全文获取类型
收费全文 | 9203篇 |
免费 | 210篇 |
国内免费 | 63篇 |
专业分类
化学 | 6111篇 |
晶体学 | 88篇 |
力学 | 286篇 |
综合类 | 1篇 |
数学 | 1432篇 |
物理学 | 1558篇 |
出版年
2022年 | 85篇 |
2021年 | 89篇 |
2020年 | 157篇 |
2019年 | 118篇 |
2018年 | 89篇 |
2017年 | 108篇 |
2016年 | 200篇 |
2015年 | 156篇 |
2014年 | 204篇 |
2013年 | 417篇 |
2012年 | 479篇 |
2011年 | 579篇 |
2010年 | 294篇 |
2009年 | 235篇 |
2008年 | 518篇 |
2007年 | 482篇 |
2006年 | 470篇 |
2005年 | 471篇 |
2004年 | 440篇 |
2003年 | 303篇 |
2002年 | 321篇 |
2001年 | 109篇 |
2000年 | 95篇 |
1999年 | 73篇 |
1998年 | 85篇 |
1997年 | 106篇 |
1996年 | 150篇 |
1995年 | 91篇 |
1994年 | 82篇 |
1993年 | 107篇 |
1992年 | 79篇 |
1991年 | 90篇 |
1990年 | 85篇 |
1989年 | 70篇 |
1988年 | 83篇 |
1987年 | 72篇 |
1986年 | 64篇 |
1985年 | 126篇 |
1984年 | 141篇 |
1983年 | 105篇 |
1982年 | 120篇 |
1981年 | 120篇 |
1980年 | 99篇 |
1979年 | 88篇 |
1978年 | 118篇 |
1977年 | 101篇 |
1976年 | 94篇 |
1975年 | 80篇 |
1974年 | 74篇 |
1973年 | 69篇 |
排序方式: 共有9476条查询结果,搜索用时 15 毫秒
41.
The silanization/hydrosilation method is used to bond an alkyne (1-octyne) to a silica hydride surface. The new bonded material is characterized by elemental analysis and diffuse reflectance infrared Fourier transform spectroscopy. The hydrophobic behavior of this material was determined by the retention characteristics of aromatic solutes and the shape selectivity as well as phase classification (monomeric or polymeric) was measured by the polycyclic aromatic hydrocarbon mixture standard reference material 869. The presence of residual silanols on the bonded phase was probed by several basic solutes at pH 7. Long-term stability studies were conducted by measuring retention and peak symmetry of basic compounds over several thousand column volumes at pH 10. 相似文献
42.
Desulfurization of dibenzothiophene, two methyldibenzothiophenes, and phenanthro[4,5-bcd]-thiophene to give 60-80% yields of hydrocarbon products was effected by means of a sulfided molydena catalyst plus methanol at 450° and a pressure of ca. one atmosphere. The methanol functions both as an in situ hydrogen donor and as a methylating agent. 相似文献
43.
Kommareddi Nagesh S. Tata Murthy Karayigitoglu Cigdem John Vijay T. McPherson Gary L. Herman Michael F. O'Connor Charles J. Lee Young-Sook Akkara Joseph A. Kaplan David L. 《Applied biochemistry and biotechnology》1995,51(1):241-252
Applied Biochemistry and Biotechnology - Horseradish peroxidase has been used as a biocatalyst to synthesize a polymeric material from alkyl-substituted phenols. The synthesis is carried out in a... 相似文献
44.
45.
PHOTOCHEMICAL CROSSLINKING OF ATP TO HISTONE H4 总被引:2,自引:0,他引:2
Abstract— A covalent crosslink occurs between histone H4 and the adenine moiety of ATP, when the complex they form is irradiated with UV light of Λ > 290 nm in the presence of acetone. Within 1 h of irradiation a 48% yield of crosslinked product is thus obtained. It is also shown that in the photosensitized reaction, 80% of the crosslinked product is monomeric, whereas protein precipitation and aggregation occur as a result of direct irradiation with 254 nm light. 相似文献
46.
Joseph I. Degraw Lawrence F. Kelly Roy L. Kisliuk Yvette Gaumont Francis M. Sirotnak 《Journal of heterocyclic chemistry》1982,19(6):1587-1588
A synthesis of 8,10-dideazaminopterin, using 2,4-diamino-6-bromomethyl-8-deazapteridine ( 2 ) as a key intermediate, is described. Condensation of the triphenylphosphinylide derived from 2 with p-formylbenzoyl-L-glutamate afforded a 9,10-dehydro-8,10-dideazaminopterin ester intermediate 5 . Hydrogenation of the olefinic linkage and subsequent hydrolysis of the glutamate ester gave the title compound. 8,10-Dideazaminopterin was a potent growth inhibitor of folate dependent bacteria. It was 16 times more potent then methotrexate as an inhibitor of dihydrofolate reductase derived from L1210 leukemia cells, and showed strong activity against L1210 in mice. 相似文献
47.
Donathan G. Beasley John Beard Joseph W. Stanfield Lee K. Roberts 《Photochemistry and photobiology》1996,64(2):303-309
Expense and inconvenience have restricted the use of the filtered xenon are lamp (solar simulator) as a UV source for conducting large-scale animal studies. Because sunscreen immunoprotective levels are significantly affected by the UV power spectrum of the source it is imperative that a solar simulating source be used for accurate measurements of sunscreen protection levels that are relevant to human UV exposures from sunlight. However, relatively inexpensive sunlamps, e. g. the UVA-340, that emit a UV power spectrum similar to that of a solar simulator are available. Unlike FS-type UVB sunlamps, which have a significant amount of effective immunosuppressive nonsolar UV energy at wavelengths below 295 nm, the immunosuppression effectiveness spectrum of UVA-340 sunlamps was nearly identical to that of a solar simulator. The purpose of this study was to evaluate this sunlamp for conducting photoimmunological and sunscreen immune protection studies. Groups of C3H mice were exposed to a range of UVA-340 sunlamp doses (0.25 KJ/m2 to 20.0 KJ/m2) to establish a dose-response curve and determine the minimum immune suppression dose (MISD) for induction of local-type suppression of contact hypersensitivity (CH). The MISD, defined as the lowest UV dose given to produce ~50% suppression of the CH response in mice, was determined to be 1.0 kJ/m2 for UVA-340 sunlamps. Immune protection tests on four marketed sunscreen lotions (sun protection factors [SPF] 4, 8, 15 and 30) were then conducted with UVA-340 sunlamps using MISD as the endpoint. The immune protection factors for these sunscreens were equivalent to the level of protection predicated by their labeled SPF. These results are similar to those we have previously obtained using a solar simulator. We conclude from these data that the immunosuppressive effects of UVA-340 sunlamps are similar to those of a solar simulator; however, further studies are needed to determine if UVA-340, or similar, sunlamps are a viable alternative to the solar simulator for conducting large-scale animal experiments that require a relevant UV solar spectrum. 相似文献
48.
The solid-phase synthesis of the octapeptide 1 AcGly-Ala-Lys-Arg-His-Arg-Lys-ValOMe, which represents the fragment 14-21 of the amino acid sequence of the chromosomal histone H4, as well as of the structurally related nonapeptide 2 AcGly-Ala-Lys-Leu-Arg-His-Arg-Lys-ValOMe, is described using a new polyacrylic resin containing a glycolamide ester linkage(resin-NHCO-CH2-OCO-peptide) acting as a labile anchoring moiety between the resin and the peptide.After elongation of the polypeptide chain using classical protecting groups, i.e. t-butyloxycarbonyl for the α-NH2 function, benzyloxycarbonyl, nitro and 2,4-dinitrophenyl groups for the side-chains of Lys, Arg and His respectively, both peptides 1 and 2 were obtained in good yields and with a high purity as shown by high-pressure liquid chromatography, by amino-acid analysis and by high-field proton NMR spectroscopy.This work demonstrates the ability of the newly introduced polyacrylic resin to act as a convenient support for solid-phase peptide synthesis. 相似文献
49.
Charles B. de Koning Sunnyboy S. Manzini Joseph P. Michael Edwin M. Mmutlane Tefo R. Tshabidi Willem A.L. van Otterlo 《Tetrahedron》2005,61(3):555-564
The synthesis of substituted anthracenes from naphthalene precursors is described. The key step involved heating ortho-allyl substituted naphthalene-2-carbaldehydes and potassium t-butoxide in DMF with concomitant irradiation from a high pressure mercury lamp to afford anthracenes in yields of 76-98%. 相似文献
50.
We employ retro models, cis-PtA2G2 (A2 = a diamine, G = guanine derivative), to assess the cross-linked head-to-head (HH) form of the cisplatin-DNA d(GpG) adduct widely postulated to be responsible for the anticancer activity. Retro models are designed to have minimal dynamic motion to overcome problems recognized in models derived from cisplatin [A2 = (NH3)2]; the latter models are difficult to understand due to rapid rotation of G bases about the Pt-N7 bond in solution and the dominance of the head-to-tail (HT) form in the solid. Observation of an HH form is unusual for cis-PtA2G2 models. Recently, we found the first HH forms for a cis-PtA2G2 model with A2 lacking NH groups in a study of new Me2ppzPtG2 models. (Me2ppz, N,N'-dimethylpiperazine, has inplane bulk which reduces dynamic motion by clashing with the G O6 as the base rotates into the coordination plane from the ground state position approximately perpendicular to this plane G = 5'-GMP and 3'-GMP.) The finding of an HH form (albeit in a mixture with HT forms) with both G H8 signals unusually downfield encouraged us to study additional Me2ppzPtG2 analogues in order to explain the unusual spectral features and to identify factors that influence the relative stability of HT and HH forms. Molecular modeling techniques suggest HH structures with the H8's close to the deshielding region of the z axis of the magnetically anisotropic Pt atom, explaining the atypical shift pattern. When G = 1-Me-5'-GMP, we obtained NMR evidence that the HH rotamer has a high abundance (34%) and that the three rotamers have nearly equal abundance. These findings and the observation that the relative HT distributions varied little or not at all as a function of pH when G = Guo, 1-MeGuo, or 1-Me-5'-GMP are consistent with two of our earlier proposals concerning phosphate groups in HT forms of cis-PtA2(GMP)2 complexes. We proposed that a G phosphate group can form hydrogen bonds with the cis G N1H ("second-sphere" communication) and (for 5'-phosphate) A2 NH groups. The new results with 1-Me-5'-GMP led us to propose a new role for a 5'-phosphate group; it can also favor the HH form by counteracting the natural preference for the G bases to adopt an HT orientation. Finally, the HH form was also sufficiently abundant to allow observation of a distinct 195Pt NMR signal (downfield of the resonance observed for the HT forms) for several complexes. This is the first report of an HH 195Pt NMR signal for cis-PtA2G2 complexes. 相似文献