Pd-doped organosilica membranes were prepared by controlling calcination atmospheres(i.e.POS-Air,POS-N2,POS-H2,POS-H2/N2)to tailor their networks for improving their gas separation performance.This study shows that Pd...Pd-doped organosilica membranes were prepared by controlling calcination atmospheres(i.e.POS-Air,POS-N2,POS-H2,POS-H2/N2)to tailor their networks for improving their gas separation performance.This study shows that Pd(Ⅱ)could be only maintained under non-reductive calcination atmosphere,while inert and reducing calcination atmosphere is more beneficial to maintain organosilica moieties in POS networks.POS-H2/N2 membrane showed the optimal H2 separation performance that its permselectivities for H2/CO2,H2/N2,H2/CH4 and H2/SF6 are 15.0,96.7,173.0 and 3400.0,re spectively.Moreover,it is found that H2 molecules pass through the four membranes based on activated diffusion,while CO2 molecules permeation through POS-N2 and POS-Air membrane is dominated by surface diffusion.This work may provide insight into the understanding of the calcination atmosphere effect on gas separation performance of metal-doped organosilica membranes.展开更多
A series of organosilica sols are prepared by the polymeric sol–gel method using 1,2-bis(triethoxysilyl)ethane(BTESE)as the precursor.Particle size distributions of the BTESE-derived sols are systematically investiga...A series of organosilica sols are prepared by the polymeric sol–gel method using 1,2-bis(triethoxysilyl)ethane(BTESE)as the precursor.Particle size distributions of the BTESE-derived sols are systematically investigated by carefully adjusting the synthesis parameters(i.e.,water ratios,acid ratios and solvent ratios)in the sol process.In certain conditions,increasing the water ratio or the acid ratio tends to cause larger sol sizes and bimodal particle size distributions.However,higher solvent ratios lead to smaller sol sizes and unimodal particle size distributions.The organosilica membranes prepared from the optimized sols show excellent H_2 permeances(up to 4.2×10^(-7)mol·m^(-2)·s^(-1)·Pa^(-1))and gas permselectitivies(H_2/CO_2 is 9.5,H_2/N_2 is 50 and H_2/CH_4 is 68).This study offers significant insights into the relationship between the sol synthesis parameters,sol sizes and membrane performance.展开更多
Monometallic doping has proved its superiority in improving either permselectivity or H_(2) permeability of organosilica membranes for H_(2)/CO_(2) separation,but it is still challenging to break the trade-off effect....Monometallic doping has proved its superiority in improving either permselectivity or H_(2) permeability of organosilica membranes for H_(2)/CO_(2) separation,but it is still challenging to break the trade-off effect.Herein,we report a series of Pd-Nb bimetallic doped 1,2-bis(triethoxysilyl)ethane(Pd-Nb-BTESE,PNB)membranes with different metal doping routes for simultaneously improving H_(2) permeance and H_(2)/CO_(2) permselectivity by the synergetic effects of Pd and Nb.The doped Pd can exist in the BTESE network as nanoparticles while the doped Nb is incorporated into BTESE network forming Nb-O-Si covalent bonds.The metal doping routes significantly influence the microstructure of PNB networks and gas separation performance of the PNB membranes.We found that the PNB membrane with Pd doping priority(PNB-Pd)exhibited the highest surface area and pore volume,comparing with Nb doping priority(PNB-Nb)or Pd-Nb simultaneous doping(PNB-PdNb).The PNB-Pd membrane could not only exhibit an excellent H_(2) permeance of~10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) but also a high H_(2)/CO_(2) permselectivity of 17.2.Our findings may provide novel insights into preparation of bimetallic doped organosilica membranes with excellent H_(2)/CO_(2) separation performance.展开更多
To date,the ability of nanoplatforms to achieve excellent therapeutic responses is hindered by short blood circulation and limited tumor accumulation/penetration.Herein,a soft mesoporous organosilica nanoplatform modi...To date,the ability of nanoplatforms to achieve excellent therapeutic responses is hindered by short blood circulation and limited tumor accumulation/penetration.Herein,a soft mesoporous organosilica nanoplatform modified with hyaluronic acid and cyanine 5.5 are prepared,denoted SMONs-HA-Cy5.5,and comparative studies between SMONs-HA-Cy5.5(24.2 MPa)and stiff counterparts(79.2 MPa)are conducted.Results indicate that,apart from exhibiting a twofold increase in tumor cellular uptake,the soft nanoplatforms also display a remarkable pharmacokinetic advantage,resulting in considerably improved tumor accumulation.Moreover,SMONs-HA-Cy5.5 exhibits a significantly higher tumor penetration,achieving 30-μm deeper tissue permeability in multicellular spheroids relative to the stiff counterparts.Results further reveal that the soft nanoplatforms have an easier extravasation from the tumor vessels,diffuse farther in the dense extracellular matrix,and reach deeper tumor tissues compared to the stiff ones.Specifically,the soft nanoplatforms generate a 16-fold improvement(43 vs.2.72μm)in diffusion distance in tumor parenchyma.Based on the significantly improved blood circulation and tumor accumulation/penetration,a soft therapeutic nanoplatform is constructed by loading photosensitizer chlorin e6 in SMONs-HA-Cy5.5.The resulting nanoplatform exhibits considerably higher therapeutic efficacy on tumors compared to the stiff ones.展开更多
Herein a novel aminopropyl-containing ionic liquid based organosilica(ILOS-NH_2) is prepared, characterized and applied as effective adsorbent for removal of crystal violet(CV) dye from wastewater. The ILOS-NH2 materi...Herein a novel aminopropyl-containing ionic liquid based organosilica(ILOS-NH_2) is prepared, characterized and applied as effective adsorbent for removal of crystal violet(CV) dye from wastewater. The ILOS-NH2 material was synthesized by hydrolysis and co-condensation of 1,3-bis-(3-trimethoxysilylpropyl)-imidazolium chloride(BTMSPIC) under acidic conditions followed by treatment with 3-aminopropyl-trimethoxysilane in toluene under reflux conditions. This material was characterized using scanning electron microscopy(SEM), diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS), thermal gravimetric analysis(TGA) and energy dispersive X-ray analysis(EDAX). The material was effectively used in the removal of crystal violet at ambient temperature and showed high capacity and stability under applied conditions. The efficacy of p H, contact time, adsorbent dose, initial dye concentration, temperature, and isotherm studies and the applicability of pseudo-first, second order and Elovich kinetic models have also been investigated.展开更多
Organic matter-induced mineralization is a green and versatile method for synthesizing hybrid nanostructured materials,where the material properties are mainly influenced by the species of natural biomolecules,linear ...Organic matter-induced mineralization is a green and versatile method for synthesizing hybrid nanostructured materials,where the material properties are mainly influenced by the species of natural biomolecules,linear synthetic polymer,or small molecules,limiting their diversity.Herein,we adopted dendrimer poly(amidoamine)(PAMAM)as the inducer to synthesize organosilica-PAMAM network(OSPN)capsules for mannose isomerase(MIase)encapsulation based on a hard-templating method.The structure of OSPN capsules can be precisely regulated by adjusting the molecular weight and concentration of PAMAM,thereby demonstrating a substantial impact on the kinetic behavior of the MIase@OSPN system.The MIase@OSPN system was used for catalytic production of mannose from Dfructose.A mannose yield of 22.24% was obtained,which is higher than that of MIase in organosilica network capsules and similar to that of the free enzyme.The overall catalytic efficiency(kcat/Km)of the MIase@OSPN system for the substrate D-fructose was up to 0.556 s^(-1)·mmol^(-1)·L.Meanwhile,the MIase@OSPN system showed excellent stability and recyclability,maintaining more than 50% of the yield even after 12 cycles.展开更多
Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher per...Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher permeance compared to commercial polymers.However,the selectivities of the reported membranes are moderate.Here,we have incorporated urea-modulated metal-organic frameworks into organosilica membranes to greatly enhance its separation performance.The urea-modulated metal-organic frameworks exhibit less-defined edges of crystallographic facets and high defect density.They can be well-dispersed in the organosilica layer,which substantially suppresses the interfacial defects between metal-organic frameworks and organosilica,which is beneficial for improving the selectivity of membranes for gas separation.The results have shown that the enhanced ideal selectivity of H_(2)/CH_(4) was 165 and that of CO_(2)/CH_(4) was 43,with H_(2) permeance of about 1.25×10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) and CO_(2) permeance of 3.27×10^(−7) mol·m^(−2)·s^(−1)·Pa^(−1) at 0.2 MPa and 25℃.In conclusion,the high level of hybrid membranes can be used to separate H_(2)(or CO_(2))from the binary gas mixture H_(2)/CH_(4)(or CO_(2)/CH_(4)),which is important for gas separation in practical applications.Moreover,the simple and feasible modulation of metal-organic framework is a promising strategy to tune different metal-organic frameworks for membranes according to the actual demands.展开更多
Core-shell structured magnetic wrinkled organosilica-based metal-enzyme integrated catalysts were synthesized,and their catalytic performances were studied in the chemoenzymatic dynamic kinetic resolution of chiral am...Core-shell structured magnetic wrinkled organosilica-based metal-enzyme integrated catalysts were synthesized,and their catalytic performances were studied in the chemoenzymatic dynamic kinetic resolution of chiral amines in an organic solvent,as well as in the chemoenzymatic synthesis of chiral alcohols in water.Structureperformance studies revealed the important influence of their tunable structure and composition on the optimization of activity,stability,and recyclability in chemoenzymatic catalysis.展开更多
Precise control over the morphology,nanostructure,composition,and particle size of molecularly organic-inorganic hybrid mesoporous organosilica nanoparticles （MONs） still remains a major challenge,which severely res...Precise control over the morphology,nanostructure,composition,and particle size of molecularly organic-inorganic hybrid mesoporous organosilica nanoparticles （MONs） still remains a major challenge,which severely restricts their broad applications.In this work an efficient bridged organic group-determined growth strategy has been proposed for the facile synthesis of highly dispersed and uniform MONs with multifarious Janus morphologies,nanostructures,organic-inorganic hybrid compositions,and particle sizes,which can be easily controlled simply by varying the bridged organic groups and the concentration of bis-silylated organosilica precursors used in the synthesis.In addition,the formation mechanism of Janus MONs determined by the bridged organic group has been discussed.Based on the specific structures,compositions,and asymmetric morphologies,all the synthesized Janus MONs with hollow structures （JHMONs） demonstrate excellent performances in nanomedicine as desirable drug carriers with high drug-loading efficiencies/capacities,pH-responsive drug releasing,and enhanced therapeutic efficiencies,as attractive contrastenhanced contrast agents for ultrasound imaging,and as excellent bilirubin adsorbents with noticeably high adsorption capacities and high blood compatibilities.The developed versatile synthetic strategy and the obtained JHMONs are extremely important in the development and applications of MONs,particularly in the areas of nanoscience and nanotechnology.展开更多
The therapeutic efficacy of cisplatin has been restricted by drug resistance of cancers.Intracellular glutathione(GSH)detoxification of cisplatin under the catalysis of glutathione S-transferases(GST)plays important r...The therapeutic efficacy of cisplatin has been restricted by drug resistance of cancers.Intracellular glutathione(GSH)detoxification of cisplatin under the catalysis of glutathione S-transferases(GST)plays important roles in the development of cisplatin resistance.Herein,a strategy of“pincer movement”based on simultaneous GSH depletion and GST inhibition is proposed to enhance cisplatin-based chemotherapy.Specifically,a redox-responsive nanomedicine based on disulfide-bridged degradable organosilica hybrid nanoparticles is developed and loaded with cisplatin and ethacrynic acid(EA),a GST inhibitor.Responding to high level of intracellular GSH,the hybrid nanoparticles can be gradually degraded due to the break of disulfide bonds,which further promotes drug release.Meanwhile,the disulfide-mediated GSH depletion and EA-induced GST inhibition cooperatively prevent cellular detoxification of cisplatin and reverse drug resistance.Moreover,the nanomedicine is integrated into microneedles for intralesional drug delivery against cisplatin-resistant melanoma.The in vivo results show that the nanomedicine-loaded microneedles can achieve significant GSH depletion,GST inhibition,and consequent tumor growth suppression.Overall,this research provides a promising strategy for the construction of new-type nanomedicines to overcome cisplatin resistance,which extends the biomedical application of organosilica hybrid nanomaterials and enables more efficient chemotherapy against drug-resistant cancers.展开更多
Volatile organic solvents were considered to have little influence on the synthesis of mesostructured materials through evaporation-induced self-assembly(EISA),because upon evaporation they leave the sol and hence do ...Volatile organic solvents were considered to have little influence on the synthesis of mesostructured materials through evaporation-induced self-assembly(EISA),because upon evaporation they leave the sol and hence do not interfere with the self-assembly process.We show here that the choice of solvent is crucial in the synthesis of thin films of phenylene-bridged periodic mesoporous organosilica(benzene PMO).Methanol is found to be a better solvent for the synthesis of thin films,whereas ethanol favors the formation of(HO)3Si-C6H4-Si(OH)3 crystals,the identity and structure of which is established by X-ray diffraction.A ternary reactant composition diagram is designed to visualize the relationship among multiple synthesis experiments and to guide the interpretation of experimental results and optimization of the quality of the periodic mesoporous organosilica film.Our study highlights the importance of solvent choice,a factor often neglected in EISA.We expect it to inspire researchers to explore the effect of solvent in designing the synthesis of mesoporous materials.展开更多
The stability of periodic mesoporous organosilica(PMO) nanoparticles in physiological solutions greatly affects their potential biomedical applications. Herein, thioether-bridged PMO nanospheres with a diameter of 61 ...The stability of periodic mesoporous organosilica(PMO) nanoparticles in physiological solutions greatly affects their potential biomedical applications. Herein, thioether-bridged PMO nanospheres with a diameter of 61 nm are synthesized. Then, the thioether-bridged PMO nanospheres are modified with different molecular weighted polyethylene glycol(PEG) via click reaction for the first time. FI-IR and thermogravimetric analysis confirm the successful modification of PEG on the PMO. The influence of PEG molecular weight on the dispersity and stability of the PMO-PEG in phosphate buffer(PBS) and Dulbecco's modified Eagle's medium(DMEM) is studied. The results show that the PEG coating increases the stability and dispersity of PMO in the biological solutions. The PMO-PEG1K, PMO-PEG2K, and PMOPEG5K have better stability in PBS solution. The PMO-PEG2K shows best stability and dispersity in DMEM. Over all, this work provides important method and knowledge to guide the modification of PMO for biomedical展开更多
The integration of organic and inorganic fragments within the pore walls of the periodic mesoporous organosilicas (PMOs) represents one of the recent breakthroughs in material science. The resulting PMOs are promising...The integration of organic and inorganic fragments within the pore walls of the periodic mesoporous organosilicas (PMOs) represents one of the recent breakthroughs in material science. The resulting PMOs are promising materials for applications in such areas as catalysis, adsorption, separation and drug-delivery. We summarize here the recent progress made in the synthesis of PMOs with hierarchical structures and large functional groups, with special emphasis on the chiral mesoporous organosilicas and their potential applications as novel chiral solids in heterogeneous asymmetric catalysis.展开更多
Multishelled hollow structures have drawn increasing interest because of their peculiar compartmentation environments and physicochemical properties.In this work,deformable double-shelled hollow mesoporous o rganosili...Multishelled hollow structures have drawn increasing interest because of their peculiar compartmentation environments and physicochemical properties.In this work,deformable double-shelled hollow mesoporous o rganosilica nanocapsules(DDHMONs)were succes s fully synthesized by a multi-interfacial etching strategy.The obtained DDHMONs have a double-shelled structure with aninorganic-organic hybrid framework,a uniform outer layer(~320 nm)and inner layer(~180 nm),ordered mesochannels(~2.21 nm),and a large specific surface area(~1233 m^(2)/g).In vitro toxicity tests show that the DDHMONs have excellent biocompatibility when coincubated with human breast cancer cells.In addition,the anti cancer substance doxorubicin(DOX)can be highly loaded in DDHMONs(~335μg/mg).The results from flow cytometry together with confocal laser scanning microscopy show that DOX can be efficiently delivered into MCF-7 cells by DDHMONs,thus improving chemotherapeutic efficiency and demonstrating that DDHMONs have potential nanomedicine applications as anticancer agents.展开更多
Volatile organic solvents were considered to have little influence on the synthesis of mesostructured materials through evaporation-induced self-assembly(EISA),because upon evaporation they leave the sol and hence do ...Volatile organic solvents were considered to have little influence on the synthesis of mesostructured materials through evaporation-induced self-assembly(EISA),because upon evaporation they leave the sol and hence do not interfere with the self-assembly process.We show here that the choice of solvent is crucial in the synthesis of thin films of phenylene-bridged periodic mesoporous organosilica(benzene PMO).Methanol is found to be a better solvent for the synthesis of thin films,whereas ethanol favors the formation of(HO)3Si-C6H4-Si(OH)3 crystals,the identity and structure of which is established by X-ray diffraction.A ternary reactant composition diagram is designed to visualize the relationship among multiple synthesis experiments and to guide the interpretation of experimental results and optimization of the quality of the periodic mesoporous organosilica film.Our study highlights the importance of solvent choice,a factor often neglected in EISA.We expect it to inspire researchers to explore the effect of solvent in designing the synthesis of mesoporous materials.展开更多
基金Supported by the National Natural Science Foundation of China(21276123,21490581)the National High Technology Research and Development Program of China(2012AA03A606)the“Summit of the Six Top Talents”Program of Jiangsu Province.
文摘Pd-doped organosilica membranes were prepared by controlling calcination atmospheres(i.e.POS-Air,POS-N2,POS-H2,POS-H2/N2)to tailor their networks for improving their gas separation performance.This study shows that Pd(Ⅱ)could be only maintained under non-reductive calcination atmosphere,while inert and reducing calcination atmosphere is more beneficial to maintain organosilica moieties in POS networks.POS-H2/N2 membrane showed the optimal H2 separation performance that its permselectivities for H2/CO2,H2/N2,H2/CH4 and H2/SF6 are 15.0,96.7,173.0 and 3400.0,re spectively.Moreover,it is found that H2 molecules pass through the four membranes based on activated diffusion,while CO2 molecules permeation through POS-N2 and POS-Air membrane is dominated by surface diffusion.This work may provide insight into the understanding of the calcination atmosphere effect on gas separation performance of metal-doped organosilica membranes.
基金Supported by the National Natural Science Foundation of China(21276123,21490581)the National High Technology Research and Development Program of China(2012AA03A606)+1 种基金the "Summit of the Six Top Talents" Program of Jiangsu Province(2011-XCL-021)the Open Research Fund Program of Collaborative Innovation Center of Membrane Separation and Water Treatment(2016YB01)
文摘A series of organosilica sols are prepared by the polymeric sol–gel method using 1,2-bis(triethoxysilyl)ethane(BTESE)as the precursor.Particle size distributions of the BTESE-derived sols are systematically investigated by carefully adjusting the synthesis parameters(i.e.,water ratios,acid ratios and solvent ratios)in the sol process.In certain conditions,increasing the water ratio or the acid ratio tends to cause larger sol sizes and bimodal particle size distributions.However,higher solvent ratios lead to smaller sol sizes and unimodal particle size distributions.The organosilica membranes prepared from the optimized sols show excellent H_2 permeances(up to 4.2×10^(-7)mol·m^(-2)·s^(-1)·Pa^(-1))and gas permselectitivies(H_2/CO_2 is 9.5,H_2/N_2 is 50 and H_2/CH_4 is 68).This study offers significant insights into the relationship between the sol synthesis parameters,sol sizes and membrane performance.
基金supported by the National Natural Science Foundation of China(21490581)China Petroleum&Chemical Corporation(317008-6)Guangxi Innovation Driven Development Foundation(AA17204092).
文摘Monometallic doping has proved its superiority in improving either permselectivity or H_(2) permeability of organosilica membranes for H_(2)/CO_(2) separation,but it is still challenging to break the trade-off effect.Herein,we report a series of Pd-Nb bimetallic doped 1,2-bis(triethoxysilyl)ethane(Pd-Nb-BTESE,PNB)membranes with different metal doping routes for simultaneously improving H_(2) permeance and H_(2)/CO_(2) permselectivity by the synergetic effects of Pd and Nb.The doped Pd can exist in the BTESE network as nanoparticles while the doped Nb is incorporated into BTESE network forming Nb-O-Si covalent bonds.The metal doping routes significantly influence the microstructure of PNB networks and gas separation performance of the PNB membranes.We found that the PNB membrane with Pd doping priority(PNB-Pd)exhibited the highest surface area and pore volume,comparing with Nb doping priority(PNB-Nb)or Pd-Nb simultaneous doping(PNB-PdNb).The PNB-Pd membrane could not only exhibit an excellent H_(2) permeance of~10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) but also a high H_(2)/CO_(2) permselectivity of 17.2.Our findings may provide novel insights into preparation of bimetallic doped organosilica membranes with excellent H_(2)/CO_(2) separation performance.
基金supported by National Key Basic Research Program of China(973 Program),China(2014CB744504)the National Natural Science Foundation of China,China(81971675,21603106 and 81971681)the Natural Science Foundation of Jiangsu Province,China(BK20160017)。
文摘To date,the ability of nanoplatforms to achieve excellent therapeutic responses is hindered by short blood circulation and limited tumor accumulation/penetration.Herein,a soft mesoporous organosilica nanoplatform modified with hyaluronic acid and cyanine 5.5 are prepared,denoted SMONs-HA-Cy5.5,and comparative studies between SMONs-HA-Cy5.5(24.2 MPa)and stiff counterparts(79.2 MPa)are conducted.Results indicate that,apart from exhibiting a twofold increase in tumor cellular uptake,the soft nanoplatforms also display a remarkable pharmacokinetic advantage,resulting in considerably improved tumor accumulation.Moreover,SMONs-HA-Cy5.5 exhibits a significantly higher tumor penetration,achieving 30-μm deeper tissue permeability in multicellular spheroids relative to the stiff counterparts.Results further reveal that the soft nanoplatforms have an easier extravasation from the tumor vessels,diffuse farther in the dense extracellular matrix,and reach deeper tumor tissues compared to the stiff ones.Specifically,the soft nanoplatforms generate a 16-fold improvement(43 vs.2.72μm)in diffusion distance in tumor parenchyma.Based on the significantly improved blood circulation and tumor accumulation/penetration,a soft therapeutic nanoplatform is constructed by loading photosensitizer chlorin e6 in SMONs-HA-Cy5.5.The resulting nanoplatform exhibits considerably higher therapeutic efficacy on tumors compared to the stiff ones.
基金Supported by the National Science Foundation of Iran
文摘Herein a novel aminopropyl-containing ionic liquid based organosilica(ILOS-NH_2) is prepared, characterized and applied as effective adsorbent for removal of crystal violet(CV) dye from wastewater. The ILOS-NH2 material was synthesized by hydrolysis and co-condensation of 1,3-bis-(3-trimethoxysilylpropyl)-imidazolium chloride(BTMSPIC) under acidic conditions followed by treatment with 3-aminopropyl-trimethoxysilane in toluene under reflux conditions. This material was characterized using scanning electron microscopy(SEM), diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS), thermal gravimetric analysis(TGA) and energy dispersive X-ray analysis(EDAX). The material was effectively used in the removal of crystal violet at ambient temperature and showed high capacity and stability under applied conditions. The efficacy of p H, contact time, adsorbent dose, initial dye concentration, temperature, and isotherm studies and the applicability of pseudo-first, second order and Elovich kinetic models have also been investigated.
基金supported by the National Key Research and Development Program of China(Grant No.2021YFC210-2300)the National Key Research and Development Program of China(Grant No.2022YFC2105902)+2 种基金Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project(Grant No.TSBICIP-KJGG-003)Open Funding Project of the State Key Laboratory of Biochemical Engineering of China(Grant No.2020KF-06)Haihe Laboratory of Sustainable Chemical Transformations.
文摘Organic matter-induced mineralization is a green and versatile method for synthesizing hybrid nanostructured materials,where the material properties are mainly influenced by the species of natural biomolecules,linear synthetic polymer,or small molecules,limiting their diversity.Herein,we adopted dendrimer poly(amidoamine)(PAMAM)as the inducer to synthesize organosilica-PAMAM network(OSPN)capsules for mannose isomerase(MIase)encapsulation based on a hard-templating method.The structure of OSPN capsules can be precisely regulated by adjusting the molecular weight and concentration of PAMAM,thereby demonstrating a substantial impact on the kinetic behavior of the MIase@OSPN system.The MIase@OSPN system was used for catalytic production of mannose from Dfructose.A mannose yield of 22.24% was obtained,which is higher than that of MIase in organosilica network capsules and similar to that of the free enzyme.The overall catalytic efficiency(kcat/Km)of the MIase@OSPN system for the substrate D-fructose was up to 0.556 s^(-1)·mmol^(-1)·L.Meanwhile,the MIase@OSPN system showed excellent stability and recyclability,maintaining more than 50% of the yield even after 12 cycles.
基金supports of this work from“Pioneer”and“Leading Goose”R&D Program of Zhejiang Province(Grant No.2022C01029)National Natural Science Foundation of China(Grant No.21978309)+3 种基金Natural Science Foundation of Zhejiang Province(Grant No.LY21E020008)Youth Innovation Promotion Association,Chinese Acadenry of Sciences(Grant No.2020300)Ningbo Natural Science Foundation(Grant No.2023J354)Ningbo S&T Innovation 2025 Major Special Program(Grant No.2020Z036).
文摘Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher permeance compared to commercial polymers.However,the selectivities of the reported membranes are moderate.Here,we have incorporated urea-modulated metal-organic frameworks into organosilica membranes to greatly enhance its separation performance.The urea-modulated metal-organic frameworks exhibit less-defined edges of crystallographic facets and high defect density.They can be well-dispersed in the organosilica layer,which substantially suppresses the interfacial defects between metal-organic frameworks and organosilica,which is beneficial for improving the selectivity of membranes for gas separation.The results have shown that the enhanced ideal selectivity of H_(2)/CH_(4) was 165 and that of CO_(2)/CH_(4) was 43,with H_(2) permeance of about 1.25×10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) and CO_(2) permeance of 3.27×10^(−7) mol·m^(−2)·s^(−1)·Pa^(−1) at 0.2 MPa and 25℃.In conclusion,the high level of hybrid membranes can be used to separate H_(2)(or CO_(2))from the binary gas mixture H_(2)/CH_(4)(or CO_(2)/CH_(4)),which is important for gas separation in practical applications.Moreover,the simple and feasible modulation of metal-organic framework is a promising strategy to tune different metal-organic frameworks for membranes according to the actual demands.
基金financially supported by the National Key Research and Development Program of China(No.2021YFC2104100)the National Natural Science Foundation of China(Nos.21901058,22178083 and 22078081)+2 种基金the S&T program of Hebei(Nos.21372805D,21372804D and 20372802D)the Natural Science Foundation of Tianjin City(No.20JCYBJC00530)the Natural Science Foundation of Hebei Province(No.B2022202014).
文摘Core-shell structured magnetic wrinkled organosilica-based metal-enzyme integrated catalysts were synthesized,and their catalytic performances were studied in the chemoenzymatic dynamic kinetic resolution of chiral amines in an organic solvent,as well as in the chemoenzymatic synthesis of chiral alcohols in water.Structureperformance studies revealed the important influence of their tunable structure and composition on the optimization of activity,stability,and recyclability in chemoenzymatic catalysis.
基金We greatly acknowledge financial support from the National Key Research and Development Program of China （No. 2016YFA0203700）, Shanghai Natural Science Foundation （No. 16ZR1440300）, the National Natural Science Foundation of China （Nos. 61275208, 51302293, and 51672303）, Shanghai Rising-Star Program （No. 14QA1404100）, Youth Innovation Promotion Associa- tion of the Chinese Academy of Sdences （No. 2013169） and Development Fund for Shanghai Talents （2015）.
文摘Precise control over the morphology,nanostructure,composition,and particle size of molecularly organic-inorganic hybrid mesoporous organosilica nanoparticles （MONs） still remains a major challenge,which severely restricts their broad applications.In this work an efficient bridged organic group-determined growth strategy has been proposed for the facile synthesis of highly dispersed and uniform MONs with multifarious Janus morphologies,nanostructures,organic-inorganic hybrid compositions,and particle sizes,which can be easily controlled simply by varying the bridged organic groups and the concentration of bis-silylated organosilica precursors used in the synthesis.In addition,the formation mechanism of Janus MONs determined by the bridged organic group has been discussed.Based on the specific structures,compositions,and asymmetric morphologies,all the synthesized Janus MONs with hollow structures （JHMONs） demonstrate excellent performances in nanomedicine as desirable drug carriers with high drug-loading efficiencies/capacities,pH-responsive drug releasing,and enhanced therapeutic efficiencies,as attractive contrastenhanced contrast agents for ultrasound imaging,and as excellent bilirubin adsorbents with noticeably high adsorption capacities and high blood compatibilities.The developed versatile synthetic strategy and the obtained JHMONs are extremely important in the development and applications of MONs,particularly in the areas of nanoscience and nanotechnology.
基金This work was financially supported by the National Natural Science Foundation of China(No.81803466)the Natural Science Foundation of Guangdong Province(No.2018A030310095,China)the Key Areas Research and Development Program of Guangdong Province(No.2019B020204002,China).
文摘The therapeutic efficacy of cisplatin has been restricted by drug resistance of cancers.Intracellular glutathione(GSH)detoxification of cisplatin under the catalysis of glutathione S-transferases(GST)plays important roles in the development of cisplatin resistance.Herein,a strategy of“pincer movement”based on simultaneous GSH depletion and GST inhibition is proposed to enhance cisplatin-based chemotherapy.Specifically,a redox-responsive nanomedicine based on disulfide-bridged degradable organosilica hybrid nanoparticles is developed and loaded with cisplatin and ethacrynic acid(EA),a GST inhibitor.Responding to high level of intracellular GSH,the hybrid nanoparticles can be gradually degraded due to the break of disulfide bonds,which further promotes drug release.Meanwhile,the disulfide-mediated GSH depletion and EA-induced GST inhibition cooperatively prevent cellular detoxification of cisplatin and reverse drug resistance.Moreover,the nanomedicine is integrated into microneedles for intralesional drug delivery against cisplatin-resistant melanoma.The in vivo results show that the nanomedicine-loaded microneedles can achieve significant GSH depletion,GST inhibition,and consequent tumor growth suppression.Overall,this research provides a promising strategy for the construction of new-type nanomedicines to overcome cisplatin resistance,which extends the biomedical application of organosilica hybrid nanomaterials and enables more efficient chemotherapy against drug-resistant cancers.
基金the Natural Sciences and Engineering Council (NSERC) of Canada for strong and sustained support of his research
文摘Volatile organic solvents were considered to have little influence on the synthesis of mesostructured materials through evaporation-induced self-assembly(EISA),because upon evaporation they leave the sol and hence do not interfere with the self-assembly process.We show here that the choice of solvent is crucial in the synthesis of thin films of phenylene-bridged periodic mesoporous organosilica(benzene PMO).Methanol is found to be a better solvent for the synthesis of thin films,whereas ethanol favors the formation of(HO)3Si-C6H4-Si(OH)3 crystals,the identity and structure of which is established by X-ray diffraction.A ternary reactant composition diagram is designed to visualize the relationship among multiple synthesis experiments and to guide the interpretation of experimental results and optimization of the quality of the periodic mesoporous organosilica film.Our study highlights the importance of solvent choice,a factor often neglected in EISA.We expect it to inspire researchers to explore the effect of solvent in designing the synthesis of mesoporous materials.
基金financial support from the Natural Science Foundation of Jiangsu Province (Nos. BK20160017 and BK20160610)the National Natural Science Foundation of China (Nos. 21603106, 51822202 and 51772050)+3 种基金the State Key Laboratory of Analytical Chemistry for Life Science (No. 5431ZZXM1717)Shanghai Rising-Star Program (No. 18QA1400100)Youth Topnotch Talent Support Program of ShanghaiDHU Distinguished Young Professor Program and Fundamental Research Funds for the Central Universities
文摘The stability of periodic mesoporous organosilica(PMO) nanoparticles in physiological solutions greatly affects their potential biomedical applications. Herein, thioether-bridged PMO nanospheres with a diameter of 61 nm are synthesized. Then, the thioether-bridged PMO nanospheres are modified with different molecular weighted polyethylene glycol(PEG) via click reaction for the first time. FI-IR and thermogravimetric analysis confirm the successful modification of PEG on the PMO. The influence of PEG molecular weight on the dispersity and stability of the PMO-PEG in phosphate buffer(PBS) and Dulbecco's modified Eagle's medium(DMEM) is studied. The results show that the PEG coating increases the stability and dispersity of PMO in the biological solutions. The PMO-PEG1K, PMO-PEG2K, and PMOPEG5K have better stability in PBS solution. The PMO-PEG2K shows best stability and dispersity in DMEM. Over all, this work provides important method and knowledge to guide the modification of PMO for biomedical
基金supported by the National Natural Science Foundation of China (Grant No. 20621063)the National Basic Research Program of China (Grant No. 2009CB623503)
文摘The integration of organic and inorganic fragments within the pore walls of the periodic mesoporous organosilicas (PMOs) represents one of the recent breakthroughs in material science. The resulting PMOs are promising materials for applications in such areas as catalysis, adsorption, separation and drug-delivery. We summarize here the recent progress made in the synthesis of PMOs with hierarchical structures and large functional groups, with special emphasis on the chiral mesoporous organosilicas and their potential applications as novel chiral solids in heterogeneous asymmetric catalysis.
基金financially supported by the National Key Research and Development Program of China(Nos.2017YFA0205301,2017YFA0205302)the Key Research and Development Program of Jiangsu(No.BE2018732)+2 种基金the National Natural Science Foundation of China(Nos.81971675,21603106)the Natural Science Foundation of Jiangsu Province(No.BK20160017)the State Key Laboratory of Analytical Chemistry for Life Science(No.5431ZZXM1717)。
文摘Multishelled hollow structures have drawn increasing interest because of their peculiar compartmentation environments and physicochemical properties.In this work,deformable double-shelled hollow mesoporous o rganosilica nanocapsules(DDHMONs)were succes s fully synthesized by a multi-interfacial etching strategy.The obtained DDHMONs have a double-shelled structure with aninorganic-organic hybrid framework,a uniform outer layer(~320 nm)and inner layer(~180 nm),ordered mesochannels(~2.21 nm),and a large specific surface area(~1233 m^(2)/g).In vitro toxicity tests show that the DDHMONs have excellent biocompatibility when coincubated with human breast cancer cells.In addition,the anti cancer substance doxorubicin(DOX)can be highly loaded in DDHMONs(~335μg/mg).The results from flow cytometry together with confocal laser scanning microscopy show that DOX can be efficiently delivered into MCF-7 cells by DDHMONs,thus improving chemotherapeutic efficiency and demonstrating that DDHMONs have potential nanomedicine applications as anticancer agents.
文摘Volatile organic solvents were considered to have little influence on the synthesis of mesostructured materials through evaporation-induced self-assembly(EISA),because upon evaporation they leave the sol and hence do not interfere with the self-assembly process.We show here that the choice of solvent is crucial in the synthesis of thin films of phenylene-bridged periodic mesoporous organosilica(benzene PMO).Methanol is found to be a better solvent for the synthesis of thin films,whereas ethanol favors the formation of(HO)3Si-C6H4-Si(OH)3 crystals,the identity and structure of which is established by X-ray diffraction.A ternary reactant composition diagram is designed to visualize the relationship among multiple synthesis experiments and to guide the interpretation of experimental results and optimization of the quality of the periodic mesoporous organosilica film.Our study highlights the importance of solvent choice,a factor often neglected in EISA.We expect it to inspire researchers to explore the effect of solvent in designing the synthesis of mesoporous materials.
