全文获取类型
收费全文 | 6486篇 |
免费 | 256篇 |
国内免费 | 46篇 |
专业分类
化学 | 4791篇 |
晶体学 | 24篇 |
力学 | 207篇 |
数学 | 887篇 |
物理学 | 879篇 |
出版年
2023年 | 67篇 |
2022年 | 87篇 |
2021年 | 126篇 |
2020年 | 118篇 |
2019年 | 148篇 |
2018年 | 91篇 |
2017年 | 82篇 |
2016年 | 197篇 |
2015年 | 166篇 |
2014年 | 206篇 |
2013年 | 370篇 |
2012年 | 465篇 |
2011年 | 501篇 |
2010年 | 271篇 |
2009年 | 240篇 |
2008年 | 425篇 |
2007年 | 437篇 |
2006年 | 392篇 |
2005年 | 361篇 |
2004年 | 338篇 |
2003年 | 299篇 |
2002年 | 249篇 |
2001年 | 86篇 |
2000年 | 80篇 |
1999年 | 66篇 |
1998年 | 56篇 |
1997年 | 60篇 |
1996年 | 74篇 |
1995年 | 50篇 |
1994年 | 36篇 |
1993年 | 27篇 |
1992年 | 32篇 |
1991年 | 34篇 |
1990年 | 35篇 |
1989年 | 27篇 |
1988年 | 18篇 |
1986年 | 21篇 |
1985年 | 26篇 |
1984年 | 39篇 |
1983年 | 28篇 |
1982年 | 38篇 |
1981年 | 25篇 |
1980年 | 37篇 |
1979年 | 24篇 |
1978年 | 29篇 |
1977年 | 37篇 |
1976年 | 27篇 |
1975年 | 28篇 |
1974年 | 16篇 |
1973年 | 18篇 |
排序方式: 共有6788条查询结果,搜索用时 46 毫秒
51.
Anzalone PW Baru AR Danielson EM Hayes PD Nguyen MP Panico AF Smith RC Mohan RS 《The Journal of organic chemistry》2005,70(6):2091-2096
[reaction: see text] Three one-pot methods for the conversion of aldehydes to homoallyl ethers catalyzed by Bi(OTf)(3).xH(2)O (1 < x < 4) have been developed. The one-pot synthesis of homoallyl ethers can be achieved either by in situ generation of the acetal followed by its reaction with allyltrialkylsilane or by a three-component synthesis in which the aldehyde, trimethylorthoformate or an alkoxytrimethylsilane and allyltrimethylsilane are mixed together in the presence of bismuth triflate (0.1-1.0 mol %). In addition, a three-component synthesis of homoallyl acetates, which is achieved by reacting the aldehyde, acetic anhydride, and allyltrimethylsilane in the presence of bismuth triflate (3.0-5.0 mol %), has been developed. The use of a relatively nontoxic, easy to handle, and inexpensive catalyst adds to the versatility of these methods. 相似文献
52.
53.
Polymeric molecules containing multiple thiol groups (polythiols) provide tenacious attachment to metal surfaces such as gold. Polythiol films are also well suited for subsequent derivatization with biomacromolecules through remnant free thiol groups of the film. In this study, 1-3 nm thick layers of a commercial polythiol, poly((mercaptopropyl)methylsiloxane) (PMPMS), are investigated with X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy. XPS is used to reveal the surface coverage of thiolate-Au bonds between the polythiol and the metal support, which is found to be approximately 30% lower than that in alkanethiol self-assembled monolayers. The surface density of thiolate-Au bonds did not depend on film thickness provided sufficient PMPMS material was present. Differential capacitance measurements show that the effective dielectric barrier presented by PMPMS films under aqueous environments corresponds closely to their physical thickness, with even approximately 1 nm films remaining impermeable to electrolyte species. Modification of the films with an oligoethylene glycol compound was also examined, in anticipation of future applications in label-free, impedance-based biomolecular diagnostics. 相似文献
54.
Abstract— In stationary-phase Escherichia coli B/r, photoreactivation (PR) at 313 nm of ultraviolet (u.v.) killing is inefficient compared with PR at 405 nm, and can be explained solely by photoenzymatic reversal of pyrimidine dimers. In Staphylococcus epidermidis, PR shows a maximum at 313 nm, suggesting that this organism shows the Type III PR proposed by Jagger et al.[5] for Streptomyces strains. Reversal of pyrimidine dimers is not sufficient to explain this PR. The mechanism of Type III PR remains unknown. With both S. epidermidis and E. coli B/r, the amount of uracil–thymine heteroadduct in DNA hydrolysates decreases if the cells are given a post-u.v. treatment at 313 nm, but no decrease is observed if the post-u.v. treatment is at 405 nm. The biological significance of this adduct and of its removal is not clear. It may play a role in Type III PR. 相似文献
55.
THE EFFECTS OF HOST-CELL REACTIVATION ON ASSAY OF U.V.-IRRADIATED HAEMOPHILUS INFLUENZAE TRANSFORMING DNA 总被引:4,自引:0,他引:4
Abstract— The host cell reactivation (HCR) mechanism in Haemophilus influenzae cells is inhibited by sub-microgram concentrations of acriflavine (as is already known to be true for Escherichia coli ). Exposure of these cells to similar concentrations of the drug during bacterial transformation increases the apparent ultraviolet light (u.v.) sensitivity of previously irradiated transforming DNA, indicating a repair of this DNA after uptake by the cells under normal conditions. Repair is inhibited by applying acriflavine at any time up to one hour after competent cells contact the irradiated transforming DNA. The fraction of the u.v. damage repaired by HCR is very different for different genetic markers. Those markers which are most u.v. sensitive when assayed in the absence of acriflavine are most poorly repaired, suggesting that this is the reason for their higher sensitivity. For all markers the fraction of the damage repairable by in vitro photoreactivation is approximately constant, and strongly overlaps the damage repairable by HCR. The degree of HCR achieved can be altered by experimental treatment of the H. influenzae DNA prior to transformation. Thus treatment of irradiated DNA with an enzyme from Micrococcus lysodeikticus –known to attack u.v. damaged, but not undamaged DNA–prevents subsequent intracellular repair of the same u.v. lesions whose repair is inhibited by acriflavine. Similarly, partial replacement of the thymine in transforming DNA by 5-bromouracil (BU) strongly inhibits repair of subsequent u.v. damage. As in bacteriophage, the BU effect is relieved if the u.v. exposure occurs in the presence of cysteamine. It is clear that intracellular repair must be considered in interpreting experiments with u.v.-irradiated transforming DNA. 相似文献
56.
We study the transient response of a Brownian particle with general damping in a system of metastable potential well. The escape rate is evaluated as a function of time after an infinite wall is removed from the potential barrier. It takes a relaxation time for the rate to reach its limit value and this rate relaxation time differs from the relaxation time of the majority of the probability around the bottom of the potential well. The rate relaxation time is found to depend on the temperature as well as the damping constant. It involves the diffusion time and the instanton time, in general agreement with recent studies of the overdamped case by Bier et al. [Phys. Rev. E 59, 6422 (1999)]. 相似文献
57.
Bhat B Swayze EE Wheeler P Dimock S Perbost M Sanghvi YS 《The Journal of organic chemistry》1996,61(23):8186-8199
A highly convergent free radical coupling of alkyl iodides and oximes, mediated by bis(trimethylstannyl) benzopinacolate (8), has been utilized to prepare a series of dimeric nucleosides as mimics of natural nucleic acids. The systematic optimization of the reaction conditions allowed for the single-step conversion of the appropriate iodides and oximes into the 2'-deoxy dimers 9 in moderate to excellent yields. For example, the reaction of 3'-deoxy-3'-iodo-5'-(triphenylmethyl)thymidine (6a) with 3'-O-(tert-butyldiphenylsilyl)-5'-O-(methyleneimino)thymidine (7a) in the presence of 8 in degassed benzene gave an 81% yield of 3'-de(oxyphosphinico)-3'-(methyleneimino)-5'-O-(triphenylmethyl)thymidylyl-(3'-->5')-3'-O-(tert-butyldiphenylsilyl)thymidine (9a). Similarly prepared were dimers containing both pyrimidine (thymine, 5-methylcytosine) and purine (adenine, guanine) bases. The reaction was highly stereoselective, giving only a single dimeric species having the ribo-configuration of the newly introduced C-3'-branched methylene moiety. Also prepared were dimers 16, incorporating 2'-O-methyl ribonucleosides in both halves of the dimer. This required the synthesis of 3'-deoxy-3'-iodo-2'-O-methyl nucleosides 12 as well as 2'-O-methyl-5'-O-methyleneimino nucleosides 15. For example, 5'-O-(tert-butyldiphenylsilyl)-3'-deoxy-3'-iodo-2'-O-methyl-5-methyluridine (12e) was prepared in 80% yield by displacement of the corresponding triflate with Bu(4)NI. Also prepared were the suitably protected 3'-deoxy-3'-iodo adenosine and guanosine derivatives. Compounds 15 were prepared in high yield by a regioselective Mitsunobu reaction to give the corresponding 5'-O-phthalimido nucleosides 13, which were subsequently converted to the requisite oximes 15. In the 2'-O-methyl series, the pinacolate coupling reaction proceeded with efficiency equal to that observed for the 2'-deoxy series 9, but with slightly less stereoselectivity, giving predominantly the C-3'ribo products 16, contaminated with 5-25% of the epimeric material. Mixed base dimers containing both pyrimidine and purine bases at all possible positions, including purine-purine dimers were prepared. The hydroxylamine or methyleneimino (MI) backbone of several representative dimers so prepared was converted via methylation to give the corresponding methylenemethylimino (MMI)-linked compounds, which are novel phosphate surrogates for use in antisense oligonucleotides. 相似文献
58.
13C Nmr, 1H nmr and ir parameters of coupling products of tetronic acids (4-hydroxy-5H-furan-2-ones) with benzene diazonium sulfate are only consistent with a phenylhydrazone formulation with an almost equal ratio of the syn and anti configurations. These results contrast with those of coupling products of acyclic 3-ketoesters, existing mainly as anti tautomers, and more sharply with the 3-parabromophenylhydrazone of L-dehydro ascorbic acid, which is exclusively syn. 相似文献
59.
The reaction between TiO(2+) and ONOOH in 0.9 M H(2)SO(4) provides evidence for direct formation, previously unobserved, of a HOONO-metal complex. The reaction proceeds via formation of an end-on complex (k = 3.0 x 10(2) M(-1) s(-1)) that rearranges to form a side-on complex (k approximately equal to 20 s(-1)). With ONOOH in excess, this rearrangement proceeds more slowly (k approximately equal to 0.1 s(-1)), probably because multiple hydrogen oxoperoxonitrate molecules form end-on complexes with oxotitanium(IV) and hinder rearrangement to the side-on complex. The absorption spectrum of the final product is that of TiO(2)(2+). Presumably, during the rearrangement or later, NO+ is lost. 相似文献
60.
HIV infection leads to progressive alterations of humoral immune functions, including B-cell hyperplasia, hypergammaglobulinemia,
elevated autoantibody titers, a poor response to neoantigens and mitogens, polyclonal B-cell activation, monoclonal gammopathies,
and a significant deterioration of the antigen-specific humoral response. There is also an important isotypic imbalance of
the antibody (Ab) response in the systemic compartment and a profound modification of mucosal immune functions. These abnormalities
may contribute to disease progression and development of opportunistic infections, despite the presence of serum-neutralizing
anti-HIV Abs. Equally important are the abnormal selection mechanisms of the Ab repertoire that seem to be responsible for
B-cell clonal deletions. The VH3 gene family, which encodes for approx 50% of immunoglobulins expressed by peripheral B-cells from normal adults, is underrepresented
in human monoclonal antibodies to HIV-1 and in the peripheral B-cells of AIDS patients. These abnormalities, together with
features of germinal center alteration, could be responsible for the clonal elimination of a subset of B-cells, and could
contribute to HIV pathogenesis. 相似文献