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
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
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
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
Recent progress in the research of atomically-precise metal nanoclusters has identified a series of exceptionally stable nanoclusters with specific chemical compositions. Structural determination on such "magic s...Recent progress in the research of atomically-precise metal nanoclusters has identified a series of exceptionally stable nanoclusters with specific chemical compositions. Structural determination on such "magic size" nanoclusters revealed a variety of unique structures such as decahedron, icosahedron, as well as hexagonal close packing(hcp) and body-centered cubic(bcc) packing arrangements in gold nanoclusters, which are largely different from the face-centered cubic(fcc) structure in conventional gold nanoparticles. The characteristic geometrical structures enable the nanoclusters to exhibit interesting properties, and these properties are in close correlation with their atomic structures according to the recent studies. Experimental and theoretical analyses have been applied in the structural identification aiming to clarify the universal principle in the structural evolution of nanoclusters. In this mini-review, we summarize recent studies on periodic structural evolution of fcc-based gold nanoclusters protected by thiolates. A series of nanoclusters exhibit one-dimensional growth along the [001] direction in a layer-by-layer manner from Au_(23)(TBBT)_(20) to Au_(36)(TBBT)_(24),Au_(44)(TBBT)_(28), and to Au_(52)(TBBT)_(32)(TBBT: 4-tert-butylbenzenethiolate). The optical properties of these nanoclusters also evolve periodically based on steady-state and ultrafast spectroscopy. In addition, two-dimensional growth from Au_(44)(TBBT)_(28) toward both [100] and [010] directions leads to the Au_(92)(TBBT)_(44) nanocluster, and the recently reported Au_(52)(PET)_(32)(PET: 2-phenylethanethiol) also follows this growth pattern with partial removal of the layer. Theoretical predictions of relevant fcc nanoclusters include Au_(60)(SCH_3)_(36), Au_(68)(SCH_3)_(40), Au_(76)(SCH_3)_(44), etc, for the continuation of 1 D growth pattern, as well as Au_(68)(SR)_(38)mediating the 2 D growth pattern from Au_(44)(TBBT)_(28) to Au_(92)(TBBT)_(44). Overall, this mini-review provides guidelines on the rules of structural evolution of fcc gold nanoclusters based on 1 D, 2 D and 3 D growth patterns.展开更多
The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF),...The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.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
A novel type of thermal stabilizer-antimony tris (thioethyl stearate) (ATS) was synthsized. Its thermal stability was measured by heat-aging oven test when incorporated into PVC. ATS was synthesized from stearic acid,...A novel type of thermal stabilizer-antimony tris (thioethyl stearate) (ATS) was synthsized. Its thermal stability was measured by heat-aging oven test when incorporated into PVC. ATS was synthesized from stearic acid, antimony trioxide and 2-mercaptoethanol in two steps. The reaction conditions of synthesis were optimized through orthogonal test. Experimental results show that the molar ratio of stearic acid and antimony tris (2-hydroxyethylthiolate) was 1.2, adding 0.6%tetra-n-butyl titanate as catalyst and xylene as azeotropic solvent, heating and refluxing for about 4 h, and the yield of ATS is 83.9%. The thermal stability time is about 40 min(at 200 °C) when added 2phr(per hundred resin) in PVC. The thermal stability of ATS is better than that of Ca-Zn complex and basic lead stabilizers, and equal to that of dibutyltin dilaurate.展开更多
（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Co...（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Complexes 1 and 2 have been characterized by elemental analysis, IR, mass spectroscopy and X-ray single-crystal diffraction analysis. Both complexes are of monoclinic with space group P21/c, formula C52H94S2Si4Y2 1 （C52H94S2Si4Er2 2） Mr = 1073.57 （1230.27）, a = 8.495（2） （8.41（2））, b = 26.913（8） （26.67（7））, c = 13.756（4） （13.68（4）） A, α = 90（90）, β = 101.184（5） （101.57（4））, γ = 90 （90）°, V= 3085.1（15） （3007（14）） A^3, Dc = 1.156 （1.359） g·cm^-3, Z= 2 （2）, F（000） = 1144 （1260）, μ = 2.046 （2.951） cm^-1, R = 0.0687 （0.0749） and wR = 0.1306 （0.1507） for observed reflections with I 〉 2σ（I）. X-ray structures of 1 and 2 definitively prove that only one sulfur atom is inserted into the Ln-C（^nBu） bond, forming a thiolate ligand.展开更多
The title complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817（2）,b = 14.3...The title complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817（2）,b = 14.3889（2）,c = 15.2136（2） ,α = 71.018（1）,β = 74.911（1）,γ = 85.146（1）°,V = 2214.86（6） 3,Z = 2,Mr = 900.4,Dc = 1.350 g/cm3,Mr = 900.40,μ（MoKα） = 0.616 mm-1,F（000） = 926,S = 1.016,the final R = 0.0478 and wR = 0.0947 for 6828 observed reflections with I 2σ（I） and 505 variables.The molecular structure of 1 consists of one neutral complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）] and one hexane solvent molecule.The geometry around ruthenium is pseudo-octahedral with two trans-binding PPh3 ligands and one chelating bidentate 4-ClPhNHCS2- ligand via two sulfur atoms.The average Ru-S,Ru-P and Ru-H bond lengths are 2.4824（8）,2.3495（8） and 1.71（2）,respectively.The electrochemical properties of 1 have been studied in CH2Cl2 solution by cyclic voltammetry.展开更多
A new tri-nuclear mixed metal thiolate complex [Ag（PPh3）2]2[Ni（edtO2）2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occu...A new tri-nuclear mixed metal thiolate complex [Ag（PPh3）2]2[Ni（edtO2）2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni（II） atom and the two silver（I） atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni（edt）2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581（11）,b = 12.239（9）,c = 22.316（17） ,β = 103.08（2）o,V = 3613（5） 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F（000） = 1604,T = 293（2） K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I 2σ（I）.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
The isomerization/chlorination of O, O-diallyl thiophosphoric (-nic) acid esters with phosphrus oxychloride gives S-allyl thiophosphoro (-no)chloride, which reacts with subsittuted phenol in chloroform in the presence...The isomerization/chlorination of O, O-diallyl thiophosphoric (-nic) acid esters with phosphrus oxychloride gives S-allyl thiophosphoro (-no)chloride, which reacts with subsittuted phenol in chloroform in the presence of triethylamine to afford eighteen new S-allyl thiophosphoric(-nic) acid derivatives. Thus, a new convenient method has been provided for synthesis of the title compounds.展开更多
In this work,azobenzene mesogen-containing tin thiolates have been synthesized,which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors.Based on the preorga...In this work,azobenzene mesogen-containing tin thiolates have been synthesized,which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors.Based on the preorganized tin thiolate precursors,Sn S nanocrystals encapsulated with in-situ N-doped carbon layer have been achieved through a simple solventless pyrolysis process with the azobenzene mesogenic thiolate precursor served as Sn,S,N,and C sources simultaneously.Thus prepared nanocomposite materials as anode of lithium ion batteries present a large specific capacity of 604.6 m Ah·g^（-1）at a current density of 100 m A·g^（-1）,keeping a high capacity retention up to 96% after 80 cycles,and display high rate capability due to the synergistic effect of well-dispersed Sn S nanocrystals and N-doped carbon layer.Such encouraging results shed a light on the controlled preparation of advanced nanocomposites based on liquid crystalline metallomesogen precursors and may boost their novel intriguing applications.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
A desulfonylative thiolation between heteroaryl sulfones and thiosulfonates for the efficient synthesis of heteroaryl sulfides was developed.The cross-electrophile couplings proceeded effectively via old C–SO2 bond c...A desulfonylative thiolation between heteroaryl sulfones and thiosulfonates for the efficient synthesis of heteroaryl sulfides was developed.The cross-electrophile couplings proceeded effectively via old C–SO2 bond cleavage and new C–S bond formation in the presence of cheapest and widely available iron powder as mediator under transition metal catalyst-free conditions,leading to a wide array of heteroaryl sulfides derived from benzo[d]thiazole,benzo[d]oxazole,thiazole,1,3,4-thiadiazole,and 1H-tetrazole in modest to excellent yields.In addition,the reaction exhibited good functional group compatibility,and the protocol could also be applicable to the use of selenosulfonate as substrate and be subjected to scale-up synthesis with equal ease.Notably,unreacted iron powder could be readily recovered after reaction by resorting to the attracting property of magnetic stir bar to iron.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
High-performance composites containing various kinds of nanofibers as reinforcing building blocks have recently received considerable attention, owing to their superior mechanical properties. One of the effective stra...High-performance composites containing various kinds of nanofibers as reinforcing building blocks have recently received considerable attention, owing to their superior mechanical properties. One of the effective strategies to reinforce these composites involves strengthening interfacial interactions via covalent bonds. However, in contrast to nanosheets, covalent bonds have been rarely used in nanofiber-reinforced composites. Herein, we report the macroscale fabrication of a series of Ag nanowire （NW）-thiolated chitosan （TCS） composite films via spray induced self-assembly. The obtained films were significantly strengthened by Ag-S covalent bonds formed between the Ag NWs and the thiol groups of TCS. The tensile strength of the optimized Ag NW-TCS film was up to 3.9 and 1.5 times higher compared with that of pure TCS and Ag NW-chitosan （CS） films, respectively.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.
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The project was supported by the Air Force Office of Scientific Research (FA9550-15-1-0154) and the U.S. National Science Foundation (DMREF-0903225).
文摘Recent progress in the research of atomically-precise metal nanoclusters has identified a series of exceptionally stable nanoclusters with specific chemical compositions. Structural determination on such "magic size" nanoclusters revealed a variety of unique structures such as decahedron, icosahedron, as well as hexagonal close packing(hcp) and body-centered cubic(bcc) packing arrangements in gold nanoclusters, which are largely different from the face-centered cubic(fcc) structure in conventional gold nanoparticles. The characteristic geometrical structures enable the nanoclusters to exhibit interesting properties, and these properties are in close correlation with their atomic structures according to the recent studies. Experimental and theoretical analyses have been applied in the structural identification aiming to clarify the universal principle in the structural evolution of nanoclusters. In this mini-review, we summarize recent studies on periodic structural evolution of fcc-based gold nanoclusters protected by thiolates. A series of nanoclusters exhibit one-dimensional growth along the [001] direction in a layer-by-layer manner from Au_(23)(TBBT)_(20) to Au_(36)(TBBT)_(24),Au_(44)(TBBT)_(28), and to Au_(52)(TBBT)_(32)(TBBT: 4-tert-butylbenzenethiolate). The optical properties of these nanoclusters also evolve periodically based on steady-state and ultrafast spectroscopy. In addition, two-dimensional growth from Au_(44)(TBBT)_(28) toward both [100] and [010] directions leads to the Au_(92)(TBBT)_(44) nanocluster, and the recently reported Au_(52)(PET)_(32)(PET: 2-phenylethanethiol) also follows this growth pattern with partial removal of the layer. Theoretical predictions of relevant fcc nanoclusters include Au_(60)(SCH_3)_(36), Au_(68)(SCH_3)_(40), Au_(76)(SCH_3)_(44), etc, for the continuation of 1 D growth pattern, as well as Au_(68)(SR)_(38)mediating the 2 D growth pattern from Au_(44)(TBBT)_(28) to Au_(92)(TBBT)_(44). Overall, this mini-review provides guidelines on the rules of structural evolution of fcc gold nanoclusters based on 1 D, 2 D and 3 D growth patterns.
文摘The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.
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.
文摘A novel type of thermal stabilizer-antimony tris (thioethyl stearate) (ATS) was synthsized. Its thermal stability was measured by heat-aging oven test when incorporated into PVC. ATS was synthesized from stearic acid, antimony trioxide and 2-mercaptoethanol in two steps. The reaction conditions of synthesis were optimized through orthogonal test. Experimental results show that the molar ratio of stearic acid and antimony tris (2-hydroxyethylthiolate) was 1.2, adding 0.6%tetra-n-butyl titanate as catalyst and xylene as azeotropic solvent, heating and refluxing for about 4 h, and the yield of ATS is 83.9%. The thermal stability time is about 40 min(at 200 °C) when added 2phr(per hundred resin) in PVC. The thermal stability of ATS is better than that of Ca-Zn complex and basic lead stabilizers, and equal to that of dibutyltin dilaurate.
基金This work was supported by the National Natural Science Foundation of China (No. 20572014)
文摘（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Complexes 1 and 2 have been characterized by elemental analysis, IR, mass spectroscopy and X-ray single-crystal diffraction analysis. Both complexes are of monoclinic with space group P21/c, formula C52H94S2Si4Y2 1 （C52H94S2Si4Er2 2） Mr = 1073.57 （1230.27）, a = 8.495（2） （8.41（2））, b = 26.913（8） （26.67（7））, c = 13.756（4） （13.68（4）） A, α = 90（90）, β = 101.184（5） （101.57（4））, γ = 90 （90）°, V= 3085.1（15） （3007（14）） A^3, Dc = 1.156 （1.359） g·cm^-3, Z= 2 （2）, F（000） = 1144 （1260）, μ = 2.046 （2.951） cm^-1, R = 0.0687 （0.0749） and wR = 0.1306 （0.1507） for observed reflections with I 〉 2σ（I）. X-ray structures of 1 and 2 definitively prove that only one sulfur atom is inserted into the Ln-C（^nBu） bond, forming a thiolate ligand.
基金supported by the National Natural Science Foundation of China (20771003)
文摘The title complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817（2）,b = 14.3889（2）,c = 15.2136（2） ,α = 71.018（1）,β = 74.911（1）,γ = 85.146（1）°,V = 2214.86（6） 3,Z = 2,Mr = 900.4,Dc = 1.350 g/cm3,Mr = 900.40,μ（MoKα） = 0.616 mm-1,F（000） = 926,S = 1.016,the final R = 0.0478 and wR = 0.0947 for 6828 observed reflections with I 2σ（I） and 505 variables.The molecular structure of 1 consists of one neutral complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）] and one hexane solvent molecule.The geometry around ruthenium is pseudo-octahedral with two trans-binding PPh3 ligands and one chelating bidentate 4-ClPhNHCS2- ligand via two sulfur atoms.The average Ru-S,Ru-P and Ru-H bond lengths are 2.4824（8）,2.3495（8） and 1.71（2）,respectively.The electrochemical properties of 1 have been studied in CH2Cl2 solution by cyclic voltammetry.
基金supported by the 973 Program (2007CB815301)the National Natural Science Foundation of China (21073192,20733003 and 20871114)+1 种基金the Science Foundation of CAS (KJCX2-YW-H20)Fujian Province (2009HZ0006-1,2006L2005)
文摘A new tri-nuclear mixed metal thiolate complex [Ag（PPh3）2]2[Ni（edtO2）2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni（II） atom and the two silver（I） atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni（edt）2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581（11）,b = 12.239（9）,c = 22.316（17） ,β = 103.08（2）o,V = 3613（5） 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F（000） = 1604,T = 293（2） K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I 2σ（I）.
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The isomerization/chlorination of O, O-diallyl thiophosphoric (-nic) acid esters with phosphrus oxychloride gives S-allyl thiophosphoro (-no)chloride, which reacts with subsittuted phenol in chloroform in the presence of triethylamine to afford eighteen new S-allyl thiophosphoric(-nic) acid derivatives. Thus, a new convenient method has been provided for synthesis of the title compounds.
基金Project supported by the National Natural Science Foundation of China(Grant No.21574062)the Huaian High-Technology Research Institute of Nanjing University,China(Grant No.2011Q1)
文摘In this work,azobenzene mesogen-containing tin thiolates have been synthesized,which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors.Based on the preorganized tin thiolate precursors,Sn S nanocrystals encapsulated with in-situ N-doped carbon layer have been achieved through a simple solventless pyrolysis process with the azobenzene mesogenic thiolate precursor served as Sn,S,N,and C sources simultaneously.Thus prepared nanocomposite materials as anode of lithium ion batteries present a large specific capacity of 604.6 m Ah·g^（-1）at a current density of 100 m A·g^（-1）,keeping a high capacity retention up to 96% after 80 cycles,and display high rate capability due to the synergistic effect of well-dispersed Sn S nanocrystals and N-doped carbon layer.Such encouraging results shed a light on the controlled preparation of advanced nanocomposites based on liquid crystalline metallomesogen precursors and may boost their novel intriguing applications.
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We gratefully acknowledge the financial support from Nanjing Tech University(Start-up Grant No.39837118).
文摘A desulfonylative thiolation between heteroaryl sulfones and thiosulfonates for the efficient synthesis of heteroaryl sulfides was developed.The cross-electrophile couplings proceeded effectively via old C–SO2 bond cleavage and new C–S bond formation in the presence of cheapest and widely available iron powder as mediator under transition metal catalyst-free conditions,leading to a wide array of heteroaryl sulfides derived from benzo[d]thiazole,benzo[d]oxazole,thiazole,1,3,4-thiadiazole,and 1H-tetrazole in modest to excellent yields.In addition,the reaction exhibited good functional group compatibility,and the protocol could also be applicable to the use of selenosulfonate as substrate and be subjected to scale-up synthesis with equal ease.Notably,unreacted iron powder could be readily recovered after reaction by resorting to the attracting property of magnetic stir bar to iron.
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(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].
文摘High-performance composites containing various kinds of nanofibers as reinforcing building blocks have recently received considerable attention, owing to their superior mechanical properties. One of the effective strategies to reinforce these composites involves strengthening interfacial interactions via covalent bonds. However, in contrast to nanosheets, covalent bonds have been rarely used in nanofiber-reinforced composites. Herein, we report the macroscale fabrication of a series of Ag nanowire （NW）-thiolated chitosan （TCS） composite films via spray induced self-assembly. The obtained films were significantly strengthened by Ag-S covalent bonds formed between the Ag NWs and the thiol groups of TCS. The tensile strength of the optimized Ag NW-TCS film was up to 3.9 and 1.5 times higher compared with that of pure TCS and Ag NW-chitosan （CS） films, respectively.
