Click reactions are not specific reactions, but they are a way of generating products that follow examples in nature by joining small moieties, with each other producing a huge molecule in a good yield. The mind of th...Click reactions are not specific reactions, but they are a way of generating products that follow examples in nature by joining small moieties, with each other producing a huge molecule in a good yield. The mind of that reaction is used in biomolecules synthesis, pharmacological and various biometric applications. The first Click reaction is the Copper compounds-catalyzed reaction of an azide with an alkyne （CuAAC）, this copper-catalyzed ＂click＂ does not require legands on the metal but the metal oxides also can accelerate the reactions. For enhancement the products of Click reactions we were replacing the copper compounds in a classical reaction by the prepared nanocopper compound （NPs）. And measure the consumption of starting material. Behind the evolution is the catalytic effect of nanocopper compounding （NPs） on （H2O2）. Owing to the huge surface area of nanocopper compound （NPs）, it was found that： the （NPs） can speed up decomposition of H2O2, also can accelerate the classical click reaction.展开更多
Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes.Polyprodrug micelles can cross-link with other hydrophobic drugs through noncovalent bonds,which ha...Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes.Polyprodrug micelles can cross-link with other hydrophobic drugs through noncovalent bonds,which has the advantage of fixed structure and avoids the use of chemical cross-linking agents.In this study,we prepared a polyprodrug with hydrophobic curcumin(CUR)and hydrophilic poly(ethylene glycol)(PEG)in the main chain through a click reaction between CUR derivatives containing azide groups and di-alkynly-capped PEG.Due to the presence of benzene rings in the structure of CUR,the polyprodrug can form non-covalent cross-linked nanoparticles(NCCL-CUR NPs)through hydrophobic andπ-πstacking interaction.The structure,molecular weight,and self-assembly properties of the polyprodrug were characterized.The anti-cancer drug camptothecin(CPT)was encapsulated in the polyprodrug nanoparticles,producing dual-drug-loaded nanoparticles(abbreviated as CPT@NCCL-CUR NPs).The test results indicate that the NPs have reductive responsiveness and can release the original drugs CUR and CPT in phosphate buffer(PB)solution containing glutathione(GSH),while remaining stability in physiological environment.Cell and in vivo experiments further demonstrate that the dualdrug-loaded CPT@NCCL-CUR NPs can inhibit the growth of tumor through synergistic effects.This work provides a valuable approach for the preparation of amphiphilic polyprodrug with anti-tumor CUR as the backbone,and the stable dual-drug-loaded NPs containing both CUR and CPT through non-covalent cross-linking for synergistic therapy.展开更多
Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this w...Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this work,we reported the synthesis of a novel porous organic polymer,FOSU-POP-1 for the separation of CH_(4)/C_(2)H_(6)/C_(3)H_(8).The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer-Emmett-Teller(BET)surface area of 1038 m^(2)·g^(-1).Exhibiting stronger affinity towards C_(3)H_(8) and C_(2)H_(6) than CH_(4),2.85 mmol·g^(-1) for C_(3)H_(8) and 2.14 mmol·g^(-1) for C_(2)H_(6) were achieved on the FOSU-POP-1 at 0.1 MPa,298 K,with an ideal adsorbed solution theory selectivity of 227 for C_(3)H_(8)/CH_(4).The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH_(4)/C_(2)H_(6)/C_(3)H_(8) ternary mixture.The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C_(3)H_(8) and C_(2)H_(6).This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH_(4)/C_(2)H_(6)/C_(3)H_(8) mixture.展开更多
A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important priv...A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important privileged heterocyclic pharmacophores which cannot be accessed by a traditional click reaction.Radical interception of cuprate-triazole,the key reaction intermediate formed in situ,is an important feature of this process.展开更多
A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisopren...A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisoprene was synthesized by anionic polymerization using n-butyl lithium as initiator,and the pendant hydroxyl groups were introduced by the thiol-ene reaction of mercaptoethanol with the double bond of 1,2-addition units of PI backbone in the presence of radical initiator azobisisobutyronitrile. Isocyanate end group capped poly（ethylene glycol）（mPEG-NCO） was grafted onto the PI backbone through alcoholisocyanate reaction between the pendant hydroxyl groups and isocyanate group of mPEG-NCO.The structure of the graft copolymer were characterized and confirmed by means of size-exclusion chromatography,~1H NMR and FTIR spectroscopy.展开更多
Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance,dimensional stability,and unique sensitivity to external stimuli.In this work,we synthesized thiol-functiona...Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance,dimensional stability,and unique sensitivity to external stimuli.In this work,we synthesized thiol-functionalized tetraphenylethylene(TPE)and constructed polymer gels through thiol-ene click reaction.The synthetic process of the polymer gels could be monitored by fluorescence emission of TPE moieties based on aggregation-induced emission mechanism.In addition,due to the dual redox-and acid responsiveness of the polymer gels,in the presence of dithiothreitol and trifluoroacetic acid,fluorescence quenching of the polymer gels can be observed.This stimuli-responsive characteristics endows the polymer gels with potential applications in fluorescent sensing and imaging,cancer diagnosis and selfhealing materials.展开更多
The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling ...The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling reaction between the binding site and the reporter. In addition, the formation 1,4-disubstituted1,2,3-triazole linker shows a high binding affinity toward both anions and metal ions. Recently researches revealed this reaction is also an efficient tool to form rigid or shape-persistent, preorganized macrocyclic species. This review summarized the recent advances in click derived macrocyclic receptors for recognition of anion, metal ion and ions pair.展开更多
Directed peptides C-terminal modification enabled by the engineered biomolecular catalyst-peptide amidase 12 B has been achieved via computational protein engineering. The engineered enzyme exhibits great promising po...Directed peptides C-terminal modification enabled by the engineered biomolecular catalyst-peptide amidase 12 B has been achieved via computational protein engineering. The engineered enzyme exhibits great promising potential in the C-terminal modification of opioid peptides using prop-2-yn-1-amine(PYA) or prop-2-en-l-amine(PEA) as the nucleophile. A variety of opioid peptides could be readily functionalized at the C-terminal chain in high yield in a mild and selective manner. Notably, modified opioid peptides bearing alkynyl moiety could be further functionalized through well-established click reaction.展开更多
Two tetrathiafulvalene-calix[4]arene assemblies （TTF-calix-1 and TFF-calix-2） have been synthesized by the click reaction. Both their cyclic voltammograms show, as expected, two one-electron quasi- reversible redox ...Two tetrathiafulvalene-calix[4]arene assemblies （TTF-calix-1 and TFF-calix-2） have been synthesized by the click reaction. Both their cyclic voltammograms show, as expected, two one-electron quasi- reversible redox behavior. The UV-vis absorption spectra studies show that these two assemblies undergo progressive oxidation at the TFF moiety in presence of increasing amounts of Cu2＋ or Hg2＋. Moreover, the absorption studies show intermolecular electron transfer between compounds TrF-calix- I or TI＇F-calix-2 and p-chloranil may be promoted by specific metal ions such as Pb2＋, Sc3＋ etc.展开更多
In this work, 1,4-bis(4-phenyl-1,2,3-triazole)benzene, 1,3-bis(4-phenyl-1,2,3-triazole)propane, bis(1-phenyl-1,2,3-triazole)-methylphenylsilane, and 1-ally-4-phenyl-1,2,3-triazole have been designed and synthesized vi...In this work, 1,4-bis(4-phenyl-1,2,3-triazole)benzene, 1,3-bis(4-phenyl-1,2,3-triazole)propane, bis(1-phenyl-1,2,3-triazole)-methylphenylsilane, and 1-ally-4-phenyl-1,2,3-triazole have been designed and synthesized via Click reaction. Fourier transform infrared spectroscopy(FT-IR) and nuclear magnetic resonance spectroscopy(NMR) were used to confirm the compounds' structures. The effect of silicon atom on the optical properties has also been studied. The UV-vis absorption wavelength of silicon-containing compound is about ca. 10 nm red-shifted when compared with that of other three compounds. The fluorescence emission bands of the compounds in CHCl_3 solutions were observed around ca. 440 nm. And the luminescent coordination compound, namely [AgL1?NO_3?3H_2O]n, based on the ligand 1-allyl-4-phenyl-1,2,3-triazole has been prepared. In addition, this complex exhibits a 1 D chain structure. The crystal structure has been determined by single-crystal X-ray diffraction, and the optical properties have been investigated by fluorescence spectrum. In summary, our work may provide new materials with luminescent property which is potentially useful in material fields.展开更多
Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic am...Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.展开更多
X-ray imaging functionalization of biodegradable polyesters is a great demand and challenge in biomedical applications.In this work,a strategy of in-chain functionalization through the combination of ring opening copo...X-ray imaging functionalization of biodegradable polyesters is a great demand and challenge in biomedical applications.In this work,a strategy of in-chain functionalization through the combination of ring opening copolymerization and oxime "Click" postfunctionalization was developed towards X-ray opaque polylactide copolymers.A functionalized cyclic carbonate was first synthesized and used as comonomer of polylactide copolymers,which were subjected to postfunctionalization of oxime "Click" reaction towards iodinated polylactide copolymers.The chemical structure and physical properties of the target products were traced and confirmed.In vitro cytotoxicity evaluation with 3T3-Swiss albino by Alamar blue demonstrated a low cytotoxicity.The X-ray radiopacity was analyzed by Micro-CT and quantified by Hounsfield Units value,which could be tailorable by the feedstock.It is a promising X-ray visible implantable biomaterial in biomedical applications.展开更多
Anion-exchange membranes(AEMs)with high conductivity and stability are essential components of hydrogen related water electrolysis and fuel cell applications.During the past decades,polynorbornene(PNB)-based AEMs have...Anion-exchange membranes(AEMs)with high conductivity and stability are essential components of hydrogen related water electrolysis and fuel cell applications.During the past decades,polynorbornene(PNB)-based AEMs have shown excellent performance due to their saturated all-carbon-based backbones and diverse strategies to prepare cross-linked membranes.However,nearly all previously reported PNB-based AEMs rely on the alkyl-substituted norbornene monomers,whose low-yielding synthesis leads to high-cost of the AEMs.In addition,the crosslinked PNB-based AEMs usually suffered from mechanical brittleness.Herein,we propose a novel semi-interpenetrating polymer network(s-IPN)strategy to simultaneously enhance mechanical modulus and ionic conductivity,while using commercial 5-vinyl-2-norbornene(VNB)as the single norbornene derivatives to prepare high-performance AEMs.A diallylphenol quaternary ammonium salt was used for photo-induced crosslinking with poly-VNB and various dithiols to produce AEMs with s-IPN structures.The resultant membranes have excellent hydroxide conductivities and alkaline stability in 1 mol/L KOH at 80℃,and are successfully applied in alkaline anion-exchange membrane water electrolyzers to stably operateforover150h.展开更多
In this study,we unveil a conceptual technology for fabricating artificial metalloenzymes(ArMs)by deeply integrating hemin into protein scaffolds via a protein refolding process,a method that transcends the convention...In this study,we unveil a conceptual technology for fabricating artificial metalloenzymes(ArMs)by deeply integrating hemin into protein scaffolds via a protein refolding process,a method that transcends the conventional scope of surface-level modifications.Our approach involves denaturing proteins,such as benzaldehyde lyase,green fluorescent protein,and Candida antarctica lipase B,to expose extensive reactive amino acid residues,which are then intricately linked with hemin using orthogonal click reactions,followed by protein refolding.This process not only retains the proteins’structural integrity but expands proteins’functionality.The most notable outcome of this methodology is the hemin@BAL variant,which demonstrated a remarkable 83.7%conversion rate in cyclopropanation reactions,far surpassing the capabilities of traditional hemin-based catalysis in water.This success highlights the significant role of protein structure in the ArMs’activity and marks a substantial leap forward in chemical modification of proteins.Our findings suggest vast potentials of protein refolding approaches for ArMs across various catalytic applications,paving the way for future advancements in synthetic biology and synthetic chemistry.展开更多
With their high drug-loading capacity and enhanced permeability and retention(EPR)effects,nanoparticles possess significant potential for the diagnosis and treatment of tumors.However,unlike active targeting,the compl...With their high drug-loading capacity and enhanced permeability and retention(EPR)effects,nanoparticles possess significant potential for the diagnosis and treatment of tumors.However,unlike active targeting,the complex tumor microenvironment influences the passive accumulation of nanoparticles in tumor areas.Hence,it is necessary to actively control the behavior of nanoparticles when they enter the tumor microenvironment.By utilizing biocompatible and efficient click reactions,the aggregation of nanoparticles at the tumor site can be controlled,thereby enhancing nanoparticle accumulation at the target location with improved imaging signals and enhanced tumor-inhibitory effects.Herein,we introduce and classify in situ nanoparticle aggregation for biomedical imaging and therapeutic applications induced by four types of common click reactions:coppercatalyzed azide–alkyne cycloaddition(CuAAC),strain-promoted azide–alkyne cycloaddition(SPAAC),click condensation between 2-cyanobenzothiazole(CBT)and cysteine(Cys),and inverse electron-demand Diels–Alder(iEDDA).Furthermore,we summarize the main strategies of these click reaction-based nanoparticle aggregation approaches.Finally,we discuss the advantages and disadvantages of click reaction-triggered aggregation and analyze future trends.展开更多
Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolym...Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.展开更多
An efficient green protocol for the preparation 3,4,6-trisubstituted 2-pyridone of employing a condensation reaction of cyanoacetamide and acetylacetone in the presence of KAl（SO4）2·12H2O in water has been desc...An efficient green protocol for the preparation 3,4,6-trisubstituted 2-pyridone of employing a condensation reaction of cyanoacetamide and acetylacetone in the presence of KAl（SO4）2·12H2O in water has been described. The present procedure offers advantage such as shorter reaction time, simple workup, and excellent yields.展开更多
A novel biodegradable copolymer, poly（5,5-dibromomethyltrimethylene carbonate-co-ε-caprolactone） （poly（DBTC-co-CL）） with pendant bromine groups, was synthesized via ring-opening polymerization （ROP） of ε-cap...A novel biodegradable copolymer, poly（5,5-dibromomethyltrimethylene carbonate-co-ε-caprolactone） （poly（DBTC-co-CL）） with pendant bromine groups, was synthesized via ring-opening polymerization （ROP） of ε-caprolactone （CL） and 5,5- dibromomethyltrimethylene carbonate （DBTC） using stannous octoate （Sn（Oct）2） as catalyst. Then the pendant bromine groups were completely converted into azide form, which permitted ＂click＂ reaction with alkyne-terminated polyethylene （A-PEG） by Huisgen 1,3-dipolar cycloadditions preparing biodegradable amphiphilic poly（DTC-co-CL）-g-PEG graft copolymer. The graft copolymer was characterized by nuclear magnetic resonance （NMR） and size-exclusion chromatography （SEC）.展开更多
Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperatu...Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu（OAc）2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a（C10H9N5O4） crystallizes in the triclinic system, space group P1 with a = 5.0894（9）, b = 8.9834（13）, c = 13.089（2） ？, α= 83.041（7）, β= 80.256（7）, γ=87.296（8）°, V = 585.24（16）？3, Z = 2, Mr = 263.22, crystal size（mm） = 0.37 × 0.20 ×0.18,（I 〉 2σ（I）） = 8557, 2493, 1229, Rint = 0.057. Compound 1b（C12H13N5O4） crystallizes in the monoclinic system, space group P21/c with a = 6.8854（5）, b = 21.783（2）, c = 9.3986（8） ？,β = 93.239（4）°, V = 1407.4（2）？3, Z = 4, Mr = 291.27, crystal size（mm） = 0.38 × 0.22 × 0.20,（I 〉 2σ（I）） = 11842, 3172, 1866, Rint = 0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.展开更多
The infection induced by implantation of biomedical materials may result from the biofilm formation after bacteria attachment.Hence,the antibiofilm surface coating represents a novel technique to improve the antibacte...The infection induced by implantation of biomedical materials may result from the biofilm formation after bacteria attachment.Hence,the antibiofilm surface coating represents a novel technique to improve the antibacterial activity of biomedical materials.The traditional antibiofilm surface coatings exhibited some disadvantages and provided a limited service life.In this work,we used polyethyleneimine grafted 3-maleimidopropionic acid(PEIM)and poly(acrylic acid)grafted 2-furfurylamine(PAAF)to achieve robust and self-healable crosslinked multilayer coatings,employing Layer-by-Layer(LbL)self-assembly technique and Diels-Alder reaction.Then,thiol-terminated poly((3-acrylamidopropyl)trimethylammonium chloride)(PAMPTMA-SH)was grafted onto the crosslinked multilayer coating by thiol-ene click reaction to form a novel multilayer coating(PEIM/PAAF)_(10)-PAMPTMA.We found that this coating showed robust and self-healable activity,and significantly inhibited the bacterial growth and biofilm formation after infection with Escherichia coli(E.coli)and Staphylococcus aureus(S.aureus)by in vitro and in vivo assays for 120 h.In addition,the multilayer coating did not induce significant hemolysis or affect the cell viability of red blood cells.In vivo studies also showed that(PEIM/PAAF)_(10)-PAMPTMA coating efficiently blocked the infiltration of inflammatory cells and gene expression in the mouse skin challenged with E coli or S.aureus.Taken together,these results showed that the prepared multilayer coating exhibited strong antibiofilm activity and provided a new strategy for the application of highly efficient antibiofilm surface coating of biomedical materials.展开更多
文摘Click reactions are not specific reactions, but they are a way of generating products that follow examples in nature by joining small moieties, with each other producing a huge molecule in a good yield. The mind of that reaction is used in biomolecules synthesis, pharmacological and various biometric applications. The first Click reaction is the Copper compounds-catalyzed reaction of an azide with an alkyne （CuAAC）, this copper-catalyzed ＂click＂ does not require legands on the metal but the metal oxides also can accelerate the reactions. For enhancement the products of Click reactions we were replacing the copper compounds in a classical reaction by the prepared nanocopper compound （NPs）. And measure the consumption of starting material. Behind the evolution is the catalytic effect of nanocopper compounding （NPs） on （H2O2）. Owing to the huge surface area of nanocopper compound （NPs）, it was found that： the （NPs） can speed up decomposition of H2O2, also can accelerate the classical click reaction.
基金supported by the National Natural Science Foundation of China(No.21975169)the Project Fund of the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions+2 种基金the Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function of Soochow Universitythe Research project of China Baoyuan Investment Co.,Ltd.Suzhou Science and Technology Plan Project(No.SKY2023051)。
文摘Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes.Polyprodrug micelles can cross-link with other hydrophobic drugs through noncovalent bonds,which has the advantage of fixed structure and avoids the use of chemical cross-linking agents.In this study,we prepared a polyprodrug with hydrophobic curcumin(CUR)and hydrophilic poly(ethylene glycol)(PEG)in the main chain through a click reaction between CUR derivatives containing azide groups and di-alkynly-capped PEG.Due to the presence of benzene rings in the structure of CUR,the polyprodrug can form non-covalent cross-linked nanoparticles(NCCL-CUR NPs)through hydrophobic andπ-πstacking interaction.The structure,molecular weight,and self-assembly properties of the polyprodrug were characterized.The anti-cancer drug camptothecin(CPT)was encapsulated in the polyprodrug nanoparticles,producing dual-drug-loaded nanoparticles(abbreviated as CPT@NCCL-CUR NPs).The test results indicate that the NPs have reductive responsiveness and can release the original drugs CUR and CPT in phosphate buffer(PB)solution containing glutathione(GSH),while remaining stability in physiological environment.Cell and in vivo experiments further demonstrate that the dualdrug-loaded CPT@NCCL-CUR NPs can inhibit the growth of tumor through synergistic effects.This work provides a valuable approach for the preparation of amphiphilic polyprodrug with anti-tumor CUR as the backbone,and the stable dual-drug-loaded NPs containing both CUR and CPT through non-covalent cross-linking for synergistic therapy.
基金financially supported by the National Natural Science Foundation of China(22208050,22108034)Guangdong Provincial Natural Science Foundation Project(2023A1515012151)Scientific Research Project of Guangdong Provincial Department of Education(2023KTSCX132).
文摘Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this work,we reported the synthesis of a novel porous organic polymer,FOSU-POP-1 for the separation of CH_(4)/C_(2)H_(6)/C_(3)H_(8).The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer-Emmett-Teller(BET)surface area of 1038 m^(2)·g^(-1).Exhibiting stronger affinity towards C_(3)H_(8) and C_(2)H_(6) than CH_(4),2.85 mmol·g^(-1) for C_(3)H_(8) and 2.14 mmol·g^(-1) for C_(2)H_(6) were achieved on the FOSU-POP-1 at 0.1 MPa,298 K,with an ideal adsorbed solution theory selectivity of 227 for C_(3)H_(8)/CH_(4).The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH_(4)/C_(2)H_(6)/C_(3)H_(8) ternary mixture.The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C_(3)H_(8) and C_(2)H_(6).This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH_(4)/C_(2)H_(6)/C_(3)H_(8) mixture.
基金financial support from the Natural Science Foundation of China and Shandong Province(Nos.21971149,92156007,ZR2019ZD45,ZR2020KB005)the Fundamental Research Funds of Shandong University。
文摘A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important privileged heterocyclic pharmacophores which cannot be accessed by a traditional click reaction.Radical interception of cuprate-triazole,the key reaction intermediate formed in situ,is an important feature of this process.
基金supports of the Special Funds for Major Basic Research Projects (NoG2011CB606001)Zhejiang Provincial Top Key Discipline of New Materials and Process Engineering(No 20110926)
文摘A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisoprene was synthesized by anionic polymerization using n-butyl lithium as initiator,and the pendant hydroxyl groups were introduced by the thiol-ene reaction of mercaptoethanol with the double bond of 1,2-addition units of PI backbone in the presence of radical initiator azobisisobutyronitrile. Isocyanate end group capped poly（ethylene glycol）（mPEG-NCO） was grafted onto the PI backbone through alcoholisocyanate reaction between the pendant hydroxyl groups and isocyanate group of mPEG-NCO.The structure of the graft copolymer were characterized and confirmed by means of size-exclusion chromatography,~1H NMR and FTIR spectroscopy.
基金supported by the National Natural Science Foundation of China (No.51773190 and No.51973206)。
文摘Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance,dimensional stability,and unique sensitivity to external stimuli.In this work,we synthesized thiol-functionalized tetraphenylethylene(TPE)and constructed polymer gels through thiol-ene click reaction.The synthetic process of the polymer gels could be monitored by fluorescence emission of TPE moieties based on aggregation-induced emission mechanism.In addition,due to the dual redox-and acid responsiveness of the polymer gels,in the presence of dithiothreitol and trifluoroacetic acid,fluorescence quenching of the polymer gels can be observed.This stimuli-responsive characteristics endows the polymer gels with potential applications in fluorescent sensing and imaging,cancer diagnosis and selfhealing materials.
基金supported by the National Natural Science Foundation of China (Nos. 21762028 and 21462027)Jiangxi Province Natural Science Foundation (Nos. 20161BAB213065 and 20171BAB203009)
文摘The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling reaction between the binding site and the reporter. In addition, the formation 1,4-disubstituted1,2,3-triazole linker shows a high binding affinity toward both anions and metal ions. Recently researches revealed this reaction is also an efficient tool to form rigid or shape-persistent, preorganized macrocyclic species. This review summarized the recent advances in click derived macrocyclic receptors for recognition of anion, metal ion and ions pair.
基金supported by the National Natural Science Foundation of China(No.31601412)the 100 Talent Program grant and Biological Resources Service Network Initiative(No.ZSYS-012)grant from the Chinese Academy of Sciences(No.SKT1604)
文摘Directed peptides C-terminal modification enabled by the engineered biomolecular catalyst-peptide amidase 12 B has been achieved via computational protein engineering. The engineered enzyme exhibits great promising potential in the C-terminal modification of opioid peptides using prop-2-yn-1-amine(PYA) or prop-2-en-l-amine(PEA) as the nucleophile. A variety of opioid peptides could be readily functionalized at the C-terminal chain in high yield in a mild and selective manner. Notably, modified opioid peptides bearing alkynyl moiety could be further functionalized through well-established click reaction.
基金supported by the National Natural Science Foundation of China(Nos.21172105 and 20872058)
文摘Two tetrathiafulvalene-calix[4]arene assemblies （TTF-calix-1 and TFF-calix-2） have been synthesized by the click reaction. Both their cyclic voltammograms show, as expected, two one-electron quasi- reversible redox behavior. The UV-vis absorption spectra studies show that these two assemblies undergo progressive oxidation at the TFF moiety in presence of increasing amounts of Cu2＋ or Hg2＋. Moreover, the absorption studies show intermolecular electron transfer between compounds TrF-calix- I or TI＇F-calix-2 and p-chloranil may be promoted by specific metal ions such as Pb2＋, Sc3＋ etc.
基金supported by the National Natural Science Foundation of China(No.21274080)
文摘In this work, 1,4-bis(4-phenyl-1,2,3-triazole)benzene, 1,3-bis(4-phenyl-1,2,3-triazole)propane, bis(1-phenyl-1,2,3-triazole)-methylphenylsilane, and 1-ally-4-phenyl-1,2,3-triazole have been designed and synthesized via Click reaction. Fourier transform infrared spectroscopy(FT-IR) and nuclear magnetic resonance spectroscopy(NMR) were used to confirm the compounds' structures. The effect of silicon atom on the optical properties has also been studied. The UV-vis absorption wavelength of silicon-containing compound is about ca. 10 nm red-shifted when compared with that of other three compounds. The fluorescence emission bands of the compounds in CHCl_3 solutions were observed around ca. 440 nm. And the luminescent coordination compound, namely [AgL1?NO_3?3H_2O]n, based on the ligand 1-allyl-4-phenyl-1,2,3-triazole has been prepared. In addition, this complex exhibits a 1 D chain structure. The crystal structure has been determined by single-crystal X-ray diffraction, and the optical properties have been investigated by fluorescence spectrum. In summary, our work may provide new materials with luminescent property which is potentially useful in material fields.
基金the National Natural Science Foundation of China(Grant no.51973073)the Fel owship of China Postdoctoral Science Foundation(2021M701303)the analytical and testing assistance from the Analysis and Testing Center of HUST for support of this work
文摘Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.
基金financially supported by the National Natural Science Foundation of China(No.31500767)the Natural ScienceFoundation of Liaoning Province of China(No.20180510037)the Fundamental Research Funds for the Central Universities(No.DUT19LAB27)。
文摘X-ray imaging functionalization of biodegradable polyesters is a great demand and challenge in biomedical applications.In this work,a strategy of in-chain functionalization through the combination of ring opening copolymerization and oxime "Click" postfunctionalization was developed towards X-ray opaque polylactide copolymers.A functionalized cyclic carbonate was first synthesized and used as comonomer of polylactide copolymers,which were subjected to postfunctionalization of oxime "Click" reaction towards iodinated polylactide copolymers.The chemical structure and physical properties of the target products were traced and confirmed.In vitro cytotoxicity evaluation with 3T3-Swiss albino by Alamar blue demonstrated a low cytotoxicity.The X-ray radiopacity was analyzed by Micro-CT and quantified by Hounsfield Units value,which could be tailorable by the feedstock.It is a promising X-ray visible implantable biomaterial in biomedical applications.
基金financially supported by the Ministry of Science and Technology of China under the National Key R&D Program of China (No.2023YFB3811200)the National Natural Science Foundation of China (No.22075292).
文摘Anion-exchange membranes(AEMs)with high conductivity and stability are essential components of hydrogen related water electrolysis and fuel cell applications.During the past decades,polynorbornene(PNB)-based AEMs have shown excellent performance due to their saturated all-carbon-based backbones and diverse strategies to prepare cross-linked membranes.However,nearly all previously reported PNB-based AEMs rely on the alkyl-substituted norbornene monomers,whose low-yielding synthesis leads to high-cost of the AEMs.In addition,the crosslinked PNB-based AEMs usually suffered from mechanical brittleness.Herein,we propose a novel semi-interpenetrating polymer network(s-IPN)strategy to simultaneously enhance mechanical modulus and ionic conductivity,while using commercial 5-vinyl-2-norbornene(VNB)as the single norbornene derivatives to prepare high-performance AEMs.A diallylphenol quaternary ammonium salt was used for photo-induced crosslinking with poly-VNB and various dithiols to produce AEMs with s-IPN structures.The resultant membranes have excellent hydroxide conductivities and alkaline stability in 1 mol/L KOH at 80℃,and are successfully applied in alkaline anion-exchange membrane water electrolyzers to stably operateforover150h.
文摘In this study,we unveil a conceptual technology for fabricating artificial metalloenzymes(ArMs)by deeply integrating hemin into protein scaffolds via a protein refolding process,a method that transcends the conventional scope of surface-level modifications.Our approach involves denaturing proteins,such as benzaldehyde lyase,green fluorescent protein,and Candida antarctica lipase B,to expose extensive reactive amino acid residues,which are then intricately linked with hemin using orthogonal click reactions,followed by protein refolding.This process not only retains the proteins’structural integrity but expands proteins’functionality.The most notable outcome of this methodology is the hemin@BAL variant,which demonstrated a remarkable 83.7%conversion rate in cyclopropanation reactions,far surpassing the capabilities of traditional hemin-based catalysis in water.This success highlights the significant role of protein structure in the ArMs’activity and marks a substantial leap forward in chemical modification of proteins.Our findings suggest vast potentials of protein refolding approaches for ArMs across various catalytic applications,paving the way for future advancements in synthetic biology and synthetic chemistry.
基金supported by the National Key Research and Development Program of China(Grant 2023YFF0724100)National Natural Science Foundation of China(Grants 22074016 and 22234002)+1 种基金Natural Science Foundation of Jiangsu Province(Grant BK20232007)the Full-time Talents Program of Hebei Province(Grant 2023HBQZYCXY027).
文摘With their high drug-loading capacity and enhanced permeability and retention(EPR)effects,nanoparticles possess significant potential for the diagnosis and treatment of tumors.However,unlike active targeting,the complex tumor microenvironment influences the passive accumulation of nanoparticles in tumor areas.Hence,it is necessary to actively control the behavior of nanoparticles when they enter the tumor microenvironment.By utilizing biocompatible and efficient click reactions,the aggregation of nanoparticles at the tumor site can be controlled,thereby enhancing nanoparticle accumulation at the target location with improved imaging signals and enhanced tumor-inhibitory effects.Herein,we introduce and classify in situ nanoparticle aggregation for biomedical imaging and therapeutic applications induced by four types of common click reactions:coppercatalyzed azide–alkyne cycloaddition(CuAAC),strain-promoted azide–alkyne cycloaddition(SPAAC),click condensation between 2-cyanobenzothiazole(CBT)and cysteine(Cys),and inverse electron-demand Diels–Alder(iEDDA).Furthermore,we summarize the main strategies of these click reaction-based nanoparticle aggregation approaches.Finally,we discuss the advantages and disadvantages of click reaction-triggered aggregation and analyze future trends.
基金financially supported by the National Key Research and Development Program of China (Nos. 2017YFB0309301 and 2017YFB0309302)the Natural Science Foundation of Shanghai, China (No. 17ZR1407200)
文摘Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.
基金Iran National Science Foundation for partial support of this work
文摘An efficient green protocol for the preparation 3,4,6-trisubstituted 2-pyridone of employing a condensation reaction of cyanoacetamide and acetylacetone in the presence of KAl（SO4）2·12H2O in water has been described. The present procedure offers advantage such as shorter reaction time, simple workup, and excellent yields.
基金financial supports from the National Natural Science Foundation of China(No. 20704036)special fund from the Major State Basic Research Project(No.2005CB623802)the Committee of Science and Technology of Zhejiang Province
文摘A novel biodegradable copolymer, poly（5,5-dibromomethyltrimethylene carbonate-co-ε-caprolactone） （poly（DBTC-co-CL）） with pendant bromine groups, was synthesized via ring-opening polymerization （ROP） of ε-caprolactone （CL） and 5,5- dibromomethyltrimethylene carbonate （DBTC） using stannous octoate （Sn（Oct）2） as catalyst. Then the pendant bromine groups were completely converted into azide form, which permitted ＂click＂ reaction with alkyne-terminated polyethylene （A-PEG） by Huisgen 1,3-dipolar cycloadditions preparing biodegradable amphiphilic poly（DTC-co-CL）-g-PEG graft copolymer. The graft copolymer was characterized by nuclear magnetic resonance （NMR） and size-exclusion chromatography （SEC）.
基金supported by the Higher Education Commision(HEC),Govt.of Pakistan
文摘Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu（OAc）2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a（C10H9N5O4） crystallizes in the triclinic system, space group P1 with a = 5.0894（9）, b = 8.9834（13）, c = 13.089（2） ？, α= 83.041（7）, β= 80.256（7）, γ=87.296（8）°, V = 585.24（16）？3, Z = 2, Mr = 263.22, crystal size（mm） = 0.37 × 0.20 ×0.18,（I 〉 2σ（I）） = 8557, 2493, 1229, Rint = 0.057. Compound 1b（C12H13N5O4） crystallizes in the monoclinic system, space group P21/c with a = 6.8854（5）, b = 21.783（2）, c = 9.3986（8） ？,β = 93.239（4）°, V = 1407.4（2）？3, Z = 4, Mr = 291.27, crystal size（mm） = 0.38 × 0.22 × 0.20,（I 〉 2σ（I）） = 11842, 3172, 1866, Rint = 0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20180963)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.19KJD430001).
文摘The infection induced by implantation of biomedical materials may result from the biofilm formation after bacteria attachment.Hence,the antibiofilm surface coating represents a novel technique to improve the antibacterial activity of biomedical materials.The traditional antibiofilm surface coatings exhibited some disadvantages and provided a limited service life.In this work,we used polyethyleneimine grafted 3-maleimidopropionic acid(PEIM)and poly(acrylic acid)grafted 2-furfurylamine(PAAF)to achieve robust and self-healable crosslinked multilayer coatings,employing Layer-by-Layer(LbL)self-assembly technique and Diels-Alder reaction.Then,thiol-terminated poly((3-acrylamidopropyl)trimethylammonium chloride)(PAMPTMA-SH)was grafted onto the crosslinked multilayer coating by thiol-ene click reaction to form a novel multilayer coating(PEIM/PAAF)_(10)-PAMPTMA.We found that this coating showed robust and self-healable activity,and significantly inhibited the bacterial growth and biofilm formation after infection with Escherichia coli(E.coli)and Staphylococcus aureus(S.aureus)by in vitro and in vivo assays for 120 h.In addition,the multilayer coating did not induce significant hemolysis or affect the cell viability of red blood cells.In vivo studies also showed that(PEIM/PAAF)_(10)-PAMPTMA coating efficiently blocked the infiltration of inflammatory cells and gene expression in the mouse skin challenged with E coli or S.aureus.Taken together,these results showed that the prepared multilayer coating exhibited strong antibiofilm activity and provided a new strategy for the application of highly efficient antibiofilm surface coating of biomedical materials.
