全文获取类型
收费全文 | 601篇 |
免费 | 83篇 |
国内免费 | 55篇 |
专业分类
化学 | 680篇 |
晶体学 | 5篇 |
综合类 | 1篇 |
物理学 | 53篇 |
出版年
2023年 | 8篇 |
2022年 | 22篇 |
2021年 | 31篇 |
2020年 | 28篇 |
2019年 | 21篇 |
2018年 | 23篇 |
2017年 | 24篇 |
2016年 | 31篇 |
2015年 | 27篇 |
2014年 | 36篇 |
2013年 | 107篇 |
2012年 | 38篇 |
2011年 | 18篇 |
2010年 | 31篇 |
2009年 | 35篇 |
2008年 | 24篇 |
2007年 | 25篇 |
2006年 | 28篇 |
2005年 | 28篇 |
2004年 | 30篇 |
2003年 | 32篇 |
2002年 | 12篇 |
2001年 | 10篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 11篇 |
1997年 | 9篇 |
1996年 | 8篇 |
1995年 | 10篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1989年 | 5篇 |
1987年 | 1篇 |
1983年 | 1篇 |
排序方式: 共有739条查询结果,搜索用时 22 毫秒
21.
Nicolai Stuhr-Hansen Jakob Kryger Srensen Kasper Moth-Poulsen Jrn Bolstad Christensen Thomas Bjrnholm Mogens Brndsted Nielsen 《Tetrahedron》2005,61(52):12288-12295
Simple and readily accessible aryl bromides are useful building blocks for thiol end-capped molecular wires. Thus, 4-bromophenyl tert-butyl sulfide and 1-bromo-4-(methoxymethyl)benzene serve as precursors for a variety of oligo(phenylenevinylene) and oligo(phenyleneethynylene) wires via efficient synthetic transformations as presented in this paper. 相似文献
22.
The review surveys methods for the synthesis, as well as structures and properties of sulfur-containing iron nitrosyl complexes serving as models of active sites of [Fe—S] nitrosyl proteins, which are potential donors of nitrogen monoxide.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2326–2345, November, 2004. 相似文献
23.
D. M. Roitershtein K. A. Lyssenko P. A. Belyakov M. Yu. Antipin E. S. Petrov 《Russian Chemical Bulletin》1997,46(9):1590-1594
The reaction of the cyclopentadienyllutetium anthracenide, C5H5Lu(C14H10)2−(THF)2 (1), with azobenzene yielded the [C5H5(THF)Lu(μ−η2:η2−PhN—NPh)]2(THF)2 (2) binuclear complex. The structure of the reaction product was established by X-ray structural analysis. The dynamic behavior
of complex2 in a THF-d8 solution was studied by1H NMR spectroscopy in the temperature range of 265–330 K.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1667–1671, September, 1997. 相似文献
24.
Burdick Brent A. Esders Theodore W. Schaeffer James R. Lynn Shirley 《Applied biochemistry and biotechnology》1987,16(1):145-156
Several hydrophilic polymeric thiols were prepared from aminoactivated polymeric supports by reaction with N-acetylhomocysteinethiolactone.
Supports include agaroses, cellulose, Glycophase™ controlled-pore glass, and Matrex™ acrylic beads. Thiol content in these
polymers was 3–72 μmol SH/g dry polymer. Several were effective solid-phase activators of the sulfhydryl-dependent enzyme
creatine phosphokinase at concentrations comparable to that of monomeric thiol required for enzyme activation. The kinetic
activation curves for the polymeric and the monomeric (thioglucose) activators were similar, suggesting unhindered interaction
of the enzyme with the polymeric activator. 相似文献
25.
Rakotondradany F Whitehead MA Lebuis AM Sleiman HF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(19):4771-4780
A new strategy to effect photoinduced control over molecular self-assembly is reported. This strategy uses the reversible trans-cis photoisomerization of a novel azobenzene system, where the trans- and cis-forms self-assemble into dramatically different higher-order structures. The trans-azobenzene form of this molecule associates into infinite hydrogen-bonded linear tapes, while the cis-azobenzene form undergoes hydrogen-bonded self-assembly into cyclic tetramers. This results in a second level of association, where the cis-hydrogen-bonded supramolecular cycles ultimately form long, rod-like aggregates through stacking interactions. 相似文献
26.
基于原子转移自由基聚合技术的偶氮苯星形液晶聚合物的合成与表征 总被引:1,自引:0,他引:1
利用原子转移自由基聚合(ATRP)技术合成了含不同端基取代基的偶氮苯三臂星形侧链液晶聚合物. 均苯三酚与2-溴异丁酰溴通过酯化反应制备三官能团引发剂, 引发偶氮苯单体6-[4-(4-甲氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(MMAzo)或6-[4-(4-乙氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(EMAzo)的ATRP反应. 利用核磁共振氢谱(1H NMR)、凝胶色谱(GPC)、差示扫描量热法(DSC)和偏光显微镜(POM)等手段对星形聚合物进行表征. 星形聚合物的液晶性与相应均聚物相似, 但偶氮苯端基取代基的不同导致星形聚合物的液晶性差别显著. 在紫外/可见光照射下星形聚合物呈现明显的异构化转变. 相似文献
27.
Jongeun Kang Eunha Hwang Hyunseung Lee Mi Young Cho Sanu Karan Hak Nam Kim Jong Seung Kim Jonathan L. Sessler Sankarprasad Bhuniya Kwan Soo Hong 《Molecules (Basel, Switzerland)》2021,26(7)
We have synthesized new magnetic resonance imaging (MRI) T1 contrast agents (CA1 and CA2) that permit the activatable recognition of the cellular vicinal thiol motifs of the protein thioredoxin. The contrast agents showed MR relaxivities typical of gadolinium complexes with a single water molecule coordinated to a Gd3+ center (i.e., ~4.54 mM−1s−1) for both CA1 and CA2 at 60 MHz. The contrast agent CA1 showed a ~140% relaxivity enhancement in the presence of thioredoxin, a finding attributed to a reduction in the flexibility of the molecule after binding to thioredoxin. Support for this rationale, as opposed to one based on preferential binding, came from 1H-15N-HSQC NMR spectral studies; these revealed that the binding affinities toward thioredoxin were almost the same for both CA1 and CA2. In the case of CA1, T1-weighted phantom images of cancer cells (MCF-7, A549) could be generated based on the expression of thioredoxin. We further confirmed thioredoxin expression-dependent changes in the T1-weighted contrast via knockdown of the expression of the thioredoxin using siRNA-transfected MCF-7 cells. The nontoxic nature of CA1, coupled with its relaxivity features, leads us to suggest that it constitutes a first-in-class MRI T1 contrast agent that allows for the facile and noninvasive monitoring of vicinal thiol protein motif expression in live cells. 相似文献
28.
Karla G. Gutiérrez-Cuevas Rosa Julia Rodríguez-González Bertrand Donnio Damaso Navarro-Rodríguez 《Liquid crystals》2013,40(4):534-545
In this article, we report on the synthesis and thermotropic behaviour of methacrylic polymers containing 4′-(4-alkyloxyphenyl)azobenzene mesogens attached to the backbone through n-alkyloxy spacers of 6 or 10 methylene groups. Polymerisations were carried out via free radicals using azobisisobutyronitrile (AIBN) as initiator. Chemical structures of polymers and their precursors were characterised by 1H NMR spectroscopy. Thermogravimetric analysis showed that azopolymers are thermally stable up to temperatures around 300°C. The thermotropic liquid-crystalline (LC) behaviour was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and X-ray diffraction (XRD). Results indicate that all synthesised mesogens, monomers and polymers developed two or more orthogonal LC phases in wide temperature ranges. Mesogens and monomers developed nematic and smectic phases, whereas polymers exhibited only smectic phase. In polymers, the arrangement of mesogens depends on the relative length of the spacer and the terminal flexible chain; two distinct structural models were proposed based on chemical interactions and steric constrains. The trans–cis photoisomerisation of monomers and polymers in solution was also studied. High cis-isomer contents (>80%) were reached in relative short irradiation times despite the steric constrains imposed by the polymer backbone. 相似文献
29.
Two new groups of azobenzene ester derivatives were synthesised: alkyl 4-[4-(nonyloxy)phenyl]diazenyl]benzoates and 4-[4-(nonyloxy)phenyl]diazenyl]phenyl alkanoates. All 35 presented homologues are mesogenic. Moreover, some of the above-mentioned compounds exhibit rich liquid-crystalline polymorphism likewise tetramorphism. During this investigation by the use of polarising optical microscopy, differential scanning calorimetry and X-Ray studies, six types of mesophases were detected: nematic, smectics (A, C, I, F) and G. Furthermore, due to the presence of the photosensitive azo moiety, the E–Z isomerisation reaction is possible. This process, which is initiated by the UV irradiation, causes significant changes in the UV-Vis absorption spectra of investigated compounds. However, the photoisomerisation is a reversible process and in the dark the thermal relaxation of Z isomer takes place. Based on the achieved data, the kinetic constants of the isomerisation and relaxation processes were calculated. It shows that conversion of the ester bond makes some changes in the optical properties. The shift of about 7 nm of the absorbance maximum was observed. Surprisingly, the inversion of the ester group has significant influence on the liquid-crystalline polymorphism replacing one mesophase (for benzoates) into four (for alkanoates). 相似文献
30.
The dynamics of π-cell liquid crystal displays was studied by detailed computer simulation. The time evolution of the director configuration and the velocity of flow reveals the mechanism of the fast response of π-cells. The effect of pretilt angle on the dynamics of π-cells was also studied. 相似文献