全文获取类型
收费全文 | 4119篇 |
免费 | 729篇 |
国内免费 | 571篇 |
专业分类
化学 | 3407篇 |
晶体学 | 25篇 |
力学 | 64篇 |
综合类 | 58篇 |
数学 | 86篇 |
物理学 | 1779篇 |
出版年
2024年 | 16篇 |
2023年 | 74篇 |
2022年 | 267篇 |
2021年 | 280篇 |
2020年 | 310篇 |
2019年 | 258篇 |
2018年 | 168篇 |
2017年 | 261篇 |
2016年 | 282篇 |
2015年 | 278篇 |
2014年 | 373篇 |
2013年 | 412篇 |
2012年 | 319篇 |
2011年 | 300篇 |
2010年 | 210篇 |
2009年 | 225篇 |
2008年 | 207篇 |
2007年 | 232篇 |
2006年 | 134篇 |
2005年 | 166篇 |
2004年 | 142篇 |
2003年 | 87篇 |
2002年 | 90篇 |
2001年 | 50篇 |
2000年 | 46篇 |
1999年 | 39篇 |
1998年 | 31篇 |
1997年 | 34篇 |
1996年 | 21篇 |
1995年 | 23篇 |
1994年 | 20篇 |
1993年 | 19篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有5419条查询结果,搜索用时 15 毫秒
131.
选用(1,1'':3'',1″-三联苯)-3,3″,4'',5,5″,6''-六羧酸(H6L)为配体,在溶剂热条件下,与Tb3+离子反应得到配合物[Tb (L)0.5(H2O)2]·7H2O (1)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、热重分析对该配合物的结构和组成进行了表征,同时,对其荧光性质进行了研究。结果表明:该配合物属于正交晶系,Cmca空间群,a=2.661 61(7) nm,b=1.421 03(4) nm,c=2.109 88(6) nm。拓扑计算表明配合物1是一个新颖的(6,6)-连接的三维网络结构,符号为(48.66.8)(49.66)。该配合物具有强的荧光发射,可以快速检测水溶液中的二甲硝咪唑和四环素且灵敏度高、检出限低、可回收性好。通过实验和密度泛函理论相结合,揭示了荧光猝灭机理。 相似文献
132.
基于H4dpa和bpy(H4dpa=4-(2,4-二羧基苯氧基)邻苯二甲酸,bpy=4,4''-联吡啶)为配体,在水热条件下设计、合成了金属锌配位聚合物(Zn-CP)[Zn(H2dpa)(bpy)1.5]n (1),并用元素分析、红外光谱、X射线单晶衍射等对其进行了结构表征。在1中相邻Zn2+与H2dpa2-离子和bpy配位形成的一维双链结构,相邻的一维双链通过氢键作用扩展形成三维超分子网结构。荧光研究表明:1是一种灵敏度高、选择性好、多响应的荧光传感器,可用于农药和硝基爆炸物的检测。有趣的是,2,4,6-三硝基苯(TNP)和嘧霉胺(Pth)对1的荧光发射显示出明显的猝灭效果,而抑霉唑(Ima)对1有荧光增强效果。此外,通过紫外可见吸收光谱、荧光寿命以及X射线光电子能谱探究了1的荧光传感机理。 相似文献
133.
134.
LUO Ya-Nan XU Xian-Zhua YU Xiao-Yang ZHU Guang-Shan QU Xiao-Shu ZHANG Xiao YU Li-Ying 《结构化学》2013,(11):1667-1672
A new coordination polymer, {[CdL(en)]'DMF}n (1, H2L = 4-[(8-hydroxy-5- quinolinyl)azo]-benzenesulfonic acid, en = ethylenediamine, DMF = N,N-dimethylformamide), has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffrac- tion, infrared (IR) spectra, elemental analysis, powder X-ray diffractions (PXRD) and thermo- gravimetric analysis (TGA). Compound 1 crystallizes in monoclinic, space group P2Jc with a = 14.6525(9), b = 13.3917(9), c = 11.8838(8) A, β = 101.2290(10)°, V = 2287.2(3) A3, Z = 4, C20H24CdN6OsS, Mr = 572.91, Dc. = 1.664 mg-mm-3, F(000) = 1160, p = 1.091 mm-1, R = 0.0232 and wR = 0.0587 for 3597 observed reflections (I 〉 2σ(I)). Compound 1 exhibits a one-dimensional (1D) double-chain structure which is further connected through hydrogen bonding and π-π interactions into a three-dimensional (3D) supramolecular network. In addition, it exhibits blue fluorescence at room temperature in the solid state. 相似文献
135.
Qiu-Juan Ma Xiao-Bing Zhang Zhi-Xiang Han Bo Huang Qin Jiang Guo-Li Shen 《International journal of environmental analytical chemistry》2013,93(1):74-86
A ratiometric fluorescent zinc probe 1 of carboxamidoquinoline with a carboxylic acid group was designed and synthesised. Probe 1 exhibits high selectivity for sensing Zn2+; about a 13-fold increase in fluorescence emission intensity and an 82?nm red-shift of fluorescence emission are observed upon binding Zn2+ in EtOH/H2O (1?:?1, V/V) solution. The ratiometric fluorescence response is attributed to the 1?:?1 complex formation between probe 1 and Zn2+ which has been utilised as the basis for the selective detection of Zn2+. The analytical performance characteristics of the proposed Zn2+-sensitive probe were investigated. The linear response range covers a concentration range of Zn2+ from 2.0?×?10?6 to 5.0?×?10?5?mol?L?1 and the detection limit is 2.7?×?10?7?mol?L?1. The determination of Zn2+ in both tap and river water samples shows satisfactory results. 相似文献
136.
Dr. Ke‐Rang Wang Yue‐Qing Wang Hong‐Wei An Jin‐Chao Zhang Prof. Dr. Xiao‐Liu Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(8):2903-2909
A new triazatruxene‐based fluorescent glycocluster has been designed, synthesized, and fully characterized by NMR spectroscopy and mass spectrometry. Furthermore, its specific and selective binding properties with concanavalin A (Con A) have been investigated by fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and turbidity assay. The obtained results showed that the multivalent mannose‐modified triazatruxene exhibited specific binding with Con A, but no binding to peanut agglutinin (PNA) lectin or bovine serum albumin (BSA), corresponding to a two‐orders‐of‐magnitude higher affinity than that of monovalent mannose ligands. Most interestingly, a fluorescence enhancement of the triazatruxene‐based glycocluster was observed upon binding with Con A because of hydrophobic interactions involving sites close to the triazatruxene moiety. Furthermore, the inhibitory ability of the triazatruxene‐based glycocluster against ORN178‐ induced haemagglutination has been investigated by haemagglutination inhibition assay. The results indicated selective binding with ORN178. 相似文献
137.
Dr. Sandra Ast Tobias Fischer Holger Müller Dr. Wulfhard Mickler Mathias Schwichtenberg Dr. Knut Rurack Prof. Dr. Hans‐Jürgen Holdt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):2990-3005
In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D‐A) substituted 1,2,3‐triazoles as conjugative π‐linkers between the alkali metal ion receptor N‐phenylaza‐[18]crown‐6 and different fluorophoric groups with different electron‐acceptor properties (4‐naphthalimide, meso‐phenyl‐BODIPY and 9‐anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge‐transfer (CT) type probes 1 , 2 and 7 , the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge‐separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting‐up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7 , which contains a 9‐anthracenyl moiety as the electron‐accepting fluorophore, is the only probe which retains light‐up features in water and works as a highly K+/Na+‐selective probe under simulated physiological conditions. Virtually decoupled BODIPY‐based 6 and photoinduced electron transfer (PET) type probes 3 – 5 , where the 10‐substituted anthracen‐9‐yl fluorophores are connected to the 1,2,3‐triazole through a methylene spacer, show strong ion‐induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3‐triazole fluoroionophores. 相似文献
138.
Xinjian Yang Zhenhua Li Meng Li Prof. Jinsong Ren Prof. Xiaogang Qu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15378-15383
A multifunctional system for intracellular drug delivery and simultaneous fluorescent imaging was constructed by using histidine‐tagged, cyan fluorescent protein (CFP)‐capped magnetic mesoporous silica nanoparticles (MMSNs). This protein‐capped multifunctional nanostructure is highly biocompatible and does not affect cell viability or proliferation. The CFP acts not only as a capping agent, but also as a fluorescent imaging agent. The nanoassembly was activated by histidine‐based replacement, leading to release of drug molecules encapsulated in the nanopores into the bulk solution. The fluorescent imaging functionality would allow noninvasive tracking of the nanoparticles in the body. By combining the drug delivery with cell‐imaging capability, these nanoparticles may provide valuable multifunctional nanoplatforms for biomedical applications. 相似文献
139.
Dr. Bishnu Prasad Bastakoti Prof. Kevin C.‐W. Wu Dr. Masamichi Inoue Prof. Shin‐ichi Yusa Prof. Kenichi Nakashima Prof. Yusuke Yamauchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(15):4812-4817
We have developed core‐shell‐corona‐type polymeric micelles that can integrate multiple functions in one system, including the capability of accommodating hydrophobic dyes into core and hydrophilic drug into the shell, as well as pH‐triggered drug‐release. The neutral and hydrophilic corona sterically stabilizes the multifunctional polymeric micelles in aqueous solution. The mineralization of calcium phosphate (CaP) on the PAA domain not only enhances the diagnostic efficacy of organic dyes, but also works as a diffusion barrier for the controlled release. 相似文献
140.
Dr. Csongor Szíjjártó Elias Pershagen Nadia O. Ilchenko Dr. K. Eszter Borbas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):3099-3109
Coumarin‐sensitized, long‐wavelength‐absorbing luminescent EuIII‐complexes have been synthesized and characterized. The lanthanide binding site consists of a cyclen‐based chelating framework that is attached through a short linker to a 7‐hydroxycoumarin, a 7‐B(OH)2‐coumarin, a 7‐O‐(4‐pinacolatoboronbenzyl)‐coumarin or a 7‐O‐(4‐methoxybenzyl)‐coumarin. The syntheses are straightforward, use readily available building blocks, and proceed through a small number of high‐yielding steps. The sensitivity of coumarin photophysics to the 7‐substituent enables modulation of the antenna‐absorption properties, and thus the lanthanide excitation spectrum. Reactions of the boronate‐based functionalities (cages) with H2O2 yielded the corresponding 7‐hydroxycoumarin species. The same species was produced with peroxynitrite in a ×106–107‐fold faster reaction. Both reactions resulted in the emergence of a strong ≈407 nm excitation band, with concomitant decrease of the 366 nm band of the caged probe. In aqueous solution the methoxybenzyl caged Eu‐complex was quenched by ONOO?. We have shown that preliminary screening of simple coumarin‐based antennae through UV/Vis absorption spectroscopy is possible as the changes in absorption profile translate with good fidelity to changes in EuIII‐excitation profile in the fully elaborated complex. Taken together, our results show that the 7‐hydroxycoumarin antenna is a viable scaffold for the construction of turn‐on and ratiometric luminescent probes. 相似文献