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单核锇配合物的合成、晶体结构及其与DNA的作用

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无机化学学报 2018年第10期34卷 1833-1840页

作者：赵雅晨李季胡炯圣刘璐王萌萌苏志钱勇 peter j.sadler 刘红科南京师范大学化学与材料科学学院南京210023 Department of Chemistry University of Warwick

使用溶剂热合成法,以p-bitmb配体(1,4-二(1-咪唑基-亚甲基)-2,3,5,6-四甲基苯)与[(η6-cymene)Os(μ-Cl)Cl]2或[(η6-bip)Os(μ-Cl)Cl]2为原料,合成了2种单核芳基锇配合物,并利用核磁、质谱、元素分析和X射线单晶衍射等手段对配合物进... 详细信息

使用溶剂热合成法,以p-bitmb配体(1,4-二(1-咪唑基-亚甲基)-2,3,5,6-四甲基苯)与[(η6-cymene)Os(μ-Cl)Cl]2或[(η6-bip)Os(μ-Cl)Cl]2为原料,合成了2种单核芳基锇配合物,并利用核磁、质谱、元素分析和X射线单晶衍射等手段对配合物进行了表征。配合物1属于单斜晶系,P21/c空间群,为一个单核锇的结构。中心锇原子与2个配体p-bitmb上的氮原子以及氯原子进行配位,2个配体的另一个咪唑基团通过一个亚甲基碳原子进行连接形成咪唑嗡离子,形成一个类似"碗"状的结构。一个氯离子通过氢键装载在结构的空腔内。利用核磁共振氢谱研究了结构中亚甲基的来源,并研究了配合物在缓冲溶液中的稳定性。用紫外吸收光谱、圆二色谱以及粘度法研究了配合物与DNA的相互作用,结果表明,配合物中的亚甲基来自于溶剂二氯甲烷。配合物以嵌入的方式与CT-DNA相互作用,结合常数分别为3.222×10~4 L·mol-1 (1)和1.53×10~4 L·mol-1 (2),同时配合物会减弱DNA的碱基堆积作用并可以使DNA发生解旋。

关键词：芳基锇配合物晶体结构 DNA作用

Diazido Mixed-Amine Platinum（Ⅳ） Anticancer Complexes Activated by Visible-Light Can Cause Guanine Oxidation

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Diazido Mixed-Amine Platinum（Ⅳ） Anticancer Complexes Acti...

联吡啶衍生物芳基钌配合物的合成及其与DNA、蛋白质相互作用

中国化学会第29届学术年会

作者： Yao Zhao peter j.sadler Fuyi Wang CAS Key Laboratory of Analytical Chemistry for Living Biosystems Institute of ChemistryChinese Academy of Sciences Department of Chemistry University of WarwickCoventryCV4 7ALUnited Kingdom

Platinum diam（m）ine anticancer complexes,such as cisplatin,are successful in clinic,but suffer from problems of resistance and *** PtIV prodrugs offer the potential of targeted drug release and new mechanisms of action.1-3 We report visible-light activated diazido complexes trans,trans,trans-[Pt（N3）2（OH）2（Am1）（Am2）]（Am1 and Am2=amines）that are inert in the dark towards hydrolysis and glutathione reduction,but undergo rapid photoreduction with UVA or blue *** complexes exhibit rapid potent photocytotoxicity towards various cancer cells and form novel DNA lesions in cancer cells,with no activity in the absence of irradiation.2 When irradiated with UVA（λmax=365 nm）or blue light（λmax=420 nm,450 nm）,they undergo photo-decomposition,releasing the azido ligands,?N3 radical,N2 and O2 gases,as monitored by UV–Vis,14N-NMR spectroscopy,GC-MS and *** photoreactions of these complexes with 5’-GMP rapidly formed PtII-5’-GMP adducts,such as[PtII（N3）（Am1）（Am2）（5’-GMP）]+and[PtII（Am1）（Am2）（5’-GMP）2]2+,as judged by LC-MS and ***,an oxidized guanine,8-OH-G,was also found in the products.3 This indicate that PtIV diazido complexes exert their anticancer effect not only by forming DNA adducts,but also by inducing oxidative *** result suggests that multiple mechanisms of action account for the high photocytoxicity of this class of compounds.

关键词： platinum antitumor agents DNA binding guanine oxidation medicinal chemistry

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无机化学学报 2018年第6期34卷 1079-1085页

作者：葛超王红艳董益利李季徐芸顾秋予苏志钱勇 peter j.sadler 刘红科南京师范大学化学与材料科学学院南京210023 Department of Chemistry University of Warwick

以2种配体4,4′-dimethyl-2,2′-bipyridine(L1)和4′-methyl-(2,2′-bipyridine)-4-carbaldehyde oxime(L2),分别与芳基钌二聚体[RuCl_2(η~6-p-cymene)]2合成了2种新型单核配合物[Ru(η~6-p-cymene)(L1)Cl]Cl(1)和[Ru(η6-p-cymene)(L2)Cl]Cl(2)。应用元素分析、ESI-MS和~1H NMR对配合物的组成和结构进行表征,通过紫外光谱法和荧光光谱法研究了配合物的水解及其与CT-DNA和血清蛋白的结合性质,并且进行了细胞毒性研究。结果表明,在水溶液中配合物1比2在动力学上更稳定(k:0.383 h^(-1)(1)、1.458 h^(-1)(2));配合物均通过嵌入作用与双链DNA结合,但2有较强的结合能力(Kb:7.8×10~3L·mol^(-1)(1)、1.86×10~4L·mol^(-1)(2))。配合物均能与蛋白质发生相互作用,引起蛋白静态猝灭,但1作用较强(KA:1.04×10~5L·mol^(-1)(1)、8.62×10~4L·mol^(-1)(2))。配合物与蛋白的较强结合能力,可能是其细胞毒性不高的原因。

关键词：芳基钌联吡啶 DNA/BSA结合作用

Diazido Mixed-Amine Platinum(Ⅳ) Anticancer Complexes Activated by Visible-Light Can Cause Guanine Oxidation

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Diazido Mixed-Amine Platinum(Ⅳ) Anticancer Complexes Activa...

Stable diffusion gradients in microfluidic conduits bounded by fluid walls

第八届全国化学生物学学术会议

作者： Yao Zhao Nicola j.Farrer jenny Butler peter j.sadler Fuyi Wang Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Analytical Chemistry for Living BiosystemsInstitute of ChemistryChinese Academy of Sciences Department of Chemistry University of Warwick

Platinum diam(m)ine anticancer complexes,such as cisplatin,are successful in clinic, but suffer from problems of resistance and *** Ptprodrugs offer the potential of targeted drug release and new mechanisms of *** report visible-light activated diazido complexes trans,trans,trans-[Pt(N)(OH)(Am1) (Am2)](Am1 and Am2=amines)that are inert in the dark towards hydrolysis and glutathione reduction,but undergo rapid photoreduction with UVA or blue light.

关键词： platinum antitumor agents DNA binding guanine oxidation medicinal chemistry

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Microsystems & Nanoengineering 2024年第3期10卷 357-367页

作者： Federico Nebuloni Cyril Deroy peter R.Cook Edmond j.Walsh Department of Engineering Science Osney Thermo-Fluids InstituteUniversity of OxfordOxford OX20ESUK Sir William Dunn School of Pathology University of OxfordOxford OX13REUK

Assays mimicking in vitro the concentration gradients triggering biological responses like those involved in fighting infections and blood clotting are essential for biomedical *** assays prove especially attractive as they allow precise control of gradient shape allied to a reduction in *** microfluidic devices are fabricated using solid plastics that prevent direct access to responding ***-walled microfluidics allows the manufacture of circuits on standard Petri dishes in seconds,coupled to simple operating methods;cell-culture medium sitting in a standard dish is confined to circuits by fluid walls made of an immiscible *** develop and experimentally validate an analytical model of diffusion between two or more aqueous streams flowing at different rates into a fluid-walled conduit with the cross-section of a circular *** solid walls,fluid walls morph during flows as pressures fall,with wall shape changing down the *** model is validated experimentally for Fourier numbers<0.1 using fluorescein diffusing between laminar *** enables a priori prediction of concentration gradients throughout a conduit,so allowing rapid circuit design as well as providing bioscientists with an accurate way of predicting local concentrations of bioactive molecules around responsive and nonresponsive cells.

关键词： walls diffusion attractive

The Global Energy and Water Exchanges(GEWEX)Project in Central Asia:The Case for a Regional Hydroclimate Project

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Advances in Atmospheric Sciences 2024年第5期41卷 777-783页

作者： Michael BRODY Maksim KULIKOV Sagynbek ORUNBAEV peter j.VAN OEVELEN International Agricultural University Tashkent 111200Uzbekistan George Mason University FairfaxVirginia 22030USA University of Central Asia Bishkek 720001Kyrgyz Republic American University of Central Asia Bishkek 720060Kyrgyz Republic International GEWEX project George Mason UniversityFairfaxVirginia 22030USA

Central Asia consists of the former Soviet Republics,Kazakhstan,Kyrgyz Republic,Tajikistan,Turkmenistan,and *** region’s climate is continental,mostly semi-arid to *** is a significant part of the region’s *** its nature of intensive water use,agriculture is extremely vulnerable to climate *** growth and irrigation development have significantly increased the demand for water in the *** climate change issues include melting glaciers and a shrinking snowpack,which are the foundation of the region’s water resources,and a changing precipitation *** glaciers are located in Kyrgyzstan and Tajikistan,leading to transboundary water resource *** already has extremely high *** indicate that Central Asia has been warming and precipitation might be *** warming is expected to increase,but its spatial and temporal distribution depends upon specific global *** of future precipitation show significant uncertainties in type,amount,and *** Hydroclimate Projects(RHPs)are an approach to studying these *** steps to develop an RHP began in 2021 with a widely distributed online survey about these climate *** was followed up with an online workshop and then,in 2023,an in-person workshop,held in Tashkent,*** for the Global Energy and Water Exchanges(GEWEX)project for the region include both observations and modeling,as well as development of better and additional precipitation observations,all of which are topics for the next workshop.A well-designed RHP should lead to reductions in critical climate uncertainties in policy-relevant timeframes that can influence decisions on necessary investments in climate adaptation.

关键词： GEWEX Central Asia climate change agriculture

Adaptation in brain structure and respiratory and olfactory structures across environmental gradients in African and North American muroid rodents

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Integrative Zoology 2024年第1期19卷 165-181页

作者： peter j.TAYLOR Aluwani NENGOVHELA Christiane DENYS Graham R.SCOTT Catherine M.IVY Department of Zoology School of Natural and Mathematical SciencesUniversity of VendaThohoyandouSouth Africa Afromontane Unit Department of Zoology and EntomologyUniversity of the Free StatePhuthaditjhabaSouth Africa Department of Mammalogy National MuseumBloemfonteinSouth Africa Institut de Systématique EvolutionBiodiversité(ISYEB)Muséum National d’Histoire NaturelleCNRSSorbonne UniversitéEPHEUniversitéDes AntillesParisFrance Department of Biology McMaster UniversityHamiltonOntarioCanada Guglielmo and Shoemaker Labs Advanced Facility for Avian ResearchUniversity of Western OntarioLondonOntarioCanada

Morphometric studies of 3D micro CT-scanned images can provide insights into the evolution of the brain and sensory structures but such data are still scarce for the most diverse mammalian order of *** reviewed and new data,we tested for convergence to extreme aridity and high elevation in the sensory and brain morphology of rodents,from morphometric data from micro-CT X-ray scans of 174 crania of 16 species of three distantly re-lated African murid(soft-furred mice,Praomyini,laminate-toothed rats,Otomyini,and gerbils,Gerbillinae)clades and one North American cricetid(deer mice and white-footed mice,Peromyscus)*** studies demon-strated convergent evolution acting on the oval window area of the cochlea(enlarged in extremely arid-adapted species of Otomyini and Gerbillinae)and on endocranial volume(reduced in high elevation taxa of Otomyini and Peromyscus).However,contrary to our predictions,we did notfind evidence of convergence in brain struc-ture to aridity,or in the olfactory/respiratory system(turbinate bones)to high *** structure differed,particularly in the petrosal lobules of the cerebellum and the olfactory bulbs,between Otomyini and Gerbillinae,with extreme arid-adapted species in each clade being highly divergent(not convergent)from other species in the same *** observed greater“packing”of the maxillary turbinate bones,which have important respiratory functions,in Peromyscus mice from high and low elevations compared to the high-elevation African Praomyini,but more complex patterns within Peromyscus,probably related to trade-offs in respiratory physiology and heat exchange in the nasal epithelium associated with high-elevation adaptation.

关键词： 3D morphometrics Africa brain size North America Rodentia sensory evolution

Full-spectrum Bi@SrTiO_(3) for bi-directional promotion effects on photocatalytic redox reaction:Insight into intermediates and mechanism

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journal of Rare Earths 2024年第5期42卷 917-929,I0004页

作者： Bin Liu Nanhao Zhou jun Liu Xinglei Wang peter K.j.Robertson Xiaoyuan Chen Chao Chen jianmin Luo Chuanyi Wang School of Chemistry and Civil Engineering Shaoguan UniversityShaoguan512005China Chengdu Customs Technology Center Chengdu610041China Key Laboratory of Pollutant Chemistry and Environmental Treatment College of Chemistry and Environmental ScienceYili Normal UniversityYining835000China School of Chemistry and Chemical Engineering Queen's University BelfastStranmillis RoadBelfastBT95AGUnited Kingdom Guangzhou Institute of Industrial Intelligence(GIII) Guangzhou511400China

The development of full-spectrum photocatalysts active in the near-infrared(NIR)region has gained increasing attention for deleterious pollutant *** integration of plasmonic metals with semico nductors is an effective way to widen the light re sponse range of photocatalysts due to the strong light absorption and fast plasmonic energy transfer of the localized surface plasmon resonance(LSPR).In this work,the full-spectrum responsive Bi@SrTiO_(3) was prepared via facile solvothermal chemical *** optimal Bi@SrTiO_(3) achieves exceptional photocatalytic Cr(VI)reduction efficiency and tetracycline degradation,realizing bi-directional promotion effects on redox *** to density functional theory(DFT)simulations,the extraordinary photocatalytic performance is attributed to the tunable builtin electric field(IEF)of the Ohmic *** favorable adaptability in real water and high stability of BSTO-25 were proved by experime ntal *** the po ssible photocatalytic mechanism was proposed based on theoretical calculation and experimental ***,the non-toxicity of the BSTO-25 was evaluated by *** cultivation,which further proves the feasibility of treating wastewater with *** work provides a new perspective on constructing full-spectrum-driven photocatalysts for applications dealing with environmental remediation.

关键词： Full-spectrum photocatalysts Localized surface plasmon resonance Ohmic contact Cr(Ⅵ)reduction Antibiotic degradation Rare earths

Effect of age on the standardized ileal amino acid digestibility of soybean meal and canola meal in broilers

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Animal Nutrition 2024年第1期16卷 11-22页

作者： Mukti Barua M.Reza Abdollahi Faegheh Zaefarian Timothy j.Wester Channarayapatna K.Girish peter V.Chrystal Velmurugu Ravindran Monogastric Research Center School of Agriculture and EnvironmentMassey UniversityPalmerston North 4442New Zealand Department of Animal Science and Nutrition Faculty of Veterinary MedicineChattogram Veterinary and Animal Sciences UniversityKhulshiChattogram 4225Bangladesh Nutrition and Care Animal NutritionEvonik(SEA)Pte.Ltd609927 Singapore Complete Feed Solutions Howick 2145AucklandNew Zealand

Standardized ileal digestibility coefficients(SIDC)of nitrogen(N)and amino acids(AA)in two protein sources(soybean meal[SBM]and canola meal[CM])were investigated at six broiler ages(d 7,14,21,28,35,and 42).Two assay diets were formulated to contain either SBM(413 g/kg)or CM(553 g/kg)as the sole dietary AA *** dioxide(5 g/kg)was added as an indigestible marker.A total of 696 male broilers at 1 d old were allotted to 12 replicate cages per age *** assay diet was offered to birds for 4 d prior to the ileal digesta collection on d 7(14 birds/cage),14(12 birds/cage),21(10 birds/cage),28(8 birds/cage),35(8 birds/cage)and 42(6 birds/cage),*** apparent digestibility coefficients were standardized using age-specific basal endogenous AA *** the SBM group,though the SIDC of N tended to be influenced(quadratic;P=0.075)by age,no linear or quadratic response of age effect was observed on the average SIDC of indispensable(IAA)and total AA(TAA).An age effect(quadratic;P<0.05)was observed on the average SIDC of dispensable AA(DAA)in SBM with the highest value recorded at d 7,followed by a decrease from d 14 to 28,which increased beyond d *** SIDC of some individual AA(Arg,Thr,Trp,Cys,Pro)were affected(P<0.05 or P<0.001)in a quadratic manner by *** the CM,the SIDC of N,average SIDC of IAA,DAA and TAA were influenced(quadratic;P<0.05 or P<0.001)by *** SIDC of N and average SIDC of DAA and TAA were higher from d 7 to 14,declined at d 21,and then increased beyond d *** average SIDC of IAA was low between d 7 and 28 and increased *** SIDC of individual AA were affected(linear or quadratic;P<0.05 or P<0.001)by different magnitudes by *** age influence on the SIDC AA was variable,depending on the protein source and *** results demonstrate that age-specific SIDC AA data might need consideration in broiler feed formulations.

关键词： Age Amino acid Broiler Digestibility Protein source