Owing to their unique biological effects and physicochemical properties,nanomaterials have garnered substantial attention in the field of bone tissue engineering(BTE),targeting the repair and restoration of impaired b...Owing to their unique biological effects and physicochemical properties,nanomaterials have garnered substantial attention in the field of bone tissue engineering(BTE),targeting the repair and restoration of impaired bone tissue.In recent years,strategies for the design and optimization of nanomaterials through thiolation modification have been widely applied in BTE.This review concisely summarizes the categories of nanomaterials commonly used in BTE and focuses on various strategies for the modification of nanomaterials via thiolation.A multifaceted analysis of the mechanisms by which thiolated nanomaterials enhance nanomaterial-cell interactions,promote drug loading and release,and modulate osteogenic differentiation is presented.Furthermore,this review introduces biomedical applications of thiolated nanomaterials in BTE,including as scaffold components for bone regeneration,coatings for bone implants,and drug delivery systems.Finally,the future perspectives and challenges in the development of this field are discussed.Thiolation modification strategies provide a platform for developing new ideas and methods for designing nanomaterials for BTE and are expected to accelerate the development and clinical translation of novel bone repair materials.展开更多
Novel oral microbeads were developed based on a biopolymer–drug conjugate of doxorubicin(DOX) conjugated with thiolated pectin via reducible disulfide bonds. The microbeads were fabricated by ionotropic gelation with...Novel oral microbeads were developed based on a biopolymer–drug conjugate of doxorubicin(DOX) conjugated with thiolated pectin via reducible disulfide bonds. The microbeads were fabricated by ionotropic gelation with cations such as Al3+, Ca2+ and Zn2+. The results showed that using zinc acetate can produce the strongest microbeads with spherical shape.However, the microbeads prepared from thiolated pectin–DOX conjugate were very soft and irregular in shape. To produce more spherical microbeads with suitable strength, the native pectin was then added to the formulations. The particle size of the microbeads ranged from 0.87 to 1.14 mm. The morphology of the microbeads was characterized by optical and scanning electron microscopy. DOX was still in crystalline form when used in preparing the microbeads, as confirmed by powder X-ray diffractometry. Drug release profiles showed that the microbeads containing thiolated pectin–DOX conjugate exhibited reduction-responsive character;in reducing environments, the thiolated pectin–DOX conjugate could uncouple resulting from a cleavage of the disulfide linkers and consequently release the DOX. The best-fit release kinetics of the microbeads containing thiolated pectin–DOX conjugate, in the medium without reducing agent, fit the Korsmeyer–Peppas model while those in the medium with reducing agent fit a zero-order release model. These results suggested that the microbeads containing thiolated pectin–DOX conjugate may be a promising platform for cancer-targeted delivery of DOX, exploiting the reducing environment typically found in tumors.展开更多
Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,t...Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.展开更多
Pyridinium 1,4-zwitterionic thiolates were applied to a formal [3+2] annulation reaction with modified activated alkynes, affording various tetrasubstituted thiophenes with aryl, alkenyl, alkyl or silyl group at the s...Pyridinium 1,4-zwitterionic thiolates were applied to a formal [3+2] annulation reaction with modified activated alkynes, affording various tetrasubstituted thiophenes with aryl, alkenyl, alkyl or silyl group at the special position. The structural modification of alkyne substrates enabled the synthesis of diverse thiophenes to be achieved using the pyridinium 1,4-zwitterionic thiolates as the sulfur-containing building blocks. This approach is metal-free and catalyst-free.展开更多
Pectin is a biopolymer that has numerous useful purposes in food and beverage industry, cosmetic products and pharmaceutical fields. One of the important properties of pectin is its bioadhesive properties. Native pect...Pectin is a biopolymer that has numerous useful purposes in food and beverage industry, cosmetic products and pharmaceutical fields. One of the important properties of pectin is its bioadhesive properties. Native pectin provides fair bioadhesive properties that can be improved by modification of pectin structure. The immobilization of thiol groups on polymer can significantly improve the bioadhesive properties due to in situ cross-linking between thiol groups of polymer and mucin [1].展开更多
A practical method for the construction of difluoromethylene-containing 1,4-thiazine moieties using readily available diethyl bromodifluoromethanephosphonate(BrCF_(2)PO(OEt)_(2))as difluorocarbene precusor has been de...A practical method for the construction of difluoromethylene-containing 1,4-thiazine moieties using readily available diethyl bromodifluoromethanephosphonate(BrCF_(2)PO(OEt)_(2))as difluorocarbene precusor has been developed.This transformation features the efficient capture of difluorocarbene by pyridinium 1,4-zwitterionic thiolates.A series of structurally novel and functionalized difluoromethylene-containing 1,4-thiazine derivatives were thus synthesized in good yields.展开更多
Two diiron dithiolate complexes [Fe2（CO）6（1,8-S2-2-CH2OOCPhC（10）H5）] 1 and[Fe2（CO）6（1,8-S2-2-CH2OOCPh-4-NO2C（10）H5）]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-r...Two diiron dithiolate complexes [Fe2（CO）6（1,8-S2-2-CH2OOCPhC（10）H5）] 1 and[Fe2（CO）6（1,8-S2-2-CH2OOCPh-4-NO2C（10）H5）]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, ^1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe2S2 core with the Fe1–Fe2 distances of 2.5237（7）A in 1 and 2.5125（12）A in 2, falling in the normal range of Fe–Fe bond length（2.49 - 2.57 A）. The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at –1.074 V, –1.535 V（1） and –0.869 V, –1.247 V（2） vs. Fc/Fc^＋, respectively. With using p-Ts OH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH3CN/NBu4PF6 solution.展开更多
Through successive one-electron reduction processes,a coordinatively unsaturated thiolate-bridged CoIICoII complex[Cp*Co(μ-SEt)_(2)CoCp*](1)was facilely generated in high yield.In the presence of O_(2),complex 1 can ...Through successive one-electron reduction processes,a coordinatively unsaturated thiolate-bridged CoIICoII complex[Cp*Co(μ-SEt)_(2)CoCp*](1)was facilely generated in high yield.In the presence of O_(2),complex 1 can smoothly take up CO_(2),and then install it at the Co_(2)S_(2)scaffold in the form of a carbonate bridge to give complex[Cp*Co(μ-SEt)_(2)(μ–η^(1):η^(1)-CO_(3))CoCp*](2).展开更多
Based on their well-defined atomic structures,chiral clusters can be utilized to describe the origin of nanomaterial-like chirality,laying the foundation for the application of chiral materials.However,their chiral ap...Based on their well-defined atomic structures,chiral clusters can be utilized to describe the origin of nanomaterial-like chirality,laying the foundation for the application of chiral materials.However,their chiral application is limited owing to chiral phosphines,amines,and carboxylic acids forming protected clusters with weak chiral stability,while thiol-protected clusters are stable;however,there are relatively few types of chiral thiols available yet,and they have a high price.In this study,chiral camphor thiols were designed and prepared from natural products.Based on the novel chiral thiol ligands,a pair of novel R/S-Au_(19)(SR)_(13)DPPM chiral clusters were obtained.Their structural anatomies showed that their chiral origins were diverse and their core distortion was more significant compared with their counterparts.Subsequent stability tests showed that both of these were stable in thermal,alkaline,and reducing environments,thus offering a solid foundation for their application in the corresponding environments.Importantly,the chiral thiol ligands designed in this study could provide new opportunities for the preparation of stable chiral nanoclusters and their applications.展开更多
Herein,we present a visible-light-driven carbo-carboxylation of alkenes with CO_(2) via catalytic electron donor-acceptor(EDA)complex activation.A variety of oxindole-3-acetic acid and derivatives were generated in mo...Herein,we present a visible-light-driven carbo-carboxylation of alkenes with CO_(2) via catalytic electron donor-acceptor(EDA)complex activation.A variety of oxindole-3-acetic acid and derivatives were generated in moderate to excellent yields from N-arylacrylamides and CO_(2).Mechanistic studies revealed the formation of an EDA complex between catalytic thiolate and alkene.Notably,this redox-neutral reaction features mild,transition-metal and photocatalyst-free conditions,good functional group tolerance and broad substrate scope.Furthermore,the facile synthesis of key intermediates in natural products underscores the utility of this methodology.展开更多
In this work,a diphosphine chelator,2-Ph_(2)PC_(6)H_(4)PH_(2),containing both primary and tertiary phosphine donors,was used to create highly stable silver(I)nanoclusters through a dynamic ligand metathesis reaction.T...In this work,a diphosphine chelator,2-Ph_(2)PC_(6)H_(4)PH_(2),containing both primary and tertiary phosphine donors,was used to create highly stable silver(I)nanoclusters through a dynamic ligand metathesis reaction.Taking advantage of thiolate-silver coordination polymers as synthetic precursors,we developed a viable synthetic approach to access Ag34 nanoclusters through dual proton and ligand exchange successfully.Owing to the stronger coordination ability of the bifunctional 2-Ph_(2)PC_(6)H_(4)PH_(2)ligand,substitution results in the formation of thermodynamically stable Ag34 nanoclusters linked by fifteen 2-Ph_(2)PC_(6)H_(4)P^(2-)chelators.Notably,thiolates as structural templates rather than protective ligands play a crucial role in directing nanocluster construction.The Ag34 nanoclusters manifest highly efficient near-infrared photoluminescence peaked at ca.800 nm with over 24%of quantum yield in fluid CH_(2)Cl_(2)solution,arising mostly from ligand-to-metal charge transfer(^(3)LMCT)and cluster-centered(^(3)CC)triplet states.Solution-processable near-infrared organic light-emitting diodes(NIR-OLEDs)achieved high-efficiency nearinfrared electroluminescence with an external quantum efficiency(EQE)of 10.2%.The unique synthetic approach can be extended to other metal systems,thereby expanding both the structural diversity and application potential of metal nanoclusters.展开更多
By using a unique temperature-dependent,chloride-mediated approach,two atom-precise silver nanoclusters[Cl@Ag_(14)(Tab)_(12)-(C_(5)H_(4)NCl)_(12)](PF_(6))_(13)(Cl@Ag_(14))and[Cl_(3)@Ag_(24)(Tab)_(20)(C_(5)H_(4)NCl)_(1...By using a unique temperature-dependent,chloride-mediated approach,two atom-precise silver nanoclusters[Cl@Ag_(14)(Tab)_(12)-(C_(5)H_(4)NCl)_(12)](PF_(6))_(13)(Cl@Ag_(14))and[Cl_(3)@Ag_(24)(Tab)_(20)(C_(5)H_(4)NCl)_(11)]Cl(PF_(6))_(20)(Cl_(3)@Ag_(24))(Tab=4-(trimethylammonio)benzenethiolate,C_(5)H_(4)NCl=3-chloropyridine)were obtained successfully.Notably,the number of chloride ions encapsulated inside the Ag-S shell could be regulated by the slow dissolution of almost insoluble KCl at various temperatures.The inclusion of additional core chloride ions results in the expansion of the surrounding Ag-S shell.This article provides a promising synthetic approach for controlling the number of Ag atoms that form a shell around the anionic core,in addition to offering a potential pathway for the introduction of other inorganic anions into silver clusters.More broadly,through the use of related ligands,the synthetic strategy offers scope for generating new families of silver thiolate clusters of varying size and composition.展开更多
Two atom-precise silver nanoclusters[Ag_(25)Cl_2(Tab)_(14)(Ph COO)_(11)(DMF)_4](PF_6)_(12)(Ag_(25),DMF=N,N-dimethylformamide)and[Ag_(26)Cl_2(Tab)_(14)(Ph COO)_(13)(DMAc)_4](PF_6)_(11)(Ag_(26),DMAc=N,N-dimethylacetamid...Two atom-precise silver nanoclusters[Ag_(25)Cl_2(Tab)_(14)(Ph COO)_(11)(DMF)_4](PF_6)_(12)(Ag_(25),DMF=N,N-dimethylformamide)and[Ag_(26)Cl_2(Tab)_(14)(Ph COO)_(13)(DMAc)_4](PF_6)_(11)(Ag_(26),DMAc=N,N-dimethylacetamide)were synthesized based on the electrically neutral thiolate protective ligand,4-(trimethylammonio)benzenethiolate(Tab).The weak Ag–S interaction in Tab-protected silver nanoclusters allows to insert or leave a single silver atom in the Ag–S skeleton through solvent-trigger core fragmentation and re-arrangement,thereby realizing the reversible conversion of Ag_(25)and Ag_(26)for the first time.展开更多
The ring-opening polymerization （ROP） of ε-caprolactone （ε-CL） using lanthanide thiolate complexes [（CH3CsH4）2Sm（μ-SPh）（THF）]2 （1） and Sm（SPh）3（HMPA）3 （2） as initiators has been investigated for t...The ring-opening polymerization （ROP） of ε-caprolactone （ε-CL） using lanthanide thiolate complexes [（CH3CsH4）2Sm（μ-SPh）（THF）]2 （1） and Sm（SPh）3（HMPA）3 （2） as initiators has been investigated for the first time. Both of 1 and 2 were found to be highly efficient initiators for the ROP of ε-CL. The poly（ε-caprolactone） （PCL） with molecular weight Mn up to 1.97 ×10^5 and relatively narrow molecular weight distributions （1.20〈MW/Mn〈 2.00） have been obtained in high yield in the temperature range of 35-65℃. According to the polymer yield, 2 showed much higher activity than 1. However, the number-average molecular weight of PCL obtained with 2 was much lower than with 1. The possible polymerization mechanism of the ε-CL polymerization has been proposed based on the results of the end group analysis of the ε-CL oligomer.展开更多
The field of biomaterials has advanced significantly in the past decade.With the growing need for high-throughput manufacturing and screening,the need for modular materials that enable streamlined fabrication and anal...The field of biomaterials has advanced significantly in the past decade.With the growing need for high-throughput manufacturing and screening,the need for modular materials that enable streamlined fabrication and analysis of tissue engineering and drug delivery schema has emerged.Microparticles are a powerful platform that have demonstrated promise in enabling these technologies without the need to modify a bulk scaffold.This building block paradigm of using microparticles within larger scaffolds to control cell ratios,growth factors and drug release holds promise.Gelatin microparticles(GMPs)are a well-established platform for cell,drug and growth factor delivery.One of the challenges in using GMPs though is the limited ability to modify the gelatin post-fabrication.In the present work,we hypothesized that by thiolating gelatin before microparticle formation,a versatile platform would be created that preserves the cytocompatibility of gelatin,while enabling post-fabrication modification.The thiols were not found to significantly impact the physicochemical properties of the microparticles.Moreover,the thiolated GMPs were demonstrated to be a biocompatible and robust platform for mesenchymal stem cell attachment.Additionally,the thiolated particles were able to be covalently modified with a maleimide-bearing fluorescent dye and a peptide,demonstrating their promise as a modular platform for tissue engineering and drug delivery applications.展开更多
Silver thiolate polymers are intercepted to form different structural fragments when reacting with variant solubilizing reagents,which usually serve as the starting point for the preparation of clusters.However,such a...Silver thiolate polymers are intercepted to form different structural fragments when reacting with variant solubilizing reagents,which usually serve as the starting point for the preparation of clusters.However,such a process is still far from clear.Herein,we report the controlled synthesis of silver-t-butylthiolate clusters from reactions of polymeric[Ag^(t)BuS]n and suitable templates in the presence of solubilizing reagents to offer a detailed look at the mechanism of cluster’s formation.As the provided solubilizing reagents have weak coordina-tion ability,such as O-or N-donating ligands,the obtained polymeric compound retains the linear structure pat-tern that S and Ag atoms are arranged alternately.When extra templates NO_(3)^(−)and CO_(3)^(2−)are applied,the disk-like clusters Ag_(19)and Ag_(20)are constructed with the same[Ag^(t)BuS]_(5)circles that may directly cyclize from the linear[Ag^(t)BuS]_(n)fragments.In contrast,(EtO)_(2)PS_(2)^(−)and(iPrO)_(2)PS_(2)^(−)anions have large size and strong coordination abil-ity rendering the structure of the polymer completely fragmented.Thus extremely short[Ag^(t)BuS]n pieces with silver ions and solubilizing ligands assemble around the templates V_(2)O_(7)^(4−)and W_(2)O_(9)^(4−),leading to the formation of clusters Ag_(22)and Ag_(24).展开更多
A highly efficient and green four-component difunctionalization of styrenes with KSCN and imidazo[1,2-a]pyridines was developed.In this protocol,readily available KSCN was used as a sulfur source and inexpensive K2S2O...A highly efficient and green four-component difunctionalization of styrenes with KSCN and imidazo[1,2-a]pyridines was developed.In this protocol,readily available KSCN was used as a sulfur source and inexpensive K2S2O8 was used as a free radical initiator.A series of C-3 thiolated imidazopyridine analogues were synthesized,in which hydroxyl group and aryl or alkyl group were incorporated.A novel method for the synthesis of multifunctionalized imidazopyridines was established.展开更多
Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially s...Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.展开更多
Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crysta...Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.52103184 and 8226030956)the National Key Research and Development Program of China(No.2022YFC2407503)+3 种基金Key Project of the Natural Science Basic Research Plan of Shaanxi Province(No.2022JZ43)Natural Science Basic Research Program of Shaanxi Province(No.2024JCYBQN-0874)Medical Research Key Project of Xi'an Science and Technology Bureau(No.2024JH-YXZD-0055)Medical Research Project of Xi'an Science and Technology Bureau(No.22YXYJ0083)
文摘Owing to their unique biological effects and physicochemical properties,nanomaterials have garnered substantial attention in the field of bone tissue engineering(BTE),targeting the repair and restoration of impaired bone tissue.In recent years,strategies for the design and optimization of nanomaterials through thiolation modification have been widely applied in BTE.This review concisely summarizes the categories of nanomaterials commonly used in BTE and focuses on various strategies for the modification of nanomaterials via thiolation.A multifaceted analysis of the mechanisms by which thiolated nanomaterials enhance nanomaterial-cell interactions,promote drug loading and release,and modulate osteogenic differentiation is presented.Furthermore,this review introduces biomedical applications of thiolated nanomaterials in BTE,including as scaffold components for bone regeneration,coatings for bone implants,and drug delivery systems.Finally,the future perspectives and challenges in the development of this field are discussed.Thiolation modification strategies provide a platform for developing new ideas and methods for designing nanomaterials for BTE and are expected to accelerate the development and clinical translation of novel bone repair materials.
文摘Novel oral microbeads were developed based on a biopolymer–drug conjugate of doxorubicin(DOX) conjugated with thiolated pectin via reducible disulfide bonds. The microbeads were fabricated by ionotropic gelation with cations such as Al3+, Ca2+ and Zn2+. The results showed that using zinc acetate can produce the strongest microbeads with spherical shape.However, the microbeads prepared from thiolated pectin–DOX conjugate were very soft and irregular in shape. To produce more spherical microbeads with suitable strength, the native pectin was then added to the formulations. The particle size of the microbeads ranged from 0.87 to 1.14 mm. The morphology of the microbeads was characterized by optical and scanning electron microscopy. DOX was still in crystalline form when used in preparing the microbeads, as confirmed by powder X-ray diffractometry. Drug release profiles showed that the microbeads containing thiolated pectin–DOX conjugate exhibited reduction-responsive character;in reducing environments, the thiolated pectin–DOX conjugate could uncouple resulting from a cleavage of the disulfide linkers and consequently release the DOX. The best-fit release kinetics of the microbeads containing thiolated pectin–DOX conjugate, in the medium without reducing agent, fit the Korsmeyer–Peppas model while those in the medium with reducing agent fit a zero-order release model. These results suggested that the microbeads containing thiolated pectin–DOX conjugate may be a promising platform for cancer-targeted delivery of DOX, exploiting the reducing environment typically found in tumors.
基金the financial support of the Training Program of the Major Research Plan of the National Natural Science Foundation of China(92061124)the National Natural Science Foundation of China(21975292,21978331,22068008,and 52101186)+3 种基金the Guangdong Basic and Applied Basic Research Foundation(2021A1515010167 and 2022A1515011196)the Guangzhou Key R&D Program/Plan Unveiled Flagship Project(20220602JBGS02)the Guangzhou Basic and Applied Basic Research Project(202201011449)the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202220 and FC202216)。
文摘Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.
基金National Natural Science Foundation of China (Nos. 21971092, 21901014, 21472072, 21871018, 21732001 and 21672017)Shenzhen Science and Technology Innovation Committee (No. JCYJ20200109141808025)Characteristic Innovation Project of Guangdong Provincial Education Department (No. 2020KTSCX295) for the financial support。
文摘Pyridinium 1,4-zwitterionic thiolates were applied to a formal [3+2] annulation reaction with modified activated alkynes, affording various tetrasubstituted thiophenes with aryl, alkenyl, alkyl or silyl group at the special position. The structural modification of alkyne substrates enabled the synthesis of diverse thiophenes to be achieved using the pyridinium 1,4-zwitterionic thiolates as the sulfur-containing building blocks. This approach is metal-free and catalyst-free.
文摘Pectin is a biopolymer that has numerous useful purposes in food and beverage industry, cosmetic products and pharmaceutical fields. One of the important properties of pectin is its bioadhesive properties. Native pectin provides fair bioadhesive properties that can be improved by modification of pectin structure. The immobilization of thiol groups on polymer can significantly improve the bioadhesive properties due to in situ cross-linking between thiol groups of polymer and mucin [1].
基金Financial support from National Natural Science Foundation of China(Nos.21931013 and 22271105)Natural Science Foundation of Fujian Province(No.2022J02009)+2 种基金Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal Universitythe Instrumental Analysis Center of Huaqiao University for analysis supportthe Subsidized Project for Cultivating Postgraduates’Innovative Ability in Scientific Research of Huaqiao University。
文摘A practical method for the construction of difluoromethylene-containing 1,4-thiazine moieties using readily available diethyl bromodifluoromethanephosphonate(BrCF_(2)PO(OEt)_(2))as difluorocarbene precusor has been developed.This transformation features the efficient capture of difluorocarbene by pyridinium 1,4-zwitterionic thiolates.A series of structurally novel and functionalized difluoromethylene-containing 1,4-thiazine derivatives were thus synthesized in good yields.
基金supported by the National Natural Science Foundation of China(Nos.21231003 and 21203195)
文摘Two diiron dithiolate complexes [Fe2（CO）6（1,8-S2-2-CH2OOCPhC（10）H5）] 1 and[Fe2（CO）6（1,8-S2-2-CH2OOCPh-4-NO2C（10）H5）]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, ^1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe2S2 core with the Fe1–Fe2 distances of 2.5237（7）A in 1 and 2.5125（12）A in 2, falling in the normal range of Fe–Fe bond length（2.49 - 2.57 A）. The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at –1.074 V, –1.535 V（1） and –0.869 V, –1.247 V（2） vs. Fc/Fc^＋, respectively. With using p-Ts OH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH3CN/NBu4PF6 solution.
基金supported by the National Natural Science Foundation of China(No.21690064,21571026,and 21231003)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT13008)the“111”project of the Ministry of Education of China.
文摘Through successive one-electron reduction processes,a coordinatively unsaturated thiolate-bridged CoIICoII complex[Cp*Co(μ-SEt)_(2)CoCp*](1)was facilely generated in high yield.In the presence of O_(2),complex 1 can smoothly take up CO_(2),and then install it at the Co_(2)S_(2)scaffold in the form of a carbonate bridge to give complex[Cp*Co(μ-SEt)_(2)(μ–η^(1):η^(1)-CO_(3))CoCp*](2).
基金financial support from the National Natural Science Foundation of China(22371003,22001002,22001003,22301001)the Ministry of Education,the University Synergy Innovation Program of Anhui Province(GXXT-2020-053)Anhui Provincial Natural Science Foundation(2308085QB40).
文摘Based on their well-defined atomic structures,chiral clusters can be utilized to describe the origin of nanomaterial-like chirality,laying the foundation for the application of chiral materials.However,their chiral application is limited owing to chiral phosphines,amines,and carboxylic acids forming protected clusters with weak chiral stability,while thiol-protected clusters are stable;however,there are relatively few types of chiral thiols available yet,and they have a high price.In this study,chiral camphor thiols were designed and prepared from natural products.Based on the novel chiral thiol ligands,a pair of novel R/S-Au_(19)(SR)_(13)DPPM chiral clusters were obtained.Their structural anatomies showed that their chiral origins were diverse and their core distortion was more significant compared with their counterparts.Subsequent stability tests showed that both of these were stable in thermal,alkaline,and reducing environments,thus offering a solid foundation for their application in the corresponding environments.Importantly,the chiral thiol ligands designed in this study could provide new opportunities for the preparation of stable chiral nanoclusters and their applications.
基金support is provided by the National Key R&D Program of China(2024YFA1509702)the National Natural Science Foundation of China(22225106,22101191)+1 种基金the Sichuan Science and Technology Program(2024ZYD0101)the Fundamental Research Funds for the Central Universities and the Open Research Fund of State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University.
文摘Herein,we present a visible-light-driven carbo-carboxylation of alkenes with CO_(2) via catalytic electron donor-acceptor(EDA)complex activation.A variety of oxindole-3-acetic acid and derivatives were generated in moderate to excellent yields from N-arylacrylamides and CO_(2).Mechanistic studies revealed the formation of an EDA complex between catalytic thiolate and alkene.Notably,this redox-neutral reaction features mild,transition-metal and photocatalyst-free conditions,good functional group tolerance and broad substrate scope.Furthermore,the facile synthesis of key intermediates in natural products underscores the utility of this methodology.
基金supported by the National Natural Science Foundation of China(Grants 92061202 and 21531008)the Fujian Province Science and Technology Project Program(Grant 2022H0041)the Self-deployment Project Research Program of Haixi Institute,Chinese Academy of Sciences(Grant CXZX-2022-GH11).
文摘In this work,a diphosphine chelator,2-Ph_(2)PC_(6)H_(4)PH_(2),containing both primary and tertiary phosphine donors,was used to create highly stable silver(I)nanoclusters through a dynamic ligand metathesis reaction.Taking advantage of thiolate-silver coordination polymers as synthetic precursors,we developed a viable synthetic approach to access Ag34 nanoclusters through dual proton and ligand exchange successfully.Owing to the stronger coordination ability of the bifunctional 2-Ph_(2)PC_(6)H_(4)PH_(2)ligand,substitution results in the formation of thermodynamically stable Ag34 nanoclusters linked by fifteen 2-Ph_(2)PC_(6)H_(4)P^(2-)chelators.Notably,thiolates as structural templates rather than protective ligands play a crucial role in directing nanocluster construction.The Ag34 nanoclusters manifest highly efficient near-infrared photoluminescence peaked at ca.800 nm with over 24%of quantum yield in fluid CH_(2)Cl_(2)solution,arising mostly from ligand-to-metal charge transfer(^(3)LMCT)and cluster-centered(^(3)CC)triplet states.Solution-processable near-infrared organic light-emitting diodes(NIR-OLEDs)achieved high-efficiency nearinfrared electroluminescence with an external quantum efficiency(EQE)of 10.2%.The unique synthetic approach can be extended to other metal systems,thereby expanding both the structural diversity and application potential of metal nanoclusters.
基金supported by the National Natural Science Foundation of China(22271203,22301205)the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry(2024KF005)+2 种基金the Open Research Fund of State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering of Nanjing Universitythe Collaborative Innovation Center of Suzhou Nano Science and Technologythe Project of Scientific and the Technologic Infrastructure of Suzhou(SZS201905)。
文摘Mixed-valence silver clusters(Ag(0/Ⅰ)),characterized by atomically precise compositions,tunable electronic structures,and remarkable photophysical properties,have shown significant promise for a variety of applications,including catalysis[1-5],optical sensing[6-10],antibacterial materials[11-15],and optoelectronic devices[16].
基金supported by the National Natural Science Foundation of China (21871196, 21773163, 21531006)the Collaborative Innovation Center of Suzhou Nano Science and Technology+1 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Project of Scientific and Technologic Infrastructure of Suzhou (SZS201905)。
文摘By using a unique temperature-dependent,chloride-mediated approach,two atom-precise silver nanoclusters[Cl@Ag_(14)(Tab)_(12)-(C_(5)H_(4)NCl)_(12)](PF_(6))_(13)(Cl@Ag_(14))and[Cl_(3)@Ag_(24)(Tab)_(20)(C_(5)H_(4)NCl)_(11)]Cl(PF_(6))_(20)(Cl_(3)@Ag_(24))(Tab=4-(trimethylammonio)benzenethiolate,C_(5)H_(4)NCl=3-chloropyridine)were obtained successfully.Notably,the number of chloride ions encapsulated inside the Ag-S shell could be regulated by the slow dissolution of almost insoluble KCl at various temperatures.The inclusion of additional core chloride ions results in the expansion of the surrounding Ag-S shell.This article provides a promising synthetic approach for controlling the number of Ag atoms that form a shell around the anionic core,in addition to offering a potential pathway for the introduction of other inorganic anions into silver clusters.More broadly,through the use of related ligands,the synthetic strategy offers scope for generating new families of silver thiolate clusters of varying size and composition.
基金supported by the National Natural Science Foundation of China(21871196,21773163,21531006)the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry(KF2021005)+1 种基金Collaborative Innovation Center of Suzhou Nano Science and Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Project of Scientific and Technologic Infrastructure of Suzhou(SZS201905).
文摘Two atom-precise silver nanoclusters[Ag_(25)Cl_2(Tab)_(14)(Ph COO)_(11)(DMF)_4](PF_6)_(12)(Ag_(25),DMF=N,N-dimethylformamide)and[Ag_(26)Cl_2(Tab)_(14)(Ph COO)_(13)(DMAc)_4](PF_6)_(11)(Ag_(26),DMAc=N,N-dimethylacetamide)were synthesized based on the electrically neutral thiolate protective ligand,4-(trimethylammonio)benzenethiolate(Tab).The weak Ag–S interaction in Tab-protected silver nanoclusters allows to insert or leave a single silver atom in the Ag–S skeleton through solvent-trigger core fragmentation and re-arrangement,thereby realizing the reversible conversion of Ag_(25)and Ag_(26)for the first time.
基金Project suported by the National Natural Science Foundation of China （No. 20272040）.
文摘The ring-opening polymerization （ROP） of ε-caprolactone （ε-CL） using lanthanide thiolate complexes [（CH3CsH4）2Sm（μ-SPh）（THF）]2 （1） and Sm（SPh）3（HMPA）3 （2） as initiators has been investigated for the first time. Both of 1 and 2 were found to be highly efficient initiators for the ROP of ε-CL. The poly（ε-caprolactone） （PCL） with molecular weight Mn up to 1.97 ×10^5 and relatively narrow molecular weight distributions （1.20〈MW/Mn〈 2.00） have been obtained in high yield in the temperature range of 35-65℃. According to the polymer yield, 2 showed much higher activity than 1. However, the number-average molecular weight of PCL obtained with 2 was much lower than with 1. The possible polymerization mechanism of the ε-CL polymerization has been proposed based on the results of the end group analysis of the ε-CL oligomer.
基金This work was supported by the National Institutes of Health(R01 AR068073 and P41 EB023833)H.A.P.,M.M.S.and E.Y.J.acknowledge support from the National Science Foundation Graduate Research Fellowship Program.M.M.S.also acknowledges support from the Ford Doctoral Fellowship Program.E.W.received support from Ruth L.Kirschstein Fellowship and the National Institute of Dental and Craniofacial Research(F31 DE027586).
文摘The field of biomaterials has advanced significantly in the past decade.With the growing need for high-throughput manufacturing and screening,the need for modular materials that enable streamlined fabrication and analysis of tissue engineering and drug delivery schema has emerged.Microparticles are a powerful platform that have demonstrated promise in enabling these technologies without the need to modify a bulk scaffold.This building block paradigm of using microparticles within larger scaffolds to control cell ratios,growth factors and drug release holds promise.Gelatin microparticles(GMPs)are a well-established platform for cell,drug and growth factor delivery.One of the challenges in using GMPs though is the limited ability to modify the gelatin post-fabrication.In the present work,we hypothesized that by thiolating gelatin before microparticle formation,a versatile platform would be created that preserves the cytocompatibility of gelatin,while enabling post-fabrication modification.The thiols were not found to significantly impact the physicochemical properties of the microparticles.Moreover,the thiolated GMPs were demonstrated to be a biocompatible and robust platform for mesenchymal stem cell attachment.Additionally,the thiolated particles were able to be covalently modified with a maleimide-bearing fluorescent dye and a peptide,demonstrating their promise as a modular platform for tissue engineering and drug delivery applications.
基金supported by the National Natural Science Foundation of China (No. 21771071, 22171094, and 21925104)the Key Scientific Research Projects of Universities in Henan Province (No. 21A150060)
文摘Silver thiolate polymers are intercepted to form different structural fragments when reacting with variant solubilizing reagents,which usually serve as the starting point for the preparation of clusters.However,such a process is still far from clear.Herein,we report the controlled synthesis of silver-t-butylthiolate clusters from reactions of polymeric[Ag^(t)BuS]n and suitable templates in the presence of solubilizing reagents to offer a detailed look at the mechanism of cluster’s formation.As the provided solubilizing reagents have weak coordina-tion ability,such as O-or N-donating ligands,the obtained polymeric compound retains the linear structure pat-tern that S and Ag atoms are arranged alternately.When extra templates NO_(3)^(−)and CO_(3)^(2−)are applied,the disk-like clusters Ag_(19)and Ag_(20)are constructed with the same[Ag^(t)BuS]_(5)circles that may directly cyclize from the linear[Ag^(t)BuS]_(n)fragments.In contrast,(EtO)_(2)PS_(2)^(−)and(iPrO)_(2)PS_(2)^(−)anions have large size and strong coordination abil-ity rendering the structure of the polymer completely fragmented.Thus extremely short[Ag^(t)BuS]n pieces with silver ions and solubilizing ligands assemble around the templates V_(2)O_(7)^(4−)and W_(2)O_(9)^(4−),leading to the formation of clusters Ag_(22)and Ag_(24).
文摘A highly efficient and green four-component difunctionalization of styrenes with KSCN and imidazo[1,2-a]pyridines was developed.In this protocol,readily available KSCN was used as a sulfur source and inexpensive K2S2O8 was used as a free radical initiator.A series of C-3 thiolated imidazopyridine analogues were synthesized,in which hydroxyl group and aryl or alkyl group were incorporated.A novel method for the synthesis of multifunctionalized imidazopyridines was established.
基金supported by the National Natural Science Foundation of China (21925303,21829501,21771186,22171268,22171267,21971246)the Anhui Provincial Natural Science Foundation(2108085MB56)+1 种基金the HFIPS Director’s Fund (BJPY2019A02,YZJJ202102,YZJJ202306-TS)the Collaborative Innovation Program of Hefei Science Center,Chinese Academy of Sciences (2020HSC-CIP005,2022HSCCIP018)。
文摘Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.
基金Project supported by the National Natural Science Foundation of China （No. 20271036）, the Natural Science Foundation of Jiangsu Province of China （No. BK2004205） and the Key Laboratory of 0rganic Synthesis of Jiangsu Province of China （No. JSK001）.
文摘Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.
