Bone grafts have been predominated used to treat bone defects,delayed union or non-union,and spinal fusion in orthopaedic clinically for a period of time,despite the emergency of synthetic bone graft substitutes.Never...Bone grafts have been predominated used to treat bone defects,delayed union or non-union,and spinal fusion in orthopaedic clinically for a period of time,despite the emergency of synthetic bone graft substitutes.Nevertheless,the integration of allogeneic grafts and synthetic substitutes with host bone was found jeopardized in long-term follow-up studies.Hence,the enhancement of osteointegration of these grafts and substitutes with host bone is considerably important.To address this problem,addition of various growth factors,such as bone morphogenetic proteins(BMPs),parathyroid hormone(PTH)and platelet rich plasma(PRP),into structural allografts and synthetic substitutes have been considered.Although clinical applications of these factors have exhibited good bone formation,their further application was limited due to high cost and potential adverse side effects.Alternatively,bioinorganic ions such as magnesium,strontium and zinc are considered as alternative of osteogenic biological factors.Hence,this paper aims to review the currently available bone grafts and bone substitutes as well as the biological and bio-inorganic factors for the treatments of bone defect.展开更多
Stimuli-responsive materials hold great potential for the development of smart materials due to their specifically tailored characteristics.However,it is challenging to understand internal molecular dynamics when the ...Stimuli-responsive materials hold great potential for the development of smart materials due to their specifically tailored characteristics.However,it is challenging to understand internal molecular dynamics when the macroscopic mechanics of materials change in response to specific applied stimuli.Herein,we present the biological composite fibers of which mechanical properties can be reversibly controlled on demand by photothermal effect of an alternating near-infrared light irradiation.In stark contrast to the weakening of the mechanical properties of conventional materials by heating,the mechanical performance of the obtained fibers are significantly enhanced,showing an increase of Young’s modulus by a factor of four.The outstanding photothermal-mechanical behavior relies on the evolution of hydrogen bonds within the system.We envision that this type of fiber material will inspire a new strategy for the construction of smart devices.展开更多
Recent progress in bioinorganic chemistry studies of rare earth elements (REE) in animal cells was outlined, and the definition of REE′s biological intelligence as well as their mechanism were also explained. The mig...Recent progress in bioinorganic chemistry studies of rare earth elements (REE) in animal cells was outlined, and the definition of REE′s biological intelligence as well as their mechanism were also explained. The migration of REE from weathering rocks to the environment is accelerated by various anthropogenic activities, which can eventually result in the entrance of REE into animal and human bodies via food chain. REE can be found in body tissues such as brain, blood, muscle as well as bone. Based on their geochemical properties, REE in low dose show their unique biological intelligence by intervening in the process of signal transduction and its regulation, arteriosclerosis and blood clotting prevention, anticancer, and the promotion of cellular defense enzymes′ activities, nucleic acid metabolism enzymes as well as ATPases, etc. The meaning of REE′s biological intelligence refers to physicochemical properties-based capability to choose the targets (e.g., biometals) in biomolecules for the chelation or replacement of REE, and change the structures and functions of biomolecules, and consequently impact or control the biological functions or behaviors in living organisms. The regulation of various cellular processes caused by REE is mainly via antagonism or replacement of essential target biometals like calcium or via chelation of organic molecules, thereby embodying the unparalleled biological intelligence of REE. Additionally, the dosage effect of REE was also discussed from the angles of yin-yang dichotomy, bioavailability, entropy and evolution. In order to make full use of REE′s biological intelligence in the application for medicine, more detailed studies concerning dosage effect of REE and REE bioaccumulation in organisms should be conducted in future research.展开更多
Bacterial infection is the leading cause of many severe inflammation diseases. The development of novel and effective therapeutic approaches to counter bacterial infections, especially for drug-resistant bacteria, is ...Bacterial infection is the leading cause of many severe inflammation diseases. The development of novel and effective therapeutic approaches to counter bacterial infections, especially for drug-resistant bacteria, is essential. Herein, we have successfully developed an ultrasound-active tricarbonyl rhenium(Ⅰ) complex with tetraphenylethylene(TPE) modification(RePyTPE) for CO gas therapy and sonodynamic therapy of bacterial infections. RePy-TPE produced reactive oxygen species and released CO under ultrasound irradiation. In addition, RePy-TPE showed aggregation-induced emission in water due to the introduction of TPE, which enhanced the yield of ^(1)O_(2) generation in a biological aqueous solution. The produced ^(1)O_(2) and released CO killed mycobacterium smegmatis(M. smegmatis) and Escherichia coli(E. coli), as shown by bacterial membrane damage and biofilm elimination. Furthermore, ultrasound-active RePy-TPE perturbed the purine metabolism of the bacteria, which disturbed the biosynthesis of DNA and energy metabolism, eventually reducing the vitality of bacteria. This article provides a novel strategy for the development of ultrasound-active metal-based antibiotics.展开更多
A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substituti...A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.展开更多
Rare earth elements （REE） and their compounds years. The bioinorganic chemical research of REE during the are widely applied in agronomic and medical fields for many past few years indicates that REE play important ...Rare earth elements （REE） and their compounds years. The bioinorganic chemical research of REE during the are widely applied in agronomic and medical fields for many past few years indicates that REE play important roles in the promotion of photosynthetic rate as well as root absorption, regulation of hormone and nitrogen metabolism, and suppression of microbes, etc. The metallic or non-metallic targets of key biomolecule in various physiological processes can be chosen by REE for the chelation or replacement, which enables REE to regulate the biological functions or behaviors of those biomolecule and consequently leads to significant embodiment of biological function of REE in plants and microbes. Overdose of REE, however, shows an inhibitory effect on living organisms. Therefore, this paper proposes two suggestions that will be available in the extension of full use of REE＇s biological function. One is to obey the dose law of REE and control REE concentrations within a safe range. The other is to further test the bioaccumulation and long-period influence of REE on organisms.展开更多
A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at t...A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at the pyridine nitrogen atom when two equivalents of HBF4·OEt2acid were added to the toluene solution of 1,leading to the formation of[（2-C5H4NH）N（μ-CH2S）2Fe2（CO）6]·BF4·OEt2（1H~＋）,whose molecular structure was further established by singlecrystal X-ray analysis.Complex 1 crystallizes in the monoclinic system,space group P21/n with α=7.728（3）,b = 11.825（4）,c = 17.888（6） A,β= 92.968（5）°,while complex 1H~＋ crystallizes in the triclinic system,space group P1 with a = 7.672（4）,b = 10.382（5）,c = 16.480（10） A,α=106.575（13）,β= 93.18（3）,γ=104.262（17）°.展开更多
Metal-based compounds with excellent photo-physical properties show good photochemotherapeutic performance.But,low in-depth tissue penetration of light limits their effectivity for deeply buried tumors.Encouraged by t...Metal-based compounds with excellent photo-physical properties show good photochemotherapeutic performance.But,low in-depth tissue penetration of light limits their effectivity for deeply buried tumors.Encouraged by the sonosensitizing ability of the traditional organic photosensitizers,here,we developed AuNPs@Ir1 as a sonosensitizer by hybridizing an organometallic Ir(Ⅲ) complex(Ir1) with ultrasmall gold nanoparticles(AuNPs) for efficient tumor sonodynamic therapy(SDT) for the first time.AuNPs@Ir1 rapidly entered the cancer cells,produced ^(1)O_(2),and catalytically oxidized NADH to NAD;under ultrasound(US)irradiation,thus resulted in cancer cells oncosis.Because of efficient passive retention in tumors post intravenous injection,AuNPs@Ir1 further efficiently inhibited the growth of tumors in-vivo under US stimulation without long-term toxicity to other organs.Overall,this work presents the excellent US triggered in-vitro and in-vivo anticancer profile of the novel AuNPs@Ir1.It is expected to increase the scope of SDT for metal-based anticancer drugs.展开更多
基金This work was supported in part by Shenzhen Science and Technology Innovation Funding JCYJ20140414090541811,JCYJ20160429190821781 and JCYJ2016429185449249Hong Kong Research Grant Council General Research Funds(RGC GRF)(Nos.718913E,17214516,N_HKU725/16)+3 种基金HKU Seeding Fund(Nos.201511160001 and 201411159045)Hong Kong Innovation Technology Fund(No.ITS/147/15)Hong Kong Health and Medical Research Fund(No.03142446)National Natural Science Foundation of China(NSFC)(Nos.31370957).
文摘Bone grafts have been predominated used to treat bone defects,delayed union or non-union,and spinal fusion in orthopaedic clinically for a period of time,despite the emergency of synthetic bone graft substitutes.Nevertheless,the integration of allogeneic grafts and synthetic substitutes with host bone was found jeopardized in long-term follow-up studies.Hence,the enhancement of osteointegration of these grafts and substitutes with host bone is considerably important.To address this problem,addition of various growth factors,such as bone morphogenetic proteins(BMPs),parathyroid hormone(PTH)and platelet rich plasma(PRP),into structural allografts and synthetic substitutes have been considered.Although clinical applications of these factors have exhibited good bone formation,their further application was limited due to high cost and potential adverse side effects.Alternatively,bioinorganic ions such as magnesium,strontium and zinc are considered as alternative of osteogenic biological factors.Hence,this paper aims to review the currently available bone grafts and bone substitutes as well as the biological and bio-inorganic factors for the treatments of bone defect.
基金supported by the National Natural Science Foundation of China(grant nos.22125701,21877104,21834007,21878258,22020102003)the National Key R&D Program of China(grant nos.2021YFB3502300,2021YFF0701800,2020YFA0908900)Grants from Natural Science Foundation of Guangdong Province,China(grant nos.2021A1515010253,202102020523).
文摘Stimuli-responsive materials hold great potential for the development of smart materials due to their specifically tailored characteristics.However,it is challenging to understand internal molecular dynamics when the macroscopic mechanics of materials change in response to specific applied stimuli.Herein,we present the biological composite fibers of which mechanical properties can be reversibly controlled on demand by photothermal effect of an alternating near-infrared light irradiation.In stark contrast to the weakening of the mechanical properties of conventional materials by heating,the mechanical performance of the obtained fibers are significantly enhanced,showing an increase of Young’s modulus by a factor of four.The outstanding photothermal-mechanical behavior relies on the evolution of hydrogen bonds within the system.We envision that this type of fiber material will inspire a new strategy for the construction of smart devices.
文摘Recent progress in bioinorganic chemistry studies of rare earth elements (REE) in animal cells was outlined, and the definition of REE′s biological intelligence as well as their mechanism were also explained. The migration of REE from weathering rocks to the environment is accelerated by various anthropogenic activities, which can eventually result in the entrance of REE into animal and human bodies via food chain. REE can be found in body tissues such as brain, blood, muscle as well as bone. Based on their geochemical properties, REE in low dose show their unique biological intelligence by intervening in the process of signal transduction and its regulation, arteriosclerosis and blood clotting prevention, anticancer, and the promotion of cellular defense enzymes′ activities, nucleic acid metabolism enzymes as well as ATPases, etc. The meaning of REE′s biological intelligence refers to physicochemical properties-based capability to choose the targets (e.g., biometals) in biomolecules for the chelation or replacement of REE, and change the structures and functions of biomolecules, and consequently impact or control the biological functions or behaviors in living organisms. The regulation of various cellular processes caused by REE is mainly via antagonism or replacement of essential target biometals like calcium or via chelation of organic molecules, thereby embodying the unparalleled biological intelligence of REE. Additionally, the dosage effect of REE was also discussed from the angles of yin-yang dichotomy, bioavailability, entropy and evolution. In order to make full use of REE′s biological intelligence in the application for medicine, more detailed studies concerning dosage effect of REE and REE bioaccumulation in organisms should be conducted in future research.
基金supported by the Natural Science Foundation of Guangdong Province (2023B1515020060, 2021B1515020050)the Science and Technology Foundation of Shenzhen (RCYX20221008092906021, JCYJ20210324095200002, JCYJ20220531103405012)the National Natural Science Foundation of China (22077085, 22177078, 22277153)。
文摘Bacterial infection is the leading cause of many severe inflammation diseases. The development of novel and effective therapeutic approaches to counter bacterial infections, especially for drug-resistant bacteria, is essential. Herein, we have successfully developed an ultrasound-active tricarbonyl rhenium(Ⅰ) complex with tetraphenylethylene(TPE) modification(RePyTPE) for CO gas therapy and sonodynamic therapy of bacterial infections. RePy-TPE produced reactive oxygen species and released CO under ultrasound irradiation. In addition, RePy-TPE showed aggregation-induced emission in water due to the introduction of TPE, which enhanced the yield of ^(1)O_(2) generation in a biological aqueous solution. The produced ^(1)O_(2) and released CO killed mycobacterium smegmatis(M. smegmatis) and Escherichia coli(E. coli), as shown by bacterial membrane damage and biofilm elimination. Furthermore, ultrasound-active RePy-TPE perturbed the purine metabolism of the bacteria, which disturbed the biosynthesis of DNA and energy metabolism, eventually reducing the vitality of bacteria. This article provides a novel strategy for the development of ultrasound-active metal-based antibiotics.
基金supported by the National Basic Research Program of China(973Program,2012CB821702)the National Natural Science Foundation of China(21173221and20903096)the State Key Laboratory of Structural Chemistry(20120015)
文摘A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.
文摘Rare earth elements （REE） and their compounds years. The bioinorganic chemical research of REE during the are widely applied in agronomic and medical fields for many past few years indicates that REE play important roles in the promotion of photosynthetic rate as well as root absorption, regulation of hormone and nitrogen metabolism, and suppression of microbes, etc. The metallic or non-metallic targets of key biomolecule in various physiological processes can be chosen by REE for the chelation or replacement, which enables REE to regulate the biological functions or behaviors of those biomolecule and consequently leads to significant embodiment of biological function of REE in plants and microbes. Overdose of REE, however, shows an inhibitory effect on living organisms. Therefore, this paper proposes two suggestions that will be available in the extension of full use of REE＇s biological function. One is to obey the dose law of REE and control REE concentrations within a safe range. The other is to further test the bioaccumulation and long-period influence of REE on organisms.
基金supported by the National Basic Research Program of China(973 Program2012CB821702)+1 种基金the National Natural Science Foundation of China(21233009 and 21173221)the State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences
文摘A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at the pyridine nitrogen atom when two equivalents of HBF4·OEt2acid were added to the toluene solution of 1,leading to the formation of[（2-C5H4NH）N（μ-CH2S）2Fe2（CO）6]·BF4·OEt2（1H~＋）,whose molecular structure was further established by singlecrystal X-ray analysis.Complex 1 crystallizes in the monoclinic system,space group P21/n with α=7.728（3）,b = 11.825（4）,c = 17.888（6） A,β= 92.968（5）°,while complex 1H~＋ crystallizes in the triclinic system,space group P1 with a = 7.672（4）,b = 10.382（5）,c = 16.480（10） A,α=106.575（13）,β= 93.18（3）,γ=104.262（17）°.
基金financial support of the National Natural Science Foundation of China (NSFC, Nos. 22077085, 22007104)the Project of the Natural Science Foundation of Guangdong Province(No. 2019A1515011958)+2 种基金the Science and Technology Foundation of Shenzhen (No. JCYJ20190808153209537)DST,the Government of India (No. DST/INSPIRE/04/2019/000492)the Instrumental Analysis Center of Shenzhen University。
文摘Metal-based compounds with excellent photo-physical properties show good photochemotherapeutic performance.But,low in-depth tissue penetration of light limits their effectivity for deeply buried tumors.Encouraged by the sonosensitizing ability of the traditional organic photosensitizers,here,we developed AuNPs@Ir1 as a sonosensitizer by hybridizing an organometallic Ir(Ⅲ) complex(Ir1) with ultrasmall gold nanoparticles(AuNPs) for efficient tumor sonodynamic therapy(SDT) for the first time.AuNPs@Ir1 rapidly entered the cancer cells,produced ^(1)O_(2),and catalytically oxidized NADH to NAD;under ultrasound(US)irradiation,thus resulted in cancer cells oncosis.Because of efficient passive retention in tumors post intravenous injection,AuNPs@Ir1 further efficiently inhibited the growth of tumors in-vivo under US stimulation without long-term toxicity to other organs.Overall,this work presents the excellent US triggered in-vitro and in-vivo anticancer profile of the novel AuNPs@Ir1.It is expected to increase the scope of SDT for metal-based anticancer drugs.
