全文获取类型
收费全文 | 5807篇 |
免费 | 184篇 |
国内免费 | 21篇 |
专业分类
化学 | 4263篇 |
晶体学 | 72篇 |
力学 | 64篇 |
数学 | 341篇 |
物理学 | 1272篇 |
出版年
2023年 | 28篇 |
2022年 | 43篇 |
2021年 | 58篇 |
2020年 | 99篇 |
2019年 | 75篇 |
2018年 | 72篇 |
2017年 | 58篇 |
2016年 | 135篇 |
2015年 | 98篇 |
2014年 | 155篇 |
2013年 | 261篇 |
2012年 | 339篇 |
2011年 | 412篇 |
2010年 | 197篇 |
2009年 | 202篇 |
2008年 | 365篇 |
2007年 | 362篇 |
2006年 | 364篇 |
2005年 | 335篇 |
2004年 | 277篇 |
2003年 | 245篇 |
2002年 | 242篇 |
2001年 | 122篇 |
2000年 | 102篇 |
1999年 | 77篇 |
1998年 | 61篇 |
1997年 | 53篇 |
1996年 | 60篇 |
1995年 | 52篇 |
1994年 | 45篇 |
1993年 | 46篇 |
1992年 | 69篇 |
1991年 | 61篇 |
1990年 | 46篇 |
1989年 | 43篇 |
1988年 | 50篇 |
1987年 | 42篇 |
1986年 | 38篇 |
1985年 | 71篇 |
1984年 | 57篇 |
1983年 | 51篇 |
1982年 | 53篇 |
1981年 | 35篇 |
1980年 | 45篇 |
1979年 | 43篇 |
1978年 | 30篇 |
1977年 | 31篇 |
1976年 | 30篇 |
1975年 | 27篇 |
1973年 | 26篇 |
排序方式: 共有6012条查询结果,搜索用时 0 毫秒
121.
Shuji Saito 《Journal of polymer science. Part A, Polymer chemistry》1970,8(1):263-271
The effects of various alkylammonium thiocyanates (ethyl, butyl, hexyl, and octyl) on aqueous solutions of polyvinylpyrrolidone (PVP) and poly(vinyl alcohol–acetate) copolymer (PVA-Ac) were studied and compared with the effects caused by the respective chlorides. Whereas the PVP solution was hardly affected by the chlorides, it was precipitated by n-octylammonium thiocyanate (OASCN) at dilute concentrations and dissolved at higher concentrations. On taking the effects of ammonium chloride and thiocyanate on the solubility of PVA-Ac as references, with increasing of alkyl chain length, alkylammonium chlorides raised the polymer solubility steadily; on the contrary, the thiocyanates at dilute concentrations, except for ethylammonium thiocyanate, lowered it, and OASCN at dilute concentrations, except for ethylammonium thiocyanate, lowered it, and OASCN at dilute concentrations was a particularly strong salting-out agent. The amount of binding of OASCN to the polymers in the precipitated systems was measured. The precipitation was attributed to ion-pair binding of OASCN to the polymers, and the mechanism was discussed in terms of the interaction between the water structure-breaking SCN? and the water structure-making hydrophobic groups. 相似文献
122.
For evaluation of a chiral C2-symmetric bis(oxazoline) ligand, its Lewis acid complexes-catalyzed asymmetric 1,3-dipolar cycloaddition reactions of nitrones with electron-deficient dipolarophiles, 3-(2-alkenoyl)-1,3-oxazolidin-2-ones, have been investigated and it was found that the cycloadditions using a Cu(II)-bis(oxazoline) complex under optimized reaction conditions induced extremely high enantioselectivity. 相似文献
123.
M Saito S Kataoka A Nasu N Yamaji A Ichikawa 《Chemical & pharmaceutical bulletin》1991,39(12):3207-3210
A series of adenosine 3',5'-cyclic monophosphoramidates (3, cAMP amidates), including long-chain alkyl amidates, were synthesized from adenosine 3',5'-cyclic monophosphate (1, cAMP) by means of a one-pot reaction. This reaction proceeded by the treatment of cAMP tributylammonium salt (2) with phosphorus pentachloride (PCl5) and alkylamine in N,N-dimethylformamide (DMF). Compounds 3 synthesized were investigated to determine their cytotoxic activities on the growth of mouse mastocytoma P-815 cells, mouse mammary tumor FM3A cells, and human mammary tumor ZR-75 cells in culture. It was found that compounds 3h-m showed significant cytotoxic activities against these cell lines, and that cAMP decylamidate (3j) was the most cytotoxic compound (the concentration required for 50% inhibition of cell growth, ID50 = 6.0, 15.0, 2.2 microM, respectively); the antitumor effect on P-815 cells by a total packed cell volume method showed 81.8% inhibition. The cytotoxic activity of 3 increased with the increase in alkyl chain length up to 10 carbon atoms and decreased in compounds having longer alkyl chain. 相似文献
124.
In this work we report a novel method that can monitor in vivo the salt permeation process into a plant Vigna angularis using two Ag/AgCl electrodes. The method is based on the electromotive force (emf) measurement using two Ag/AgCl electrodes, one inserted into the V. angularis pith cavity and the other placed into saline ([NaCl]=1 M) surrounding the roots. Temporary change of emf ranging from 0 to ca. 0.115 V was measured in vivo using the system, and the possible physiological phenomenon during the period was discussed. 相似文献
125.
Satoshi ObikaJyun-ichi Andoh Mayumi OnodaOsamu Nakagawa Akiko HirotoTomomi Sugimoto Takeshi Imanishi 《Tetrahedron letters》2003,44(28):5267-5270
A novel bridged nucleic acid monomer, 3′-amino-3′-deoxy-5-methyl-3′-N,4′-C-methyleneuridine, was successfully synthesized via a useful and convenient azetidine ring formation under Staudinger's conditions. A 1H NMR experiment and a PM3 calculation revealed that the sugar moiety of the novel bridged nucleic acid monomer, 3′-amino-3′,4′-BNA, was restricted to S-type conformation. 相似文献
126.
Atsuyoshi Ohno Yuji Ishihara Satoshi Ushida Shinzaburo Oka 《Tetrahedron letters》1982,23(31):3185-3188
Benzaldehyde are reduced to benzyl alcohol by a model compound of NAD(P)H almost quantitatively. Reductions of some other aldehydes are also mentioned. 相似文献
127.
Poly(1,4-dimethyl-6-vinylnaphthalene) and poly(1,2,4-trimethyl-6-vinylnaphthalene) react with singlet oxygen to give corresponding endoperoxide polymers which on warming generate singlet oxygen efficiently. Singlet oxygenations by the use of these polymers have been described. 相似文献
128.
Katsutoshi Kubota Makoto Minakata Shoichi Saito Shingo Uehara 《Optical and Quantum Electronics》1978,10(3):205-210
A low drive-voltage optical modulator using a Ti-diffused UNbO3 optical waveguide has been fabricated. Stabilization against ambient temperature change was realized by using a miniature halfwave plate. The halfwave voltage, 3 dB bandwidth, optical insertion loss and extinction ratio were 3·8 V (at 1·06m wavelength), 850 MHz, 10 dB and 13 dB, respectively. A reduction scheme for the optical absorption caused by metallic electrodes, and an analysis of the modulator high frequency response are also reported. 相似文献
129.
Abe I Oguro S Utsumi Y Sano Y Noguchi H 《Journal of the American Chemical Society》2005,127(36):12709-12716
The chalcone synthase (CHS) superfamily of type III polyketide synthases (PKSs) produces a variety of plant secondary metabolites with remarkable structural diversity and biological activities (e.g., chalcones, stilbenes, benzophenones, acrydones, phloroglucinols, resorcinols, pyrones, and chromones). Here we describe an octaketide-producing novel plant-specific type III PKS from aloe (Aloe arborescens) sharing 50-60% amino acid sequence identity with other plant CHS-superfamily enzymes. A recombinant enzyme expressed in Escherichia coli catalyzed seven successive decarboxylative condensations of malonyl-CoA to yield aromatic octaketides SEK4 and SEK4b, the longest polyketides known to be synthesized by the structurally simple type III PKS. Surprisingly, site-directed mutagenesis revealed that a single residue Gly207 (corresponding to the CHS's active site Thr197) determines the polyketide chain length and product specificity. Small-to-large substitutions (G207A, G207T, G207M, G207L, G207F, and G207W) resulted in loss of the octaketide-forming activity and concomitant formation of shorter chain length polyketides (from triketide to heptaketide) including a pentaketide chromone, 2,7-dihydroxy-5-methylchromone, and a hexaketide pyrone, 6-(2,4-dihydroxy-6-methylphenyl)-4-hydroxy-2-pyrone, depending on the size of the side chain. Notably, the functional diversity of the type III PKS was shown to evolve from simple steric modulation of the chemically inert single residue lining the active-site cavity accompanied by conservation of the Cys-His-Asn catalytic triad. This provided novel strategies for the engineered biosynthesis of pharmaceutically important plant polyketides. 相似文献
130.
Density functional theory calculations were carried out for the title reactions. Ethylene oxide and methylamine were adopted as reactants. Amine clusters (dimer, trimer, tetramer, and pentamer) were considered, because the combination of one oxide and one amine molecule gave a large activation energy. An amine tetramer was found to react favorably with the oxide via various zwitterionic intermediates. A back-side S(N)2 nucleophilic attack of one amine and the subsequent proton relay up to the front side provide a stabilized reaction field. The amine-alcohol mixed reactant may react readily with the oxide, because the alcoholic O-H group is in contact with the oxide oxygen with the strong hydrogen-bond stabilization. 相似文献