Co-reporter:Shaobo Ji, Fuqiang Fan, Chenxing Sun, Ying Yu, and Huaping Xu
ACS Applied Materials & Interfaces September 27, 2017 Volume 9(Issue 38) pp:33169-33169
Publication Date(Web):September 8, 2017
DOI:10.1021/acsami.7b11188
Plasticity of thermoset polymers has been realized by introducing exchangeable bonds, and the plasticity is mostly triggered via heat or UV light. Visible light is a relatively mild trigger that has not been used to induce plasticity in polymer materials. Herein, thermoset polyurethanes (PUs) containing diselenide bonds are fabricated that possess visible light-induced plasticity along with shape memory behavior. A series of PUs with different diselenide bond contents were tested and their shape memory properties and plasticity varied. With a higher diselenide bond content, both shape memory and light-induced plasticity are achieved. By combining these two properties, reshaping the permanent shapes of the PUs is easier. Compared with heat or UV light, visible light has the advantage of spatial control. For instance, a pattern of visible light was introduced by a commercial projector to demonstrate facile reshaping of the materials. Because visible light can be introduced via various methods, PUs with visible light-induced plasticity have great potential applications.Keywords: diselenide bonds; dynamic covalent bonds; photoinduce plasticity; shape memory polymers; visible light;
Co-reporter:Lu Wang, Wei Cao, Yu Yi, and Huaping Xu
Langmuir May 20, 2014 Volume 30(Issue 19) pp:5628-5636
Publication Date(Web):May 1, 2014
DOI:10.1021/la501054z
A general approach is reported to fabricate a stimuli responsive system via coassembly of diselenide-containing block copolymers with polymer lipids, which integrates the stimuli-responsiveness of diselenide chemistry and the biocompatibility of polymer lipids. By using dynamic light scattering, transmission electron microscopy, and zeta potential analyzer, coassembly behavior of these two kinds of polymers and responsiveness of coassemblies have been investigated. These coassemblies can exhibit redox-responsiveness inheriting from the diselenide-containing block copolymers. In the presence of low concentration of hydrogen peroxide or glutathione, the coassemblies can be disrupted.
Co-reporter:Dr. Feng Li;Tianyu Li;Chenxing Sun;Jiahao Xia;Yang Jiao; Huaping Xu
Angewandte Chemie 2017 Volume 129(Issue 33) pp:10042-10046
Publication Date(Web):2017/08/07
DOI:10.1002/ange.201705989
AbstractHeteroatom doping is an effective way to adjust the fluorescent properties of carbon quantum dots. However, selenium-doped carbon dots have rarely been reported, even though selenium has unique chemical properties such as redox-responsive properties owing to its special electronegativity. Herein, a facile and high-output strategy to fabricate selenium-doped carbon quantum dots (Se-CQDs) with green fluorescence (quantum yield 7.6 %) is developed through the hydrothermal treatment of selenocystine under mild conditions. Selenium heteroatoms endow the Se-CQDs with redox-dependent reversible fluorescence. Furthermore, free radicals such as .OH can be effectively scavenged by the Se-CQDs. Once Se-CQDs are internalized into cells, harmful high levels of reactive oxygen species (ROS) in the cells are decreased. This property makes the Se-CQDs capable of protecting biosystems from oxidative stress.
Co-reporter:Dr. Feng Li;Tianyu Li;Chenxing Sun;Jiahao Xia;Yang Jiao; Huaping Xu
Angewandte Chemie International Edition 2017 Volume 56(Issue 33) pp:9910-9914
Publication Date(Web):2017/08/07
DOI:10.1002/anie.201705989
AbstractHeteroatom doping is an effective way to adjust the fluorescent properties of carbon quantum dots. However, selenium-doped carbon dots have rarely been reported, even though selenium has unique chemical properties such as redox-responsive properties owing to its special electronegativity. Herein, a facile and high-output strategy to fabricate selenium-doped carbon quantum dots (Se-CQDs) with green fluorescence (quantum yield 7.6 %) is developed through the hydrothermal treatment of selenocystine under mild conditions. Selenium heteroatoms endow the Se-CQDs with redox-dependent reversible fluorescence. Furthermore, free radicals such as .OH can be effectively scavenged by the Se-CQDs. Once Se-CQDs are internalized into cells, harmful high levels of reactive oxygen species (ROS) in the cells are decreased. This property makes the Se-CQDs capable of protecting biosystems from oxidative stress.
Co-reporter:Shaobo Ji;Hicham El Mard;Mario Smet;Wim Dehaen
Science China Chemistry 2017 Volume 60( Issue 9) pp:1191-1196
Publication Date(Web):03 July 2017
DOI:10.1007/s11426-017-9059-4
Macrocycles possess potential applications in supramolecular chemistry and biosystems. Thus development of new kinds of macrocycles is of significance. Herein, novel macrocycles containing Se–Se/Se–S bonds were synthesized via transformation between selenium related dynamic covalent bonds. A monomer containing two ebselen moieties was synthesized (M1). The Se–N bonds in M1 were reduced by dithiothreitol, forming Se–S linked dimer (D1). To realize the transformation from Se–S bonds to Se–Se bonds, guest molecules were added as template, triggering the formation of Se–Se linked dimer (D2). The formation of these two new kinds of macrocycles was determined by 1H NMR and 77Se NMR, and the necessity of guest molecules was also confirmed. The introduction of ebselen moieties and Se–S bonds or Se–Se bonds into macrocycles may endow it with new responsiveness and bioactivities, as well as new types of host-guest chemistry.
Co-reporter:Feng Li, Tianyu Li, Wei Cao, Lu Wang, Huaping Xu
Biomaterials 2017 Volume 133(Volume 133) pp:
Publication Date(Web):1 July 2017
DOI:10.1016/j.biomaterials.2017.04.032
Cisplatin (CDDP) has received worldwide approval for clinical use in the past decades. However, its development in cancer chemotherapy was overshadowed by severe side effects and drug resistance. Herein, we developed a CDDP drug delivery system with high encapsulation efficiency and near-infrared light stimuli-responsive drug release properties based on the coordination of novel tellurium-containing block polymer (PEG-PUTe-PEG) and CDDP. The nanocarriers made from PEG-PUTe-PEG were loaded with CDDP and indocyanine green (ICG) simultaneously. The coordination chemistry between CDDP and tellurium guaranteed the nanocarrier a high stability in plasma and prolonged circulation time in vivo by reducing possible penetration of water molecule into the nanoparticles. Under the stimuli of a near-infrared laser, an amount of ROS can be generated by irradiation of ICG. The tellurium is easily oxidized by ROS because of the low electronegativity of tellurium. The CDDP could be rapidly released from the nanocarriers along with the oxidation of the tellurium at the tumor sites as the oxidized tellurium will weaken the coordination interaction with CDDP. In addition, the encapsulated ICG played a synergistic antitumor effect through photothermal effect with mild laser irradiation. The integrated strategy achieved higher antitumor efficacy and showed minimal side effects compared with the CDDP alone.Photo-responsive cisplatin delivery system: Using the coordination chemistry between platinum and tellurium and the ultra-sensitive ROS responsiveness of tellurium, a CDDP delivery system with near-infrared light-responsive property is developed by encapsulating platinum and photosensitizer ICG in tellurium-containing polymer based nanoparticles simultaneously.Download high-res image (335KB)Download full-size image
Co-reporter:Lu Wang;Wencong Wang;Wei Cao
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 31) pp:4520-4527
Publication Date(Web):2017/08/08
DOI:10.1039/C7PY00971B
Nanomaterials with hierarchical responsiveness are of great significance not only for fundamental science but also for future biomedical applications due to sophisticated and hierarchical physiological environments. Herein, we report a selenium- and tellurium-containing block copolymer that can be stepwise oxidized by both chemical methods and electrochemical methods. Differences in sensitivity to the oxidation of selenium and tellurium were employed. By tuning the concentration of the oxidant and oxidation periods, self-assembly behaviors of the copolymer were tuned by stepwise chemical oxidation. After oxidation, some interesting morphological evolution was observed that the polymer micelles crosslinked with each other without any swelling. In the case of electrochemical oxidation, the voltage during the electrochemical oxidation and the oxidation period also affected the level of oxidation. Furthermore, we showed that the degree of electrochemical oxidation varied with a different PEG block length. Considering sophisticated physiological conditions in vivo, this hierarchically responsive system may provide new possibilities as smart delivery vehicles in biological environments.
Co-reporter:Fuqiang Fan, Lu Wang, Feng Li, Yu Fu, and Huaping Xu
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 26) pp:17004-17010
Publication Date(Web):June 15, 2016
DOI:10.1021/acsami.6b04998
Tellurium-containing photoresponsive polyelectrolyte multilayer films were fabricated by layer-by-layer assembly of a tellurium-containing polymer, photosensitizer, and poly(styrenesulfonate). The resulting films were investigated by UV/vis spectroscopy, XPS, EPR, and fluorescence spectroscopy. Under visible light, the photosensitizer in the film is excited and transforms triplet oxygen into singlet oxygen in aqueous solution. Singlet oxygen oxidizes −Te– to high valence state (Te═O) on the polymer backbone. The generated (Te═O) group makes the micelles more hydrophilic and looser, thereby facilitating the controlled release of the loaded cargo of micelles. These results show that the film has the potential to be used for cargo loading and controlled release, thus may provide a new way to combine photodynamic therapy and chemotherapy.
Co-reporter:Tianyu Li, Feng Li, Wentian Xiang, Yu Yi, Yuyan Chen, Liang Cheng, Zhuang Liu, and Huaping Xu
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 34) pp:22106
Publication Date(Web):August 12, 2016
DOI:10.1021/acsami.6b08282
Selenium has attracted increasing interest in recent decades because of the function of regulating the redox balance in the human body. However, biomedical studies of selenium are still limited. Gold nanoparticles (AuNPs), typically prepared by a first reduction step followed by a second stabilization step, are widely applied in biomedical studies. However, their own anticancer activity is less studied. Here, we report 2 nm AuNPs with significant anticancer activity (IC50 = 20 μM) that is stabilized by a selenium-containing amphiphile EGSe-tMe. The AuNPs are prepared by simply mixing chloroauric acid (HAuCl4) with EGSe-tMe, which acts as both a reducing agent and a stabilizer. In contrast to AuNPs prepared by EGSe-tMe, EGSe-tMe alone and typically prepared AuNPs show little anticancer activity even at concentrations up to 250 μM. Mechanistic studies suggest that selenium in cooperation with AuNPs can induce high concentrations of reactive oxygen species (ROS) in cancer cells, leading to cellular apoptosis.Keywords: anticancer; gold nanoparticle; reactive oxygen species; selenium; self-assembly
Co-reporter:Shaobo Ji, Jiahao Xia, and Huaping Xu
ACS Macro Letters 2016 Volume 5(Issue 1) pp:78
Publication Date(Web):December 22, 2015
DOI:10.1021/acsmacrolett.5b00849
The application of selenium in the responsive polymer system and the enzyme mimic system have been well studied. Our group initiated this line of research in 2009 by first extending selenium chemistry to dynamic chemistry. In this article, the discovery, progress, and application of selenium-related dynamic covalent bonds will be introduced. The dynamic property of Se–N bond and Se–Se bond were revealed and have been applied in the polymer system as enzyme mimic and self-healing materials, respectively. Further studies that need to be done and potential application of selenium-related dynamic chemistry will also be discussed.
Co-reporter:Huaping Xu
Nanomedicine: Nanotechnology, Biology and Medicine 2016 Volume 12(Issue 2) pp:465
Publication Date(Web):February 2016
DOI:10.1016/j.nano.2015.12.057
Co-reporter:Lu Wang;Wei Cao ; Huaping Xu
ChemNanoMat 2016 Volume 2( Issue 6) pp:479-488
Publication Date(Web):
DOI:10.1002/cnma.201600076
Abstract
Tellurium-containing polymers have become increasingly attractive owing to their unique properties as biomaterials and optoelectronic materials. The relatively large atomic size and low electronegativity of tellurium give it with many unique properties, such as coordination ability and redox sensitivity. The introduction of tellurium can endow materials with different responsiveness, which makes it possible for them to be employed as biomaterials. The narrow band gap of polytellurophene also allows its use in optoelectronic materials. In this focus review, we highlight a series of recent advances in tellurium-containing polymers. First, tellurium-containing amphiphilic block copolymers are summarized; these species can self-assemble to form aggregates with coordination-responsive and reactive oxygen species-responsive properties. Then, we describe both tellurophene-containing homopolymers and copolymers, including their synthesis, chemical properties, and applications in different optoelectronic devices. It is anticipated that tellurium-containing polymers will have more applications in material science.
Co-reporter:Shaobo Ji;Wei Cao;Ying Yu
Advanced Materials 2015 Volume 27( Issue 47) pp:7740-7745
Publication Date(Web):
DOI:10.1002/adma.201503661
Co-reporter:Lu Wang, Fuqiang Fan, Wei Cao, and Huaping Xu
ACS Applied Materials & Interfaces 2015 Volume 7(Issue 29) pp:16054
Publication Date(Web):July 8, 2015
DOI:10.1021/acsami.5b04419
Reactive oxygen species (ROS) play crucial roles in cell signaling and redox homeostasis and are strongly related to metabolic activities. The increase of the ROS concentration in organisms can result in several diseases, such as cardiovascular diseases and cancer. The concentration of ROS in biologically relevant conditions is typically as low as around tens of micromolars to 100 μM H2O2, which makes it necessary to develop ultrasensitive ROS-responsive systems. A general approach is reported here to fabricate an ultrasensitive ROS-responsive system via coassembly between tellurium-containing molecules and phospholipids, combining the ROS-responsiveness of tellurium and the biocompatibility of phospholipids. By using dynamic light scattering, transmission electron microscopy, scanning electron microscopy, and NMR spectra, coassembly behaviors and the responsiveness of the coassemblies have been investigated. These coassemblies can respond to 100 μM H2O2, which is a biologically relevant ROS concentration, and demonstrate reversible redox properties.Keywords: coassembly; phospholipid; reactive oxygen species; tellurium; ultrasensitive;
Co-reporter:Wei Cao, Yuwei Gu, Tianyu Li and Huaping Xu
Chemical Communications 2015 vol. 51(Issue 32) pp:7069-7071
Publication Date(Web):20 Mar 2015
DOI:10.1039/C5CC01779C
A novel tellurium-containing polymer micelle system is reported to be responsive to 100 μM H2O2 and can undergo a series of morphological changes. The polymer micelles also respond to 2 Gy gamma radiation, which is the exact dosage a patient receives per day for clinical radiation therapy.
Co-reporter:Wei Cao, Lu Wang and Huaping Xu
Chemical Communications 2015 vol. 51(Issue 25) pp:5520-5522
Publication Date(Web):21 Nov 2014
DOI:10.1039/C4CC08588D
A coordination-responsive tellurium containing film was fabricated for controlled release. The coordination chemistry between telluride molecules and cisplatin was utilized for the loading of cisplatin, while competitive ligands were used for triggered release. This work could enrich the coordination responsive system and further tune the release kinetics of cisplatin.
Co-reporter:Ruochen Fang, Huaping Xu, Wei Cao, Liulin Yang and Xi Zhang
Polymer Chemistry 2015 vol. 6(Issue 15) pp:2817-2821
Publication Date(Web):10 Feb 2015
DOI:10.1039/C5PY00050E
Materials responsive to reactive oxygen species (ROS) at a physiological level are of great significance in diagnostic and therapeutic applications. We have synthesized a water-soluble tellurium-containing hyperbranched polymer and demonstrated that it forms a kind of ROS-responsive aggregate. In aqueous environment, the polymer aggregates can swell under biologically relevant concentration of H2O2, which could be expected to find applications in fields such as elimination of excess ROS.
Co-reporter:Wei Cao ; Yuwei Gu ; Myriam Meineck ; Tianyu Li
Journal of the American Chemical Society 2014 Volume 136(Issue 13) pp:5132-5137
Publication Date(Web):March 7, 2014
DOI:10.1021/ja500939m
Nanomaterials capable of achieving tunable cargo release kinetics are of significance in a fundamental sense and various biological or medical applications. We report a competitive coordination system based on a novel tellurium-containing polymer and its ligand-regulated release manners. Tellurium was introduced to water-soluble polymers for the first time as drug delivery vehicles. The coordination chemistry between platinum and tellurium was designed to enable the load of platinum-based drugs. Through the competitive coordination of biomolecules, the drugs could be released in a controlled manner. Furthermore, the release kinetics could be modulated by the competitive ligands involved due to their different coordination ability. This tellurium-containing polymer may enrich the family of delivery systems and provide a new platform for future biomedical nanotechnologies.
Co-reporter:Wei Cao;Yuwei Gu;Myriam Meineck;Dr. Huaping Xu
Chemistry – An Asian Journal 2014 Volume 9( Issue 1) pp:48-57
Publication Date(Web):
DOI:10.1002/asia.201301294
Abstract
Research on anticancer therapies has advanced significantly in recent years. New therapeutic platforms that can further improve the health of patients are still highly demanded. We propose the idea of combining regular chemotherapy with radiation therapy to minimize side effects as well as increase drug-delivery efficiency. In this Focus Review, we seek to provide an overview of recent advances that can combine chemotherapy and radiotherapy. We begin by reviewing the current state of systems that can combine chemotherapy and gamma radiation. Among them, diselenide-containing polymers are highlighted as sensitive drug-delivery vehicles that can disassemble under gamma radiation. Then X-ray responsive materials as promising alternative systems are summarized, including X-ray responsive drug-delivery vehicles, prodrugs that can be activated by X-rays, and radiation-site-targeting systems. Finally, we describe strategies that involve phototherapies.
Co-reporter:Shaobo Ji;Wei Cao;Ying Yu ; Huaping Xu
Angewandte Chemie International Edition 2014 Volume 53( Issue 26) pp:6781-6785
Publication Date(Web):
DOI:10.1002/anie.201403442
Abstract
Dynamic covalent bonds are extensively employed in dynamic combinatorial chemistry. The metathesis reaction of disulfide bonds is widely used, but requires catalysis or irradiation with ultraviolet (UV) light. It was found that diselenide bonds are dynamic covalent bonds and undergo dynamic exchange reactions under mild conditions for diselenide metathesis. This reaction is induced by irradiation with visible light and stops in the dark. The exchange is assumed to proceed through a radical mechanism, and experiments with 2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO) support this assumption. Furthermore, the reaction can be conducted in different solvents, including protic solvents. Diselenide metathesis can also be used to synthesize diselenide-containing asymmetric block copolymers. This work thus entails the use of diselenide bonds as dynamic covalent bonds, the development of a dynamic exchange reaction under mild conditions, and an extension of selenium-related dynamic chemistry.
Co-reporter:Shaobo Ji;Wei Cao;Ying Yu ; Huaping Xu
Angewandte Chemie 2014 Volume 126( Issue 26) pp:6899-6903
Publication Date(Web):
DOI:10.1002/ange.201403442
Abstract
Dynamic covalent bonds are extensively employed in dynamic combinatorial chemistry. The metathesis reaction of disulfide bonds is widely used, but requires catalysis or irradiation with ultraviolet (UV) light. It was found that diselenide bonds are dynamic covalent bonds and undergo dynamic exchange reactions under mild conditions for diselenide metathesis. This reaction is induced by irradiation with visible light and stops in the dark. The exchange is assumed to proceed through a radical mechanism, and experiments with 2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO) support this assumption. Furthermore, the reaction can be conducted in different solvents, including protic solvents. Diselenide metathesis can also be used to synthesize diselenide-containing asymmetric block copolymers. This work thus entails the use of diselenide bonds as dynamic covalent bonds, the development of a dynamic exchange reaction under mild conditions, and an extension of selenium-related dynamic chemistry.
Co-reporter:Lu Wang, Wei Cao, Yu Yi, and Huaping Xu
Langmuir 2014 Volume 30(Issue 19) pp:5628-5636
Publication Date(Web):May 1, 2014
DOI:10.1021/la501054z
A general approach is reported to fabricate a stimuli responsive system via coassembly of diselenide-containing block copolymers with polymer lipids, which integrates the stimuli-responsiveness of diselenide chemistry and the biocompatibility of polymer lipids. By using dynamic light scattering, transmission electron microscopy, and zeta potential analyzer, coassembly behavior of these two kinds of polymers and responsiveness of coassemblies have been investigated. These coassemblies can exhibit redox-responsiveness inheriting from the diselenide-containing block copolymers. In the presence of low concentration of hydrogen peroxide or glutathione, the coassemblies can be disrupted.
Co-reporter:Huaping Xu, Wei Cao, and Xi Zhang
Accounts of Chemical Research 2013 Volume 46(Issue 7) pp:1647
Publication Date(Web):April 12, 2013
DOI:10.1021/ar4000339
Although researchers have made great progress in the development of responsive polymeric materials for controlled drug release or diagnostics over the last 10 years, therapeutic results still lag behind expectations. The development of special materials that respond to physiological relevant concentrations, typically within the micromolar or nanomolar concentration regime, remains challenging. Therefore, researchers continue to pursue new biomaterials with unique properties and that respond to mild biochemical signals or biomarkers.Selenium is an essential element in human body with potential antioxidant properties. Because of selenium’s electronegativity and atomic radius, selenium-containing compounds exhibit unique bond energy (C–Se bond 244 kJ mol–1; Se–Se bond 172 kJ mol–1). These values give the C–Se or Se–Se covalent bonds dynamic character and make them responsive to mild stimuli. Therefore, selenium-containing polymers can disassemble in response to changes under physiological relevant conditions. This property makes them a promising biomaterial for controlled release of drugs or synthetic enzyme mimics.Until recently, few researchers have looked at selenium-containing polymers as novel biomaterials. In this Account, we summarize our recent research on selenium-containing polymers and show their potential application as mild-responsive drug delivery vehicles and artificial enzymes. We begin by reviewing the current state of the art in the synthesis of selenium-containing main chain block copolymers. We highlight the dual redox and gamma-irradiation behaviors of diselenide-containing block copolymers assemblies, discussing the possibility of their use in a combination of chemotherapy and actinotherapy. We also describe the coordination of platinum with monoselenide containing block copolymers. Such structures offer the possibility of fabricating multidrug systems for cooperative chemotherapy. In addition, we summarize the methods for the covalent and noncovalent preparation of selenium-containing polymers with side chains, which highlight the opportunity to reversibly tune the amphiphilicity of selenium-containing polymers. Finally, we present strategies for the design of highly efficient selenium-containing dendritic polymers that can mimic enzymes. This field is still in its infancy period, and further research can only be limited by our imagination.
Co-reporter:Peng Han, Sichao Li, Wei Cao, Yang Li, Zhiwei Sun, Zhiqiang Wang and Huaping Xu
Journal of Materials Chemistry A 2013 vol. 1(Issue 6) pp:740-743
Publication Date(Web):14 Dec 2012
DOI:10.1039/C2TB00186A
We showed here that red light can be used to tune the self-assembly of amphiphilic diselenide-containing block copolymers, via the production of singlet oxygen in the presence of chromophores such as porphyrin derivatives. Furthermore, red light can be used to trigger the release of encapsulated cargo in polymeric micelles.
Co-reporter:Yu Yi;Dr. Huaping Xu;Lu Wang;Wei Cao ; Xi Zhang
Chemistry - A European Journal 2013 Volume 19( Issue 29) pp:9506-9510
Publication Date(Web):
DOI:10.1002/chem.201301446
Abstract
A new kind of SeN dynamic covalent bond has been found that can form between the Se atom of a phenylselenyl halogen species and the N atom of a pyridine derivative, such as polystyrene-b-poly(4-vinylpyridine). This SeN dynamic covalent bond can be reversibly and rapidly formed or cleaved under acidic or basic conditions, respectively. Furthermore, the bond can be dynamically cleaved by heating or treatment with stronger electron-donating pyridine derivatives. The multiple responses of SeN bond to external stimuli has enriched the existing family of dynamic covalent bonds. It can be used for controlled and reversible self-assembly and disassembly, which may find potential applications in a number of areas, including self-healing materials and responsive assemblies.
Co-reporter:Wei Cao, Yang Li, Yu Yi, Shaobo Ji, Lingwu Zeng, Zhiwei Sun and Huaping Xu
Chemical Science 2012 vol. 3(Issue 12) pp:3403-3408
Publication Date(Web):30 Aug 2012
DOI:10.1039/C2SC21315J
A novel coordination-responsive system for the controlled release of doxorubicin was fabricated by complexing platinum cations with selenium-containing polymers. Doxorubicin loaded in the platinum-coordinating micelles can be released in a controlled manner through the competitive coordination of the platinum cations with glutathione. The coordination micelles are quite biocompatible as vehicles of drug delivery, thus opening a new avenue in multidrug systems for cooperative chemotherapy.
Co-reporter:Yu Yi, Shixin Fa, Wei Cao, Lingwu Zeng, Meixiang Wang, Huaping Xu and Xi Zhang
Chemical Communications 2012 vol. 48(Issue 60) pp:7495-7497
Publication Date(Web):13 Jun 2012
DOI:10.1039/C2CC33760F
We have employed a selenium containing amphiphile to assist the formation of well-defined azacalixarene nanosheets, in which the Se⋯N non-covalent interaction plays an important role.
Co-reporter:Yu Fu;Junyi Chen;Chantal Van Oosterwijck;Xi Zhang;Wim Dehaen;Mario Smet
Macromolecular Rapid Communications 2012 Volume 33( Issue 9) pp:798-804
Publication Date(Web):
DOI:10.1002/marc.201100860
Abstract
A novel glutathione peroxidase (GPx) mimic has been prepared by incorporation of a selenium-based catalytic unit into the focal point of a fully-branched hyperbranched polymer. First, an AB2 monomer consisting of isatin and an electron rich aromatic moiety was polycondensed in the presence of 5-nitroisatin as a core reagent, resulting in a polymer with 100% degree of branching. The latter was coupled to the catalytically active moiety, Br(CH2)5SeSe(CH2)5Br, by nucleophilic substitution of the bromides by the residual amide groups of the incorporated nitroisatin core. The obtained polymer has demonstrated prominent GPx activity as desired, which could be attributed to the hydrophobic, densely branched and core-shell structure of the polymer surrounding the catalytic center.
Co-reporter:Huifeng Ren, Yaoting Wu, Ning Ma, Huaping Xu and Xi Zhang
Soft Matter 2012 vol. 8(Issue 5) pp:1460-1466
Publication Date(Web):08 Dec 2011
DOI:10.1039/C1SM06673K
In this paper we report the synthesis and study of a series of side-chain selenium-containing amphiphilic poly(ethylene oxide-b-acrylic acid) block copolymers PEO-b-PAA-Se. These block copolymers can self-assemble in aqueous solution and form spherical micellar aggregates. The selenide group of PEO-b-PAA-Se can change into hydrophilic selenoxide under mild oxidation of 0.1% hydrogen peroxide, leading to the disassembly of the spherical micellar aggregates. Small compounds like Nile Red can be encapsulated into the micellar aggregates and show fast release upon the addition of 0.1% hydrogen peroxide. More interestingly, the oxidation state of selenoxide can be reversed to selenide under reduction of Vitamin C, thus recovering the spherical aggregates. The reversible oxidation and reduction process shows good reversibility and can be repeated at least 7 times. It is hoped that this reversible redox controlled system may function as nanocontainers for potential application in the areas such as responsive drug delivery and anti-oxidation studies.
Co-reporter:Ning Ma, Huaping Xu, Liping An, Juan Li, Zhiwei Sun, and Xi Zhang
Langmuir 2011 Volume 27(Issue 10) pp:5874-5878
Publication Date(Web):April 13, 2011
DOI:10.1021/la2009682
We have developed a potential radiation-sensitive drug-delivery system using active diselenide-containing block co-polymer aggregates in aqueous solution that can load and release anticancer drugs. These aggregates were sensitive to even a low dose of γ-radiation, such as 5 Gy, which is close to the radiation dose received by patients during a single radiotherapy treatment. This line of research may open an avenue for the combination of radiotherapy and chemotherapy.
Co-reporter:Zhihua Liu;Yu Yi;Xi Zhang;Thien Huynh Ngo;Mario Smet
Advanced Materials 2010 Volume 22( Issue 24) pp:2689-2693
Publication Date(Web):
DOI:10.1002/adma.201000469
Co-reporter:Ning Ma, Ying Li, Huifeng Ren, Huaping Xu, Zhibo Li and Xi Zhang
Polymer Chemistry 2010 vol. 1(Issue 10) pp:1609-1614
Publication Date(Web):08 Jul 2010
DOI:10.1039/C0PY00144A
A selenium-containing amphiphilic block copolymer (PEG-PUSe-PEG) with a hydrophobic polyselenide block and two hydrophilic poly(ethylene glycol) (PEG) blocks was synthesized via polymerization of toluene diisocyanate (TDI) with monoselenide-containing diols and subsequent termination with PEG monomethylether. PEG-PUSe-PEG is able to self-assemble in aqueous solution to form block copolymer aggregates. Interestingly, it was found that the aggregates have a good oxidation-responsiveness and undergo a structural dissociation in a mild oxidative environment (such as 0.1% H2O2 v/v) due to the unique sensitivity of selenide groups in presence of oxidants. Compared with the sulfide analogue PEG-PUS-PEG, PEG-PUSe-PEG is more sensitive to oxidants. It is anticipated that selenium-containing block copolymer aggregates may find application in the field of drug delivery systems.
Co-reporter:Jian Gao, Yiliu Liu, Huaping Xu, Zhiqiang Wang and Xi Zhang
Langmuir 2010 Volume 26(Issue 12) pp:9673-9676
Publication Date(Web):February 17, 2010
DOI:10.1021/la100256b
We present a very efficient and convenient approach to obtain smart biosurfaces by directly replicating biological surface structures. It is realized by a two-step replication process combining regular replica molding and tempetature-induced phase separation micromolding (PSμM). The negative replicas of biological surface structures using poly(dimethylsiloxane) as the replication material are durable molds for further replication. The positive replicas of biological surface structures are obtained by the second step replication using PSμM of poly(N-isopropylacrylamide) aqueous solution, which can be easily carried out just by adjusting temperature. With cold water as good solvent and hot water as nonsolvent, an environmentally friendly PSμM process is successfully achieved, and organic solvents for PSμM are completely avoided. Our study has demonstrated that the micro- and nanostructures of the lotus leaf and rice leaf can be well replicated using this two-step replication process, and the replicated artificial lotus leaf and rice leaf using poly(N-isopropylacrylamide) exhibit good thermally responsive wettability.
Co-reporter:Huaping Xu Dr.;Jurriaan Huskens Dr.
Chemistry - A European Journal 2010 Volume 16( Issue 8) pp:2342-2348
Publication Date(Web):
DOI:10.1002/chem.200902504
Abstract
Microcontact printing is a heavily used surface modification method in materials and life science applications. This concept article focuses on the development of versatile stamps for microcontact printing that can be used to bind and release inks through molecular recognition or through an ink reservoir, the latter being used for the transfer of heavy inks, such as biomolecules and particles. Conceptually, such stamp properties can be introduced at the stamp surface or by changing the bulk stamp material; both lines of research will be reviewed here. Examples include supramolecular stamps with affinity properties, polymer-layer-grafted PDMS stamps, and porous multilayer-grafted PDMS stamps for the first case, and hydrogel stamps and porous stamps made by phase-separation micromolding for the second. Potential directions for future advancement of this field are also discussed.
Co-reporter:Peng Han, Ning Ma, Huifeng Ren, Huaping Xu, Zhibo Li, Zhiqiang Wang, and Xi Zhang
Langmuir 2010 Volume 26(Issue 18) pp:14414-14418
Publication Date(Web):August 19, 2010
DOI:10.1021/la102837a
We have fabricated a polymeric superamphiphile based on the electrostatic interaction between the double hydrophilic block copolymer of poly(ethylene glycol)-b-acrylic acid (PEG-b-PAA) and a selenium-containing surfactant (SeQTA). The polymeric superamphiphiles are able to self-assemble to form micelles in solution. The micelles can be disassembled with the addition of 0.1% H2O2 because SeQTA is very sensitive to oxidation. The selenide group in SeQTA is oxidized into selenoxide (SeQTA-Ox) by H2O2, which makes the surfactant more hydrophilic, thus leading to the disassembly of the micelles. In addition, small guest molecules such as fluorescein sodium can be loaded into the micelles made from the polymeric superamphiphiles and released in a controlled way under mild oxidation conditions. This study represents a new way to fabricate stimuli-responsive superamphiphiles for controlled self-assembly and disassembly.
Co-reporter:Huaping Xu, Alberto Gomez-Casado, Zhihua Liu, David N. Reinhoudt, Rob G. H. Lammertink and Jurriaan Huskens
Langmuir 2009 Volume 25(Issue 24) pp:13972-13977
Publication Date(Web):July 13, 2009
DOI:10.1021/la901797n
A polyelectrolyte multilayer was assembled on top of a patterned PDMS stamp employing the layer-by-layer (LbL) assembly technique. By post-treatment with a base and further cross-linking, a porous multilayer-coated PDMS composite stamp was obtained. With the pore structures acting as an ink reservoir, the multiple printing of proteins was successfully achieved without the need to re-ink the stamp.
Co-reporter:Jian Gao, Yiliu Liu, Huaping Xu, Zhiqiang Wang and Xi Zhang
Langmuir 2009 Volume 25(Issue 8) pp:4365-4369
Publication Date(Web):March 25, 2009
DOI:10.1021/la9008027
In this letter, we present a very convenient and efficient technique of direct replication of biological structures via a two-step phase-separation micromolding process (PSμM). Our study has demonstrated that PSμM can be used to replicate the surface structure of a lotus leaf. On one hand, the micro/nanostructures of the lotus leaf are well replicated after a two-step PSμM. On the other hand, the replicated artificial lotus leaf shows good superhydrophobicity, similar to that of the natural lotus leaf. In addition, we have also applied the same technique to replicate a rice leaf and have confirmed that replicated artificial rice leaves can exhibit not only a very similar structure of the natural rice leaf but also surface anisotropic wetting. It is greatly anticipated that this PSμM can be extended to mimic many other biostructures, therefore opening new avenues for surface molecular engineering.
Co-reporter:Ning Ma ; Ying Li ; Huaping Xu ; Zhiqiang Wang ;Xi Zhang
Journal of the American Chemical Society () pp:
Publication Date(Web):2017-2-22
DOI:10.1021/ja908124g
A block copolymer with diselenide bonds in the polymer backbone was reported. This block copolymer was capable of forming micellar aggregates that were responsive to redox stimuli. Compared with other redox responsive aggregates, this type of diselenide-containing block copolymer aggregates could be responsive to both oxidants and reductants even in a solution with a very low concentration under mild conditions.
Co-reporter:Wei Cao, Yuwei Gu, Tianyu Li and Huaping Xu
Chemical Communications 2015 - vol. 51(Issue 32) pp:NaN7071-7071
Publication Date(Web):2015/03/20
DOI:10.1039/C5CC01779C
A novel tellurium-containing polymer micelle system is reported to be responsive to 100 μM H2O2 and can undergo a series of morphological changes. The polymer micelles also respond to 2 Gy gamma radiation, which is the exact dosage a patient receives per day for clinical radiation therapy.
Co-reporter:Peng Han, Sichao Li, Wei Cao, Yang Li, Zhiwei Sun, Zhiqiang Wang and Huaping Xu
Journal of Materials Chemistry A 2013 - vol. 1(Issue 6) pp:NaN743-743
Publication Date(Web):2012/12/14
DOI:10.1039/C2TB00186A
We showed here that red light can be used to tune the self-assembly of amphiphilic diselenide-containing block copolymers, via the production of singlet oxygen in the presence of chromophores such as porphyrin derivatives. Furthermore, red light can be used to trigger the release of encapsulated cargo in polymeric micelles.
Co-reporter:Wei Cao, Yang Li, Yu Yi, Shaobo Ji, Lingwu Zeng, Zhiwei Sun and Huaping Xu
Chemical Science (2010-Present) 2012 - vol. 3(Issue 12) pp:NaN3408-3408
Publication Date(Web):2012/08/30
DOI:10.1039/C2SC21315J
A novel coordination-responsive system for the controlled release of doxorubicin was fabricated by complexing platinum cations with selenium-containing polymers. Doxorubicin loaded in the platinum-coordinating micelles can be released in a controlled manner through the competitive coordination of the platinum cations with glutathione. The coordination micelles are quite biocompatible as vehicles of drug delivery, thus opening a new avenue in multidrug systems for cooperative chemotherapy.
Co-reporter:Yu Yi, Shixin Fa, Wei Cao, Lingwu Zeng, Meixiang Wang, Huaping Xu and Xi Zhang
Chemical Communications 2012 - vol. 48(Issue 60) pp:NaN7497-7497
Publication Date(Web):2012/06/13
DOI:10.1039/C2CC33760F
We have employed a selenium containing amphiphile to assist the formation of well-defined azacalixarene nanosheets, in which the Se⋯N non-covalent interaction plays an important role.
Co-reporter:Wei Cao, Lu Wang and Huaping Xu
Chemical Communications 2015 - vol. 51(Issue 25) pp:NaN5522-5522
Publication Date(Web):2014/11/21
DOI:10.1039/C4CC08588D
A coordination-responsive tellurium containing film was fabricated for controlled release. The coordination chemistry between telluride molecules and cisplatin was utilized for the loading of cisplatin, while competitive ligands were used for triggered release. This work could enrich the coordination responsive system and further tune the release kinetics of cisplatin.