a new theranostic nanoformulation to shuttle multiple chemotherapeutic agents for successfully exterminating cancer cells. This strategy is based on the fabrication of magnetite doped mesoporous silica nanoparticles (MSNs) in which both internal porous and external surface of MSN are respectively exploited to load two different kinds of cytotoxic cargoes. Notably, an exceptionally high quantity (29%) of poorly hydrophobic drug camptothecin (CPT) is loaded into the nanopores of MSNs; however, in previous reports less than 1% loading efficiency is reported. Following CPT loading in the pores of MSNs, another unconventional but FDA approved arsenic trioxide (ATO) is conjugated onto the surface of nanocomposite via exploiting the thiophilic nature of ATO. Cell inhibition performance of dual drug nanoformulation is significantly higher than single drug formulation, possibly due to additional or synergistic effect, as low as 3 μg/ml of double drug nanocarrier were found effective to exterminate cancer cells. Besides drug delivery, the presence of superparamagnetic magnetite nanocrystals additionally empowers this system to be used as a contrast agent in magnetic resonance (MR) imaging for either monitoring diseased tissues or feedback of chemotherapy. We anticipate that the integration of combination therapy with nanotechnology coupled with versatile magnetic manipulation feature may prove a significant step forward toward the development of effective theranostic agents.
Co-reporter:Dr. Jiangtao Jia;Lei Wang;Fuxing Sun;Xiaofei Jing;Dr. Zheng Bian; Lianxun Gao; Rajamani Krishna; Guangshan Zhu
Chemistry - A European Journal 2014 Volume 20( Issue 29) pp:9073-9080
Publication Date(Web):
DOI:10.1002/chem.201304962
Abstract
Three isoreticular metal–organic frameworks, JUC-100, JUC-103 and JUC-106, were synthesized by connecting six-node dendritic ligands to a [Zn4O(CO2)6] cluster. JUC-103 and JUC-106 have additional methyl and ethyl groups, respectively, in the pores with respect to JUC-100. The uptake measurements of the three MOFs for CH4, C2H4, C2H6 and C3H8 were carried out. At 298 K, 1 atm, JUC-103 has relatively high CH4 uptake, but JUC-100 is the best at 273 K, 1 atm. JUC-100 and JUC-103 have similar C2H4 absorption ability. In addition, JUC-100 has the best absorption capacity for C2H6 and C3H8. These results suggest that high surface area and appropriate pore size are important factors for gas uptake. Furthermore, ideal adsorbed solution theory (IAST) analyses show that all three MOFs have good C3H8/CH4 and C2H6/CH4 selectivities for an equimolar quaternary CH4/C2H4/C2H6/C3H8 gas mixture maintained at isothermal conditions at 298 K, and JUC-106 has the best C2H6/CH4 selectivity. The breakthrough simulations indicate that all three MOFs have good capability for separating C2 hydrocarbons from C3 hydrocarbons. The pulse chromatographic simulations also indicate that all three MOFs are able to separate CH4/C2H4/C2H6/C3H8 mixture into three different fractions of C1, C2 and C3 hydrocarbons.
Co-reporter:Juhyon Yu, Mingyi Guo, Faheem Muhammad, Aifei Wang, Guangli Yu, Heping Ma, Guangshan Zhu
Microporous and Mesoporous Materials 2014 190() pp: 117-127
Publication Date(Web):
DOI:10.1016/j.micromeso.2014.02.009
Co-reporter:Ye Yuan;Fuxing Sun;Feng Zhang;Hao Ren;Mingyi Guo;Kun Cai;Xiaofei Jing;Xue Gao
Advanced Materials 2013 Volume 25( Issue 45) pp:6619-6624
Publication Date(Web):
DOI:10.1002/adma.201301955
Co-reporter:Xiaoqiang Liang, Feng Zhang, Wei Feng, Xiaoqin Zou, Chengji Zhao, Hui Na, Cong Liu, Fuxing Sun and Guangshan Zhu
Chemical Science 2013 vol. 4(Issue 3) pp:983-992
Publication Date(Web):23 Nov 2012
DOI:10.1039/C2SC21927A
A chiral two-dimensional MOF, {[Ca(D-Hpmpc)(H2O)2]·2HO0.5}n (1, D-H3pmpc = D-1-(phosphonomethyl) piperidine-3-carboxylic acid), with intrinsic proton conductivity has been synthesized and characterized. Structure analysis shows that compound 1 possesses protonated tertiary amines as proton carriers and hydrogen-bonding chains served as proton-conducting pathways. Further, MOF–polymer composite membranes have been fabricated via assembling polymer PVP with different contents of rod-like 1 submicrometer crystals. Interestingly, the proton conductivity of this composite membrane containing 50 wt% 1 is rapidly increased, compared with that of pure submicrometer crystals at 298 K and ∼53% RH. Therefore, it is feasible to introduce humidification of PVP into composite membranes to enhance low-humidity proton conductivity; and humidified PVP with adsorbed water molecules plays an important role in proton conduction indicated by the results of water physical sorption and TG/DTG analyses. This study may offer a facile strategy to prepare a variety of solid electrolyte materials with distinctive proton-conducting properties under a low humidity.
Co-reporter:Xiaofei Jing, Donglei Zou, Peng Cui, Hao Ren and Guangshan Zhu
Journal of Materials Chemistry A 2013 vol. 1(Issue 44) pp:13926-13931
Publication Date(Web):2013/09/18
DOI:10.1039/C3TA13115G
Porous aromatic frameworks (PAF-32s) derived from tetrahedral monomers as basic building units have been successfully synthesized via the Friedel–Crafts alkylation reaction in the presence of the inexpensive catalyst FeCl3. The resulting PAF-32 materials possess high stabilities and high surface areas up to 1679 m2 g−1. In particular, amino and hydroxyl functional groups have been introduced into the networks. The corresponding functionalized PAF materials (PAF-32-NH2 and PAF-32-OH) display enhanced CO2 adsorption capacities and higher heats of adsorption (Qst) than the non-functionalized PAF-32.
Co-reporter:Songjie Fan, Fuxing Sun, Jijiang Xie, Jin Guo, Laiming Zhang, Chunrui Wang, Qikun Pan and Guangshan Zhu
Journal of Materials Chemistry A 2013 vol. 1(Issue 37) pp:11438-11442
Publication Date(Web):19 Jul 2013
DOI:10.1039/C3TA11604B
Cu(bipy)2(SiF6) is a highly porous metal–organic framework (MOF) and represents a prototypal “pillared sheet” platform offering opportunities to control the pore sizes. Its structural features, low cost and facile synthesis make it a great candidate to fabricate membranes for gas separation. The key to obtaining thin, continuous Cu(bipy)2(SiF6) membranes is to control the Cu(bipy)2(SiF6) crystal growth and enhance the binding between membrane and substrate. Here we explored a new route by direct synthesis and successfully obtained a continuous thin Cu(bipy)2(SiF6) membrane on a macroporous glass-frit disk with high robustness. It is speculated that the SiF62− used to construct the Cu(bipy)2(SiF6) membrane came from the fluorinated substrate. The Cu(bipy)2(SiF6) membrane shows the separation factors of H2–CO2, H2–CH4 and H2–N2 are 8.0, 7.5, and 6.8 respectively at 293 K and 1 bar with H2 permeance of 2.7 × 10−7 mol m−2 s−1 Pa−1 as well as high thermal stability. We expect to explore more membranes of Cu(bipy)2(SiF6) analogues with tuneable pore sizes using this route and to obtain membranes with higher gas separation performance.
Co-reporter:Heping Ma, Hao Ren, Xiaoqin Zou, Fuxing Sun, Zhuojun Yan, Kun Cai, Dayang Wang and Guangshan Zhu
Journal of Materials Chemistry A 2013 vol. 1(Issue 3) pp:752-758
Publication Date(Web):18 Oct 2012
DOI:10.1039/C2TA00616B
Novel porous aromatic frameworks, PAF-18-OH and its lithiated derivative PAF-18-OLi, have been successfully synthesized. In particular, PAF-18-OLi displays significant enhancement of H2 and CO2 adsorption capacity, especially for CO2 uptake (14.4 wt%). More valuably, the stable PAF-18-OLi material exhibits high CO2/N2 selectivity, as high as 129 in the case of CO2 capture from simulated post-combustion flue gas mixtures (85% N2 and 15% CO2). Furthermore, the PAF-18-OLi has shown improved H2 storage capacity after lithiation.
Co-reporter:Mingyi Guo, Faheem Muhammad, Aifei Wang, Wenxiu Qi, Nan Wang, Yingjie Guo, Yen Wei and Guangshan Zhu
Journal of Materials Chemistry A 2013 vol. 1(Issue 39) pp:5273-5278
Publication Date(Web):28 Jun 2013
DOI:10.1039/C3TB20466A
The cost of conventional chemotherapeutic drugs is substantially high, and biomedical researchers are constantly hunting for cheap and effective chemotherapeutic alternatives. Recently, curcumin has emerged as a cost effective anticancer remedy, however, the low bioavailability of curcumin has been a major impediment to its successful utilization for disease management. In this work, we developed a highly biocompatible magnesium hydroxide as an intelligent nanocarrier for delivering curcumin into cancer cells. Curcumin was loaded onto magnesium hydroxide nanoplates via a complexation strategy. Furthermore, these drug conjugated nanoparticles not only achieve efficient loading of a highly hydrophobic drug, but also exhibit pH responsive release in extracellular or intracellular acid environments, validated by in vitro drug release, confocal microscopy and MTT assay. These biocompatible nanoplates can be promising candidates for the further development of smart drug delivery nanodevices.
Co-reporter:Jiangtao Jia, Fuxing Sun, Heping Ma, Lei Wang, Kun Cai, Zheng Bian, Lianxun Gao and Guangshan Zhu
Journal of Materials Chemistry A 2013 vol. 1(Issue 35) pp:10112-10115
Publication Date(Web):08 Jul 2013
DOI:10.1039/C3TA11840A
A new dendritic aromatic six-node ligand has been used to construct a MOF. It takes an octahedral and trigonal prismatic conformation in JUC-103 and JUC-104, respectively. JUC-103 exhibits high ethane uptake and has the separation ability for ethane to nitrogen. JUC-104 has an unusual (6,12)-connected CaSi2 topology.
Co-reporter:Xue Gao, Xiaoqin Zou, Feng Zhang, Shixing Zhang, Heping Ma, Nian Zhao and Guangshan Zhu
Chemical Communications 2013 vol. 49(Issue 78) pp:8839-8841
Publication Date(Web):25 Jul 2013
DOI:10.1039/C3CC44515A
The synthesis of continuous and low-siliceous ZSM-5 membranes was achieved without organic templates under mild conditions (a low temperature of 100 °C and ambient pressure). The resultant high-quality membranes with good water perm-selectivity were further applied in water–alcohol separation, exhibiting an extraordinarily high separation factor of above 10000 and an improved water flux (3.43–6.88 kg m−2 h−1) for ethanol and isopropanol aqueous azeotropes.
Co-reporter:Faheem Muhammad, Aifei Wang, Mingyi Guo, Jianyun Zhao, Wenxiu Qi, Guo Yingjie, Jingkai Gu, and Guangshan Zhu
ACS Applied Materials & Interfaces 2013 Volume 5(Issue 22) pp:11828
Publication Date(Web):October 18, 2013
DOI:10.1021/am4035027
Combination therapy has been a norm in clinical practice to effectively treat cancer. Besides polytherapy, nowadays, smart and nanobased drug carriers are extensively being explored to deliver drugs according to pathophysiological environment of diseases. In this regard, herein we designed intelligent mesoporous architecture, incorporating both combinational therapy with smart nanotechnology, to simultaneously deliver two highly hydrophobic chemotherapeutic drugs in response to extracellular and/or intracellular acidic environ of tumor. Novelty of the system lies in the employment of acid responsive ZnO QDs to clog not only the nanochannels of mesoporous silica, encapsulating one hydrophobic drug, but also exploitation of chelate forming propensity of another hydrophobic drug (curcumin) to load a significant quantity onto the surface of ZnO nanolids. Cell viability results revealed an extraordinarily high cytotoxic efficiency of that lethal drug cocktail even at a concentration as low as 3 μg/mL nanocarrier. We envision that this sophisticated nanocarrier, which utilizes both interior pore and exterior surface of nanolids for loading different hydrophobic guest molecules and their subsequent acid responsive release, will undoubtedly, illustrates its remarkable potential in targeted chemotherapy.Keywords: Chemotherapy; controlled release; curcumin; mesoporous silica; stimuli responsive;
Co-reporter:Jia Liu, Feng Zhang, Xiaoqin Zou, Guangli Yu, Nian Zhao, Songjie Fan and Guangshan Zhu
Chemical Communications 2013 vol. 49(Issue 67) pp:7430-7432
Publication Date(Web):26 Jun 2013
DOI:10.1039/C3CC42287A
The preparation of highly hydrophobic and stable MIL-53(Al) nanomaterials was achieved by an ionothermal synthesis strategy. The hydrophobicity of MIL-53(Al)it was studied by water adsorption; and the enhancement in this property was discussed with respect to its reference to MIL-53(Al)ht.
Co-reporter:Xiaoqin Zou, Hao Ren and Guangshan Zhu
Chemical Communications 2013 vol. 49(Issue 38) pp:3925-3936
Publication Date(Web):27 Feb 2013
DOI:10.1039/C3CC00039G
Porous organic frameworks (POFs) as an important subclass of nanoporous materials are of great interest in materials science. In recent years, the discovery and creation of POFs with excellent properties for advanced applications have attracted much attention and intensive efforts have been contributed to this field. As a result, the design of materials with multi-functionalities is an ever-pursued dream of materials scientists and engineers. In this respect, a new concept based on topology chemistry is introduced for the rational and targeted synthesis of POF materials. The present feature article provides an overview of the relationship between building blocks or starting monomers, underlying topological nets, and pre-determined structures. Several important nets are included successively from one to three dimensions. In addition, special emphasis is given to the advanced applications of designed POF materials in the current paper.
Co-reporter:Huanyu Zhao, Zhao Jin, Hongmin Su, Jinlei Zhang, Xiangdong Yao, Huijun Zhao and Guangshan Zhu
Chemical Communications 2013 vol. 49(Issue 27) pp:2780-2782
Publication Date(Web):06 Feb 2013
DOI:10.1039/C3CC38474H
A novel porous aromatic framework based on tetra-(4-anilyl)-methane and cyanuric chloride has been designed and synthesized successfully, which possesses permanent porosity and high selectivity of CO2 towards CH4.
Co-reporter:Heping Ma, Hao Ren, Shuang Meng, Zhuojun Yan, Huanyu Zhao, Fuxing Sun and Guangshan Zhu
Chemical Communications 2013 vol. 49(Issue 84) pp:9773-9775
Publication Date(Web):23 Aug 2013
DOI:10.1039/C3CC45217D
Here we present a new 3D microporous COF with a uniform pore size (0.64 nm). MCOF-1 exhibits high adsorption selectivity towards C3H8, C2H6 and C2H4 over CH4 owing to the pore size and preferential adsorption.
Co-reporter:Tingting Zhang, Yan Yang, Haitao Wang, Fuxing Sun, Xiaojun Zhao, Jiangtiao Jia, Jingrui Liu, Wei Guo, Xiaoqiang Cui, Jingkai Gu, and Guangshan Zhu
Crystal Growth & Design 2013 Volume 13(Issue 12) pp:5261-5266
Publication Date(Web):November 1, 2013
DOI:10.1021/cg4010104
The crystal engineering strategy was used to facilitate the supramolecular synthesis of a new crystalline phase of iloperidone, an atypical psychotropic drug with known problems related to poor dissolution and absorption profile. The novel crystal forms Jilin University China-Cocrystal-1 (JUC-C1), Jilin University China-Cocrystal-2 (JUC-C2), and Jilin University China-Cocrystal-3 (JUC-C3) of iloperidone with 3-hydroxybenzoic acid (3-HBA), 2,3-dihydroxybenzoic acid (2,3-DHBA), and 3,5-dihydroxybenzoic acid (3,5-DHBA) were obtained using the reaction crystallization method (RCM). The dissolution and pharmacokinetics studies were performed to exploit this atypical psychotropic drug. In the dissolution experiment, JUC-C1, JUC-C2, and JUC-C3 (JUC-C1–3) showed a much faster dissolution rate than the original active pharmaceutical ingredient (API) in simulated gastric fluid media (pH = 1.2). Furthermore, pharmacokinetic behavior of JUC-C1–3 and API was investigated to evaluate the effectiveness of this strategy for enhancing the oral absorption of iloperidone. The in vitro and in vivo studies revealed that JUC-C2 possessed an excellent dissolution behavior and improved pharmacokinetic profile.
Co-reporter:Lina Li, Fuxing Sun, Jiangtao Jia, Tsolmon Borjigin and Guangshan Zhu
CrystEngComm 2013 vol. 15(Issue 20) pp:4094-4098
Publication Date(Web):15 Mar 2013
DOI:10.1039/C3CE40137E
Through the optimization of synthesis conditions, we obtained large Cu3(BTC)2 crystals with a diameter of 2–4 mm. Such large crystals could be utilized as “chromatographic columns” for effective separation of organic dyes such as thionine (TH) and pyronin B (PB). It was found that the concentration of hydron was the key factor to obtain the large pure crystals. This strategy could be used to grow other hydrophilic MOFs.
Co-reporter:Zhuojun Yan, Hao Ren, Heping Ma, Rongrong Yuan, Ye Yuan, Xiaoqin Zou, Fuxing Sun, Guangshan Zhu
Microporous and Mesoporous Materials 2013 Volume 173() pp:92-98
Publication Date(Web):June 2013
DOI:10.1016/j.micromeso.2013.02.006
We report here pyrene-based fluorescent porous aromatic frameworks (PAF-19 and PAF-20), which are constructed by a quadrilateral building unit 1,3,6,8-tetrabromopyrene (TBrPy) with linkers 1,4-diethynylbenzene and 1,3,5-triethynylbenzene via Sonogashira–Hagihara coupling reaction, respectively. TG analysis shows that PAF-19 and PAF-20 are thermally stable up to 350 °C in air condition. Both materials also exhibit high chemical stability and cannot dissolve or decompose in any common organic solvents. N2 sorption results reveal that the BET surface areas of PAF-19 and PAF-20 are 250 m2 g−1 and 702 m2 g−1, respectively. They also display relatively high sorption abilities for hydrogen and carbon dioxide. H2O sorption measurements demonstrate that the skeletons of PAF-19 and PAF-20 are highly hydrophobic. Interestingly, PAF-19 and PAF-20 exhibit excellent sorption abilities to organic chemical pollutants at the saturated vapor pressure and room temperature. PAF-20 can adsorb large amounts of methanol and benzene, with values of 609 mg g−1 and 1038 mg g−1, respectively. The good performances of PAF-19 and PAF-20 with high sorption selectivity promise their potential application for eliminating environmental pollutants in presence of H2O.Graphical abstractTargeted synthesis of pyrene-based porous aromatic frameworks has been achieved via Sonogashira–Hagihara coupling reaction. PAF-19 and PAF-20 are highly hydrophobic materials with high methanol and benzene uptakes at the saturated vapor pressure and room temperature.Highlights► Pyrene-based porous aromatic frameworks are synthesized via Sonogashira–Hagihara coupling reaction. ► The plentiful phenyl rings in the networks lead to an enhancement for the adsorption enthalpies of H2 and CO2. ► Materials with hydrophobic skeletons for highly selective sorption of benzene and methanol.
Co-reporter:Xiaofei Jing, Fuxing Sun, Hao Ren, Yuyang Tian, Mingyi Guo, Lina Li, Guangshan Zhu
Microporous and Mesoporous Materials 2013 Volume 165() pp:92-98
Publication Date(Web):1 January 2013
DOI:10.1016/j.micromeso.2012.07.048
A micro–mesoporous inorganic–organic hybrid material PAF-12, derived from octaphenylsilsesquioxane (OPS, [C6H5(SiO1.5)]8) as basic building units, was successfully synthesized via Suzuki cross-coupling reaction. Thermogravimetric analysis (TGA) shows that PAF-12 is thermally stable up to 500 °C in air condition. According to Ar sorption isotherm, the network of PAF-12 shows classic type IV isotherm and also exhibits a sharp uptake at low relative pressures indicating micro–mesoporous texture. The pore size distribution of PAF-12 calculated from non-linear density functional theory (NLDFT) gives only two clear narrow peaks centered at 1.57 and 3.17 nm. To the best of our knowledge, PAF-12 is the first hybrid material containing both micropore and mesopore reported for silsesquioxane-based materials. Additionally, PAF-12 exhibits high adsorption abilities for organic chemical pollutants such as benzene and methanol. The effects of different solvent systems to synthesize PAF-12 were also investigated and the optimal condition was found out.Graphical abstractAn inorganic–organic hybrid material PAF-12 was successfully synthesized via Suzuki cross-coupling reaction. Remarkably, the pore size of PAF-12 reaches mesoporous range through a reasonable design and extension. To the best of our knowledge, PAF-12 is the first micro–mesoporous hybrid framework reported for silsesquioxane-based materials.Highlights► Inorganic–organic hybrid material built from double four ring building units. ► Structural extension to mesoporous range with a reasonable design. ► High adsorption abilities for organic chemical pollutants. ► Effects of different solvent systems to Suzuki coupling reactions are not obvious.
Co-reporter:Shuyuan Zhou, Xiaoqin Zou, Fuxing Sun, Hao Ren, Jia Liu, Feng Zhang, Nian Zhao, Guangshan Zhu
International Journal of Hydrogen Energy 2013 Volume 38(Issue 13) pp:5338-5347
Publication Date(Web):1 May 2013
DOI:10.1016/j.ijhydene.2013.02.074
Hydrogen provides reliable, sustainable, environmental and climatic friendly energy to meet world's energy requirement and it also has high energy density. Hydrogen is relevant to all of the energy sectors-transportation, buildings, utilities and industry. In all of these sectors, hydrogen-rich gas streams are needed. Thus, hydrogen-selective membrane technology with superior performances is highly demanded for separation and purification of hydrogen gas mixtures. In this study, novel [Al4(OH)2(OCH3)4(H2N-BDC)3]·xH2O (CAU-1) MOF membranes with accessible pore size of 0.38 nm are evaluated for this goal of hydrogen purification. High-quality CAU-1 membranes have been successfully synthesized on α-Al2O3 hollow ceramic fibers (HCFs) by secondary growth assisted with the homogenously deposited CAU-1 nanocrystals with a size of 500 nm as seeds. The energy-dispersive X-ray spectroscopy study shows that the HCFs substrates play dual roles in the membrane preparation, namely aluminum source and as a support. The crystals in the membrane are intergrown together to form a continuous and crack-free layer with a thickness of 4 μm. The gas sorption ability of CAU-1 MOF materials is examined by gas adsorption measurement. The isosteric heats of adsorption with average values of 4.52 kJ/mol, 12.90 kJ/mol, 12.82 kJ/mol and 27.99 kJ/mol are observed for H2, N2, CH4, and CO2 respectively, indicating different interactions between CAU-1 framework and these gases. As-prepared HCF supported CAU-1 membranes are tested by single and binary gas permeation of H2/CO2, H2/N2 and H2/CH4 at different temperatures, feed pressures and testing time. The permeation results show preferential permeance of H2 over CO2, N2, and CH4 with high separation factors of 12.34, 10.33, and 10.42 for H2/CO2, H2/N2, H2/CH4, respectively. The temperature, pressure and test time dependent studies reveal that HCFs supported CAU-1 membranes possess high stability, resistance to cracking, temperature cycling, high reproducibility, these of which combined with high separation efficiency make this type of MOF membranes are promising for hydrogen recycling from industrial exhausts.Highlights► A dual-metal-source approach is innovated for the fabrication of MOF membranes. ► Gas separation by molecular sieving with CAU-1 MOF membranes. ► Adsorption and permeation properties of CAU-1 membranes are studied. ► High performance for hydrogen separation is obtained using CAU-1 membranes.
Co-reporter:Lei Liu, Bing Han, Xiaoqiang Liang, Zhi Yang, Jiangtao Jia, Fuxing Sun, Guangshan Zhu
Journal of Molecular Structure 2013 Volume 1047() pp:338-343
Publication Date(Web):5 September 2013
DOI:10.1016/j.molstruc.2013.04.067
•Three new diverse structural metal–organic coordination polymers are synthesized and characterized.•The ligand used here is flexible.•We study how are the structures affected by cations.Three new diverse structural metal–organic coordination polymers, [Pb(anti-btx)(H2O) (NO3)2] (1), [Cd(anti-btx)(H2O)2(NO3)2] (2), and [Zn(anti-btx) (syn-btx)(H2O)2] (NO3)2 (3) [btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene], have been prepared under room temperature. Their structures were characterized by elemental analysis, IR, single-crystal X-ray diffraction analysis and thermogravimetric (TG) analysis. 1 is a 1D serration chain; 2 is an infinite ladder 1D chain; and 3 is generated as an infinite 1D chain. The 1D chain of the three complexes are all formed 3D framework through hydrogen bondings and π–π stacking interactions.
Co-reporter:Aifei Wang, Wenxiu Qi, Nan Wang, Jianyun Zhao, Faheem Muhammad, Kun Cai, Hao Ren, Fuxing Sun, Liang Chen, Yingjie Guo, Mingyi Guo, Guangshan Zhu
Microporous and Mesoporous Materials 2013 180() pp: 1-7
Publication Date(Web):
DOI:10.1016/j.micromeso.2013.06.015
Co-reporter:Feng Zhang;Xiaoqin Zou;Xue Gao;Songjie Fan;Fuxing Sun;Hao Ren
Advanced Functional Materials 2012 Volume 22( Issue 17) pp:3583-3590
Publication Date(Web):
DOI:10.1002/adfm.201200084
Abstract
Hydrogen-based energy is a promising renewable and clean resource. Thus, hydrogen selective microporous membranes with high performance and high stability are demanded. Novel NH2-MIL-53(Al) membranes are evaluated for hydrogen separation for this goal. Continuous NH2-MIL-53(Al) membranes have been prepared successfully on macroporous glass frit discs assisted with colloidal seeds. The gas sorption ability of NH2-MIL-53(Al) materials is studied by gas adsorption measurement. The isosteric heats of adsorption in a sequence of CO2 > N2 > CH4 ≈ H2 indicates different interactions between NH2-MIL-53(Al) framework and these gases. As-prepared membranes are measured by single and binary gas permeation at different temperatures. The results of singe gas permeation show a decreasing permeance in an order of H2 > CH4 > N2 > CO2, suggesting that the diffusion and adsorption properties make significant contributions in the gas permeation through the membrane. In binary gas permeation, the NH2-MIL-53(Al) membrane shows high selectivity for H2 with separation factors of 20.7, 23.9 and 30.9 at room temperature (288 K) for H2 over CH4, N2 and CO2, respectively. In comparison to single gas permeation, a slightly higher separation factor is obtained due to the competitive adsorption effect between the gases in the porous MOF membrane. Additionally, the NH2-MIL-53(Al) membrane exhibits very high permeance for H2 in the mixtures separation (above 1.5 × 10−6 mol m−2 s−1 Pa−1) due to its large cavity, resulting in a very high separation power. The details of the temperature effect on the permeances of H2 over other gases are investigated from 288 to 353 K. The supported NH2-MIL-53(Al) membranes with high hydrogen separation power possess high stability, resistance to cracking, temperature cycling and show high reproducibility, necessary for the potential application to hydrogen recycling.
Co-reporter:Feng Zhang, Xiaoqin Zou, Wei Feng, Xiaojun Zhao, Xiaofei Jing, Fuxing Sun, Hao Ren and Guangshan Zhu
Journal of Materials Chemistry A 2012 vol. 22(Issue 48) pp:25019-25026
Publication Date(Web):21 Sep 2012
DOI:10.1039/C2JM34618D
An indium trimesate metal–organic framework (JUC-120) which possesses a cubic zeolitic MTN topology, as a new analogue to MIL-100(Al, Fe or Cr) compounds, has been successfully synthesized. Its structure exhibits a mesoporous cage (26 Å) and high thermal stability. The assembly of nitrobenzospiropyran derivatives (BSP) into JUC-120 nanocrystals (BSP/JUC-120) is achieved by a microwave-assisted crystallization inclusion approach. The BSP/JUC-120 films have been prepared on quartz wafers by a spin-coating method. The successful encapsulation of BSP molecules into the mesopores of the JUC-120 structure has been verified by N2 adsorption and TGA measurements. The photochromic properties of BSP/JUC-120 films are studied by the UV-Vis and fluorescence spectroscopies. More interestingly, metastable open merocyanine (OMC) species are directly generated from the closed spiropyran form (CSP) without photoirradiation and stabilized for a long period in the BSP/JUC-120 film. The open merocyanine isomer bleaches to the closed spiropyran form by ultraviolet or visible light, and the coloration is regained upon standing in the dark, exhibiting antidromic photochromism. Moreover, the BSP/JUC-120 film shows high reversibility and thermal stability of photochromism. This highly efficient MOF film is expected to be promising in the applications of optical devices.
Co-reporter:Ye Yuan, Hao Ren, Fuxing Sun, Xiaofei Jing, Kun Cai, Xiaojun Zhao, Yue Wang, Yen Wei and Guangshan Zhu
Journal of Materials Chemistry A 2012 vol. 22(Issue 47) pp:24558-24562
Publication Date(Web):11 Sep 2012
DOI:10.1039/C2JM35341E
A three-dimensional (3D) porous aromatic framework (PAF-14) with high fluorescence quantum yield was synthesized from luminescent monomer of tetra(4-dihydroxyborylphenyl)germanium (TBPGe) building blocks. The powder X-ray diffraction (PXRD) analysis of the experimental and simulated patterns indicate that PAF-14 is highly crystalline with ctn topology. The Argon sorption measurement indicates that PAF-14 possesses high surface area (Brunauer Emmet Teller surface area: 1288 m2 g−1). Significantly, the introduction of germanium into PAF-14 skeletons may bring about a low-lying lowest unoccupied molecular orbital (LUMO) and the crystalline polymeric backbones enhance the sensitivity of electron delocalization. Therefore the designed PAF-14 exhibits high fluorescence quenching ability for hazardous explosives, such as nitrobenzene, 2,4-DNT (2,4-dinitrotoluene) and TNT (2,4,6-trinitrotoluene).
Co-reporter:Shuyuan Zhou, Xiaoqin Zou, Fuxing Sun, Feng Zhang, Songjie Fan, Huijun Zhao, Thomas Schiestel and Guangshan Zhu
Journal of Materials Chemistry A 2012 vol. 22(Issue 20) pp:10322-10328
Publication Date(Web):27 Mar 2012
DOI:10.1039/C2JM16371C
High-performance and continuous Cu3(BTC)2 membranes have been successfully fabricated using a secondary growth approach on pre-seeded α-Al2O3 hollow ceramic fibers (HCFs) modified with chitosan. Facile synthesis of Cu3(BTC)2 nanocrystals can be achieved by a modified solvothermal protocol. A stable and homogeneous Cu3(BTC)2 seed precusor obtained with particle size of 300 nm, the size of which is suitable for seeding HCFs without any pore jam of HCFs supports (pore size of 200 nm for HCFs). A new substrate HCFs was introduced as the support of Cu3(BTC)2 membranes. Moreover, for the first time, chitosan is used to improve the binding force between seeds and the support owing to its abundance of both amino and hydroxyl groups. As-prepared Cu3(BTC)2 membrane is studied for hydrogen separation by binary gas permeation of H2/N2, H2/CO2 and H2/CH4. The synthesized membrane shows high H2 selectivity with separation factors of 8.66, 13.56 and 6.19 for the gas mixtures of H2/N2, H2/CO2 and H2/CH4 respectively. A preferred permeance for H2 in the binary gas mixture is obtained in the range of 3.23 × 10−8 to 4.1 × 10−8 mol m−2 s−1 Pa−1 due to the unique properties of the Cu3(BTC)2 MOF material, which is expected in the potential applications of industrial hydrogen recycling.
Co-reporter:Jiangtao Jia, Fuxing Sun, Tsolmon Borjigin, Hao Ren, Tingting Zhang, Zheng Bian, Lianxun Gao and Guangshan Zhu
Chemical Communications 2012 vol. 48(Issue 48) pp:6010-6012
Publication Date(Web):27 Apr 2012
DOI:10.1039/C2CC32347H
Two non-interpenetrated and isomorphous MOFs with nia topology, cationic JUC-101 and anionic JUC-102, are synthesized by connecting a trigonal prismatic metal cluster with an octahedral organic ligand. JUC-101 obtains a BET surface area of 3742 m2 g−1 and can absorb 4.18 wt% of H2 at 30 atm and 77 K, while JUC-102 can absorb cationic dye molecules and release them under the triggering of ions.
Co-reporter:Tsolmon Borjigin, Fuxing Sun, Jinlei Zhang, Kun Cai, Hao Ren and Guangshan Zhu
Chemical Communications 2012 vol. 48(Issue 61) pp:7613-7615
Publication Date(Web):12 Jun 2012
DOI:10.1039/C2CC33023G
A novel 44 square grid microporous metal–organic framework (MOF) JUC-110 with 1D open channels has been synthesized, which shows exceptional hydrothermal stability and capability for separating alcohols from water in gas chromatographic (GC) separation.
Co-reporter:Wei Wang, Hao Ren, Fuxing Sun, Kun Cai, Heping Ma, Jianshi Du, Huijun Zhao and Guangshan Zhu
Dalton Transactions 2012 vol. 41(Issue 14) pp:3933-3936
Publication Date(Web):13 Feb 2012
DOI:10.1039/C2DT11996J
PAF-16 which is based on tetrahedral units (TCPSi) and triangular building units, shows both high thermal stability and high chemical stability. The surface area of PAF-16 can be tuned by changing the reaction temperature and ratio of monomer and catalyst. PAF-16 also shows considerable adsorption capacity of CO2.
Co-reporter:Mingyi Guo;Aifei Wang;Faheem Muhammad;Wenxiu Qi;Hao Ren;Yingjie Guo
Chinese Journal of Chemistry 2012 Volume 30( Issue 9) pp:2115-2120
Publication Date(Web):
DOI:10.1002/cjoc.201200657
Abstract
Targeted drug delivery systems have attracted a great deal of interest by virtue of their potential use in chemotherapy. In this study, multicomponent halloysite nanotubes (HNTs) have been evaluated as a platform to assist and direct the delivery of anticancer drug doxorubicin (DOX) into cancer cells. Folic acid (FA) and magnetite nanoparticles were successfully grafted onto HNTs via amide reaction whereas the drug has been introduced by capitalizing electrostatic interaction between cationic drug and anionic exterior of HNTs, which eventually leads to pH responsive release. The resultant DOX loaded FA-Fe3O4@HNTs were well characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and XRD. The clinical efficacy of the system was validated by confocal microscopy and cell cytotoxicity assay (MTT assay). MTT assay results revealed a high biocompatibility up to a concentration of 200 µg/mL of HNTs, while, DOX loaded FA-Fe3O4@HNTs were markedly cytotoxic to HeLa cells. This multifunctional nanovehicle has a great potential for cancer diagnosis and therapy, and could further advance the clinical use of nanomedicine.
Co-reporter:Ye Yuan, Hao Ren, Fuxing Sun, Xiaofei Jing, Kun Cai, Xiaojun Zhao, Yue Wang, Yen Wei, and Guangshan Zhu
The Journal of Physical Chemistry C 2012 Volume 116(Issue 50) pp:26431-26435
Publication Date(Web):November 29, 2012
DOI:10.1021/jp309068x
A three-dimensional (3D) crystalline porous aromatic framework (PAF-15) with high fluorescence quantum yield was synthesized through assembling luminescent building blocks of tetra(4-dihydroxyborylphenyl)germanium (TBPGe) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP). Powder X-ray diffraction (PXRD) analysis displays the high crystallinity of PAF-15. The topology known from the PXRD of the experimental and simulated patterns is ctn type. The Ar sorption measurement on activated PAF-15 results in the high surface area (BET model: 747 m2 g–1). Significantly, PAF-15 exhibits high luminescence quenching ability by hazardous and explosive molecules, such as nitrobenzene, 2,4-dinitrotoluene (2,4-DNT), and 2,4,6-trinitrotoluene (TNT), and may serve as a new sensing material. It should be caused by the introduction of germanium into crystalline PAFs skeletons which may bring up a low reduction potential and low-lying LUMO and provide the amplification of electron delocalization.
Co-reporter:Faheem Muhammad ; Mingyi Guo ; Wenxiu Qi ; Fuxing Sun ; Aifei Wang ; Yingjie Guo
Journal of the American Chemical Society 2011 Volume 133(Issue 23) pp:8778-8781
Publication Date(Web):May 17, 2011
DOI:10.1021/ja200328s
Acid-decomposable, luminescent ZnO quantum dots (QDs) have been employed to seal the nanopores of mesoporous silica nanoparticles (MSNs) in order to inhibit premature drug (doxorubicin) release. After internalization into HeLa cells, the ZnO QD lids are rapidly dissolved in the acidic intracellular compartments, and as a result, the loaded drug is released into the cytosol from the MSNs. The ZnO QDs behave as a dual-purpose entity that not only acts as a lid but also has a synergistic antitumor effect on cancer cells. We anticipate that these nanoparticles may prove to be a significant step toward the development of a pH-sensitive drug delivery system that minimizes drug toxicity.
Co-reporter:Ye Yuan, Fuxing Sun, Hao Ren, Xiaofei Jing, Wei Wang, Heping Ma, Huijun Zhao and Guangshan Zhu
Journal of Materials Chemistry A 2011 vol. 21(Issue 35) pp:13498-13502
Publication Date(Web):03 Aug 2011
DOI:10.1039/C1JM11998B
Tetrakis(4-bromophenyl)methane (TBPM) as a tetrahedral unit and a diboronic acid as a linker were selected to couple the phenyl rings into a porous aromatic framework, PAF-11. PAF-11 was polymerized via a Suzuki coupling reaction. A TG analysis showed that PAF-11 is thermally stable up to 400 °C in air. PAF-11 also has a high chemical stability and cannot be dissolved or decomposed in common solvents or concentrated hydrochloric acid. A N2 sorption measurement on activated PAF-11 revealed a surface area of 952 m2 g−1 in the Langmuir model. PAF-11 also shows a considerable adsorption capacity for H2. Interestingly, PAF-11 is a highly hydrophobic material but with a high methanol uptake (654 mg g−1 at saturated vapour pressure and room temperature). PAF-11 also exhibits high adsorption abilities for small aromatic molecules such as benzene and toluene (874 and 780 mg g−1, respectively, at saturated vapour pressure and room temperature) due to its aromatic framework. This ability of PAF-11 could be very useful to eliminate harmful small aromatic molecules produced by industry.
Co-reporter:Faheem Muhammad, Mingyi Guo, Yingjie Guo, Wenxiu Qi, Fengyu Qu, Fuxing Sun, Huijun Zhao and Guangshan Zhu
Journal of Materials Chemistry A 2011 vol. 21(Issue 35) pp:13406-13412
Publication Date(Web):04 Aug 2011
DOI:10.1039/C1JM12119G
Efficacious chemotherapy mainly hinges on the tumor-specific delivery of anticancer drugs. Herein we report a successful fabrication of highly photoluminescent and water dispersible ZnO quantum dotsvia a new ligand exchange free strategy. In addition to bioimaging, ZnO QDs have also been evaluated as a platform for targeted and pH responsive intracellular delivery of an anticancer drug. The cancer targeting feature is endowed by conjugating folic acid on to the surface of ZnO–NH2 QDs via an amidation reaction. Doxorubicin (DOX) is then successfully loaded onto the folic acid functionalized ZnO QDs by capitalizing on its marked tendency towards the formation of metal complexes. Drug loaded ZnO-FA QDs remain stable at physiological pH but readily disintegrate in the mildly acidic intracellular environment of cancer cells as validated by a drug release profile, confocal microscopy and a cell-cytotoxicity assay. Compared to the conventional drug nanovector, ZnO-FA QDs themselves manifest a significant therapeutic activity after reaching their targeted site, therefore, combined DOX and ZnO QDs can be more efficacious than either alone. Hence, this approach provides a valuable ZnO QDs-based nanovector that can simultaneously realize targeting, diagnosis, and therapy of cancer cells.
Co-reporter:Jiangtao Jia, Fuxing Sun, Qianrong Fang, Xiaoqiang Liang, Kun Cai, Zheng Bian, Huijun Zhao, Lianxun Gao and Guangshan Zhu
Chemical Communications 2011 vol. 47(Issue 32) pp:9167-9169
Publication Date(Web):13 Jul 2011
DOI:10.1039/C1CC12891D
A novel low density two-fold interpenetrated MOF-5 analogue with pcu topology, JUC-100, was designed and prepared successfully. It can be regarded as MOF-5 in which half of the Zn4O(CO2)6 units are replaced by organic 1,3,5-triphenylbenzene segments. JUC-100 exhibits H2 uptake ability comparable to interpenetrated MOF-5, but relatively low initial isosteric heat of adsorption.
Co-reporter:Huanyu Zhao, Zhao Jin, Hongmin Su, Xiaofei Jing, Fuxing Sun and Guangshan Zhu
Chemical Communications 2011 vol. 47(Issue 22) pp:6389-6391
Publication Date(Web):06 May 2011
DOI:10.1039/C1CC00084E
A novel 2D porous organic framework based on the nucleophilic substitution of cyanuric chloride has been designed and synthesized successfully, which possesses an ordered structure, permanent porosity and drug release ability towards ibuprofen.
Co-reporter:Ye Peng, Teng Ben, Jun Xu, Ming Xue, Xiaofei Jing, Feng Deng, Shilun Qiu and Guangshan Zhu
Dalton Transactions 2011 vol. 40(Issue 12) pp:2720-2724
Publication Date(Web):13 Dec 2010
DOI:10.1039/C0DT01268H
By a Yamamoto-type of Ullmann cross-coupling reaction, a well-defined covalently-linked microporous organic-inorganic hybrid framework polyoctaphenylsilsesquioxane (JUC-Z1) was effectively prepared from the nano building block p-iodio-octaphenylsilsesquioxane (I8OPS) with a yield of ca. 100%. The structure of JUC-Z1 was characterized by 13C CP/MAS NMR and 29Si MAS NMR experiments. Fourier transform infrared spectroscopy (FTIR) was performed to confirm the presence of functions in the framework. The results showed that inorganic silsesquioxane cubes were linearly covalently-linked by biphenyls, offering a highly cross-coupling framework. The powder X-ray diffraction (PXRD) pattern and transmission electron microscope (TEM) image show that JUC-Z1 is spherical with uniform micropores. N2 adsorption results suggest that the hybrid framework has a narrow pore size distribution from 11.8 to 20.0 Å, with a BET surface area of 283 m2g−1 and a pore volume of 0.226 cm3g−1. A thermogravimetric (TG) analysis indicates the thermal stability of JUC-Z1 up to 397 °C in air. Moreover, a liquid sorption experiment reveals the favorable sorption of benzene and water.
Co-reporter:Hao Ren, Teng Ben, Ensi Wang, Xiaofei Jing, Ming Xue, Bingbing Liu, Yan Cui, Shilun Qiu and Guangshan Zhu
Chemical Communications 2010 vol. 46(Issue 2) pp:291-293
Publication Date(Web):11 Nov 2009
DOI:10.1039/B914761F
A novel 3D porous aromatic framework (PAF) based on a tetraphenylmethane block and a triangular triazine ring been designed and synthesized, with 1109 m2 g−1 Langmuir surface area, and shows selective sorption of benzene.
Co-reporter:Teng Ben;Hao Ren;Shengqian Ma;Dapeng Cao ;Jianhui Lan;Xiaofei Jing;Wenchuan Wang ;Jun Xu;Feng Deng ;JasonM. Simmons ;Shilun Qiu
Angewandte Chemie International Edition 2009 Volume 48( Issue 50) pp:9457-9460
Publication Date(Web):
DOI:10.1002/anie.200904637
Co-reporter:Ning Zhang, Yafei Zhao, Yanjie Lu, Guangshan Zhu
Materials Science and Engineering: B (April 2017) Volume 218() pp:
Publication Date(Web):April 2017
DOI:10.1016/j.mseb.2017.02.004
•Aligned W18O49 nanowire clusters were prepared by a facile hydrothermal method.•W18O49 has unique structure, high degree of crystallinity and large surface area.•W18O49 nanowire clusters exhibited high photocatalytic degradation activity.The aligned W18O49 nanowire clusters were synthesized via a facile and economic ethanol-assisted hydrothermal method using peroxopolytungstic acid as precursor. Results show that the as-prepared W18O49 exhibits a high yield and ultrathin structure with preferential growth direction along [0 1 0]. The amount of peroxopolytungstic acid and reaction time play significant role on the morphology of W18O49 nanowires. The nanowires have unique structure, high degree of crystallinity, large specific surface area, and large number of defects such as oxygen vacancies, which are responsible for their high photocatalytic performance for degradation of methylene blue. The photocatalytic conversion of methylene blue can reach above 98% after degradation. W18O49 also exhibits good photodegradation stability after five cycles of reuse. The results demonstrate that the as-prepared W18O49 nanowire clusters are expected to be a promising material for applications in the field of environment.
Co-reporter:Hongming He, Fuxing Sun, Briana Aguila, Jason A. Perman, Shengqian Ma and Guangshan Zhu
Journal of Materials Chemistry A 2016 - vol. 4(Issue 39) pp:NaN15246-15246
Publication Date(Web):2016/09/12
DOI:10.1039/C6TA05098K
A bifunctional MOF (JUC-199) featuring dual functionality, open metal sites (Zn2+) and Lewis basic sites (–NH2), has been successfully synthesized using a custom-designed ligand. JUC-199 demonstrated good selective gas sorption behaviours with IAST selectivity values of 9, 30, 37 and 64 at 298 K and 101 kPa for CO2/CH4, CO2/N2, C2H6/CH4 and C2H4/CH4 respectively; surpassing those of most MOFs reported thus far. Moreover, JUC-199 can serve as a heterogeneous cascade catalyst to efficiently catalyse the tandem one-pot deacatalization-Knoevenagel condensation reaction.
Co-reporter:Kun Cai, Fuxing Sun, Xiaoqiang Liang, Cong Liu, Nian Zhao, Xiaoqin Zou and Guangshan Zhu
Journal of Materials Chemistry A 2017 - vol. 5(Issue 25) pp:NaN12950-12950
Publication Date(Web):2017/05/24
DOI:10.1039/C7TA00169J
Use of a proton exchange membrane (PEM) is a key technique in proton exchange membrane fuel cells (PEMFCs) for clean energy applications. Recently, use of metal–organic frameworks (MOFs) as well as their composite membranes with polymers as PEM have been one research focus in this area. In this paper, the synthesis and proton conductive properties of a novel hexaphosphate ester-based MOF, JUC-200, prepared by the reaction of the inositol hexaphosphoric ligand (phytic acid) and Zn(II) is described. JUC-200 shows excellent water tolerance and acid resistance in a solution of pH = 2.0, and exhibits a proton conductivity of 1.62 × 10−3 S cm−1 at 80 °C. Furthermore, the polymer composite membranes of poly(vinyl alcohol) (PVA) and JUC-200 were fabricated for use as fillers with different mass percentages (X%, the membrane denoted as JUC-200@PVA-X). The measurement of proton conductivity of these membranes shows that JUC-200@PVA-10 has the advantage of a good proton conductivity of 1.25 × 10−3 S cm−1 at 50 °C. As far as is known, this is the first water-stable and acid-stable composite made of MOFs and polymers as proton exchange membranes. This research may make some contribution to the further development of MOFs in the field of the PEMFCs.
Co-reporter:Ye Yuan, Fuxing Sun, Hao Ren, Xiaofei Jing, Wei Wang, Heping Ma, Huijun Zhao and Guangshan Zhu
Journal of Materials Chemistry A 2011 - vol. 21(Issue 35) pp:NaN13502-13502
Publication Date(Web):2011/08/03
DOI:10.1039/C1JM11998B
Tetrakis(4-bromophenyl)methane (TBPM) as a tetrahedral unit and a diboronic acid as a linker were selected to couple the phenyl rings into a porous aromatic framework, PAF-11. PAF-11 was polymerized via a Suzuki coupling reaction. A TG analysis showed that PAF-11 is thermally stable up to 400 °C in air. PAF-11 also has a high chemical stability and cannot be dissolved or decomposed in common solvents or concentrated hydrochloric acid. A N2 sorption measurement on activated PAF-11 revealed a surface area of 952 m2 g−1 in the Langmuir model. PAF-11 also shows a considerable adsorption capacity for H2. Interestingly, PAF-11 is a highly hydrophobic material but with a high methanol uptake (654 mg g−1 at saturated vapour pressure and room temperature). PAF-11 also exhibits high adsorption abilities for small aromatic molecules such as benzene and toluene (874 and 780 mg g−1, respectively, at saturated vapour pressure and room temperature) due to its aromatic framework. This ability of PAF-11 could be very useful to eliminate harmful small aromatic molecules produced by industry.
Co-reporter:Faheem Muhammad, Mingyi Guo, Yingjie Guo, Wenxiu Qi, Fengyu Qu, Fuxing Sun, Huijun Zhao and Guangshan Zhu
Journal of Materials Chemistry A 2011 - vol. 21(Issue 35) pp:NaN13412-13412
Publication Date(Web):2011/08/04
DOI:10.1039/C1JM12119G
Efficacious chemotherapy mainly hinges on the tumor-specific delivery of anticancer drugs. Herein we report a successful fabrication of highly photoluminescent and water dispersible ZnO quantum dotsvia a new ligand exchange free strategy. In addition to bioimaging, ZnO QDs have also been evaluated as a platform for targeted and pH responsive intracellular delivery of an anticancer drug. The cancer targeting feature is endowed by conjugating folic acid on to the surface of ZnO–NH2 QDs via an amidation reaction. Doxorubicin (DOX) is then successfully loaded onto the folic acid functionalized ZnO QDs by capitalizing on its marked tendency towards the formation of metal complexes. Drug loaded ZnO-FA QDs remain stable at physiological pH but readily disintegrate in the mildly acidic intracellular environment of cancer cells as validated by a drug release profile, confocal microscopy and a cell-cytotoxicity assay. Compared to the conventional drug nanovector, ZnO-FA QDs themselves manifest a significant therapeutic activity after reaching their targeted site, therefore, combined DOX and ZnO QDs can be more efficacious than either alone. Hence, this approach provides a valuable ZnO QDs-based nanovector that can simultaneously realize targeting, diagnosis, and therapy of cancer cells.
Co-reporter:Feng Zhang, Xiaoqin Zou, Wei Feng, Xiaojun Zhao, Xiaofei Jing, Fuxing Sun, Hao Ren and Guangshan Zhu
Journal of Materials Chemistry A 2012 - vol. 22(Issue 48) pp:NaN25026-25026
Publication Date(Web):2012/09/21
DOI:10.1039/C2JM34618D
An indium trimesate metal–organic framework (JUC-120) which possesses a cubic zeolitic MTN topology, as a new analogue to MIL-100(Al, Fe or Cr) compounds, has been successfully synthesized. Its structure exhibits a mesoporous cage (26 Å) and high thermal stability. The assembly of nitrobenzospiropyran derivatives (BSP) into JUC-120 nanocrystals (BSP/JUC-120) is achieved by a microwave-assisted crystallization inclusion approach. The BSP/JUC-120 films have been prepared on quartz wafers by a spin-coating method. The successful encapsulation of BSP molecules into the mesopores of the JUC-120 structure has been verified by N2 adsorption and TGA measurements. The photochromic properties of BSP/JUC-120 films are studied by the UV-Vis and fluorescence spectroscopies. More interestingly, metastable open merocyanine (OMC) species are directly generated from the closed spiropyran form (CSP) without photoirradiation and stabilized for a long period in the BSP/JUC-120 film. The open merocyanine isomer bleaches to the closed spiropyran form by ultraviolet or visible light, and the coloration is regained upon standing in the dark, exhibiting antidromic photochromism. Moreover, the BSP/JUC-120 film shows high reversibility and thermal stability of photochromism. This highly efficient MOF film is expected to be promising in the applications of optical devices.
Co-reporter:Ye Yuan, Hao Ren, Fuxing Sun, Xiaofei Jing, Kun Cai, Xiaojun Zhao, Yue Wang, Yen Wei and Guangshan Zhu
Journal of Materials Chemistry A 2012 - vol. 22(Issue 47) pp:NaN24562-24562
Publication Date(Web):2012/09/11
DOI:10.1039/C2JM35341E
A three-dimensional (3D) porous aromatic framework (PAF-14) with high fluorescence quantum yield was synthesized from luminescent monomer of tetra(4-dihydroxyborylphenyl)germanium (TBPGe) building blocks. The powder X-ray diffraction (PXRD) analysis of the experimental and simulated patterns indicate that PAF-14 is highly crystalline with ctn topology. The Argon sorption measurement indicates that PAF-14 possesses high surface area (Brunauer Emmet Teller surface area: 1288 m2 g−1). Significantly, the introduction of germanium into PAF-14 skeletons may bring about a low-lying lowest unoccupied molecular orbital (LUMO) and the crystalline polymeric backbones enhance the sensitivity of electron delocalization. Therefore the designed PAF-14 exhibits high fluorescence quenching ability for hazardous explosives, such as nitrobenzene, 2,4-DNT (2,4-dinitrotoluene) and TNT (2,4,6-trinitrotoluene).
Co-reporter:Shuyuan Zhou, Xiaoqin Zou, Fuxing Sun, Feng Zhang, Songjie Fan, Huijun Zhao, Thomas Schiestel and Guangshan Zhu
Journal of Materials Chemistry A 2012 - vol. 22(Issue 20) pp:NaN10328-10328
Publication Date(Web):2012/03/27
DOI:10.1039/C2JM16371C
High-performance and continuous Cu3(BTC)2 membranes have been successfully fabricated using a secondary growth approach on pre-seeded α-Al2O3 hollow ceramic fibers (HCFs) modified with chitosan. Facile synthesis of Cu3(BTC)2 nanocrystals can be achieved by a modified solvothermal protocol. A stable and homogeneous Cu3(BTC)2 seed precusor obtained with particle size of 300 nm, the size of which is suitable for seeding HCFs without any pore jam of HCFs supports (pore size of 200 nm for HCFs). A new substrate HCFs was introduced as the support of Cu3(BTC)2 membranes. Moreover, for the first time, chitosan is used to improve the binding force between seeds and the support owing to its abundance of both amino and hydroxyl groups. As-prepared Cu3(BTC)2 membrane is studied for hydrogen separation by binary gas permeation of H2/N2, H2/CO2 and H2/CH4. The synthesized membrane shows high H2 selectivity with separation factors of 8.66, 13.56 and 6.19 for the gas mixtures of H2/N2, H2/CO2 and H2/CH4 respectively. A preferred permeance for H2 in the binary gas mixture is obtained in the range of 3.23 × 10−8 to 4.1 × 10−8 mol m−2 s−1 Pa−1 due to the unique properties of the Cu3(BTC)2 MOF material, which is expected in the potential applications of industrial hydrogen recycling.
Co-reporter:Faheem Muhammad, Wenxiu Qi, Aifei Wang, Jingkai Gu and Guangshan Zhu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 28) pp:NaN5719-5719
Publication Date(Web):2015/06/01
DOI:10.1039/C5TB00554J
In addition to their well-known antibacterial property, silver nanoparticles (Ag NPs) have also been highlighted as anti-leukemic agents; however, the underlying mechanism responsible for inhibiting the growth of hematopoietic cancer cells is so far poorly understood. In previous reports, Ag NP-induced oxidative stress was implicated for therapeutic efficacy but the excessive production of ROS in several hematopoietic malignant cells, which can potentially induce the dissolution of Ag NPs, was not taken into consideration. In this study we proposed Ag NP dissolution, in response to increased oxidative stress in leukemic cells, as the most probable mechanism for their anticancer activity. Hypochlorous acid-mediated dissolution of therapeutically active and ultrasmall (<5 nm) Ag NPs was also exploited to develop an oxidant responsive combinatorial drug delivery system. When Ag-capped and anticancer drug loaded pores of mesoporous silica were exposed to HOCl, the ready disintegration of Ag NPs resulted in a controlled release of drug molecules. The drug release profile and growth inhibition of myeloperoxidase positive (MOLM-13) leukemic cells support the role of the oxidant in the dissolution of Ag NPs. Besides combinational chemotherapy, the current study also provides us with an opportunity to investigate the interaction of Ag NPs with biorelevant oxidants.
Co-reporter:Mingyi Guo, Faheem Muhammad, Aifei Wang, Wenxiu Qi, Nan Wang, Yingjie Guo, Yen Wei and Guangshan Zhu
Journal of Materials Chemistry A 2013 - vol. 1(Issue 39) pp:NaN5278-5278
Publication Date(Web):2013/06/28
DOI:10.1039/C3TB20466A
The cost of conventional chemotherapeutic drugs is substantially high, and biomedical researchers are constantly hunting for cheap and effective chemotherapeutic alternatives. Recently, curcumin has emerged as a cost effective anticancer remedy, however, the low bioavailability of curcumin has been a major impediment to its successful utilization for disease management. In this work, we developed a highly biocompatible magnesium hydroxide as an intelligent nanocarrier for delivering curcumin into cancer cells. Curcumin was loaded onto magnesium hydroxide nanoplates via a complexation strategy. Furthermore, these drug conjugated nanoparticles not only achieve efficient loading of a highly hydrophobic drug, but also exhibit pH responsive release in extracellular or intracellular acid environments, validated by in vitro drug release, confocal microscopy and MTT assay. These biocompatible nanoplates can be promising candidates for the further development of smart drug delivery nanodevices.
Co-reporter:Faheem Muhammad, Wenxiu Qi, Aifei Wang, Jingkai Gu, Jianshi Du and Guangshan Zhu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 8) pp:NaN1604-1604
Publication Date(Web):2014/12/23
DOI:10.1039/C4TB01709A
Inflammation is a complex and dynamic defensive cellular approach to safeguard against deleterious agents; however, an overexpression of such responses frequently results in the development of a number of devastating diseases, such as atherosclerosis, cancer, inflammatory bowel, Alzheimer's and Parkinson's diseases. At the site of the inflammation, excessive amount of reactive oxygen species (ROS) are produced, and therefore researchers are now earnestly trying to exploit ROS pathological signals to design oxidative triggered drug release systems. In this study, we report a straightforward strategy to develop an oxidative stress responsive drug release systems. Newly developed, ultra-small, and thiol stabilized zinc sulfide quantum dots (ZnS QDs) are used as nanocaps to regulate the release of anticancer drug (camptothecin) from mesoporous silica nanoparticles (MSNs) in response to oxidative environment. The exposure of capped nanocarrier to a higher concentration of H2O2 fails to open the drug loaded nanochannels; however, an addition of a minute amount of divalent iron, the most abundant transition-metal in the body, readily unseals the nanochannels at considerably lower H2O2 concentrations due to the generation of highly reactive hydroxyl radicals (˙OH). Thiol groups, which stabilize the ZnS nanolids, are actually oxidized by ˙OH and as a result unleash the loaded drug molecules from the channels of silica. In addition to the inflammation-induced drug delivery, this study also provides basic insight into the fate of thiol stabilized nanoparticles upon interaction with hydroxyl radicals.
Co-reporter:Jiangtao Jia, Fuxing Sun, Heping Ma, Lei Wang, Kun Cai, Zheng Bian, Lianxun Gao and Guangshan Zhu
Journal of Materials Chemistry A 2013 - vol. 1(Issue 35) pp:NaN10115-10115
Publication Date(Web):2013/07/08
DOI:10.1039/C3TA11840A
A new dendritic aromatic six-node ligand has been used to construct a MOF. It takes an octahedral and trigonal prismatic conformation in JUC-103 and JUC-104, respectively. JUC-103 exhibits high ethane uptake and has the separation ability for ethane to nitrogen. JUC-104 has an unusual (6,12)-connected CaSi2 topology.
Co-reporter:Xiaofei Jing, Donglei Zou, Peng Cui, Hao Ren and Guangshan Zhu
Journal of Materials Chemistry A 2013 - vol. 1(Issue 44) pp:NaN13931-13931
Publication Date(Web):2013/09/18
DOI:10.1039/C3TA13115G
Porous aromatic frameworks (PAF-32s) derived from tetrahedral monomers as basic building units have been successfully synthesized via the Friedel–Crafts alkylation reaction in the presence of the inexpensive catalyst FeCl3. The resulting PAF-32 materials possess high stabilities and high surface areas up to 1679 m2 g−1. In particular, amino and hydroxyl functional groups have been introduced into the networks. The corresponding functionalized PAF materials (PAF-32-NH2 and PAF-32-OH) display enhanced CO2 adsorption capacities and higher heats of adsorption (Qst) than the non-functionalized PAF-32.
Co-reporter:Guangli Yu, Xiaoqin Zou, Aifei Wang, Jian Sun and Guangshan Zhu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 37) pp:NaN15427-15427
Publication Date(Web):2014/07/22
DOI:10.1039/C4TA02565B
In the present study, a facile strategy is proposed for generating bimodal porosity in porous carbons by using a sacrificed metal–organic framework (ZIF-8) as the precursor and additional silica colloids as extra porogenes via further self-assembly. Details in the formation of hierarchical structures are studied by time-dependent XRD and TEM characterizations. As-synthesized hierarchical porous carbons possess micropores (1.0 nm) and mesopores (3–20 nm) that are verified by TEM and N2-sorption measurements. Specific information on carbon structures is supplied by XRD and Raman data. Electrochemical properties have been briefly investigated by cyclic voltammetry and impedance spectroscopy. A highest capacitance of 181 F g−1 and lowest resistance of 0.21 Ω cm2 are obtained between series of ZIF-8 derivative carbons, both of which, along with high electro-stability, show promising applications for these nanoporous carbons in supercapacitors.
Co-reporter:Wei Wang, Hao Ren, Fuxing Sun, Kun Cai, Heping Ma, Jianshi Du, Huijun Zhao and Guangshan Zhu
Dalton Transactions 2012 - vol. 41(Issue 14) pp:NaN3936-3936
Publication Date(Web):2012/02/13
DOI:10.1039/C2DT11996J
PAF-16 which is based on tetrahedral units (TCPSi) and triangular building units, shows both high thermal stability and high chemical stability. The surface area of PAF-16 can be tuned by changing the reaction temperature and ratio of monomer and catalyst. PAF-16 also shows considerable adsorption capacity of CO2.
Co-reporter:Ye Peng, Teng Ben, Jun Xu, Ming Xue, Xiaofei Jing, Feng Deng, Shilun Qiu and Guangshan Zhu
Dalton Transactions 2011 - vol. 40(Issue 12) pp:NaN2724-2724
Publication Date(Web):2010/12/13
DOI:10.1039/C0DT01268H
By a Yamamoto-type of Ullmann cross-coupling reaction, a well-defined covalently-linked microporous organic-inorganic hybrid framework polyoctaphenylsilsesquioxane (JUC-Z1) was effectively prepared from the nano building block p-iodio-octaphenylsilsesquioxane (I8OPS) with a yield of ca. 100%. The structure of JUC-Z1 was characterized by 13C CP/MAS NMR and 29Si MAS NMR experiments. Fourier transform infrared spectroscopy (FTIR) was performed to confirm the presence of functions in the framework. The results showed that inorganic silsesquioxane cubes were linearly covalently-linked by biphenyls, offering a highly cross-coupling framework. The powder X-ray diffraction (PXRD) pattern and transmission electron microscope (TEM) image show that JUC-Z1 is spherical with uniform micropores. N2 adsorption results suggest that the hybrid framework has a narrow pore size distribution from 11.8 to 20.0 Å, with a BET surface area of 283 m2g−1 and a pore volume of 0.226 cm3g−1. A thermogravimetric (TG) analysis indicates the thermal stability of JUC-Z1 up to 397 °C in air. Moreover, a liquid sorption experiment reveals the favorable sorption of benzene and water.
Co-reporter:Hao Ren, Teng Ben, Ensi Wang, Xiaofei Jing, Ming Xue, Bingbing Liu, Yan Cui, Shilun Qiu and Guangshan Zhu
Chemical Communications 2010 - vol. 46(Issue 2) pp:NaN293-293
Publication Date(Web):2009/11/11
DOI:10.1039/B914761F
A novel 3D porous aromatic framework (PAF) based on a tetraphenylmethane block and a triangular triazine ring been designed and synthesized, with 1109 m2 g−1 Langmuir surface area, and shows selective sorption of benzene.
Co-reporter:Jiangtao Jia, Fuxing Sun, Qianrong Fang, Xiaoqiang Liang, Kun Cai, Zheng Bian, Huijun Zhao, Lianxun Gao and Guangshan Zhu
Chemical Communications 2011 - vol. 47(Issue 32) pp:NaN9169-9169
Publication Date(Web):2011/07/13
DOI:10.1039/C1CC12891D
A novel low density two-fold interpenetrated MOF-5 analogue with pcu topology, JUC-100, was designed and prepared successfully. It can be regarded as MOF-5 in which half of the Zn4O(CO2)6 units are replaced by organic 1,3,5-triphenylbenzene segments. JUC-100 exhibits H2 uptake ability comparable to interpenetrated MOF-5, but relatively low initial isosteric heat of adsorption.
Co-reporter:Tsolmon Borjigin, Fuxing Sun, Jinlei Zhang, Kun Cai, Hao Ren and Guangshan Zhu
Chemical Communications 2012 - vol. 48(Issue 61) pp:NaN7615-7615
Publication Date(Web):2012/06/12
DOI:10.1039/C2CC33023G
A novel 44 square grid microporous metal–organic framework (MOF) JUC-110 with 1D open channels has been synthesized, which shows exceptional hydrothermal stability and capability for separating alcohols from water in gas chromatographic (GC) separation.
Co-reporter:Xue Gao, Xiaoqin Zou, Feng Zhang, Shixing Zhang, Heping Ma, Nian Zhao and Guangshan Zhu
Chemical Communications 2013 - vol. 49(Issue 78) pp:NaN8841-8841
Publication Date(Web):2013/07/25
DOI:10.1039/C3CC44515A
The synthesis of continuous and low-siliceous ZSM-5 membranes was achieved without organic templates under mild conditions (a low temperature of 100 °C and ambient pressure). The resultant high-quality membranes with good water perm-selectivity were further applied in water–alcohol separation, exhibiting an extraordinarily high separation factor of above 10000 and an improved water flux (3.43–6.88 kg m−2 h−1) for ethanol and isopropanol aqueous azeotropes.
Co-reporter:Xiaoqin Zou, Hao Ren and Guangshan Zhu
Chemical Communications 2013 - vol. 49(Issue 38) pp:NaN3936-3936
Publication Date(Web):2013/02/27
DOI:10.1039/C3CC00039G
Porous organic frameworks (POFs) as an important subclass of nanoporous materials are of great interest in materials science. In recent years, the discovery and creation of POFs with excellent properties for advanced applications have attracted much attention and intensive efforts have been contributed to this field. As a result, the design of materials with multi-functionalities is an ever-pursued dream of materials scientists and engineers. In this respect, a new concept based on topology chemistry is introduced for the rational and targeted synthesis of POF materials. The present feature article provides an overview of the relationship between building blocks or starting monomers, underlying topological nets, and pre-determined structures. Several important nets are included successively from one to three dimensions. In addition, special emphasis is given to the advanced applications of designed POF materials in the current paper.
Co-reporter:Hongmin Su, Fuxing Sun, Jiangtao Jia, Hongming He, Aifei Wang and Guangshan Zhu
Chemical Communications 2015 - vol. 51(Issue 26) pp:NaN5777-5777
Publication Date(Web):2015/02/20
DOI:10.1039/C4CC10159F
A highly porous bio-MOF, medi-MOF-1, constructed from Zn and the pharmaceutical ingredient curcumin has been successfully synthesized. It can display permanent porosity with a surface area as high as ca. 3002 m2 g−1, which exhibits great potential in bioapplications. Its ibuprofen delivery ability, biodegradation and cytotoxicity were also studied.
Co-reporter:Heping Ma, Hao Ren, Shuang Meng, Zhuojun Yan, Huanyu Zhao, Fuxing Sun and Guangshan Zhu
Chemical Communications 2013 - vol. 49(Issue 84) pp:NaN9775-9775
Publication Date(Web):2013/08/23
DOI:10.1039/C3CC45217D
Here we present a new 3D microporous COF with a uniform pore size (0.64 nm). MCOF-1 exhibits high adsorption selectivity towards C3H8, C2H6 and C2H4 over CH4 owing to the pore size and preferential adsorption.
Co-reporter:Xiaoqiang Liang, Feng Zhang, Haixia Zhao, Wei Ye, Lasheng Long and Guangshan Zhu
Chemical Communications 2014 - vol. 50(Issue 49) pp:NaN6516-6516
Publication Date(Web):2014/03/27
DOI:10.1039/C4CC00458B
A multifunctional metal–organic framework generated from chiral tricarboxylate ligands and gadolinium ions has been successfully synthesized and characterized. It shows proton conduction, dielectric anomalous behaviour and a second-order NLO effect.
Co-reporter:Huanyu Zhao, Zhao Jin, Hongmin Su, Jinlei Zhang, Xiangdong Yao, Huijun Zhao and Guangshan Zhu
Chemical Communications 2013 - vol. 49(Issue 27) pp:NaN2782-2782
Publication Date(Web):2013/02/06
DOI:10.1039/C3CC38474H
A novel porous aromatic framework based on tetra-(4-anilyl)-methane and cyanuric chloride has been designed and synthesized successfully, which possesses permanent porosity and high selectivity of CO2 towards CH4.
Co-reporter:Jia Liu, Feng Zhang, Xiaoqin Zou, Guangli Yu, Nian Zhao, Songjie Fan and Guangshan Zhu
Chemical Communications 2013 - vol. 49(Issue 67) pp:NaN7432-7432
Publication Date(Web):2013/06/26
DOI:10.1039/C3CC42287A
The preparation of highly hydrophobic and stable MIL-53(Al) nanomaterials was achieved by an ionothermal synthesis strategy. The hydrophobicity of MIL-53(Al)it was studied by water adsorption; and the enhancement in this property was discussed with respect to its reference to MIL-53(Al)ht.
Co-reporter:Jiangtao Jia, Fuxing Sun, Tsolmon Borjigin, Hao Ren, Tingting Zhang, Zheng Bian, Lianxun Gao and Guangshan Zhu
Chemical Communications 2012 - vol. 48(Issue 48) pp:NaN6012-6012
Publication Date(Web):2012/04/27
DOI:10.1039/C2CC32347H
Two non-interpenetrated and isomorphous MOFs with nia topology, cationic JUC-101 and anionic JUC-102, are synthesized by connecting a trigonal prismatic metal cluster with an octahedral organic ligand. JUC-101 obtains a BET surface area of 3742 m2 g−1 and can absorb 4.18 wt% of H2 at 30 atm and 77 K, while JUC-102 can absorb cationic dye molecules and release them under the triggering of ions.
Co-reporter:Huanyu Zhao, Zhao Jin, Hongmin Su, Xiaofei Jing, Fuxing Sun and Guangshan Zhu
Chemical Communications 2011 - vol. 47(Issue 22) pp:NaN6391-6391
Publication Date(Web):2011/05/06
DOI:10.1039/C1CC00084E
A novel 2D porous organic framework based on the nucleophilic substitution of cyanuric chloride has been designed and synthesized successfully, which possesses an ordered structure, permanent porosity and drug release ability towards ibuprofen.
Co-reporter:Xiaoqiang Liang, Feng Zhang, Wei Feng, Xiaoqin Zou, Chengji Zhao, Hui Na, Cong Liu, Fuxing Sun and Guangshan Zhu
Chemical Science (2010-Present) 2013 - vol. 4(Issue 3) pp:NaN992-992
Publication Date(Web):2012/11/23
DOI:10.1039/C2SC21927A
A chiral two-dimensional MOF, {[Ca(D-Hpmpc)(H2O)2]·2HO0.5}n (1, D-H3pmpc = D-1-(phosphonomethyl) piperidine-3-carboxylic acid), with intrinsic proton conductivity has been synthesized and characterized. Structure analysis shows that compound 1 possesses protonated tertiary amines as proton carriers and hydrogen-bonding chains served as proton-conducting pathways. Further, MOF–polymer composite membranes have been fabricated via assembling polymer PVP with different contents of rod-like 1 submicrometer crystals. Interestingly, the proton conductivity of this composite membrane containing 50 wt% 1 is rapidly increased, compared with that of pure submicrometer crystals at 298 K and ∼53% RH. Therefore, it is feasible to introduce humidification of PVP into composite membranes to enhance low-humidity proton conductivity; and humidified PVP with adsorbed water molecules plays an important role in proton conduction indicated by the results of water physical sorption and TG/DTG analyses. This study may offer a facile strategy to prepare a variety of solid electrolyte materials with distinctive proton-conducting properties under a low humidity.
Co-reporter:Hongming He, Fuxing Sun, Tsolmon Borjigin, Nian Zhao and Guangshan Zhu
Dalton Transactions 2014 - vol. 43(Issue 9) pp:NaN3721-3721
Publication Date(Web):2013/11/26
DOI:10.1039/C3DT53013B
Metal–organic frameworks (MOFs) are a rapidly growing class of hybrid materials with many multifunctional properties. The permanent porosity plays a central role in the functional properties. In particular, the luminescent MOFs with a permanent porosity have wide applications in guest species recognition and adsorption. In this contribution, we aim to develop tunable colors and white-light luminescence materials by the encapsulation of Ln3+ species in microporous luminescent MOFs. A semi-rigid trivalent carboxylic acid 1,3,5-tri(4-carboxyphenoxy)benzene (H3TCPB) was selected as the organic building block, not only because it is suitable to construct microporous frameworks, but also by reason of its blue luminescent emission. Under solvothermal reactions, a microporous MOF material, [Zn3(TCPB)2(H2O)2]·2H2O·4DMF (JUC-113, JUC = Jilin University, China), was synthesized, which has a permanent porosity and emits blue light. According to three-primary colors, the guest luminescent species should be Tb3+ and Eu3+ owing to their distinctive colors (Tb3+, green; Eu3+, red). In addition, the luminescent properties of JUC-113 can be easily tuned by different combinations of the encapsulation amount of Tb3+ and Eu3+, obtaining white-light emission materials.
Co-reporter:Hongming He, Yang Song, Fuxing Sun, Zheng Bian, Lianxun Gao and Guangshan Zhu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 32) pp:NaN16603-16603
Publication Date(Web):2015/07/13
DOI:10.1039/C5TA03537F
A V-shaped aromatic ligand 1,3-di(4-carboxyphenyl)benzene (H2DCPB), retaining only one branch of the H6TDCPB ligand, was utilized. The assembly of this ligand with Zn(II) ions forms a two-fold interpenetrated porous MOF with pcu topology (JUC-135). The N2 adsorption isotherm of the activated sample at 77 K revealed type-I microporous characteristics. The BET and Langmuir surface areas are calculated to be 503.7 m2 g−1 and 718.9 m2 g−1, respectively. Notably, by the fluorescence technique, JUC-135 can be used to detect nitroaromatic explosives. In particular, it is one of the most efficient porous material-based sensors for TNP (KSV = 3.7 × 104 M−1). Furthermore, JUC-135 also can distinguish TNP (blue-shift) from NB, 1,3-DNB and 2,4-DNT (red-shift) by virtue of the shift direction of fluorescence spectra.
Co-reporter:Shuang Meng, Heping Ma, Lingchang Jiang, Hao Ren and Guangshan Zhu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 35) pp:NaN14541-14541
Publication Date(Web):2014/06/30
DOI:10.1039/C4TA00984C
Porous organic frameworks (POFs) have attracted a great deal of attention thanks to their high surface areas, high stability and controllable skeletons. We synthesize a series of porphyrin-based porous aromatic frameworks (PAF-40s) through a cost-effective approach. The PAF-40s exhibit high surface areas and excellent chemical and thermal stability. Specifically, these PAF materials possess high adsorption capacity of small hydrocarbons, such as methane, ethylene, ethane and propane, at room temperature. Furthermore, the PAFs have remarkably high adsorption selectivity values of C2 and C3 hydrocarbons over CH4.
Co-reporter:Lina Li, Hao Ren, Ye Yuan, Guangli Yu and Guangshan Zhu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 29) pp:NaN11098-11098
Publication Date(Web):2014/04/11
DOI:10.1039/C4TA01252F
Currently, synthesis of most porous organic frameworks (POFs) requires noble metals as the main catalyst. Herein we report a low-cost and straightforward synthetic strategy to develop porous aromatic frameworks (PAFs). With AlCl3 as the catalyst, the Scholl coupling reaction could occur between the phenyl rings of aromatic compounds. Using 3-dimensional monomers, such as triphenylamine, tetraphenylmethane, tetraphenylsilane, and tetraphenylgermane, we successfully obtained a series of PAFs with moderate Brunauer–Emmett–Teller (BET) surface areas ranging from 515 m2 g−1 to 1119 m2 g−1. Among the obtained PAF materials, PAF-41 exhibited the best CH4 and CO2 sorption capacity with CH4 (1.04 mmol g−1) and CO2 (3.52 mmol g−1) at 273 K. In addition, PAF-43 demonstrated its comparably high isosteric heat of adsorption at 34.8 kJ mol−1 for CO2 and 29.7 kJ mol−1 for CH4. It is also worth mentioning that the developed approach also overcomes typical flaws of some classic PAFs, such as high cost and complexity of precursor preparation.
Co-reporter:Heping Ma, Hao Ren, Xiaoqin Zou, Fuxing Sun, Zhuojun Yan, Kun Cai, Dayang Wang and Guangshan Zhu
Journal of Materials Chemistry A 2013 - vol. 1(Issue 3) pp:NaN758-758
Publication Date(Web):2012/10/18
DOI:10.1039/C2TA00616B
Novel porous aromatic frameworks, PAF-18-OH and its lithiated derivative PAF-18-OLi, have been successfully synthesized. In particular, PAF-18-OLi displays significant enhancement of H2 and CO2 adsorption capacity, especially for CO2 uptake (14.4 wt%). More valuably, the stable PAF-18-OLi material exhibits high CO2/N2 selectivity, as high as 129 in the case of CO2 capture from simulated post-combustion flue gas mixtures (85% N2 and 15% CO2). Furthermore, the PAF-18-OLi has shown improved H2 storage capacity after lithiation.
Co-reporter:Songjie Fan, Fuxing Sun, Jijiang Xie, Jin Guo, Laiming Zhang, Chunrui Wang, Qikun Pan and Guangshan Zhu
Journal of Materials Chemistry A 2013 - vol. 1(Issue 37) pp:NaN11442-11442
Publication Date(Web):2013/07/19
DOI:10.1039/C3TA11604B
Cu(bipy)2(SiF6) is a highly porous metal–organic framework (MOF) and represents a prototypal “pillared sheet” platform offering opportunities to control the pore sizes. Its structural features, low cost and facile synthesis make it a great candidate to fabricate membranes for gas separation. The key to obtaining thin, continuous Cu(bipy)2(SiF6) membranes is to control the Cu(bipy)2(SiF6) crystal growth and enhance the binding between membrane and substrate. Here we explored a new route by direct synthesis and successfully obtained a continuous thin Cu(bipy)2(SiF6) membrane on a macroporous glass-frit disk with high robustness. It is speculated that the SiF62− used to construct the Cu(bipy)2(SiF6) membrane came from the fluorinated substrate. The Cu(bipy)2(SiF6) membrane shows the separation factors of H2–CO2, H2–CH4 and H2–N2 are 8.0, 7.5, and 6.8 respectively at 293 K and 1 bar with H2 permeance of 2.7 × 10−7 mol m−2 s−1 Pa−1 as well as high thermal stability. We expect to explore more membranes of Cu(bipy)2(SiF6) analogues with tuneable pore sizes using this route and to obtain membranes with higher gas separation performance.
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hylethylidene)-1,4-phenylene]](http://img.cochemist.com/ccimg/41300/41205-96-3.png)
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hylethylidene)-1,4-phenylene]](http://img.cochemist.com/ccimg/41300/41205-96-3_b.png)
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