全文获取类型
收费全文 | 875篇 |
免费 | 25篇 |
国内免费 | 4篇 |
专业分类
化学 | 659篇 |
晶体学 | 3篇 |
力学 | 18篇 |
数学 | 136篇 |
物理学 | 88篇 |
出版年
2023年 | 7篇 |
2022年 | 18篇 |
2021年 | 10篇 |
2019年 | 10篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 18篇 |
2015年 | 17篇 |
2014年 | 24篇 |
2013年 | 41篇 |
2012年 | 40篇 |
2011年 | 67篇 |
2010年 | 28篇 |
2009年 | 22篇 |
2008年 | 59篇 |
2007年 | 50篇 |
2006年 | 69篇 |
2005年 | 44篇 |
2004年 | 43篇 |
2003年 | 41篇 |
2002年 | 41篇 |
2001年 | 5篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 19篇 |
1995年 | 8篇 |
1994年 | 9篇 |
1993年 | 15篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 7篇 |
1982年 | 5篇 |
1981年 | 11篇 |
1980年 | 13篇 |
1979年 | 9篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1973年 | 3篇 |
1915年 | 2篇 |
排序方式: 共有904条查询结果,搜索用时 15 毫秒
41.
Roy A. Meoded Dr. Reiko Ueoka Dr. Eric J. N. Helfrich Dr. Katja Jensen Nancy Magnus Prof. Dr. Birgit Piechulla Prof. Dr. Jörn Piel 《Angewandte Chemie (International ed. in English)》2018,57(36):11644-11648
Enzymatic core components from trans‐acyltransferase polyketide synthases (trans‐AT PKSs) catalyze exceptionally diverse biosynthetic transformations to generate structurally complex bioactive compounds. Here we focus on a group of oxygenases identified in various trans‐AT PKS pathways, including those for pederin, oocydins, and toblerols. Using the oocydin pathway homologue (OocK) from Serratia plymuthica 4Rx13 and N‐acetylcysteamine (SNAC) thioesters as test surrogates for acyl carrier protein (ACP)‐tethered intermediates, we show that the enzyme inserts oxygen into β‐ketoacyl moieties to yield malonyl ester SNAC products. Based on these data and the identification of a non‐hydrolyzed oocydin congener with retained ester moiety, we propose a unified biosynthetic pathway of oocydins, haterumalides, and biselides. By providing access to internal ester, carboxylate pseudostarter, and terminal hydroxyl functions, oxygen insertion into polyketide backbones greatly expands the biosynthetic scope of PKSs. 相似文献
42.
NirmlaDevi Thakur Vilas G. Gaikar Debasis Sen Subhasish Mazumder Nancy S. Pandita 《Analytical letters》2017,50(4):690-711
A green method using Juglans regia bark extract was used to synthesize silver nanoparticles at room temperature with monitoring by absorption spectroscopy. The size and shape of the synthesized nanoparticles were characterized by infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, high-resolution transmission electron microscopy, and small-angle X-ray scattering. The average particle size was from 10 to 30?nm. Gas chromatography–mass spectrometry (GC–MS) was used for the separation, identification, and quantification of components of the plant extracts. A possible mechanism for the synthesis of nanoparticles was elucidated based on the GC–MS results. The synthesized silver nanoparticles showed effective inhibition against Streptococcus mutans, which is the main causative agent for dental caries. The nanoparticles also showed promising antibiofilm activity by inhibiting the glucosyltransferase enzyme. 相似文献
43.
Abstract Optical spectroscopy and proton nuclear magnetic resonance spectroscopy have been used to investigate the non-covalent and covalent binding of 8-azidoethidium (8-azido-3-amino-5-ethyl-6-phe-nyl-phenanthridium) with transfer RNA (tRNA) molecules. The nuclear magnetic resonance measurements demonstrate that ethidium and ethidium monoazide bind to the same unique binding site on tRNA molecules. However, the optical studies demonstrate that the photochemical reaction between ethidium monoazide and tRNA generates at least three different photoproducts. One of the covalent photoproducts has fluorescence properties which mimic those of intercalated, non-covalently bound ethidium, but it is produced only in about 10% yield. The major photoproduct(s) is(are) virtually non-fluorescent. The ethidium monoazide photochemistry with tRNA molecules is obviously complex and this may complicate its use as a photolabel of polynucleotides. 相似文献
44.
Combinatorial libraries of substituted 3-thio-1,2,4-triazoles and 2-thioimidazoles were synthesized in good yield by alkylation of the products via the reaction of isothiocyanates and carboxylic acid hydrazides or beta-aminoketones, respectively. A total of 275 3-thio-1,2,4-triazoles and 283 2-thioimidazoles were synthesized out of the attempted 288 in each case. Most the yields were between 45% and 98%, and all the compounds synthesized were purified to >85% purity. Variations in yields revealed no definitive trends and were mainly attributed to bulky alkylating agents used and the plate well location of the reaction mixtures. 相似文献
45.
46.
We consider two tests of the null hypothesis that the k-th derivative of a regression function is uniformly bounded by a specified constant. These tests can be used to study the shape of the regression function. For instance, we can test for convexity of the regression function by setting k=2 and the constant equal to zero. Our tests are based on k-th order divided difference of the observations. The asymptotic distribution and efficacies of these tests are computed and simulation results presented.Research supported by Natural Sciences and Engineering Research Council of Canada Grant OGP0007969.Research supported by National Science Foundation Grant DMS-9306738. 相似文献
47.
When a glassy polymer containing a uniformly dispersed solute is brought in contact with a penetrant, solute diffusion will be associated with the transport mechanism and penetration velocity of the penetrant in the polymer. Analysis and prediction of mechanisms of diffusional solute release may be obtained through a new dimensionless number, the swelling interface number, Sw, which compares the relative mobilities of the penetrant and the solute in the presence of macromolecular relaxations in the polymer. It is shown that a sufficient and necessary criterion for time-independent diffusional solute release rates from these swellable systems is that the Sw be smaller than 10?2. The swelling interface number Sw may be related to easily determined structural and thermodynamic parameters of the solute/polymer/penetrant system. Preliminary experimental results of dynamic water swelling of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) and diffusional release of theophylline from initially glassy copolymers show that decreasing values of Sw are related to increased pseudo-case-II transport kinetics of the solute. 相似文献
48.
Several oxidation products of the retinoid retinylidene dimedone (RD) have been synthesized and characterized for biological testing in the expectation that they may be found as metabolites of RD. 相似文献
49.
Al-Brithen HA Yang R Haider MB Constantin C Lu E Smith AR Sandler N Ordejón P 《Physical review letters》2005,95(14):146102
Scanning tunneling microscopy images confirm electron diffraction studies that the zinc-blende GaN(001)-4x reconstruction consists of rows aligned along [110] with a spacing along [110] of 4a. Dual-bias imaging shows a 180 degree shift of the corrugation maximum position between the profiles of empty and occupied states, in agreement with surface simulations based on the 4 x 1 linear tetramer model of Neugebauer et al. [Phys. Rev. Lett. 80, 3097 (1998)]. Electronic structure calculations predict a surface band gap of 1.1 eV, close to the measured value of 1.14 eV and the previously predicted value (1.2 eV). Despite the successes of this model, high-resolution images reveal an unexpected 3x periodicity (not seen in diffraction) along the [110] row direction, indicating the need for a 4 x 3 model, and putting into question the existence of linear Ga tetramers. 相似文献
50.
[structure: see text] Tetrabromobutatriene, C(4)Br(4), can be prepared directly from dibromobutadiyne by reaction with Br(2) at -25 degrees C in concentrated hexanes solution. The cumulene precipitates out of the reaction mixture as a yellow powder. Under palladium-catalyzed coupling conditions, C(4)Br(4) can undergo allylic rearrangement, giving a mixture of products, including some with butenyne backbones. However, in furan solution, C(4)Br(4) reacts cleanly at its central double bond to give the furan Diels-Alder adduct. Under Suzuki conditions, this adduct reacts at the furan double bond rather than at bromide. 相似文献