全文获取类型
收费全文 | 24047篇 |
免费 | 2255篇 |
国内免费 | 5060篇 |
专业分类
化学 | 27792篇 |
晶体学 | 144篇 |
力学 | 280篇 |
综合类 | 120篇 |
数学 | 429篇 |
物理学 | 2597篇 |
出版年
2024年 | 67篇 |
2023年 | 388篇 |
2022年 | 752篇 |
2021年 | 893篇 |
2020年 | 1305篇 |
2019年 | 1070篇 |
2018年 | 1085篇 |
2017年 | 986篇 |
2016年 | 1125篇 |
2015年 | 1046篇 |
2014年 | 1528篇 |
2013年 | 2367篇 |
2012年 | 1357篇 |
2011年 | 1635篇 |
2010年 | 1229篇 |
2009年 | 1340篇 |
2008年 | 1437篇 |
2007年 | 1553篇 |
2006年 | 1443篇 |
2005年 | 1342篇 |
2004年 | 1321篇 |
2003年 | 1010篇 |
2002年 | 605篇 |
2001年 | 495篇 |
2000年 | 519篇 |
1999年 | 433篇 |
1998年 | 390篇 |
1997年 | 355篇 |
1996年 | 321篇 |
1995年 | 308篇 |
1994年 | 257篇 |
1993年 | 197篇 |
1992年 | 206篇 |
1991年 | 146篇 |
1990年 | 117篇 |
1989年 | 103篇 |
1988年 | 83篇 |
1987年 | 54篇 |
1986年 | 48篇 |
1985年 | 53篇 |
1984年 | 49篇 |
1983年 | 28篇 |
1982年 | 36篇 |
1981年 | 35篇 |
1980年 | 26篇 |
1979年 | 24篇 |
1978年 | 28篇 |
1977年 | 29篇 |
1976年 | 36篇 |
1974年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
81.
82.
具有超顺磁性和荧光特性的CdTe@Fe_3O_4/P(NIPAM-co-AA)多功能复合微球是以P(NIPAMco-AA)为模板制备而成.首先,采用溶胀法使模板微球带有磁性;其次,辅助TEOS和APTES两种化学试剂实现对Fe_3O_4/P(NIPAM-co-AA)微球表面的氨基功能化;最后,携带氨基的磁性微球与巯基乙酸修饰的CdTe量子点通过酰胺缩合反应,将量子点键合到磁性微球表面上,最终获得单分散的磁性荧光高分子复合微球.分别采用扫描电子显微镜、透射电子显微镜、倒置荧光显微成像系统、荧光分光光度计以及振动样品磁强计等方法对所获复合材料的结构与性能进行了表征.结果表明:复合微球单分散性良好,平均粒径约为30μm,饱和磁化强度可达5.4emu/g,具有良好的超顺磁性和较高的荧光发光效率.该材料将磁性、荧光结合到微米级高分子共聚物上,不仅解决了纳米粒子分离和处理的困难,而且奠定了多功能材料在生物标记、荧光成像等诸多领域潜在的应用基础. 相似文献
83.
The first member of the single‐isomer, dicationic cyclodextrin (CD) family, 6A‐ammonium‐6C‐butylimidazolium‐β‐cyclodextrin chlorides (AMBIMCD), has been synthesized, analytically characterized, and used to separate a variety of acidic enantiomers and amino acids by CE. Starting from mono‐6A‐azido‐β‐cyclodextrin, the cationic imidazolium and ammonium moieties were subsequently introduced onto primary ring of β‐cyclodextrin via nucleophilic addition and Staudinger reaction. The analytically pure AC regio‐isomer CD was further obtained via column chromatography. This dicationic CD exhibited excellent enantioselectivities for selected analytes at concentration as low as 0.5 mM, which were even better than those of its mono‐imidazolium or ammonium‐substitued counterpart CDs at 10 equivalent concentrations. The effective mobilities of all studied analytes were found to decrease with the concentration of AMBIMCD. Inclusion complexation in combination with eletrostatic interactions seemed to account for the enhanced chiral discrimination process. 相似文献
84.
M. Paleologou W. C. Purdy S. K. Misra S. Z. Korczak 《International journal of environmental analytical chemistry》2013,93(4):215-242
Abstract A novel reaction for the dechlorination of polychlorinated biphenyls (PCBs) as well as most other chlorinated aromatic and aliphatic compounds is evaluated and discussed in terms of its potential for analytical purposes. The active dechlorinating agent is prepared through the reaction of molten sodium or potassium with polyethylene glycols (MW >200), in the absence of oxygen, to form the corresponding alkali metal glycolate, a powerful nucleophilic agent. Special emphasis is given to the mechanistic aspects of the reaction and their importance in terms of achieving high and reproducible yields with analytical quantities of substrate, in short periods of time. The contribution of the techniques: ESR, NMR, IR, UV, MS, GC-ECD, LC-EC, CIDNP-NMR, conductimetry and chloride analysis (amperometric) in elucidating the reaction mechanism and providing valuable kinetic data is illustrated. This reaction can potentially be applied to the determination of PCBs in waste oils. 相似文献
85.
An VK-Z-Rohren zur Herstellung von Polyamid wurden Verweilzeitspektren mit der Methode der radioaktiven Markierung und der Methode der Indikatoraktivierungsanalyse gemessen. Die nach den beiden Methoden ermittelten Verweilzeitspektren werden miteinander verglichen. Die Übereinstimmung der Verweilzeitspektren wird durch Gegenüberstellung der statistischen Momente und durch einen Test nach Kolmogoroff-Smirnov geprüft. Es wird der experimentelle Aufwand beider Verfahren diskutiert und eine Fehlerabschätzung durchgeführt. 相似文献
86.
Eleven triazolyl substituted tetrahydrobenzofuran derivatives were synthesized in high yields as novel H+/K+‐ATPase inhibitor via one‐pot CuI‐catalyzed three‐component click reaction of azide, secondary amine and 3‐bromopropyne under mild conditions in water. Their structures were characterized by NMR, IR, ESI‐MS, elemental analysis and single‐crystal X‐ray diffraction analysis. Most of the target compounds exhibited better H+/K+‐ATPase inhibitory activity than commercial omeprazole with IC50 values less than 15 µmol·L?1. The initial structure‐activity analysis suggested that the triazole substituted by cycloalkyl, aromatic ring or O‐containing side‐chain seemed to be beneficial for enhancing the activity. 相似文献
87.
An unusual substitution reaction of an aromatic sulfonic group based on 3-carbonyl-4-phenolsulfonic acid was discovered in a diazo-coupling process.The reaction occurred under mild reaction conditions (pH 8.0-9.0.0-5 C,solvent:water) within a short reaction time(1h).A plausible substitution reaction mechanism by phenol-ketone resonance was proposed. 相似文献
88.
Jordanka Petrova Nikolai G. Vassilev Marko Kirilov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):457-463
Abstract The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time. 相似文献
89.
Junting Li Brian C. Benicewicz 《Journal of polymer science. Part A, Polymer chemistry》2013,51(17):3572-3582
Monoalkynyl‐functionalized fullerene was precisely synthesized starting with pristine fullerene (C60) and characterized by multiple techniques. Methyl methacrylate and 6‐azido hexyl methacrylate were then randomly copolymerized via reversible addition fragmentation chain transfer polymerization to build polymer backbones with well‐controlled molecular weights and copolymer compositions. Finally, these two moieties were covalently assembled into a series of well‐defined side chain fullerene polymers (SFPs) via the copper‐mediated click reaction which was verified by Fourier transform infrared spectroscopy and 1H NMR. The fullerene loadings of the resultant polymers were estimated by thermogravimetric analysis and UV–vis spectroscopy, demonstrating consistent and high conversions in most of the samples. The morphology studies of the SFPs were performed both in solution and on solid substrates. Very intriguing self‐aggregation behaviors were detected by both gel permeation chromatography and dynamic light scattering analyses. Furthermore, the scanning electron microscopic images of these polymers showed the formation of various supramolecular nanoparticle assemblies and crystalline‐like clusters depending on the fullerene contents and polymer chain lengths. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3572–3582 相似文献
90.