(S,S)-Me-BI-DIME/Pd(0)-catalyzed ennantioselective C-H functionalization of N-ferrocenyl o-bromobenzanilides has been realized,affording isoquinolinone-fused ferrocenes with up to 97% ee.The products can be transforme...(S,S)-Me-BI-DIME/Pd(0)-catalyzed ennantioselective C-H functionalization of N-ferrocenyl o-bromobenzanilides has been realized,affording isoquinolinone-fused ferrocenes with up to 97% ee.The products can be transformed into planar chiral ferrocenyl monophosphines,which demonstrate their preliminary application.展开更多
Four chiral 1,1?bis(oxazolinyl)ferrocenes(1a-1d) have been prepared and used as ligands in the copper catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate (EDA) and the magnesium catalyzed Diels-Al...Four chiral 1,1?bis(oxazolinyl)ferrocenes(1a-1d) have been prepared and used as ligands in the copper catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate (EDA) and the magnesium catalyzed Diels-Alder reaction between 3-acryloyl-2-oxazolidinone and cyclopentadiene. Enantioselectivities up to 24% and 41%, respectively, for cyclopropanation and Diels-Alder reaction were observed.展开更多
Ferrocene is an organometallic compound that readily undergoes oxidation in atmosphere under acidic conditions. However, because of its diamagnetic nature, ferrocene does not lend itself to structural analysis by nucl...Ferrocene is an organometallic compound that readily undergoes oxidation in atmosphere under acidic conditions. However, because of its diamagnetic nature, ferrocene does not lend itself to structural analysis by nuclear magnetic resonance (NMR) spectroscopy. In this work, the oxidation of ferrocene and several of its derivatives were analyzed by liquid chromatography-mass spectrometry (LC-MS). An electrospray ionization (ESI) source was used, with picrate serving as the counter ion. This method is particularly effective for studying oxidation of ferrocenes because their reactivity toward oxygen under ambient conditions is low.展开更多
Planar organofluorine compounds are highly sought-after structural motifs.Herein,we present an enantioselective strategy for the synthesis of planar chiral fluoroalkenes via kinetic resolution of gem-difluorovinylferr...Planar organofluorine compounds are highly sought-after structural motifs.Herein,we present an enantioselective strategy for the synthesis of planar chiral fluoroalkenes via kinetic resolution of gem-difluorovinylferrocenes by copper-catalyzed hydrodefluorination in the presence of a base and diboron.This method was successfully applied to provide a diverse range of planar chiral gem-difluoroalkenes and Z-monofluoroalkenes with excellent regio-,stereo-and enantioselectivity.The resulting enantioenriched planar chiral fluoroalkenes could undergo various enantioretaining transformations,broadening their synthetic utility.Furthermore,density functional theory(DFT)calculations provide mechanistic insights into the origin of enantioselectivity,enhancing the understanding of this transformation.展开更多
Herein,we report an intramolecular 6-endo-dig cyclization of N-ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation.By using this protocol,a variety of pla...Herein,we report an intramolecular 6-endo-dig cyclization of N-ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation.By using this protocol,a variety of planar chiral ferrocenopyridin-2(1H)-ones were obtained in good yields and excellent enantioselectivities(up to 96%ee).展开更多
Oxy-substituted planar chiral ferrocenes are of great importance in asymmetric synthesis and pharmaceuticals.However,enantioselective C–H activation of ferrocenes that form C–O bonds remains a huge challenge and has...Oxy-substituted planar chiral ferrocenes are of great importance in asymmetric synthesis and pharmaceuticals.However,enantioselective C–H activation of ferrocenes that form C–O bonds remains a huge challenge and has not yet been reported.Herein,the asymmetric synthesis of oxy-substituted planar chiral ferrocenes is achieved by cobalt-catalyzed enantioselective dehydrogenative C–H acyloxylation.The use of a dual-ligand system consisting of a chiral salicyloxazoline(Salox)ligand and a neutral phosphine oxide ligand,which is oxidized in situ from the corresponding phosphine,resulted in good yield(up to 83%)and excellent enantioselectivity(90–99%ee).The utility of this unprecedented protocol is highlighted by its versatile synthetic transformations.展开更多
Planar chiral ferrocenes are widely applied in organic synthesis,materials science,and medicinal chemistry,but their synthesis is not trivial.Herein,a highly efficient synthesis of planar chiral ferrocene-based pyridi...Planar chiral ferrocenes are widely applied in organic synthesis,materials science,and medicinal chemistry,but their synthesis is not trivial.Herein,a highly efficient synthesis of planar chiral ferrocene-based pyridine derivatives via Rh(I)-catalyzed direct coupling of pyridylferrocenes with aryl halides was developed.Good yields and excellent enantioselectivity(95–>99%ee)are obtained for a wide range of substrates.The compatibility of gram-scale synthesis and relatively low catalyst loading(down to 1 mol%based on[Rh])enhance the practicality of the current method.The generated coupling products can be readily transformed into chiral ligands.Mechanistic studies suggest that the C–H bond cleavage of pyridylferrocene may be a reversible step and not the rate-determining step.Significant nonlinear effects indicate the existence of multiple metals or ligands in the active catalyst.展开更多
Diabetic wounds are among the most challenging chronic wounds to heal,due to the presence of multiple factors,including continuous oxidative stress,impaired vascular integrity,and biofilm formation.The development of ...Diabetic wounds are among the most challenging chronic wounds to heal,due to the presence of multiple factors,including continuous oxidative stress,impaired vascular integrity,and biofilm formation.The development of innovative treatment strategies is of paramount importance for the management of diabetic wounds.Stemmed from the pleiotropic physicochemical properties of ferrocene and spermidine,this essay reported the ferrocene-spermidine co-polymer(Fc S)for the first time through facile amidation reaction.Molecular dynamics simulation revealed its self-assembly through hydrogen bonds,van der Waals forces instead of traditional nanoprecipitation.The self-assembled nanoparticles were demonstrated to exhibit great antioxidant property on cells to facilitate their migration and angiogenesis.Moreover,the integration with photocuring hydrogel,gelatin methacrylate(Gel MA),to construct Fc S nanoparticles loaded wound dressing(Gel MA@Fc S)further confirmed the potential on promoting diabetic wound enclosure through enhancement of re-epithelization and collagen deposition.Together with its great biocompatibility and biosafety,Gel MA@Fc S is expected to be developed into a wound dressing for clinical diabetic wounds management.展开更多
Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely...Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely FcTF-COF and FcBD-COF,are successfully synthesized for the first time through a solvothermal method,and the obtained Fc-COFs powders are used to adsorb Congo red(CR)from water.The results show that both FcTF-COF and FcBD-COF have superb adsorption performance towards CR with ultrahigh adsorption capability of 1672.2 mg g−1 and 1983.7 mg g−1 at pH=4.0,respectively,outperforming the majority of the reported solid porous adsorbents.The maximum adsorption of both Fc-COFs agrees with the Sips adsorption isothermal model,indicating that their adsorption was dominated by heterogeneous adsorption.The Coulombic interactions,hydrogen bonding,π-πinteractions and ion-dipolar interactions should all contribute to their ultrahigh CR adsorption capability and high-pH resistance performance regardless of the pH in the range of 4-9.In addition,after five cycles,both COFs still remain their exceptional high CR adsorption capabilities.This study offers a prospective organic porous adsorbent with promising applications for organic dye removal in sewage processing.展开更多
The diversity,complexity,heterogeneity,and drug resistance of tumors make it challenging to meet the clinical needs of a single apoptosis-inducing chemotherapy.The combination of apoptosis and ferroptosis is expected ...The diversity,complexity,heterogeneity,and drug resistance of tumors make it challenging to meet the clinical needs of a single apoptosis-inducing chemotherapy.The combination of apoptosis and ferroptosis is expected to address the side effects of chemotherapy and enhance therapeutic efficacy.Here,an amphiphilic pH-responsive doxorubicin(DOX)and ferrocene(Fc)-containing copolyprodrug(P(ADH-DOXFc)-PEG)was designed with high DOX and Fc content of 66.5%and 0.58 mmol/g by a facile polycondensation for combining chemotherapy with ferroptosis in cancer treatment.A drug self-delivery system(DSDS)with an average hydrodynamic diameter(D_(h))of 135 nm can be easily obtained via self-assembly with the polyprodrug blocks as the hydrophobic core and PEG as the hydrophilic brush.The cumulative DOX release reached 72.7%in the simulated tumor intracellular acidic microenvironment within 56 h,whereas the premature drug leakage was only 6.2%in the simulated normal physiological medium.The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT)assay results indicated an IC_(50)of 8.2μg/mL,exhibiting enhanced anti-tumor efficacy and a successful combination of apoptosis and ferroptosis,with a combination index(CI)of 0.88.展开更多
This study was carried out to evaluate the response of Nile tilapia(Oreochromis niloticus)fingerlings to acute copper sulphate and ferrocene toxicity.Nile tilapia fingerlings weighing 2.3±0.2 g were acclimated an...This study was carried out to evaluate the response of Nile tilapia(Oreochromis niloticus)fingerlings to acute copper sulphate and ferrocene toxicity.Nile tilapia fingerlings weighing 2.3±0.2 g were acclimated and randomly distributed at a rate of 10 fish per 30 L aquarium.Fish were exposed to a range of copper sulphate and ferrocene concentrations of 4 mg/L,8 mg/L,12 mg/L,16 mg/L and 2.5 mg/L,5 mg/L,7.5 mg/L,10 mg/L respectively.Fish not exposed to any toxicant served as control.Mortality was assessed and median lethal concentration(LC_(50))and median lethal time(LT_(50))were calculated.The 96-h LC50 values obtained for copper sulphate and ferrocene were 7.49 mg/L(confidence interval CI:6.35 to 8.57 mg/L)and 3.55 mg/L(CI:0.98 to 5.17 mg/L)respectively.The LC_(50) decreased with time of exposure implying that toxicity increased over time,however,LT50 decreased as concentration increased.The safe concentration for copper sulphate derived was 1.913 mg/L and 1.196 mg/L for ferrocene.Histological analyses were carried out on fish gills and skin.The skin histomorphology showed marked and widespread epidermal loss and widespread mycocytic degeneration in treatments with high concentration for both toxicants.The gill morphology showed moderate to severe hyperplasia of the primary gill epithelia leading to partial or complete loss of the secondary lamellae.展开更多
A new approach for assembling amperometric mushroom pulp tissue based membrane electrode for determination of L tyrosine analysis is proposed. Ferrocene is used as a mediator of electron transfer between tyrosinase ...A new approach for assembling amperometric mushroom pulp tissue based membrane electrode for determination of L tyrosine analysis is proposed. Ferrocene is used as a mediator of electron transfer between tyrosinase in mushroom tissue and a graphite electrode. The optimal operation conditions are studied. The linear response range of the biosensor is 2 0×10 -4 to 4 5×10 -3 mol·L -1 with response time of less than 5 min and lifetime of at least 30 d. The biosensor can be applied to practical sample analysis.展开更多
A titanocene-ferrocenyl complex, （5-ferrocenyl-2-hydroxybenzenecarboxylato- O,O′）-bis（methylcyclopentadienyl）titanium（IV） 4, and an unexpected ionic complex, [C7H8NO3]- [（C5H5）Fe（C5H4）SO3]·H2O3 were sy...A titanocene-ferrocenyl complex, （5-ferrocenyl-2-hydroxybenzenecarboxylato- O,O′）-bis（methylcyclopentadienyl）titanium（IV） 4, and an unexpected ionic complex, [C7H8NO3]- [（C5H5）Fe（C5H4）SO3]·H2O3 were synthesized and characterized by IR, ^1H NMR and elemental analysis. Compound 3 is of triclinic, space group P1 with a = 5.954（2）, b = 13.208（5）, c = 13.252（5） A, α = 60.993（7）,β = 84.342（8）,γ = 86.933（8）°, Z = 2, V = 906.8（6）A^3, Dc = 1.601 g/cm^3, μ（MoKα） = 0.987 mm^-1, F（000） = 452, the final R = 0.0647 and wR = 0.1333 for 2311 observed reflections （I 〉 2σ（I））. Compound 4 belongs to the monoclinic system, space group P2 1/c with α = 14.3310（9）, b = 12.5065（8）, c = 12.9406（10） A, β = 95.101（4）°, Z = 4, V = 2310.2（3） A^3, Dc = 1.513 g/cm^3, μ（MoKα） = 1.004 mm^-1, F（000） = 1088, the final R = 0.0461 and wR = 0.1048 for 2112 observed reflections （1 〉 2σ（I））.展开更多
A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix. The ...A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix. The electrochemical behavior of captopril (CAP) at the surface of the modified electrode was investigated using electroanalytical methods. The modified electrode showed excellent electrocatalytic activity for the oxidation of CAP in aqueous solutions at physiological pH values. Cyclic voltammetric curves showed that the oxidation of CAP at the surface of the modified electrode reduced its overpotential by more than 290 mV. The modified electrode was used for detecting captopril using cyclic voltammetry and square wave voltammetry techniques. A calibration curve in the range of 0.03 to 2400 μmol/L was obtained that had a detection limit of 0.0096 μmol/L (3?) under the optimized conditions. The modified electrode was successfully used for the determination of captopril in pharmaceutical and biological samples.展开更多
In order to study the gas explosion suppression performance based on ferrocene, the self-constructed experimental facility was used to accomplish the experiment of gas explosion suppression. By means of thermogravimet...In order to study the gas explosion suppression performance based on ferrocene, the self-constructed experimental facility was used to accomplish the experiment of gas explosion suppression. By means of thermogravimetric analysis, the thermal characteristics of ferrocene have been gotten and the gas explosion suppression mechanism of ferrocene has been analyzed. The results show that ferrocene had good effects on gas explosion suppression, and the explosion pressure and flame propagation speed declined obviously. When ferrocene concentration is 0.08 g/L and methane volume concentration is 9.5%, the maximum explosion overpressure and maximum flame propagation speed of methane-air respectively decreased by about 59.5% and 19.6%, respectively. TG and DSC curves showed that the mass loss of ferrocene consists of two processes, which are sublimation and lattice fracture. The temperature of mass loss ranged from 128 ℃ to 230 ℃. The results showed profoundly theoretical significance to gas explosion suppression by ferrocene in coal mines.展开更多
Coordination bonds are relatively unstable compared to covalent bonds,and common carbon-based absorbing material precursors are bonded in the form of coordination bonds.In this work,we have introduced ferrocene units ...Coordination bonds are relatively unstable compared to covalent bonds,and common carbon-based absorbing material precursors are bonded in the form of coordination bonds.In this work,we have introduced ferrocene units into conjugated microporous polymers(CMP)in one step by Suzuki reaction.By adjusting the proportion of ferrocene units,a series of magnetic Fe-C nanocomposites(Fe-P-XC)derived from conjugated ferrocene polymers without heteroatom doping(N,S,P,etc.)were formed.The Fe-P-2C composite has good absorption properties with minimum reflection loss at 4.4 GHz(-58.66 dB)and effective absorption bandwidth(EAB)of 6.28 GHz at 2.4 mm(11.72-18 GHz).Compared with the precursor materials formed by coordination bonds,the present work reveals the electromagnetic wave absorption mechanism of carbon-based materials without heteroatom doping through a simple and effective strategy.展开更多
A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedicarboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ),which is a twisted...A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedicarboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ),which is a twisted non-coplanar heterocyclic bisphenol-like monomer.The newly generated polymer was evaluated based on characterization of its solubility,viscosity measurements,elemental analysis,FTIR spectroscopy,differential scanning calorimetric and thermogravimetric studies.展开更多
A carbon/PVC-COOH/ferrocene composite electrode used for the determination of glucose has been prepared. The ferrocene acted as mediator was incorporated into the PVC-COOH polymer and the leakage could be prevented. T...A carbon/PVC-COOH/ferrocene composite electrode used for the determination of glucose has been prepared. The ferrocene acted as mediator was incorporated into the PVC-COOH polymer and the leakage could be prevented. The presence of carboxyl groups on the electrode surface allowed immobilizing enzyme via EDC and NHS. The ratio of PVC-COOH to graphite powder （w/w） has been studied. Amperometric determination of glucose has been performed at potential of 0.30 V vs SCE. The response time was 〈 15 s. The linear response range was of 0.1-20 mmol/L with a detection limit of 48μmol/L.展开更多
4-（2-Ferrocenylethenyl）-phenyl-POSS Fc-CH=CH-C6H6-（C5H9）7Si8O12 （FEPS, Fc： ferrocene）, containing metal and C=C double bond, was firstly synthesized as a mixture of E/Z isomers by the Wittig reaction. The chemi...4-（2-Ferrocenylethenyl）-phenyl-POSS Fc-CH=CH-C6H6-（C5H9）7Si8O12 （FEPS, Fc： ferrocene）, containing metal and C=C double bond, was firstly synthesized as a mixture of E/Z isomers by the Wittig reaction. The chemical structure of FEPS was characterized by FTIR, ^1H-, ^13C and ^29Si- NMR.展开更多
A novel chiral stationary phase （CSP） was prepared by immobilizing mono（6A-N-1-（2-hydroxyl）-phenylethylimino-6A- deoxy）-β-cyclodextrin onto the surface of silica gel via a longer spacer. This chiral stationary ...A novel chiral stationary phase （CSP） was prepared by immobilizing mono（6A-N-1-（2-hydroxyl）-phenylethylimino-6A- deoxy）-β-cyclodextrin onto the surface of silica gel via a longer spacer. This chiral stationary phase exhibited good enantioselectivity for a variety of chiral compounds under reversed-phase conditions.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.21572126,21202095,14HASTIT016)Technicians Troop Construction Projects of Henan Province(No.C20150030)Program of Science and Technology Innovation Talents of Henan Province(No.184100510011)。
文摘(S,S)-Me-BI-DIME/Pd(0)-catalyzed ennantioselective C-H functionalization of N-ferrocenyl o-bromobenzanilides has been realized,affording isoquinolinone-fused ferrocenes with up to 97% ee.The products can be transformed into planar chiral ferrocenyl monophosphines,which demonstrate their preliminary application.
文摘Four chiral 1,1?bis(oxazolinyl)ferrocenes(1a-1d) have been prepared and used as ligands in the copper catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate (EDA) and the magnesium catalyzed Diels-Alder reaction between 3-acryloyl-2-oxazolidinone and cyclopentadiene. Enantioselectivities up to 24% and 41%, respectively, for cyclopropanation and Diels-Alder reaction were observed.
文摘Ferrocene is an organometallic compound that readily undergoes oxidation in atmosphere under acidic conditions. However, because of its diamagnetic nature, ferrocene does not lend itself to structural analysis by nuclear magnetic resonance (NMR) spectroscopy. In this work, the oxidation of ferrocene and several of its derivatives were analyzed by liquid chromatography-mass spectrometry (LC-MS). An electrospray ionization (ESI) source was used, with picrate serving as the counter ion. This method is particularly effective for studying oxidation of ferrocenes because their reactivity toward oxygen under ambient conditions is low.
基金supported by the NSFC(No.22471063)the Natural Science Foundation of Henan Province(242300421351,252300421719)+1 种基金Education Department of Henan Province Natural Science Research Program(23A150037)Henan Postdoctoral Science Foundation(202103087)。
文摘Planar organofluorine compounds are highly sought-after structural motifs.Herein,we present an enantioselective strategy for the synthesis of planar chiral fluoroalkenes via kinetic resolution of gem-difluorovinylferrocenes by copper-catalyzed hydrodefluorination in the presence of a base and diboron.This method was successfully applied to provide a diverse range of planar chiral gem-difluoroalkenes and Z-monofluoroalkenes with excellent regio-,stereo-and enantioselectivity.The resulting enantioenriched planar chiral fluoroalkenes could undergo various enantioretaining transformations,broadening their synthetic utility.Furthermore,density functional theory(DFT)calculations provide mechanistic insights into the origin of enantioselectivity,enhancing the understanding of this transformation.
基金support from the National Natural Science Foundation of China(No.21572126)Natural Science Foundation of Henan(No.232300421234)+2 种基金Key Scientific and Technological Project of Henan Province(No.222102310372)Leading Talents in Scientific and Technological Innovation in Shangqiu(No.SQRC202212004)Shangqiu Normal University(Program of Ecological Environmental Protection in the Area of Old Course of Yellow River).
文摘Herein,we report an intramolecular 6-endo-dig cyclization of N-ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation.By using this protocol,a variety of planar chiral ferrocenopyridin-2(1H)-ones were obtained in good yields and excellent enantioselectivities(up to 96%ee).
基金supported by the National Key R&D Program of China(grant nos.2021YFF0701603 and 2022YFA1504302)the National Natural Science Foundation of China(grant nos.21925109,U22A20388,and 92256302)+1 种基金the Fundamental Research Funds for the Central Universities(grant nos.226-2023-00115 and 226-2022-00224)the College of Material Chemistry and Chemical Engineering,Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University(grant no.KFJJ2023003).
文摘Oxy-substituted planar chiral ferrocenes are of great importance in asymmetric synthesis and pharmaceuticals.However,enantioselective C–H activation of ferrocenes that form C–O bonds remains a huge challenge and has not yet been reported.Herein,the asymmetric synthesis of oxy-substituted planar chiral ferrocenes is achieved by cobalt-catalyzed enantioselective dehydrogenative C–H acyloxylation.The use of a dual-ligand system consisting of a chiral salicyloxazoline(Salox)ligand and a neutral phosphine oxide ligand,which is oxidized in situ from the corresponding phosphine,resulted in good yield(up to 83%)and excellent enantioselectivity(90–99%ee).The utility of this unprecedented protocol is highlighted by its versatile synthetic transformations.
基金the National Key R&D Program of China(2016YFA0202900),NSFC(21821002,91856201)the CAS(XDB20000000,QYZDY-SSW-SLH012)Science and Technology Commission of Shanghai Municipality(18JC1411302)。
文摘Planar chiral ferrocenes are widely applied in organic synthesis,materials science,and medicinal chemistry,but their synthesis is not trivial.Herein,a highly efficient synthesis of planar chiral ferrocene-based pyridine derivatives via Rh(I)-catalyzed direct coupling of pyridylferrocenes with aryl halides was developed.Good yields and excellent enantioselectivity(95–>99%ee)are obtained for a wide range of substrates.The compatibility of gram-scale synthesis and relatively low catalyst loading(down to 1 mol%based on[Rh])enhance the practicality of the current method.The generated coupling products can be readily transformed into chiral ligands.Mechanistic studies suggest that the C–H bond cleavage of pyridylferrocene may be a reversible step and not the rate-determining step.Significant nonlinear effects indicate the existence of multiple metals or ligands in the active catalyst.
基金supported by National Natural Science Foundation of China(Nos.52173150 and U22A20315)the Guangzhou Science and Technology Program City-University Joint Funding Project(No.2024A03J0604)+2 种基金the Science and Technology Program of Guangzhou(No.2024A03J0431)the start-up funding for the Seventh Affiliated Hospital of Sun Yat-sen University(Shenzhen)(No.ZSQYRSFPD0053)Guangdong Basic and Applied Basic Research Foundation(No.2023A1515111126)。
文摘Diabetic wounds are among the most challenging chronic wounds to heal,due to the presence of multiple factors,including continuous oxidative stress,impaired vascular integrity,and biofilm formation.The development of innovative treatment strategies is of paramount importance for the management of diabetic wounds.Stemmed from the pleiotropic physicochemical properties of ferrocene and spermidine,this essay reported the ferrocene-spermidine co-polymer(Fc S)for the first time through facile amidation reaction.Molecular dynamics simulation revealed its self-assembly through hydrogen bonds,van der Waals forces instead of traditional nanoprecipitation.The self-assembled nanoparticles were demonstrated to exhibit great antioxidant property on cells to facilitate their migration and angiogenesis.Moreover,the integration with photocuring hydrogel,gelatin methacrylate(Gel MA),to construct Fc S nanoparticles loaded wound dressing(Gel MA@Fc S)further confirmed the potential on promoting diabetic wound enclosure through enhancement of re-epithelization and collagen deposition.Together with its great biocompatibility and biosafety,Gel MA@Fc S is expected to be developed into a wound dressing for clinical diabetic wounds management.
基金supported by the National Nat-ural Science Foundation of China(22465012)the Key Research and Development Project of Hainan Province,China(ZDYF2024GXJS005)the Major Science and Technology Plan of Hainan Province,China(ZDKJ202016).
文摘Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely FcTF-COF and FcBD-COF,are successfully synthesized for the first time through a solvothermal method,and the obtained Fc-COFs powders are used to adsorb Congo red(CR)from water.The results show that both FcTF-COF and FcBD-COF have superb adsorption performance towards CR with ultrahigh adsorption capability of 1672.2 mg g−1 and 1983.7 mg g−1 at pH=4.0,respectively,outperforming the majority of the reported solid porous adsorbents.The maximum adsorption of both Fc-COFs agrees with the Sips adsorption isothermal model,indicating that their adsorption was dominated by heterogeneous adsorption.The Coulombic interactions,hydrogen bonding,π-πinteractions and ion-dipolar interactions should all contribute to their ultrahigh CR adsorption capability and high-pH resistance performance regardless of the pH in the range of 4-9.In addition,after five cycles,both COFs still remain their exceptional high CR adsorption capabilities.This study offers a prospective organic porous adsorbent with promising applications for organic dye removal in sewage processing.
文摘The diversity,complexity,heterogeneity,and drug resistance of tumors make it challenging to meet the clinical needs of a single apoptosis-inducing chemotherapy.The combination of apoptosis and ferroptosis is expected to address the side effects of chemotherapy and enhance therapeutic efficacy.Here,an amphiphilic pH-responsive doxorubicin(DOX)and ferrocene(Fc)-containing copolyprodrug(P(ADH-DOXFc)-PEG)was designed with high DOX and Fc content of 66.5%and 0.58 mmol/g by a facile polycondensation for combining chemotherapy with ferroptosis in cancer treatment.A drug self-delivery system(DSDS)with an average hydrodynamic diameter(D_(h))of 135 nm can be easily obtained via self-assembly with the polyprodrug blocks as the hydrophobic core and PEG as the hydrophilic brush.The cumulative DOX release reached 72.7%in the simulated tumor intracellular acidic microenvironment within 56 h,whereas the premature drug leakage was only 6.2%in the simulated normal physiological medium.The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT)assay results indicated an IC_(50)of 8.2μg/mL,exhibiting enhanced anti-tumor efficacy and a successful combination of apoptosis and ferroptosis,with a combination index(CI)of 0.88.
文摘This study was carried out to evaluate the response of Nile tilapia(Oreochromis niloticus)fingerlings to acute copper sulphate and ferrocene toxicity.Nile tilapia fingerlings weighing 2.3±0.2 g were acclimated and randomly distributed at a rate of 10 fish per 30 L aquarium.Fish were exposed to a range of copper sulphate and ferrocene concentrations of 4 mg/L,8 mg/L,12 mg/L,16 mg/L and 2.5 mg/L,5 mg/L,7.5 mg/L,10 mg/L respectively.Fish not exposed to any toxicant served as control.Mortality was assessed and median lethal concentration(LC_(50))and median lethal time(LT_(50))were calculated.The 96-h LC50 values obtained for copper sulphate and ferrocene were 7.49 mg/L(confidence interval CI:6.35 to 8.57 mg/L)and 3.55 mg/L(CI:0.98 to 5.17 mg/L)respectively.The LC_(50) decreased with time of exposure implying that toxicity increased over time,however,LT50 decreased as concentration increased.The safe concentration for copper sulphate derived was 1.913 mg/L and 1.196 mg/L for ferrocene.Histological analyses were carried out on fish gills and skin.The skin histomorphology showed marked and widespread epidermal loss and widespread mycocytic degeneration in treatments with high concentration for both toxicants.The gill morphology showed moderate to severe hyperplasia of the primary gill epithelia leading to partial or complete loss of the secondary lamellae.
文摘A new approach for assembling amperometric mushroom pulp tissue based membrane electrode for determination of L tyrosine analysis is proposed. Ferrocene is used as a mediator of electron transfer between tyrosinase in mushroom tissue and a graphite electrode. The optimal operation conditions are studied. The linear response range of the biosensor is 2 0×10 -4 to 4 5×10 -3 mol·L -1 with response time of less than 5 min and lifetime of at least 30 d. The biosensor can be applied to practical sample analysis.
基金Supported by the National Natural Science Foundation of China (20771071)the Program for New Century Excellent Talents in University of China,and Natural Science Foundation of Shaanxi Province (2007B06)
文摘A titanocene-ferrocenyl complex, （5-ferrocenyl-2-hydroxybenzenecarboxylato- O,O′）-bis（methylcyclopentadienyl）titanium（IV） 4, and an unexpected ionic complex, [C7H8NO3]- [（C5H5）Fe（C5H4）SO3]·H2O3 were synthesized and characterized by IR, ^1H NMR and elemental analysis. Compound 3 is of triclinic, space group P1 with a = 5.954（2）, b = 13.208（5）, c = 13.252（5） A, α = 60.993（7）,β = 84.342（8）,γ = 86.933（8）°, Z = 2, V = 906.8（6）A^3, Dc = 1.601 g/cm^3, μ（MoKα） = 0.987 mm^-1, F（000） = 452, the final R = 0.0647 and wR = 0.1333 for 2311 observed reflections （I 〉 2σ（I））. Compound 4 belongs to the monoclinic system, space group P2 1/c with α = 14.3310（9）, b = 12.5065（8）, c = 12.9406（10） A, β = 95.101（4）°, Z = 4, V = 2310.2（3） A^3, Dc = 1.513 g/cm^3, μ（MoKα） = 1.004 mm^-1, F（000） = 1088, the final R = 0.0461 and wR = 0.1048 for 2112 observed reflections （1 〉 2σ（I））.
文摘A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix. The electrochemical behavior of captopril (CAP) at the surface of the modified electrode was investigated using electroanalytical methods. The modified electrode showed excellent electrocatalytic activity for the oxidation of CAP in aqueous solutions at physiological pH values. Cyclic voltammetric curves showed that the oxidation of CAP at the surface of the modified electrode reduced its overpotential by more than 290 mV. The modified electrode was used for detecting captopril using cyclic voltammetry and square wave voltammetry techniques. A calibration curve in the range of 0.03 to 2400 μmol/L was obtained that had a detection limit of 0.0096 μmol/L (3?) under the optimized conditions. The modified electrode was successfully used for the determination of captopril in pharmaceutical and biological samples.
基金Supported by the National Natural Science Foundation of China （50974055, 50476033） the Doctor Foundation Project from the Henan Polytechnic University （B2011 - 101）
文摘In order to study the gas explosion suppression performance based on ferrocene, the self-constructed experimental facility was used to accomplish the experiment of gas explosion suppression. By means of thermogravimetric analysis, the thermal characteristics of ferrocene have been gotten and the gas explosion suppression mechanism of ferrocene has been analyzed. The results show that ferrocene had good effects on gas explosion suppression, and the explosion pressure and flame propagation speed declined obviously. When ferrocene concentration is 0.08 g/L and methane volume concentration is 9.5%, the maximum explosion overpressure and maximum flame propagation speed of methane-air respectively decreased by about 59.5% and 19.6%, respectively. TG and DSC curves showed that the mass loss of ferrocene consists of two processes, which are sublimation and lattice fracture. The temperature of mass loss ranged from 128 ℃ to 230 ℃. The results showed profoundly theoretical significance to gas explosion suppression by ferrocene in coal mines.
基金supported by the National Natural Science Foundation of China(No.11975124)the Fundamental Research Funds for the Central universities(Nos.30920041102 and 30920041103)the Open Fund of Key Laboratory of Materials Preparation and Protection for Harsh Environment(Nanjing University of Aeronautics and Astronautics),Ministry of Industry and Information Technology(No.56XCA22042).
文摘Coordination bonds are relatively unstable compared to covalent bonds,and common carbon-based absorbing material precursors are bonded in the form of coordination bonds.In this work,we have introduced ferrocene units into conjugated microporous polymers(CMP)in one step by Suzuki reaction.By adjusting the proportion of ferrocene units,a series of magnetic Fe-C nanocomposites(Fe-P-XC)derived from conjugated ferrocene polymers without heteroatom doping(N,S,P,etc.)were formed.The Fe-P-2C composite has good absorption properties with minimum reflection loss at 4.4 GHz(-58.66 dB)and effective absorption bandwidth(EAB)of 6.28 GHz at 2.4 mm(11.72-18 GHz).Compared with the precursor materials formed by coordination bonds,the present work reveals the electromagnetic wave absorption mechanism of carbon-based materials without heteroatom doping through a simple and effective strategy.
基金supported by Education Office of Liaoning Province(No.2008567)
文摘A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedicarboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ),which is a twisted non-coplanar heterocyclic bisphenol-like monomer.The newly generated polymer was evaluated based on characterization of its solubility,viscosity measurements,elemental analysis,FTIR spectroscopy,differential scanning calorimetric and thermogravimetric studies.
基金This project was supported by Hunan Provincial Natural Science Foundation(Grant No.04JJ30047).
文摘A carbon/PVC-COOH/ferrocene composite electrode used for the determination of glucose has been prepared. The ferrocene acted as mediator was incorporated into the PVC-COOH polymer and the leakage could be prevented. The presence of carboxyl groups on the electrode surface allowed immobilizing enzyme via EDC and NHS. The ratio of PVC-COOH to graphite powder （w/w） has been studied. Amperometric determination of glucose has been performed at potential of 0.30 V vs SCE. The response time was 〈 15 s. The linear response range was of 0.1-20 mmol/L with a detection limit of 48μmol/L.
基金We gratefully acknowledge the financial support of the National Natural Science Foundation of China(Project No.CN-20374007 and CN-50203002)Key Project of Science and Technology Foundation of Ministry of Education(03023).
文摘4-（2-Ferrocenylethenyl）-phenyl-POSS Fc-CH=CH-C6H6-（C5H9）7Si8O12 （FEPS, Fc： ferrocene）, containing metal and C=C double bond, was firstly synthesized as a mixture of E/Z isomers by the Wittig reaction. The chemical structure of FEPS was characterized by FTIR, ^1H-, ^13C and ^29Si- NMR.
基金Financial support from the National Natural Science Foundation of China (No.20572009)
文摘A novel chiral stationary phase （CSP） was prepared by immobilizing mono（6A-N-1-（2-hydroxyl）-phenylethylimino-6A- deoxy）-β-cyclodextrin onto the surface of silica gel via a longer spacer. This chiral stationary phase exhibited good enantioselectivity for a variety of chiral compounds under reversed-phase conditions.
