Co-reporter:Ping Hu, Rui Wang, Lei Zhou, Lei Chen, Qingsheng Wu, Ming-Yong Han, Ahmed Mohamed El-Toni, Dongyuan Zhao, and Fan Zhang
Analytical Chemistry March 21, 2017 Volume 89(Issue 6) pp:3492-3492
Publication Date(Web):February 21, 2017
DOI:10.1021/acs.analchem.6b04548
As a light-activated noninvasive cancer treatment paradigm, photodynamic therapy (PDT) has attracted extensive attention because of its high treatment efficacy and low side effects. Especially, spatiotemporal control of singlet oxygen (1O2) release is highly desirable for realizing on-demand PDT, which, however, still remains a huge challenge. To address this issue, a novel switchable near-infrared (NIR)-responsive upconversion nanoprobe has been designed and successfully applied for controlled PDT that can be optically activated by tumor-associated disruption of labile Zn2+ (denoted as Zn2+ hereafter) homeostasis stimuli. Upon NIR irradiation, this theranostic probe can not only quantitatively detect the intracellular endogenous Zn2+ in situ but also selectively generate a great deal of cytotoxic reactive oxygen species (ROS) for efficiently killing breast cancer cells under the activation of excessive endogenous Zn2+, so as to maximally avoid adverse damage to normal cells. This study aims to propose a new tumor-specific PDT paradigm and, more importantly, provide a new avenue of thought for efficient cancer theranostics based on our designed highly sensitive upconversion nanoprobes.
Co-reporter:Wenxing Wang, Peiyuan Wang, Xueting Tang, Ahmed A. Elzatahry, Shuwen Wang, Daifallah Al-Dahyan, Mengyao Zhao, Chi Yao, Chin-Te Hung, Xiaohang Zhu, Tiancong Zhao, Xiaomin Li, Fan Zhang, and Dongyuan Zhao
ACS Central Science August 23, 2017 Volume 3(Issue 8) pp:839-839
Publication Date(Web):July 26, 2017
DOI:10.1021/acscentsci.7b00257
The low-efficiency cellular uptake property of current nanoparticles greatly restricts their application in the biomedical field. Herein, we demonstrate that novel virus-like mesoporous silica nanoparticles can easily be synthesized, showing greatly superior cellular uptake property. The unique virus-like mesoporous silica nanoparticles with a spiky tubular rough surface have been successfully synthesized via a novel single-micelle epitaxial growth approach in a low-concentration-surfactant oil/water biphase system. The virus-like nanoparticles’ rough surface morphology results mainly from the mesoporous silica nanotubes spontaneously grown via an epitaxial growth process. The obtained nanoparticles show uniform particle size and excellent monodispersity. The structural parameters of the nanoparticles can be well tuned with controllable core diameter (∼60–160 nm), tubular length (∼6–70 nm), and outer diameter (∼6–10 nm). Thanks to the biomimetic morphology, the virus-like nanoparticles show greatly superior cellular uptake property (invading living cells in large quantities within few minutes, <5 min), unique internalization pathways, and extended blood circulation duration (t1/2 = 2.16 h), which is much longer than that of conventional mesoporous silica nanoparticles (0.45 h). Furthermore, our epitaxial growth strategy can be applied to fabricate various virus-like mesoporous core–shell structures, paving the way toward designed synthesis of virus-like nanocomposites for biomedicine applications.
Co-reporter:Peiyuan Wang, Yujie Bai, Chi Yao, Xiaomin Li, Lei Zhou, Wenxing Wang, Ahmed Mohamed El-Toni, Jian Zi, Dongyuan ZhaoLei Shi, Fan Zhang
Analytical Chemistry 2017 Volume 89(Issue 4) pp:
Publication Date(Web):January 25, 2017
DOI:10.1021/acs.analchem.6b04860
Cyanide is extremely toxic to organisms but difficult to detect in living biological specimens. Here, we report a new CN– sensing platform based on unmodified Au–Ag alloy nanoboxes that etch in the presence of this analyte, yielding a shift in plasmon frequency that correlates with the analyte concentration. Significantly, when combined with dark field microscopy, these particle probes can be used to measure CN– concentrations in HeLa cells and in vivo in Zebra fish embryos. The limit of detection (LOD) of the novel method is 1 nM (below the acceptable limit defined by the World Health Organization), and finite-difference time-domain (FDTD) calculations are used to understand the CN– induced spectral shifts.
Co-reporter:Peiyuan Wang, Chengli Wang, Lingfei Lu, Xiaomin Li, Wenxing Wang, Mengyao Zhao, Lidan Hu, Ahmed Mohamed El-Toni, Qin Li, Fan Zhang
Biomaterials 2017 Volume 141(Volume 141) pp:
Publication Date(Web):1 October 2017
DOI:10.1016/j.biomaterials.2017.06.040
•NaYF4:Yb,Er@NaGdF4:Yb@NaNdF4:Yb nanoplates were synthesized under the guidance of kinetics-mediation strategy.•The obtained nanoplates can be applied for NIR II bioimaging and MRI in vivo.•Six-petal nanoplates with high roughness surfance exhibit excellent performance in BBB trasportation and tumor targeting.Effective delivery of imaging agents or therapeutics to the brain has remained elusive due to the poor blood-brain barrier (BBB) permeability, resulting in the apparent risks of inefficient diagnosis and therapeutic agents for brain disease. Herein, we report on the surface roughness mediated BBB transportation for the first time. The lanthanide-based core/shell/shell structured NaYF4:Yb,Er@NaGdF4:Yb@NaNdF4:Yb nanoplates with controllable surface roughness and multi-model bioimaging features were synthesized and used to evaluate the surface roughness dependent BBB permeability without any surface bio-functionalization. By controlling the kinetics of the shell coating process, the hexagon-disc, multi-petals and six-petals nanoplates with different surface roughness can be obtained. Comparing with the NPs with less Ra and receptor-conjugated NPs, the obtained six-petals nanoplates with highest roughness exhibit excellent performance in BBB transportation and tumor targeting, which lay solid foundation for the diagnosis and the therapy of brain tumor.Download high-res image (291KB)Download full-size image
Co-reporter:Chi Yao, Jia Tian, Hui Wang, Dan-Wei Zhang, ... Zhan-Ting Li
Chinese Chemical Letters 2017 Volume 28, Issue 4(Volume 28, Issue 4) pp:
Publication Date(Web):1 April 2017
DOI:10.1016/j.cclet.2017.01.005
Four water-soluble porous supramolecular organic framework drug delivery systems (sof-DDSs) have been used to adsorb doxorubicin (DOX) in water at physiological pH of 7.4, which is driven exclusively by hydrophobicity. The resulting complexes DOX@SOFs are formed instantaneously upon dissolving the components in water. The drug-adsorbed sof-DDSs can undergo plasm circulation with important maintenance of the drug and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells. DOX is released readily in the cancer cells due to the protonation of its amino group in the acidic medium of cancer cells. In vitro and in vivo experiments reveal that the delivery of SOF-a-d remarkably improve the cytotoxicity of DOX for the MCF-7/Adr cells and tumors, leading to 13-19-fold reduction of the IC50 values as compared with that of DOX. This new sof-DDSs strategy omits the indispensable loading process required by most of reported nano-scaled carriers for neutral hydrophobic chemotherapeutic agents, and thus should be highly valuable for future development of low-cost delivery systems.With doxorubicin as model, we demonstrate loading-free supramolecular organic framework drug delivery systems (sof-DDSs) for the delivery and controlled release of the neutral hydrophobic chemotherapeutic agent doxorubicin for the treatment of multidrug resistant human breast cancer.Download high-res image (131KB)Download full-size image
Co-reporter:Jia Tian, Chi Yao, Wen-Lin Yang, Lei Zhang, ... Zhan-Ting Li
Chinese Chemical Letters 2017 Volume 28, Issue 4(Volume 28, Issue 4) pp:
Publication Date(Web):1 April 2017
DOI:10.1016/j.cclet.2017.01.010
Water-soluble three-dimensional porous supramolecular organic frameworks (SOFs) have been demonstrated as a new generation of homogeneous polycationic platforms for anti-cancer drug delivery. The new SOF drug delivery systems (sof-DDSs) can adsorb dianionic pemetrexed (PMX), a clinically used chemotherapeutic agent instantaneously upon dissolving in water, which is driven by both electrostatic attraction and hydrophobicity. The in situ-prepared PMX@SOFs are highly stable and can avoid important release of the drug during plasm circulation and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells to enter the cancer cells. Acidic microenvironment of cancer cells promotes the release of the drug in cancer cells. Both in vitro and in vivo studies have revealed that sof-DDSs considerably improve the treatment efficacy of PMX, leading to 6-12-fold reduction of the IC50 values, as compared with that of PMX alone. The new drug delivery strategy omits the loading process required by most of reported nanoparticle-based delivery systems and thus holds promise for future development of low-cost drug delivery systemsDownload high-res image (233KB)Download full-size imageSupramolecular organic framework drug delivery systems (sof-DDSs) have been developed as loading-free porous nanocarriers, which enable efficient delivery of pemetrexed, an anti-cancer chemotherapeutic agent, into multidrug-resistant human breast cancer cells and the acidic medium-responsive drug release.
Co-reporter:Lidan Hu;Yong Fan;Lu Liu;Xiaomin Li;Baozhou Zhao;Rui Wang;Peiyuan Wang;Ahmed Mohamed El-Toni
Advanced Optical Materials 2017 Volume 5(Issue 22) pp:
Publication Date(Web):2017/11/01
DOI:10.1002/adom.201700680
AbstractThe orthogonal luminescence encoding technique is developed for the first time based on a novel near-infrared (NIR) rechargeable upconverting persistent luminescence (UCPL) composites. The orthogonal encoding signals with multicolor upconversion emission and long persistent phosphorescence can be activated and work independently in the presence and absence of 980 nm excitation. The orthogonal encoding technique allows for a marked increase in the coding capacity compared with conventional luminescence encoding strategies. This strategy can offer a greatly increased coding capacity with less naked-eye certifiable colors to decrease the decoding error rate induced by the chromatic aberration of the similar colors, which can be effectively decoded by the portable charge-coupled device. In addition, the obtained NIR rechargeable UCPL materials show great potential applications for anticounterfeiting, rewriteable data encryption and decryption, zero-background bioimaging, and noninvasive photo-biostimulation, etc.
Co-reporter:Hongwei Zhu, Yesheng Shang, Yunke Jing, Yang Liu, Yupu Liu, Ahmed Mohamed El-Toni, Fan Zhang, and Dongyuan Zhao
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 38) pp:25586
Publication Date(Web):September 2, 2016
DOI:10.1021/acsami.6b06534
Exploring facile and reproducible methods to prepare mesoporous TiO2 nanospheres is crucial for improving the performance of TiO2 materials for energy conversion and storage. Herein, we report a simple and reproducible double-surfactant assembly-directed method to prepare monodisperse mesoporous TiO2 nanospheres. A double-surfactant system of n-dodecylamine (DDA) and Pluronic F127 was adopted to control the hydrolysis and condensation rates of tetrabutyl titanate in a mixture of water and alcohol at room temperature. In this process, the diameter size of mesoporous TiO2 nanospheres can be simply tuned from ∼50 to 250 nm by varying the concentration of H2O and surfactants. The double-surfactant system of DDA and F127 plays an effective role in determining the size, morphology, and monodispersity of mesoporous TiO2 nanospheres to reduce agglomeration during the sol–gel process. The resultant mesoporous anatase TiO2 nanospheres after solvothermal treatment at 160 °C are built of interpenetrating nanocrystals with a size of ∼10 nm, which are arranged to obtain a large number of connecting mesopores. Mesoporous TiO2 nanospheres with a small diameter size of around 50 nm possess a high surface area (∼160 m2/g) and mesopores with sizes of 4–30 nm. The small diameter size, high crystallinity, and mesoporous structure of TiO2 nanospheres lead to excellent performance in cycling stability and rate capability for lithium-ion batteries. After 500 cycles, the monodisperse mesoporous TiO2 nanospheres exhibit a charge capacity as high as 156 mAhg–1 without obvious fade, and the Coulombic efficiency can reach up to 100%.Keywords: lithium storage; mesoporous materials; nanospheres; sol−gel process; surfactant assembly; synthesis; titania colloids
Co-reporter:Chi Yao, Caiyi Wei, Zhi Huang, Yiqing Lu, Ahmed Mohamed El-Toni, Dianwen Ju, Xiangmin Zhang, Wenning Wang, and Fan Zhang
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 11) pp:6935
Publication Date(Web):March 1, 2016
DOI:10.1021/acsami.6b01085
Peptide modification of nanoparticles with high efficiency is critical in determining the properties and bioapplications of nanoparticles, but the methodology remains a challenging task. Here, by using the phosphorylated linear and cyclic peptide with the arginine–glycine–aspartic acid (RGD) targeting motifs as typical examples, the peptides binding efficiency for the inorganic metal compound nanoparticles was increased significantly after the phosphorylation treatment, and the modification allowed for improving the selectivity and signal-to-noise ratio for cancer targeting and reduced the toxicity derived from nonspecific interactions of nanoparticles with cells owing to the higher amount of phosphopeptide binding. In addition, molecular dynamics (MD) simulations of various peptides on inorganic metal compound surfaces revealed that the peptide adsorption on the surface is mainly driven by electrostatic interactions between phosphate oxygen and the polarized interfacial water layer, consistent with the experimental observation of the strong binding propensity of phosphorylated peptides. Significantly, with the RGD phosphopeptide surface modification, these nanoparticles provide a versatile tool for tuning material–cell interactions to achieve the desired level of autophagy and may prove useful for various diagnostic and therapeutic applications.Keywords: autophagy; cancer target; lanthanide upconversion nanoparticles; peptide; phosphorylation
Co-reporter:Chi Yao, Peiyuan Wang, Rui Wang, Lei Zhou, Ahmed Mohamed El-Toni, Yiqing Lu, Xiaomin Li, and Fan Zhang
Analytical Chemistry 2016 Volume 88(Issue 3) pp:1930
Publication Date(Web):January 11, 2016
DOI:10.1021/acs.analchem.5b04385
Peptide modification of nanoparticles is a challenging task for bioapplications. Here, we show that noncovalent surface engineering based on ligand exchange of peptides for lanthanide based upconversion and downconversion near-infrared (NIR) luminescent nanoparticles can be efficiently realized by modifying the hydroxyl functional group of a side grafted serine of peptides into a phosphate group (phosphorylation). By using the phosphorylated peptide with the arginine-glycine-aspartic acid (RGD) targeting motifs as typical examples, the modification allows improving the selectivity, sensitivity, and signal-to-noise ratio for the cancer targeting and bioimaging and reducing the toxicity derived from nonspecific interactions of nanoparticles with cells. The in vivo NIR bioimaging signal could even be detected at low injection amounts down to 20 μg per animal.
Co-reporter:Chengli Wang, Xiaomin Li and Fan Zhang
Analyst 2016 vol. 141(Issue 12) pp:3601-3620
Publication Date(Web):01 Mar 2016
DOI:10.1039/C6AN00150E
Upconversion nanoparticles (UCNPs), which can emit ultraviolet/visible (UV/Vis) light under near-infrared (NIR) excitation, are regarded as a new generation of nanoprobes because of their unique optical properties, including a virtually zero auto-fluorescence background for the improved signal-to-noise ratio, narrow emission bandwidths and high resistance to photo-bleaching. These properties make UCNPs promising candidates as luminescent bioprobes in biomedicine and biotechnology. In this review, we focus on the recent progress in the development of UCNP-based nanoprobes for biosensing. Firstly, as the FRET process is a widely used method for biosensing to improve the sensitivity, we summarize recent research studies about UCNP-based nanocomposites utilizing the FRET process for biosensing. Different energy acceptors (organic dyes, noble metal nanoparticles, carbon nanomaterials and semiconductor nanomaterials) with their own advantages and limitations are well summarized in this review. Secondly, since UCNPs have been utilized for the detection of different kinds of analytes, we introduce recent research studies about UCNPs for ions, gas molecules, biomolecules and thermal sensing. Finally, we highlight the typical detection techniques and UCNP based devices for bioapplications.
Co-reporter:Dr. Xiaomin Li;Zhenzhen Guo;Tiancong Zhao;Yang Lu;Lei Zhou; Dongyuan Zhao ; Fan Zhang
Angewandte Chemie International Edition 2016 Volume 55( Issue 7) pp:2464-2469
Publication Date(Web):
DOI:10.1002/anie.201510609
Abstract
Lanthanide doped core–multishell structured NaGdF4:Yb,Er@NaYF4:Yb@NaGdF4:Yb,Nd@NaYF4@NaGdF4:Yb,Tm@NaYF4 nanoparticles with power-density independent orthogonal excitations-emissions upconversion luminescence (UCL) were fabricated for the first time. The optical properties of these core–multishell structured nanoparticles were related to the absorption filtration effect of the NaGdF4:Yb,Tm layer. By tuning the thickness of the filtration layer, the nanoparticles can exhibit unique two independent groups of UCL: Tm3+ prominent UV/blue (UV=ultraviolet) UCL under the excitation at 980 nm and Er3+ prominent green/red UCL under the excitation at 796 nm. The filtration-shell mediated orthogonal excitations-emissions UCL are power-density independent. As a proof of concept, the core–multishell nanoparticles are used in multi-dimensional security design and imaging-guided combined photodynamic therapy and chemotherapy.
Co-reporter:Dr. Xiaomin Li;Zhenzhen Guo;Tiancong Zhao;Yang Lu;Lei Zhou; Dongyuan Zhao ; Fan Zhang
Angewandte Chemie 2016 Volume 128( Issue 7) pp:2510-2515
Publication Date(Web):
DOI:10.1002/ange.201510609
Abstract
Lanthanide doped core–multishell structured NaGdF4:Yb,Er@NaYF4:Yb@NaGdF4:Yb,Nd@NaYF4@NaGdF4:Yb,Tm@NaYF4 nanoparticles with power-density independent orthogonal excitations-emissions upconversion luminescence (UCL) were fabricated for the first time. The optical properties of these core–multishell structured nanoparticles were related to the absorption filtration effect of the NaGdF4:Yb,Tm layer. By tuning the thickness of the filtration layer, the nanoparticles can exhibit unique two independent groups of UCL: Tm3+ prominent UV/blue (UV=ultraviolet) UCL under the excitation at 980 nm and Er3+ prominent green/red UCL under the excitation at 796 nm. The filtration-shell mediated orthogonal excitations-emissions UCL are power-density independent. As a proof of concept, the core–multishell nanoparticles are used in multi-dimensional security design and imaging-guided combined photodynamic therapy and chemotherapy.
Co-reporter:Xiaomin Li, Fan Zhang and Dongyuan Zhao
Chemical Society Reviews 2015 vol. 44(Issue 6) pp:1346-1378
Publication Date(Web):23 Jul 2014
DOI:10.1039/C4CS00163J
Over the past decade, high-quality lanthanide doped upconverting nanoparticles (UCNPs) have been successfully synthesized with the rapid development of nanotechnology. Due to the unique electron configuration of lanthanide ions, there are rich energy level structures in the near-infrared, visible and ultraviolet spectral range. However, for UCNPs, only a limited number of efficient upconversion excitation and emission have been generated due to the limited number of sensitizer (Yb3+) and activator (Tm3+, Er3+, and Ho3+) ions, and the application is mainly focused on the bio-imaging by using the upconversion luminescence of UCNPs. Recently, more and more researchers have started to focus on tuning of upconversion optical properties and developing of multi-functional UCNPs by using the combination of sub-lattice mediated energy migration, core@shell structural engineering and UCNPs based nanocomposites which greatly expands the range of applications for lanthanide-doped UCNPs. Therefore, a “nanolab” can be created on UCNPs, where the property modulation can be realized via the designed host-dopants combinations, core@shell nanostructure, energy exchange with “alien species” (organic dyes, quantum dots, etc.), and so on. In this paper, we provide a comprehensive survey of the latest advances made in developing lanthanide-doped UCNPs, which include excitation and emission energy levels guided designing of the UCNP nanostructure, the synthesis techniques to fabricate the nanostructure with optimum energy level structure and optical properties, the fabrication of UCNPs-based nanocomposites to extend the applications by introducing the additional functional components, or integrating the functional moiety into one nanocomposite.
Co-reporter:Xiaomin Li; Lei Zhou; Yong Wei; Ahmed Mohamed El-Toni; Fan Zhang;Dongyuan Zhao
Journal of the American Chemical Society 2015 Volume 137(Issue 18) pp:5903-5906
Publication Date(Web):April 24, 2015
DOI:10.1021/jacs.5b03207
Asymmetric single-hole mesoporous silica nanocages, which are eccentric hollow structured spheres and consist of mesoporous shell with an open hole on their surface, with uniform particle size (100–240 nm), have successfully been synthesized via a novel anisotropic encapsulation of the mesoporous silica. In this unique nanocarrier, the eccentric hollow cavity and big hole (∼25 nm) can serve as a storage space and passage for large guest molecules. Meanwhile, the uniform mesopores (2–10 nm) with a high surface area (∼500 m2/g) in the silica shells of the nanocages can provide storage space for small guest molecules. The obtained single-hole mesoporous nanocages can be endowed upconversion luminescence. The obtained upconversion nanoparticles functionalized eccentric single-hole nanorattles were used to codeliver bovine serum albumin and doxorubicin dual-sized guests. The release of the dual-sized guests can be well controlled independently by heat and near-infrared (NIR) light with the assistance of NIR to ultraviolet/visible (UV/vis) optical properties of upconversion nanoparticles and heat-sensitive phase change materials.
Co-reporter:Lingzhi Wang, Chen Cheng, Sen Tapas, Juying Lei, Masaya Matsuoka, Jinlong Zhang and Fan Zhang
Journal of Materials Chemistry A 2015 vol. 3(Issue 25) pp:13357-13364
Publication Date(Web):14 May 2015
DOI:10.1039/C5TA01652E
Periodic mesoporous organosilica embedded with carbon dots are adopted as the adsorbent for removal of the toxic organic pollutant 2,4-dichlorophenol and inorganic metal ions Hg(II), Cu(II), and Pb(II). The composite possesses an ordered 2D hexagonal mesostructure with a space group of p6mm, high specific surface area (∼468.46 m2 g−1), and uniform pore size (∼5.50 nm). The surface is covered by about 1–2 layers of carbon dot nanoparticles. The maximum adsorption capacity for 2,4-dichlorophenol is 99.70 mg g−1, and the distribution coefficient of metal ions between adsorbent and solution phases is in the range of 2.60–7.41, following the order of Hg(II) > Cu(II) > Pb(II). The Cu(II) and Pb(II) adsorption stays nearly fixed while Hg(II) adsorption is depressed by ∼45% in a mixed solution of metal ions. The Cu(II) and Hg(II) adsorption shows unapparent variation but Pb(II) adsorption is improved by ∼55% in a mixed solution of metal ion and 2,4-dichlorophenol. In contrast, all metal ions lead to the depression of 2,4-dichlorophenol adsorption by 37% (Pb(II)), 45% (Cu(II)), and 48% (Hg(II)). Finally, the n–π electron donor–acceptor interaction between O- and N-containing groups in mesoporous organosilica and the benzene ring in 2,4-dichlorophenol is revealed to be responsible for the enhanced adsorption of 2,4-dichlorophenol, while the electrostatic force and complex formation between metal ions and amide groups co-contribute to the improvement of metal ions adsorption.
Co-reporter:Lei Chen, Xiaomin Li, Dengke Shen, Lei Zhou, Dan Zhu, Chunhai Fan, and Fan Zhang
Analytical Chemistry 2015 Volume 87(Issue 11) pp:5745
Publication Date(Web):May 7, 2015
DOI:10.1021/acs.analchem.5b00944
Multiplexed detection technology has been attractive for its simultaneous assay of several analytes, which play significant roles in applications such as screening for combinatorial chemistry, genetic analysis, and clinical diagnostics. This work reports a novel and potentially powerful encoding system based upon dispersible suspension arrays of multilayer rare earth core/shell nanoparticles that are capable of multiplexed, high-sensitivity reporting for biomolecule detection by the Z-contrast imaging. These nanobarcode arrays are encoded by nanostructure design based on different atomic numbers. With the well-resolved high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) decoding technique, many thousands of unique nanobarcodes can be identified by multilayer core/shell nanostructure. Their applications to multiplexed biodetection of DNA demonstrated the highly sensitive (picomole) features of this novel nanobarcode system.
Co-reporter:Xiaomin Li, Rui Wang, Fan Zhang, and Dongyuan Zhao
Nano Letters 2014 Volume 14(Issue 6) pp:3634-3639
Publication Date(Web):May 29, 2014
DOI:10.1021/nl501366x
Upconversion nanoparticles (UCNPs) have shown considerable promises in many fields; however, their low upconversion efficiency is still the most serious limitation of their applications. Herein, we report for first time that the homogeneous doping approach based on the successive layer-by-layer method can greatly improve the efficiency of the UCNPs. The quantum yield as high as 0.89 ± 0.05% is realized for the homogeneous doping NaGdF4:Yb,Er/NaYF4 UCNPs, which is nearly 2 times higher than that of the heterogeneous doping NaGdF4:Yb,Er/NaYF4 UCNPs (0.47 ± 0.05%). The influences of spatial distributions and local relative concentrations of the dopants on the optical properties of UCNPs were investigated in the single particle level. It was found that heterogeneous doping indeed existed during the spontaneous growth process of the nanoparticles. The heterogeneous doping property can further induce many negative effects on the optical properties of UCNPs, especially the luminescent efficiency. The spatial distributions and local relative concentrations of the dopants can be well controlled by the successive layer-by-layer homogeneous doping method on the monolayer level and homogeneously distributed in the single particle level. Furthermore, by using homogeneous doping NaGdF4:Yb,Tm as initial core, the multicolor emission intensity of NaGdF4:Yb,Tm/NaGdF4:A (A = Tb3+, Eu3+) core/shell nanoparticles can also exhibit 20%–30% improvement. We believe that such a homogeneous doping model can open the door to improve the upconversion optical properties by engineering the local distribution of the sensitizer, activator, host, etc., in a microcosmic and provide a track for engineering the high quality UCNPs with advanced nanostructure and optical properties.
Co-reporter:Dengke Shen, Jianping Yang, Xiaomin Li, Lei Zhou, Renyuan Zhang, Wei Li, Lei Chen, Rui Wang, Fan Zhang, and Dongyuan Zhao
Nano Letters 2014 Volume 14(Issue 2) pp:923-932
Publication Date(Web):January 27, 2014
DOI:10.1021/nl404316v
A kind of novel uniform monodispersed three-dimensional dendritic mesoporous silica nanospheres (3D-dendritic MSNSs) has been successfully synthesized for the first time. The 3D-dendritic MSNSs can have hierarchical mesostructure with multigenerational, tunable center-radial, and dendritic mesopore channels. The synthesis was carried out in the heterogeneous oil–water biphase stratification reaction system, which allowed the self-assembly of reactants taking place in the oil–water interface for one-pot continuous interfacial growth. The average pore size of each generation for the 3D-dendritic MSNSs can be adjusted from 2.8 to 13 nm independently, which can be controlled by the varied hydrophobic solvents and concentration of silica source in the upper oil phase. The thickness of each generation can be tuned from ∼5 to 180 nm as desired, which can be controlled by the reaction time and amount of silica source. The biphase stratification approach can also be used to prepare other core–shell and functional mesoporous materials such as Au nanoparticle@3D-dendritic MSNS and Ag nanocube@3D-dendritic MSNS composites. The 3D-dendritic MSNSs show their unique advantage for protein loading and releasing due to their tunable large pore sizes and smart hierarchical mesostructures. The maximum loading capacity of bovine β-lactoglobulin with 3D-dendritic MSNSs can reach as high as 62.1 wt % due to their large pore volume, and the simulated protein releasing process can be tuned from 24 to 96 h by flexible mesostructures. More importantly, the releasing rates are partly dependent on the hierarchical biodegradation, because the 3D-dendritic MSNSs with larger pore sizes have faster simulated biodegradation rates in simulated body fluid. The most rapid simulated biodegradation can be finished entirely in 24 h, which has been greatly shortened than two weeks for the mesoporous silica reported previously. As the inorganic mesoporous materials, 3D-dendritic MSNSs show excellent biocompatibility, and it would have a hopeful prospect in the clinical applications.
Co-reporter:Xiaomin Li ; Lei Zhou ; Yong Wei ; Ahmed Mohamed El-Toni ; Fan Zhang ;Dongyuan Zhao
Journal of the American Chemical Society 2014 Volume 136(Issue 42) pp:15086-15092
Publication Date(Web):September 24, 2014
DOI:10.1021/ja508733r
Multifunctional dual-compartment Janus mesoporous silica nanocomposites of UCNP@SiO2@mSiO2&PMO (UCNP = upconversion nanoparticle, PMO = periodic mesoporous organosilica) containing core@shell@shell structured UCNP@SiO2@mSiO2 nanospheres and PMO single-crystal nanocubes have been successfully synthesized via a novel anisotropic island nucleation and growth approach with the ordered mesostructure. The asymmetric Janus nanocomposites show a very uniform size of ∼300 nm and high surface area of ∼1290 m2/g. Most importantly, the Janus nanocomposites possess the unique dual independent mesopores with different pore sizes (2.1 nm and 3.5–5.5 nm) and hydrophobicity/hydrophilicity for loading of multiple guests. The distinct chemical properties of the silica sources and the different mesostructures of the dual-compartments are the necessary prerequisites for the formation of the Janus nanostructure. With the assistance of the near-infrared (NIR) to ultraviolet/visible (UV–vis) optical properties of UCNPs and heat-sensitive phase change materials, the dual-compartment Janus mesoporous silica nanocomposites can be further applied into nanobiomedicine for heat and NIR light bimodal-triggered dual-drugs controllable release. It realizes significantly higher efficiency for cancer cell killing (more than 50%) compared to that of the single-triggered drugs delivery system (∼25%).
Co-reporter:Rui Wang and Fan Zhang
Journal of Materials Chemistry A 2014 vol. 2(Issue 17) pp:2422-2443
Publication Date(Web):06 Dec 2013
DOI:10.1039/C3TB21447H
Luminescent labels have been widely used for biological applications, primarily in bioimaging and assays. Recently much attention has been focused on the development of luminescent nanoprobes with excitation/emission maxima falling in the region of minimal tissue absorbance/autofluorescence between 650 and 1450 nm, an “imaging window”. Tissues have minimal absorbance in this wavelength range allowing for deep penetration of light. This enables whole animal imaging with high sensitivity in core organs in real time without the need for dissection. While several excellent reviews cover various aspects of imaging, there has not been a review that covers NIR imaging nanomaterials adequately. In the present review, we will focus on nanomaterials which can be excited or emitted in NIR I (650–900 nm) and NIR II (1000–1450 nm) regions, including lanthanide based nanoparticles, carbon based nanoparticles, quantum dots and noble metal nanomaterials. We systematically summarize the recent progress in their fabrication and application in biomedical imaging, and discuss the shortcomings, challenges and opportunities in it.
Co-reporter:Jianping Yang, Fan Zhang, Wei Li, Dong Gu, Dengke Shen, Jianwei Fan, Wei-xian Zhang and Dongyuan Zhao
Chemical Communications 2014 vol. 50(Issue 6) pp:713-715
Publication Date(Web):07 Nov 2013
DOI:10.1039/C3CC47813K
Herein, large pore mesostructured cellular silica foam coated magnetic oxide composites (MO@MCFs) with multilamellar vesicle shells (MO@MLVs) were obtained, which exhibited a large pore (>10 nm), strong magnetic response (38 emu g−1), excellent protein adsorption and slow drug-release capacity.
Co-reporter:Jianping Yang;Dengke Shen;Lei Zhou;Wei Li;Jianwei Fan;Ahmed Mohamed El-Toni;Wei-xian Zhang;Dongyuan Zhao
Advanced Healthcare Materials 2014 Volume 3( Issue 10) pp:1620-1628
Publication Date(Web):
DOI:10.1002/adhm.201400053
The design and fabrication of core–shell and yolk–shell nanostructures with surface plasmon resonance (SPR)-active center protected by permeable mesoporous channels can raise the new vitality into the catalysis and biological applications. Hybrid plasmonic-mesoporous silica nanocarriers consisting of Ag and Au–Ag alloy nanoparticles are fabricated through spatially confined galvanic replacement approach. The plasmonic absorption peaks can be finely controlled to the near-infrared (NIR) region (500–790 nm) that is beneficial for tissue transmittance. The mesoporous silica shell facilitates also protection of Au–Ag cores and affords the channels between the exterior and interior capsule environments, thereby endowing the multiple applications. In the present work, it is successfully demonstrated that mesoporous silica-coated Au–Ag alloy core–shell and yolk–shell nanocarriers can serve as good substrates for surface-enhanced Raman scattering (SERS) detection. The SERS signal intensities of nanocarriers are highly dependent on the SPR peaks and the contents of gold. Simultaneously, the synthesized Au-Ag@mSiO2 nanocarriers with SPR peak at ≈790 nm can be applied in NIR-sensitive SERS detection and photothermal therapy.
Co-reporter:Chi Yao, Peiyuan Wang, Lei Zhou, Rui Wang, Xiaomin Li, Dongyuan Zhao, and Fan Zhang
Analytical Chemistry 2014 Volume 86(Issue 19) pp:9749
Publication Date(Web):July 30, 2014
DOI:10.1021/ac5023259
The potential of upconversion nanoparticles (UCNPs) in various biomedical applications, including immunoassays, biomedical imaging, and molecular sensing, requires their surface derivatized to be hydrophilic and biocompatible. Here, a new family of compact zwitterionic ligand systems composed with functional phospholipids was designed and used for the surface modification of UCNPs. The zwitterionic UCNPs are hydrophilic, compact, and easily functionalized. It was proved that zwitterionic phospholipids could provide UCNPs with not only extended pH and salt stability but also little nonspecific interactions to positively and negatively charged proteins, low nonspecific adhesion in live-cell imaging process. Most notably, the efficient in vivo tumor imaging performance and long blood circulation half-life suggests the excellent biocompatibility for in vivo imaging of the zwitterionic UCNPs.
Co-reporter:Rui Wang;Xiaomin Li;Lei Zhou ;Dr. Fan Zhang
Angewandte Chemie 2014 Volume 126( Issue 45) pp:
Publication Date(Web):
DOI:10.1002/ange.201408164
Co-reporter:Rui Wang;Xiaomin Li;Lei Zhou ;Dr. Fan Zhang
Angewandte Chemie 2014 Volume 126( Issue 45) pp:12282-12286
Publication Date(Web):
DOI:10.1002/ange.201407420
Abstract
Novel β-NaGdF4/Na(Gd,Yb)F4:Er/NaYF4:Yb/NaNdF4:Yb core/shell 1/shell 2/shell 3 (C/S1/S2/S3) multi-shell nanocrystals (NCs) have been synthesized and used as probes for in vivo imaging. They can be excited by near-infrared (800 nm) radiation and emit short-wavelength infrared (SWIR, 1525 nm) radiation. Excitation at 800 nm falls into the “biological transparency window”, which features low absorption by water and low heat generation and is considered to be the ideal excitation wavelength with the least impact on biological tissues. After coating with phospholipids, the water-soluble NCs showed good biocompatibility and low toxicity. With efficient SWIR emission at 1525 nm, the probe is detectable in tissues at depths of up to 18 mm with a low detection threshold concentration (5 nM for the stomach of nude mice and 100 nM for the stomach of SD rats). These results highlight the potential of the probe for the in vivo monitoring of areas that are otherwise difficult to analyze.
Co-reporter:Rui Wang;Xiaomin Li;Lei Zhou ;Dr. Fan Zhang
Angewandte Chemie International Edition 2014 Volume 53( Issue 45) pp:
Publication Date(Web):
DOI:10.1002/anie.201408164
Co-reporter:Rui Wang;Xiaomin Li;Lei Zhou ;Dr. Fan Zhang
Angewandte Chemie International Edition 2014 Volume 53( Issue 45) pp:12086-12090
Publication Date(Web):
DOI:10.1002/anie.201407420
Abstract
Novel β-NaGdF4/Na(Gd,Yb)F4:Er/NaYF4:Yb/NaNdF4:Yb core/shell 1/shell 2/shell 3 (C/S1/S2/S3) multi-shell nanocrystals (NCs) have been synthesized and used as probes for in vivo imaging. They can be excited by near-infrared (800 nm) radiation and emit short-wavelength infrared (SWIR, 1525 nm) radiation. Excitation at 800 nm falls into the “biological transparency window”, which features low absorption by water and low heat generation and is considered to be the ideal excitation wavelength with the least impact on biological tissues. After coating with phospholipids, the water-soluble NCs showed good biocompatibility and low toxicity. With efficient SWIR emission at 1525 nm, the probe is detectable in tissues at depths of up to 18 mm with a low detection threshold concentration (5 nM for the stomach of nude mice and 100 nM for the stomach of SD rats). These results highlight the potential of the probe for the in vivo monitoring of areas that are otherwise difficult to analyze.
Co-reporter:Jianping Yang, Dengke Shen, Lei Zhou, Wei Li, Xiaomin Li, Chi Yao, Rui Wang, Ahmed Mohamed El-Toni, Fan Zhang, and Dongyuan Zhao
Chemistry of Materials 2013 Volume 25(Issue 15) pp:3030
Publication Date(Web):July 16, 2013
DOI:10.1021/cm401115b
In this work, we have successfully developed a novel multifunctional near-infrared (NIR)-stimulus controlled drug release system based on gold nanocages as photothermal cores, mesoporous silica shells as supporters to increase the anticancer drug loading and thermally responsive poly(N-isopropylacrylamide) (PNIPAM) as NIR-stimuli gatekeepers (Au-nanocage@mSiO2@ PNIPAM). The unique Au-nanocage@mSiO2 nanocarrier was elaborately fabricated by utilizing yolk-shell Ag-nanocube@mSiO2 nanostructure as a template by means of spatially confined galvanic replacement. The Au nanocage cores can effectively absorb and convert light to heat upon irradiation with a NIR laser, resulting in the collapse of the PNIPAM shell covering the exterior of mesoporous silica, and exposes the pores of mesoporous silica shell, realizing the triggered release of entrapped DOX drugs. The in vitro studies have clearly demonstrated the feasibility and advantage of the novel nanocarriers for remote-controlled drug release systems.Keywords: core−shell; galvanic replacement; mesoporous materials; nanocarrier; photothermal trigger;
Co-reporter:Xiaomin Li, Dengke Shen, Jianping Yang, Chi Yao, Renchao Che, Fan Zhang, and Dongyuan Zhao
Chemistry of Materials 2013 Volume 25(Issue 1) pp:106
Publication Date(Web):December 10, 2012
DOI:10.1021/cm3033498
One pot successive layer-by-layer (SLBL) strategy is introduced to fabricate the core/shell upconversion nanoparticles (NPs) for the first time by using high boiling-point Re-OA (rare-earth chlorides dissolved in oleic acid at 140 °C) and Na-TFA-OA (sodium trifluoroacetate dissolved in oleic acid at room temperature) as shell precursor solutions. This protocol is flexible to deposit uniform multishell on both hexagonal (β) and cubic (α) phase cores by successive introducing of the shell precursor solutions. Shell thickness of the obtained NPs with narrow size distribution (σ < 10%) can be well controlled from 1 monolayer (∼0.36 nm) to more than 20 monolayers (∼8 nm) by simply tuning the amounts of the shell precursors. Furthermore, the tunable doping positions (core doping and shell doping) can also be achieved by adjusting the species and addition sequence of the shell precursors. As a result of the high quality uniform shell and advanced core/shell structures, the optical properties of the obtained core/shell NPs could be improved in upconversion luminescence efficiency (up to 0.51 ± 0.08%), stability (more resistant to quenching by water) and multicolor luminescence emission.Keywords: core/shell; fluorescence; nanoparticles; upconversion;
Co-reporter:Xiaomin Li, Fan Zhang, Dongyuan Zhao
Nano Today 2013 Volume 8(Issue 6) pp:643-676
Publication Date(Web):December 2013
DOI:10.1016/j.nantod.2013.11.003
•We summarize the recent progresses for the enhancement of efficiency of UCNPs.•The challenges and opportunities for the highly efficient UCNPs were discussed.•Advantages and shortcomings of UCNPs were systematic compared with QDs & dyes.•The recent progresses of UCNPs based applications were summarized.Over the past decade, high-quality lanthanide doped upconverting nanoparticles (UCNPs) have been successfully synthesized with the rapid development of nanotechnology and are becoming more prominent in wide application fields, especially in biological sciences. Compared with the traditionally used biological labels such as organic dyes and quantum dots (QDs), upconversion nanomaterials have many advantages, including higher chemical stability, lower toxicity, and higher signal-to-noise ratio. However, the low upconversion efficiency of the lanthanide UCNPs is still the most serious limitation for their applications. Improvements are still needed to optimize upconversion optical properties for further applications. In this review, we summarize the recent progresses for the enhancement of upconversion efficiency of UCNPs and discuss the challenges and opportunities to realize the highly efficient upconversion nanomaterials by systematic comparison of the advantages and shortcomings between UCNPs and QDs & organic dyes from various aspects, such as the luminescence mechanism, multicolor emission, luminescent stability, efficiency, ultra-small nanocrystals fabrication and so on. Furthermore, this review describes the recent progresses of UCNPs based applications in multiplexed encoding, guest delivery and release system, photodynamic therapy (PDT), solar cell, photocatalysis and so on. We also detail the major barriers that currently prevent UCNPs from mainstream applications.
Co-reporter:Fan Zhang, Renchao Che, Xiaomin Li, Chi Yao, Jianping Yang, Dengke Shen, Pan Hu, Wei Li, and Dongyuan Zhao
Nano Letters 2012 Volume 12(Issue 6) pp:2852-2858
Publication Date(Web):April 30, 2012
DOI:10.1021/nl300421n
Lanthanide-doped upconversion nanoparticles have shown considerable promise in solid-state lasers, three-dimensional flat-panel displays, and solar cells and especially biological labeling and imaging. It has been demonstrated extensively that the epitaxial coating of upconversion (UC) core crystals with a lattice-matched shell can passivate the core and enhance the overall upconversion emission intensity of the materials. However, there are few papers that report a precise link between the shell thickness of core/shell nanoparticles and their optical properties. This is mainly because rare earth fluoride upconversion core/shell structures have only been inferred from indirect measurements to date. Herein, a reproducible method to grow a hexagonal NaGdF4 shell on NaYF4:Yb,Er nanocrystals with monolayer control thickness is demonstrated for the first time. On the basis of the cryo-transmission electron microscopy, rigorous electron energy loss spectroscopy, and high-angle annular dark-field investigations on the core/shell structure under a low operation temperature (96 K), direct imaging the NaYF4:Yb,Er@NaGdF4 nanocrystal core/shell structure at the subnanometer level was realized for the first time. Furthermore, a strong linear link between the NaGdF4 shell thickness and the optical response of the hexagonal NaYF4:Yb,Er@NaGdF4 core/shell nanocrystals has been established. During the epitaxial growth of the NaGdF4 shell layer by layer, surface defects of the nanocrystals can be gradually passivated by the homogeneous shell deposition process, which results in the obvious enhancement in overall UC emission intensity and lifetime and is more resistant to quenching by water molecules.
Co-reporter:Fan Zhang, Gary B. Braun, Alessia Pallaoro, Yichi Zhang, Yifeng Shi, Daxiang Cui, Martin Moskovits, Dongyuan Zhao, and Galen D. Stucky
Nano Letters 2012 Volume 12(Issue 1) pp:61-67
Publication Date(Web):December 1, 2011
DOI:10.1021/nl202949y
Nanorattles consisting of hydrophilic, rare-earth-doped NaYF4 shells each containing a loose magnetic nanoparticle were fabricated through an ion-exchange process. The inner magnetic Fe3O4 nanoparticles are coated with a SiO2 layer to avoid iron leaching in acidic biological environments. This multifunctional mesoporous nanostructure with both upconversion luminescent and magnetic properties has excellent water dispersibility and a high drug-loading capacity. The material emits visible luminescence upon NIR excitation and can be directed by an external magnetic field to a specific target, making it an attractive system for a variety of biological applications. Measurements on cells incubated with the nanorattles show them to have low cytotoxicity and excellent cell imaging properties. In vivo experiments yield highly encouraging tumor shrinkage with the antitumor drug doxorubicin (DOX) and significantly enhanced tumor targeting in the presence of an applied magnetic field.
Co-reporter:Yingying Lv, Fan Zhang, Yuqian Dou, Yunpu Zhai, Jinxiu Wang, Haijing Liu, Yongyao Xia, Bo Tu and Dongyuan Zhao
Journal of Materials Chemistry A 2012 vol. 22(Issue 1) pp:93-99
Publication Date(Web):11 Oct 2011
DOI:10.1039/C1JM12742J
Activation of ordered mesoporous carbon orientates the development and application of new carbonaceous supercapacitor materials with high energy density and power density. Ordered mesoporous carbons FDU-15 are synthesized in large scale via a soft template method through evaporation induced self-assembly of mesostructure on the sacrificed polyurethane foam. Common activating agent potassium hydroxide (KOH) is utilized to improve the surface area and tailor the pore texture of the ordered mesoporous carbon by adjusting KOH/carbon mass ratio as well as activation time. At low KOH/carbon ratio, the generated micropores increase in volume and either connect to other micropores or eventually become mesopores. At high KOH/carbon ratio, an excess amount of micropores would be generated. Meanwhile, the continuous shrinkage of carbon framework is carried through as prolonged time at high activation temperature. Competition between KOH etching and shrinkage of mesopores is existed during the activation. The latter obviously preponderates over the former at low KOH/carbon ratio, which is reversed at high KOH/carbon ratio. Thus, an optimized micro-mesostructure is achieved under certain activation conditions: maintained ordered mesostructure, suitable microporosity, high surface area (1410 m2 g−1) and large pore volume (0.73 cm3 g−1). The activated sample exhibits improved electrochemical behavior with a gravimetric capacitance of 200 F/g, excellent rate performance and good cycling stability with capacitance retention of ∼98% over 300 cycles.
Co-reporter:Chunfeng Xue, Yingying Lv, Fan Zhang, Limin Wu and Dongyuan Zhao
Journal of Materials Chemistry A 2012 vol. 22(Issue 4) pp:1547-1555
Publication Date(Web):28 Nov 2011
DOI:10.1039/C1JM14349B
Ordered mesoporous carbon with a 2-D hexagonal mesostructure was prepared by an organic–organic co-assembly method. The mesoporous carbon was activated by using CuO to improve its mesoporosity. Compared with pristine mesoporous carbon (PMC-900) carbonized at 900 °C, the mean mesopore size of the activated mesoporous carbon (AMC-900) is increased from 3.2 to 5.5 nm by an etching reaction between copper oxide and the inner layer of the carbonaceous mesochannels. Mass spectrometry profiles confirm that dehydrogenation and oxidation reactions happened during the CuO activation process. The total pore volume of AMC-900 is increased from 0.48 to 1.06 cm3 g−1 and the specific surface area increased from 827 to 1084 m2 g−1 after the CuO activation. Compared with the common activation processes, the simple CuO reduction method is a more effective pathway for the production of ordered porous carbons with large mesopores. AMC-900 shows good rate capability and typical rectangular-shaped cyclic voltammetry curves over a range of scan rates from 5 to 200 mV s−1, with a large specific capacitance of 7.2 μF cm−2 in organic (1.0 M tetraethyl ammonium tetrafluoroborate/polypropylene carbonate) electrolyte solutions.
Co-reporter:Chunfeng Xue, Fan Zhang, Limin Wu, Dongyuan Zhao
Microporous and Mesoporous Materials 2012 Volume 151() pp:495-500
Publication Date(Web):15 March 2012
DOI:10.1016/j.micromeso.2011.09.001
Ordered mesoporous carbon–silica composite was “in situ” transformed into hierarchically porous zeolites ZSM-5 (H-ZSM-5) under water vapor, which synthesized from evaporation induced “tri-constituent” co-assembly of resin, silica and surfactant. The vapor assisted transformation was realized within 2-D hexagonally mesochannels of carbon–silica composite infused with tetrapropylammonium hydroxide at 130 °C for 72 h. The calcined H-ZSM-5-570 possesses a mesostructure with mean pore sizes of 0.6 and 9.0 nm, BET surface area of 409 cm2/g, and pore volume of 0.54 cm3/g. High-resolution TEM images of H-ZSM-5-570 display that mesoporous walls consisted of zeolite nanocrystals of about 6 nm in the same domain. Weak acidity of H-ZSM-5-570 has also been concluded from ammonia desorption measurements.Graphical abstractOrdered mesoporous carbon–silica composite was used as a digestible template for “in situ” transforming into hierarchically porous zeolites (H-ZSM-5) under vapor. After calcination in air, H-ZSM-5 still possesses a mesostructure with uniform pores of 0.6 and 9.0 nm. High-resolution TEM images of H-ZSM-5 displays that mesoporous walls consisted of zeolite nanocrystals of about 6 nm in the same domain.Highlights► Hierarchically porous zeolites are prepared from mesoporous carbon–silica composite. ► The experiment was confined in mesochannels containing tetrapropylammonium hydroxide. ► The final samples inherit mesostructure from template and have pore size of 9.0 nm. ► HRTEM images confirm that mesoporous walls are composed of nano-zeolites of 6 nm. ► The vapor assisted zeolitization from composite can be extended to other zeolites.
Co-reporter:Jianping Yang;Dr. Dengke Shen;Xiaomin Li;Wei Li;Yin Fang;Yong Wei;Chi Yao; Bo Tu; Fan Zhang; Dongyuan Zhao
Chemistry - A European Journal 2012 Volume 18( Issue 43) pp:13642-13650
Publication Date(Web):
DOI:10.1002/chem.201202336
Abstract
In this paper, we report a facile one-step hydrothermal method to synthesize phase-, size-, and shape-controlled carboxyl-functionalized rare-earth fluorescence upconversion phosphors by using a small-molecule binary acid, such as malonic acid, oxalic acid, succinic acid, or tartaric acid as capping agent. The crystals, from nano- to microstructures with diverse shapes that include nanospheres, microrods, hexagonal prisms, microtubes, microdisks, polygonal columns, and hexagonal tablets, can be obtained with different reaction times, reaction temperatures, molar ratios of capping agent to sodium hydroxide, and by varying the binary acids. Fourier transform infrared, thermogravimetric analysis, and upconversion luminescence spectra measurements indicate that the synthesized NaYF4:Yb/Er products with hydrophilic carboxyl-functionalized surface offer efficient upconversion luminescent performance. Furthermore, the antibody/secondary antibody conjugation can be realized by the carboxyl-functionalized surfaces of the upconversion phosphors, thus indicating the potential bioapplications of these kinds of materials.
Co-reporter:Fan Zhang;Qihui Shi;Yichi Zhang;Yifeng Shi;Kunlun Ding;Dongyuan Zhao;Galen D. Stucky
Advanced Materials 2011 Volume 23( Issue 33) pp:
Publication Date(Web):
DOI:10.1002/adma.201190129
Co-reporter:Fan Zhang;Qihui Shi;Yichi Zhang;Yifeng Shi;Kunlun Ding;Dongyuan Zhao;Galen D. Stucky
Advanced Materials 2011 Volume 23( Issue 33) pp:3775-3779
Publication Date(Web):
DOI:10.1002/adma.201101868
Co-reporter:Jianping Yang, Fan Zhang, Yiran Chen, Sheng Qian, Pan Hu, Wei Li, Yonghui Deng, Yin Fang, Lu Han, Mohammad Luqman and Dongyuan Zhao
Chemical Communications 2011 vol. 47(Issue 42) pp:11618-11620
Publication Date(Web):04 Oct 2011
DOI:10.1039/C1CC15304H
A novel mesoporous nanocarrier consisting of a silver core, a silica spacer with controlled thickness and a fluorophores-loaded mesoporous silica shell was fabricated for the metal-enhanced fluorescence (MEF) and Förster resonance energy transfer (FRET) effects.
Co-reporter:Jinxiu Wang, Chunfeng Xue, Yingying Lv, Fan Zhang, Bo Tu, Dongyuan Zhao
Carbon 2011 Volume 49(Issue 13) pp:4580-4588
Publication Date(Web):November 2011
DOI:10.1016/j.carbon.2011.06.069
An efficient post-cure approach has been demonstrated for the kilogram-scale synthesis of high-quality ordered mesoporous carbons (OMC) by using triblock copolymer Pluronic F127 as a template, phenolic resol as a carbon precursor and polyurethane foam as a sacrificial scaffold through an organic–organic self-assembly. The effects of the concentration and the loading amount of resol on the mesostructure of the carbons are systematically investigated. The small-angle X-ray scattering, nitrogen sorption and transmission electron microscopy results reveal that the resultant OMC in kilogram-scale quantities possesses high surface area (∼690 m2 g−1), large pore volume (∼0.45 cm3 g−1) and uniform, large pore size (∼4.5 nm) as well as thick pore walls (∼6.5 nm). The OMC exhibits good electrochemical performance of about 130 F g−1 in KOH electrolyte.
Co-reporter:Qingling Wu, Fan Zhang, Jianping Yang, Qiang Li, Bo Tu, Dongyuan Zhao
Microporous and Mesoporous Materials 2011 Volume 143(2–3) pp:406-412
Publication Date(Web):September 2011
DOI:10.1016/j.micromeso.2011.03.033
Alumina materials with ordered mesostructure and hierarchical porosity have been synthesized via a one-step process using aluminum iso-propoxide as an inorganic precursor, pluronic P123 as a template, hydrochloric acid and citric acid as the pH adjustors, and 1,3,5-trimethylbenzene (TMB) as a swelling agent. These mesoporous aluminas have relatively high surface areas (up to 309 m2/g), pore volumes (∼0.51 cm3/g), large pore sizes (up to 7.5 nm), and high thermal stability (up to 900 °C). In addition, the weight ratios of TMB/P123 play an important role in the synthesis process for controlling the mesostructures and pore sizes of the materials. The alumina with highly ordered 2-D hexagonal mesostructure (space group p6mm) can be synthesized with the weight ratios of TMB/P123 ranging from 0 to 3. Simultaneously, the pore sizes of ordered mesoporous aluminas were gradually enlarged with the increase of the TMB content. However, phase transformation of the mesoporous alumina from the 2-D hexagonal to hierarchical could be realized when the TMB/P123 weight ratio was increased to 5.Graphical abstractDepending on the ratios of TMB to block copolymer, alumina materials with ordered mesoporosity and hierarchical porosity are obtained via a one-step process.Highlights► TMB as a swelling agent and hydrochloric acid and citric acid as the pH adjustors. ► Fabrication of ordered mesoporosity alumina by adding small amount of TMB. ► Ordered mesoporosity alumina with p6mm mesostructure and large pore size. ► Incremental addition of TMB leads to an increase in both d-spacing and pore size. ► Hierarchical porosity alumina in the presence of large amount of TMB.
Co-reporter:Peiyuan Wang, Xiaomin Li, Chi Yao, Wenxing Wang, Mengyao Zhao, Ahmed Mohamed El-Toni, Fan Zhang
Biomaterials (May 2017) Volume 125() pp:
Publication Date(Web):May 2017
DOI:10.1016/j.biomaterials.2017.02.017
•A novel orthogonal excitations-emissions UCNPs anchored red blood cells (RBC) microcarrier for O2 delivery and PDT.•RBC microcarriers can be generated a large amount of O2 and ROS in hypoxia region under near-infrared irradiation.•RBC microcarriers exhibit abilities to overcome hypoxia and biological barriers with efficient tumor treatment.Pre-existing hypoxia in tumors can result in an inadequate oxygen supply during photodynamic therapy (PDT), which in turn hampers photodynamic efficacy. To overcome this problem, we developed an orthogonal near-infrared upconversion controlled red blood cell (RBC) microcarriers to selectively deliver O2 in hypoxia area. Moreover, this RBC microcarriers are able to overcome a series of complex biological barriers which include transporting across the inflamed endothelium, evading mononuclear phagocyte system, reducing reticuloendothelial system uptake. Based on these abilities, RBC microcarriers have efficient tumors accumulation and are capable of delivery a large amount of O2 for PDT under near-infrared (NIR) irradiation to realize effective solid tumor eradication.
Co-reporter:Jianping Yang, Fan Zhang, Wei Li, Dong Gu, Dengke Shen, Jianwei Fan, Wei-xian Zhang and Dongyuan Zhao
Chemical Communications 2014 - vol. 50(Issue 6) pp:NaN715-715
Publication Date(Web):2013/11/07
DOI:10.1039/C3CC47813K
Herein, large pore mesostructured cellular silica foam coated magnetic oxide composites (MO@MCFs) with multilamellar vesicle shells (MO@MLVs) were obtained, which exhibited a large pore (>10 nm), strong magnetic response (38 emu g−1), excellent protein adsorption and slow drug-release capacity.
Co-reporter:Jianping Yang, Fan Zhang, Yiran Chen, Sheng Qian, Pan Hu, Wei Li, Yonghui Deng, Yin Fang, Lu Han, Mohammad Luqman and Dongyuan Zhao
Chemical Communications 2011 - vol. 47(Issue 42) pp:NaN11620-11620
Publication Date(Web):2011/10/04
DOI:10.1039/C1CC15304H
A novel mesoporous nanocarrier consisting of a silver core, a silica spacer with controlled thickness and a fluorophores-loaded mesoporous silica shell was fabricated for the metal-enhanced fluorescence (MEF) and Förster resonance energy transfer (FRET) effects.
Co-reporter:Xiaomin Li, Fan Zhang and Dongyuan Zhao
Chemical Society Reviews 2015 - vol. 44(Issue 6) pp:NaN1378-1378
Publication Date(Web):2014/07/23
DOI:10.1039/C4CS00163J
Over the past decade, high-quality lanthanide doped upconverting nanoparticles (UCNPs) have been successfully synthesized with the rapid development of nanotechnology. Due to the unique electron configuration of lanthanide ions, there are rich energy level structures in the near-infrared, visible and ultraviolet spectral range. However, for UCNPs, only a limited number of efficient upconversion excitation and emission have been generated due to the limited number of sensitizer (Yb3+) and activator (Tm3+, Er3+, and Ho3+) ions, and the application is mainly focused on the bio-imaging by using the upconversion luminescence of UCNPs. Recently, more and more researchers have started to focus on tuning of upconversion optical properties and developing of multi-functional UCNPs by using the combination of sub-lattice mediated energy migration, core@shell structural engineering and UCNPs based nanocomposites which greatly expands the range of applications for lanthanide-doped UCNPs. Therefore, a “nanolab” can be created on UCNPs, where the property modulation can be realized via the designed host-dopants combinations, core@shell nanostructure, energy exchange with “alien species” (organic dyes, quantum dots, etc.), and so on. In this paper, we provide a comprehensive survey of the latest advances made in developing lanthanide-doped UCNPs, which include excitation and emission energy levels guided designing of the UCNP nanostructure, the synthesis techniques to fabricate the nanostructure with optimum energy level structure and optical properties, the fabrication of UCNPs-based nanocomposites to extend the applications by introducing the additional functional components, or integrating the functional moiety into one nanocomposite.
Co-reporter:Lingzhi Wang, Chen Cheng, Sen Tapas, Juying Lei, Masaya Matsuoka, Jinlong Zhang and Fan Zhang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 25) pp:NaN13364-13364
Publication Date(Web):2015/05/14
DOI:10.1039/C5TA01652E
Periodic mesoporous organosilica embedded with carbon dots are adopted as the adsorbent for removal of the toxic organic pollutant 2,4-dichlorophenol and inorganic metal ions Hg(II), Cu(II), and Pb(II). The composite possesses an ordered 2D hexagonal mesostructure with a space group of p6mm, high specific surface area (∼468.46 m2 g−1), and uniform pore size (∼5.50 nm). The surface is covered by about 1–2 layers of carbon dot nanoparticles. The maximum adsorption capacity for 2,4-dichlorophenol is 99.70 mg g−1, and the distribution coefficient of metal ions between adsorbent and solution phases is in the range of 2.60–7.41, following the order of Hg(II) > Cu(II) > Pb(II). The Cu(II) and Pb(II) adsorption stays nearly fixed while Hg(II) adsorption is depressed by ∼45% in a mixed solution of metal ions. The Cu(II) and Hg(II) adsorption shows unapparent variation but Pb(II) adsorption is improved by ∼55% in a mixed solution of metal ion and 2,4-dichlorophenol. In contrast, all metal ions lead to the depression of 2,4-dichlorophenol adsorption by 37% (Pb(II)), 45% (Cu(II)), and 48% (Hg(II)). Finally, the n–π electron donor–acceptor interaction between O- and N-containing groups in mesoporous organosilica and the benzene ring in 2,4-dichlorophenol is revealed to be responsible for the enhanced adsorption of 2,4-dichlorophenol, while the electrostatic force and complex formation between metal ions and amide groups co-contribute to the improvement of metal ions adsorption.
Co-reporter:Rui Wang and Fan Zhang
Journal of Materials Chemistry A 2014 - vol. 2(Issue 17) pp:NaN2443-2443
Publication Date(Web):2013/12/06
DOI:10.1039/C3TB21447H
Luminescent labels have been widely used for biological applications, primarily in bioimaging and assays. Recently much attention has been focused on the development of luminescent nanoprobes with excitation/emission maxima falling in the region of minimal tissue absorbance/autofluorescence between 650 and 1450 nm, an “imaging window”. Tissues have minimal absorbance in this wavelength range allowing for deep penetration of light. This enables whole animal imaging with high sensitivity in core organs in real time without the need for dissection. While several excellent reviews cover various aspects of imaging, there has not been a review that covers NIR imaging nanomaterials adequately. In the present review, we will focus on nanomaterials which can be excited or emitted in NIR I (650–900 nm) and NIR II (1000–1450 nm) regions, including lanthanide based nanoparticles, carbon based nanoparticles, quantum dots and noble metal nanomaterials. We systematically summarize the recent progress in their fabrication and application in biomedical imaging, and discuss the shortcomings, challenges and opportunities in it.
Co-reporter:Yingying Lv, Fan Zhang, Yuqian Dou, Yunpu Zhai, Jinxiu Wang, Haijing Liu, Yongyao Xia, Bo Tu and Dongyuan Zhao
Journal of Materials Chemistry A 2012 - vol. 22(Issue 1) pp:NaN99-99
Publication Date(Web):2011/10/11
DOI:10.1039/C1JM12742J
Activation of ordered mesoporous carbon orientates the development and application of new carbonaceous supercapacitor materials with high energy density and power density. Ordered mesoporous carbons FDU-15 are synthesized in large scale via a soft template method through evaporation induced self-assembly of mesostructure on the sacrificed polyurethane foam. Common activating agent potassium hydroxide (KOH) is utilized to improve the surface area and tailor the pore texture of the ordered mesoporous carbon by adjusting KOH/carbon mass ratio as well as activation time. At low KOH/carbon ratio, the generated micropores increase in volume and either connect to other micropores or eventually become mesopores. At high KOH/carbon ratio, an excess amount of micropores would be generated. Meanwhile, the continuous shrinkage of carbon framework is carried through as prolonged time at high activation temperature. Competition between KOH etching and shrinkage of mesopores is existed during the activation. The latter obviously preponderates over the former at low KOH/carbon ratio, which is reversed at high KOH/carbon ratio. Thus, an optimized micro-mesostructure is achieved under certain activation conditions: maintained ordered mesostructure, suitable microporosity, high surface area (1410 m2 g−1) and large pore volume (0.73 cm3 g−1). The activated sample exhibits improved electrochemical behavior with a gravimetric capacitance of 200 F/g, excellent rate performance and good cycling stability with capacitance retention of ∼98% over 300 cycles.
Co-reporter:Chunfeng Xue, Yingying Lv, Fan Zhang, Limin Wu and Dongyuan Zhao
Journal of Materials Chemistry A 2012 - vol. 22(Issue 4) pp:NaN1555-1555
Publication Date(Web):2011/11/28
DOI:10.1039/C1JM14349B
Ordered mesoporous carbon with a 2-D hexagonal mesostructure was prepared by an organic–organic co-assembly method. The mesoporous carbon was activated by using CuO to improve its mesoporosity. Compared with pristine mesoporous carbon (PMC-900) carbonized at 900 °C, the mean mesopore size of the activated mesoporous carbon (AMC-900) is increased from 3.2 to 5.5 nm by an etching reaction between copper oxide and the inner layer of the carbonaceous mesochannels. Mass spectrometry profiles confirm that dehydrogenation and oxidation reactions happened during the CuO activation process. The total pore volume of AMC-900 is increased from 0.48 to 1.06 cm3 g−1 and the specific surface area increased from 827 to 1084 m2 g−1 after the CuO activation. Compared with the common activation processes, the simple CuO reduction method is a more effective pathway for the production of ordered porous carbons with large mesopores. AMC-900 shows good rate capability and typical rectangular-shaped cyclic voltammetry curves over a range of scan rates from 5 to 200 mV s−1, with a large specific capacitance of 7.2 μF cm−2 in organic (1.0 M tetraethyl ammonium tetrafluoroborate/polypropylene carbonate) electrolyte solutions.
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