Transarterial chemoembolization(TACE)has been widely introduced to treat hepatocellular carcinoma(HCC)especially for unresectable patients for decades.However,TACE evokes an angiogenic response due to the secretion of...Transarterial chemoembolization(TACE)has been widely introduced to treat hepatocellular carcinoma(HCC)especially for unresectable patients for decades.However,TACE evokes an angiogenic response due to the secretion of vascular endothelial growth factor(VEGF),resulting in the formation of new blood vessels and eventually tumor recurrence.Thus,we aimed to develop regorafenib(REGO)-loaded poly(lactide-co-glycolide)(PLGA)microspheres that enabled localized and sustained drug delivery to limit proangiogenic responses following TACE in HCC treatment.REGO-loaded PLGA microspheres were prepared using the emulsion-solvent evaporation/extraction method,in which DMF was selected as an organic phase co-solvent.Accordingly,we optimized the proportion of DMF,which the optimal ratio to DCM was 1:9(v/v).After preparation,the microspheres provided high drug loading capacity of 28.6%,high loading efficiency of 91.5%,and the average particle size of 149μm for TACE.IR spectra and XRD were applied to confirming sufficient REGO entrapment.The in vitro release profiles demonstrated sustained drug release of microspheres for more than 30 d To confirm the role of REGO-loaded microspheres in TACE,the cell cytotoxic activity on HepG2 cells and anti-angiogenic effects in HUVECs Tube-formation assay were studied in combination with miriplatin.Moreover,the microspheres indicated the potential of antagonizing miriplatin resistance of HepG2 cells in vitro.Pharmacokinetics preliminary studies exhibited that REGO could be sustainably released from microspheres for more than 30d after TACE in vivo.In vivo anti-tumor efficacy was further determined in HepG2 xenograft tumor mouse model,demonstrating that REGO microspheres could improve the antitumor efficacy of miriplatin remarkably compared with miriplatin monotherapy.In conclusion,the obtained REGO microspheres demonstrated promising therapeutic effects against HCC when combined with TACE.展开更多
Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utili...Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utilization of HOF-based mixed-matrix membrane for CO_(2) separation.HOF-21,a unique metallo-hydrogen-bonded organic framework material,was designed and processed into nanofillers via amine modulator,uniformly dispersing with Pebax polymer.Featured with the mix-bonded framework,HOF-21 possessed moderate pore size of 0.35 nm and displayed excellent stability under humid feed gas.The chemical functions of multiple binding sites and continuous hydrogen-bonded network jointly facilitated the mass transport of CO_(2).The resulting HOF-21 mixed-matrix membrane exhibited a permeability above 750 Barrer,a selectivity of~40 for CO_(2)/CH_(4) and~60 for CO_(2)/N_(2),surpassing the 2008 Robeson upper bound.This work enlarges the family of mixed-matrix membranes and lays the foundation for HOF membrane development.展开更多
Chloromethylated mesoporous silica nanoparticles （CM MSN） were synthesized through co-condensation of tetraethoxysilane and （chloro） phenyltrimethoxysilane precursors using hexadecyl trimethyl ammonium bromide as ...Chloromethylated mesoporous silica nanoparticles （CM MSN） were synthesized through co-condensation of tetraethoxysilane and （chloro） phenyltrimethoxysilane precursors using hexadecyl trimethyl ammonium bromide as template.With the addition of the particles into chloromethylated poly （ether ether ketone） （PEEK）,the hybrid membranes were prepared by a solution-casting method after complete quatemization of the casting solution.The successful synthesis of the particles was verified by transmission electron microscopy,X-ray diffraction and Fourier transform infrared spectroscopy while the effect of CM MSN incorporation on membrane performance including thermal stability,mechanical strength and hydroxide conductivity was investigated by thermal gravimetric analysis,electronic stretching machine,alternating-current impedance and so on.Owing to the large pore volume and high surface area of the particles,the hybrid membranes exhibited enhanced hydroxide conductivity （88.7% increase at 60 ℃,100% RH with 5.0 wt% filling content） due to an increase in ion concentration and optimization of the channel morphology.Besides,higher mechanical strength,thermal and dimensional stability of hybrid membranes were obtained compared with those of the imidazolium PEEK membrane.展开更多
CONSPECTUS:Membrane technology plays an increasingly important role for sustainable development of our society owing to its huge capability to tackle the energy crisis,water scarcity,environmental pollution,and carbon...CONSPECTUS:Membrane technology plays an increasingly important role for sustainable development of our society owing to its huge capability to tackle the energy crisis,water scarcity,environmental pollution,and carbon neutrality.To fully unlock the potential of membranes,it is in high demand to develop advanced membrane materials that significantly outperform conventional polymer membrane materials in separation performance and longterm stability.The emergent covalent organic frameworks(COFs)have been deemed as potent membrane materials because of their unique structure and properties in comparison with polymers,zeolites,and metal organic frameworks(MOFs).(i)First,the highly tunable and ordered crystalline pore structure,high porosity,and excellent stability render COFs an ideal membrane material.COFs are more stable than MOFs and,in some cases,are even more stable than zeolite.Moreover,it is easier to introduce functional groups into the COF nanochannels compared with zeolite and MOFs.Further,COFs are ideally suitable for constructing ordered nanochannels with size in the range of 0.6−3 nm which is difficult to be realized by other materials.(ii)Second,along with the unremitting discovery of diverse platform chemistries such as reticular chemistry,the in-depth understanding of nucleation/growth mechanisms of COFs as well as the rapid progress of manufacturing technologies and various routes to fabricating COF membranes with favorable physical and chemical structures inside the nanochannels are being actively exploited.COFs generally show better membrane-formation ability owing to their abundant 2D structures,which make it easier to fabricate ultrathin membranes compared with zeolite and MOFs.(iii)Last,a great number of COF membranes exhibit exceptionally high separation performance and stability,establishing their position as the next-generation membranes.In this Account,we discuss three types of engineering toward COF membranes based on Schiff base reaction for high-efficiency molecules/ion separations,i.e.,reticular engineering,crystal engineering,and nanochannel engineering.First,we discuss the reticular engineering of COF membranes with a focus on the bond types,chemical structure,and architecture design.The membraneformation ability and methods of COFs are also analyzed.Second,we discuss the crystal engineering of COF membranes with a focus on the key thermodynamical and kinetic factors to drive the disorder-to-order transition where we attempt to dig deeper into the crystallization habit of COF membranes.Third,we discuss nanochannel engineering of COF membranes with a focus on the construction and modulation of the physical and chemical microenvironments of nanochannels for efficient and selective transport of molecules/ions.Last,we conclude with a perspective on the opportunities and major challenges in the R&D of COF membranes,targeting at identifying the future directions.展开更多
With well-defined channels and tunable functionality, metal-organic frameworks （MOFs） have inspired the design of a new class of ion-conductive compounds. In contrast to the extensive studies on proton- conductive M...With well-defined channels and tunable functionality, metal-organic frameworks （MOFs） have inspired the design of a new class of ion-conductive compounds. In contrast to the extensive studies on proton- conductive MOFs and related membranes attractive for fuel cells, rare reports focus on MOFs in preparation of anion exchange membranes. In this study, chloromethylated MIL-101 （Cr） was prepared and incor- porated into chloromethylated poly （ether ether ketone） （PEEK） as a multifunctional filler to prepare imidazolium PEEK/imidazolium MIL-101（Cr） （ImPEEK/ImMIL-101（Cr）） anion exchange membrane after synchronous quaternization. The successful synthesis and chloromethylation of MIL-101（Cr） were veri- fied by transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy while the enhanced performance of composite membranes in hydroxide conductivity, mechanical strength and dimensional stability were evaluated by alternating-current impedance, electronic stretching machine and measurement of swelling ratio. Specifically, incorporating 5.0wt% ImMIL-101（Cr） afforded a 71.4% increase in hydroxide conductivity at 20℃, 100% RH. Besides, the composite membranes exhibited enhanced dimensional stability and mechanical strength due to the rigid framework of ImMIL- 101（Cr）. At room temperature and the ImM1L-101（Cr） content of 10wt%, the swelling ratio of the ImPEEK/lmMIL-101（Cr） was 70.04% lower while the tensile strength was 47.5% higher than that of the pure membrane.展开更多
Polymers of intrinsic microporosity(PIMs),integrating unique microporous structure and solution-processability,are one class of the most promising membrane materials for energy-efficient gas separations.However,the mi...Polymers of intrinsic microporosity(PIMs),integrating unique microporous structure and solution-processability,are one class of the most promising membrane materials for energy-efficient gas separations.However,the micropores generated from inefficient chain packing often exhibit wide pore size distribution,making it very challenging to achieve efficient olefin/paraffin separations.Here,we propose a coordination-driven reconstruction(CDR)strategy,where metal ions are incorporated into amidoxime-functionalized PIM-1(AO-PIM)to in situ generate coordination crosslinking networks.By varying the type and content of metal ions,the resulting crosslinking structures can be optimized,and the molecular sieving capability of PIM membranes can be dramatically enhanced.Particularly,the introduction of alkali or alkaline earth metals renders more precise micropores contributing to superior C3H6/C3H8 separation performance.K+incorporated AO-PIM membranes exhibit a high ideal C3H6/C3H8 selectivity of 50,surpassing almost all the reported polymer membranes.Moreover,the coordination crosslinking structure significantly improves the membrane stability under higher pressure as well as the plasticization resistant performance.We envision that this straightforward and generic CDR strategy could potentially unlock the potentials of PIMs for olefin/paraffin separations and many other challenging gas separations.展开更多
基金the National Natural Science Foundation of China(81872819 and 81573379)Natural Science Foundation of Jiangsu Province(BK20171390)+2 种基金supported by"Double First-Class"University project(CPU2018GY26)the Project of State Key Laboratory of Natural Medicines,China Pharmaceutical University(SKLNMZZCX201816)the financial support from Development Funds for Priority Academic Programs in Jiangsu Higher Education Institutions。
文摘Transarterial chemoembolization(TACE)has been widely introduced to treat hepatocellular carcinoma(HCC)especially for unresectable patients for decades.However,TACE evokes an angiogenic response due to the secretion of vascular endothelial growth factor(VEGF),resulting in the formation of new blood vessels and eventually tumor recurrence.Thus,we aimed to develop regorafenib(REGO)-loaded poly(lactide-co-glycolide)(PLGA)microspheres that enabled localized and sustained drug delivery to limit proangiogenic responses following TACE in HCC treatment.REGO-loaded PLGA microspheres were prepared using the emulsion-solvent evaporation/extraction method,in which DMF was selected as an organic phase co-solvent.Accordingly,we optimized the proportion of DMF,which the optimal ratio to DCM was 1:9(v/v).After preparation,the microspheres provided high drug loading capacity of 28.6%,high loading efficiency of 91.5%,and the average particle size of 149μm for TACE.IR spectra and XRD were applied to confirming sufficient REGO entrapment.The in vitro release profiles demonstrated sustained drug release of microspheres for more than 30 d To confirm the role of REGO-loaded microspheres in TACE,the cell cytotoxic activity on HepG2 cells and anti-angiogenic effects in HUVECs Tube-formation assay were studied in combination with miriplatin.Moreover,the microspheres indicated the potential of antagonizing miriplatin resistance of HepG2 cells in vitro.Pharmacokinetics preliminary studies exhibited that REGO could be sustainably released from microspheres for more than 30d after TACE in vivo.In vivo anti-tumor efficacy was further determined in HepG2 xenograft tumor mouse model,demonstrating that REGO microspheres could improve the antitumor efficacy of miriplatin remarkably compared with miriplatin monotherapy.In conclusion,the obtained REGO microspheres demonstrated promising therapeutic effects against HCC when combined with TACE.
基金support from National Key Research and Development Program of China(No.2021YFB3802200)National Natural Science Foundation of China(No.U20B2023,22208238,U1732120)+1 种基金the Haihe Laboratory of Sustainable Chemical TransformationsNingbo Natural Science Foundation(No.2021J004).
文摘Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utilization of HOF-based mixed-matrix membrane for CO_(2) separation.HOF-21,a unique metallo-hydrogen-bonded organic framework material,was designed and processed into nanofillers via amine modulator,uniformly dispersing with Pebax polymer.Featured with the mix-bonded framework,HOF-21 possessed moderate pore size of 0.35 nm and displayed excellent stability under humid feed gas.The chemical functions of multiple binding sites and continuous hydrogen-bonded network jointly facilitated the mass transport of CO_(2).The resulting HOF-21 mixed-matrix membrane exhibited a permeability above 750 Barrer,a selectivity of~40 for CO_(2)/CH_(4) and~60 for CO_(2)/N_(2),surpassing the 2008 Robeson upper bound.This work enlarges the family of mixed-matrix membranes and lays the foundation for HOF membrane development.
文摘Chloromethylated mesoporous silica nanoparticles （CM MSN） were synthesized through co-condensation of tetraethoxysilane and （chloro） phenyltrimethoxysilane precursors using hexadecyl trimethyl ammonium bromide as template.With the addition of the particles into chloromethylated poly （ether ether ketone） （PEEK）,the hybrid membranes were prepared by a solution-casting method after complete quatemization of the casting solution.The successful synthesis of the particles was verified by transmission electron microscopy,X-ray diffraction and Fourier transform infrared spectroscopy while the effect of CM MSN incorporation on membrane performance including thermal stability,mechanical strength and hydroxide conductivity was investigated by thermal gravimetric analysis,electronic stretching machine,alternating-current impedance and so on.Owing to the large pore volume and high surface area of the particles,the hybrid membranes exhibited enhanced hydroxide conductivity （88.7% increase at 60 ℃,100% RH with 5.0 wt% filling content） due to an increase in ion concentration and optimization of the channel morphology.Besides,higher mechanical strength,thermal and dimensional stability of hybrid membranes were obtained compared with those of the imidazolium PEEK membrane.
基金funded by the National Natural Science Foundation of China(21838008,21621004,21878215,and 91934302)Program of Introducing Talents of Discipline to Universities(No.BP0618007).
文摘CONSPECTUS:Membrane technology plays an increasingly important role for sustainable development of our society owing to its huge capability to tackle the energy crisis,water scarcity,environmental pollution,and carbon neutrality.To fully unlock the potential of membranes,it is in high demand to develop advanced membrane materials that significantly outperform conventional polymer membrane materials in separation performance and longterm stability.The emergent covalent organic frameworks(COFs)have been deemed as potent membrane materials because of their unique structure and properties in comparison with polymers,zeolites,and metal organic frameworks(MOFs).(i)First,the highly tunable and ordered crystalline pore structure,high porosity,and excellent stability render COFs an ideal membrane material.COFs are more stable than MOFs and,in some cases,are even more stable than zeolite.Moreover,it is easier to introduce functional groups into the COF nanochannels compared with zeolite and MOFs.Further,COFs are ideally suitable for constructing ordered nanochannels with size in the range of 0.6−3 nm which is difficult to be realized by other materials.(ii)Second,along with the unremitting discovery of diverse platform chemistries such as reticular chemistry,the in-depth understanding of nucleation/growth mechanisms of COFs as well as the rapid progress of manufacturing technologies and various routes to fabricating COF membranes with favorable physical and chemical structures inside the nanochannels are being actively exploited.COFs generally show better membrane-formation ability owing to their abundant 2D structures,which make it easier to fabricate ultrathin membranes compared with zeolite and MOFs.(iii)Last,a great number of COF membranes exhibit exceptionally high separation performance and stability,establishing their position as the next-generation membranes.In this Account,we discuss three types of engineering toward COF membranes based on Schiff base reaction for high-efficiency molecules/ion separations,i.e.,reticular engineering,crystal engineering,and nanochannel engineering.First,we discuss the reticular engineering of COF membranes with a focus on the bond types,chemical structure,and architecture design.The membraneformation ability and methods of COFs are also analyzed.Second,we discuss the crystal engineering of COF membranes with a focus on the key thermodynamical and kinetic factors to drive the disorder-to-order transition where we attempt to dig deeper into the crystallization habit of COF membranes.Third,we discuss nanochannel engineering of COF membranes with a focus on the construction and modulation of the physical and chemical microenvironments of nanochannels for efficient and selective transport of molecules/ions.Last,we conclude with a perspective on the opportunities and major challenges in the R&D of COF membranes,targeting at identifying the future directions.
基金supported by the National Science Fund for Distinguished Young Scholars(21125627)the National Natural Science Founds of China(21490583 and 21621004)the Program of Introducing Talents of Discipline to Universities(B06006).
文摘With well-defined channels and tunable functionality, metal-organic frameworks （MOFs） have inspired the design of a new class of ion-conductive compounds. In contrast to the extensive studies on proton- conductive MOFs and related membranes attractive for fuel cells, rare reports focus on MOFs in preparation of anion exchange membranes. In this study, chloromethylated MIL-101 （Cr） was prepared and incor- porated into chloromethylated poly （ether ether ketone） （PEEK） as a multifunctional filler to prepare imidazolium PEEK/imidazolium MIL-101（Cr） （ImPEEK/ImMIL-101（Cr）） anion exchange membrane after synchronous quaternization. The successful synthesis and chloromethylation of MIL-101（Cr） were veri- fied by transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy while the enhanced performance of composite membranes in hydroxide conductivity, mechanical strength and dimensional stability were evaluated by alternating-current impedance, electronic stretching machine and measurement of swelling ratio. Specifically, incorporating 5.0wt% ImMIL-101（Cr） afforded a 71.4% increase in hydroxide conductivity at 20℃, 100% RH. Besides, the composite membranes exhibited enhanced dimensional stability and mechanical strength due to the rigid framework of ImMIL- 101（Cr）. At room temperature and the ImM1L-101（Cr） content of 10wt%, the swelling ratio of the ImPEEK/lmMIL-101（Cr） was 70.04% lower while the tensile strength was 47.5% higher than that of the pure membrane.
基金support from the National Natural Science Foundation of China(21838008,U20B2023,21621004,and 21878215)National Key R&D Program of China(2017YFB0603400)+1 种基金the Chemistry and Chemical Engineering Guangdong Laboratory(Grant No.1922013)Program of Introducing Talents of Discipline to Universities(No.BP0618007)。
文摘Polymers of intrinsic microporosity(PIMs),integrating unique microporous structure and solution-processability,are one class of the most promising membrane materials for energy-efficient gas separations.However,the micropores generated from inefficient chain packing often exhibit wide pore size distribution,making it very challenging to achieve efficient olefin/paraffin separations.Here,we propose a coordination-driven reconstruction(CDR)strategy,where metal ions are incorporated into amidoxime-functionalized PIM-1(AO-PIM)to in situ generate coordination crosslinking networks.By varying the type and content of metal ions,the resulting crosslinking structures can be optimized,and the molecular sieving capability of PIM membranes can be dramatically enhanced.Particularly,the introduction of alkali or alkaline earth metals renders more precise micropores contributing to superior C3H6/C3H8 separation performance.K+incorporated AO-PIM membranes exhibit a high ideal C3H6/C3H8 selectivity of 50,surpassing almost all the reported polymer membranes.Moreover,the coordination crosslinking structure significantly improves the membrane stability under higher pressure as well as the plasticization resistant performance.We envision that this straightforward and generic CDR strategy could potentially unlock the potentials of PIMs for olefin/paraffin separations and many other challenging gas separations.
