全文获取类型
收费全文 | 4369篇 |
免费 | 1022篇 |
国内免费 | 612篇 |
专业分类
化学 | 3428篇 |
晶体学 | 171篇 |
力学 | 115篇 |
综合类 | 41篇 |
数学 | 241篇 |
物理学 | 2007篇 |
出版年
2024年 | 15篇 |
2023年 | 69篇 |
2022年 | 178篇 |
2021年 | 189篇 |
2020年 | 224篇 |
2019年 | 195篇 |
2018年 | 177篇 |
2017年 | 153篇 |
2016年 | 251篇 |
2015年 | 219篇 |
2014年 | 238篇 |
2013年 | 650篇 |
2012年 | 306篇 |
2011年 | 280篇 |
2010年 | 223篇 |
2009年 | 243篇 |
2008年 | 243篇 |
2007年 | 262篇 |
2006年 | 234篇 |
2005年 | 231篇 |
2004年 | 196篇 |
2003年 | 180篇 |
2002年 | 178篇 |
2001年 | 93篇 |
2000年 | 92篇 |
1999年 | 70篇 |
1998年 | 84篇 |
1997年 | 80篇 |
1996年 | 88篇 |
1995年 | 68篇 |
1994年 | 39篇 |
1993年 | 28篇 |
1992年 | 30篇 |
1991年 | 22篇 |
1990年 | 22篇 |
1989年 | 25篇 |
1988年 | 19篇 |
1987年 | 13篇 |
1986年 | 3篇 |
1985年 | 15篇 |
1984年 | 7篇 |
1983年 | 13篇 |
1982年 | 10篇 |
1980年 | 3篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1976年 | 3篇 |
1975年 | 7篇 |
1974年 | 7篇 |
1973年 | 6篇 |
排序方式: 共有6003条查询结果,搜索用时 15 毫秒
61.
Constable EC Handel RW Housecroft CE Farràn Morales A Ventura B Flamigni L Barigelletti F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(13):4024-4034
A new series of V-shaped trinuclear metallorods and X-shaped pentanuclear metallostars has been prepared by the reaction of metal complexes bearing pendant phenolic functionalities with complexes containing electrophilic ligands. Specifically, {M(tpy)2} motifs (M=Ru or Os; tpy=2,2':6',2'-terpyridine) bearing one or two pendant 3,5-dihydroxyphenyl substituents at the 4-position of the central ring of the tpy have been reacted with the complexes [Ru(tpy)(Xtpy)]2+ (X=Cl or Br) to form new ether-linked species. The energy transfer from ruthenium to osmium in these complexes has been investigated in detail and the efficiency of transfer shown to be highly temperature dependent; the energy transfer is highly efficient at low temperature, whereas at room temperature nonradiative and nontransfer deactivation of the excited {Ru(tpy)2}* domains is most significant. 相似文献
62.
Guy Guelachvili K. Narahari Rao Richard H. Tipping Brenda P. Winnewisser Manfred Winnewisser 《Mikrochimica acta》1988,95(1-6):339-343
This paper reports the observation of the far infrared absorption spectrum of a single crystal of N2, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed. 相似文献
63.
Sergey Y. Savinov Hwaung Lee Hyung Keun Song Byung-Ki Na 《Plasma Chemistry and Plasma Processing》2003,23(1):159-173
An experimental study of plasmachemical reaction involving CH4 and N2 molecules in rf discharge was studied in order to know the effect of vibrational excitation of N2 molecules. When the relative nitrogen concentration was greater than 0.8, the main product of CH4 decomposition was HCN, and the rate of methane decomposition at this condition was faster than that one in pure methane. These results could be confirmed through the mass spectroscopic method. The reason for these results is the vibrational energy of N2 excited by rf discharge. The chain reaction mechanisms of producing HCN by vibrational excitation of N2 were examined closely through numerical simulation. The rate-controlling step was the dissociation reaction of excited nitrogen molecule to the atomic nitrogen, so the process of HCN synthesis was limited by the value of reaction constant, kN. 相似文献
64.
Aquino AJ Tunega D Haberhauer G Gerzabek MH Lischka H 《Journal of computational chemistry》2003,24(15):1853-1863
Hydrogen-bonded interactions between local defect structures on broken clay surfaces modeled as molecular clusters and the organic molecules acetic acid, acetate, and N-methylacetamide (NMA) have been investigated. Density functional theory and polarized basis sets have been used for the computation of optimized interaction complexes and formation energies. The activity of the defect structures has been characterized as physical or chemical in terms of the strength of the hydrogen bonds formed. Chemical defects lead to significantly enhanced interactions with stronger hydrogen bonds and larger elongation of OH bonds in comparison to the physical defects. The type of interaction with the defect structure significantly influences the planarity of the model peptide bond in NMA. Both cases, enhancement of the planarity by increase of the CN double bond character and strong deviations from planarity, are observed. 相似文献
65.
Pyrocarbon/silica gel adsorbents (carbosils, CS) with mesoporous Si-60 (Merck, granule size 0.2–0.5 mm) modified by pyrolysis of CH2Cl2 at 823 K and reaction time from 0.5 to 6 h and then hydrothermally treated at 473 K for 6 h were studied by means of TEM, adsorption and 1H NMR methods. Changes in the structural and adsorptive characteristics of hybrid adsorbents before and after hydrothermal treatment, which depend on pyrocarbon content (C
C), were analyzed on the basis of TEM micrographs and p-nitrophenol and nitrogen adsorption isotherms treated using a constrained regularization method. Interfacial water layers in aqueous suspension of CS were investigated by means of 1H NMR with freezing-out of bulk water at T < 273 K showing nonlinear changes in the Gibbs free energy of interfacial water with increasing C
C because of nonlinear dependence of the structural characteristics of pyrocarbon deposits and CS as a whole on C
C. 相似文献
66.
总结了铌酸锂晶体的各项性能指标,显示了其对晶体实际组成的强烈依赖性.利用化学键模型定量地解释了这种依赖性产生的根源,从而说明了制约该晶体性能提高的关键因素是晶体结构中的缺陷控制. 相似文献
67.
F Schneider 《Angewandte Chemie (International ed. in English)》1978,17(8):583-592
The presence of histidine in the active center of an enzyme can be demonstrated by kinetic measurements, chemical modification, NMR spectroscopy or X-ray structure analysis. Histidine is the only naturally occurring amino acid to contain an imidazole residue as a side chain. The role of histidine in enzyme catalysis depends, inter alia, upon the special features of the imidazole residue: it thus tends to form hydrogen bonds, combines donor and acceptor properties and can take part in either nucleophilic or base catalysis. In some of these enzymes the position of each atom is known; however, the theories as to how the catalysis proceeds at a molecular level are controversial. 相似文献
68.
环己胺与手性元5-(R)-(1′R,2′S,5′R)-孟氧基-3-溴-2(5H)-呋喃酮的不对称M ichael加成/分子内亲核取代反应,得到含有两个新手性中心的氮杂环丙烷/稠合丁内酯标题化合物。对其进行了谱学表征和X-射线单晶衍射测定。标题化合物分子式为C20H33NO3,M r=335.47,三斜晶系,P1空间群,晶胞参数:a=5.438(11)。A,b=8.117(2)。A,c=11.572(2)。A,α=96.84(3)°,β=94.48(3)°,γ=101.86(3),°V=493.5(2)。A3,Z=1,D c=1.129g/cm3,R=0.0867,wR=0.2344。 相似文献
69.
作者定义了Gorenstein AC导出范畴 Dbgac(R)并且和导出范畴作了一些比较.作者定义了Gorenstein AC奇点范畴 Dbgacsg(R),在这个范畴中具有有限Gorenstein AC- 投射维数的模都是零对象.同时, 作者给出了由Gorenstein AC- 投射模构成的稳定范畴到奇点范畴的三角嵌入 F : GAC → Dbsg(R) .通过作函子 F 的商引入Gorenstein AC亏范畴 Dbgacd(R),并且给出三角等价 Dbgacd(R) = Dbgacsg(R) 相似文献
70.
Volkmar Nejedl Michael Panzner Stefan Baunack Ulrich Franz Arnold Luft Klaus Wetzig 《Mikrochimica acta》1998,130(1-2):89-95
The laser induced modification of iron surfaces with atmospheric species was investigated by means of Auger electron spectroscopy (AES) and scanning electron microscopy (SEM). Different laser systems were used for irradiating iron samples in a wide range of the laser processing parameters up to small foci and ultra short pulses.A nitriding of iron connected with an oxidation of the near surface region was observed in the wavelength range between 193 nm and 10.6 m using large foci (0.1 cm2) and short pulses (10...1400ns). In case of small foci (7·10–6cm2) with ns-pulses (50 ns) an enrichment of the iron melt with nitrogen and an advanced oxidation of the surrounding area of the laser spot were detected. When using shorter pulses (200 fs, 40 ps) no indications for a nitriding were found. 相似文献