全文获取类型
收费全文 | 1069篇 |
免费 | 15篇 |
国内免费 | 105篇 |
专业分类
化学 | 959篇 |
晶体学 | 2篇 |
力学 | 9篇 |
综合类 | 1篇 |
数学 | 140篇 |
物理学 | 78篇 |
出版年
2024年 | 20篇 |
2023年 | 200篇 |
2022年 | 13篇 |
2021年 | 10篇 |
2020年 | 18篇 |
2019年 | 26篇 |
2018年 | 30篇 |
2017年 | 26篇 |
2016年 | 13篇 |
2015年 | 17篇 |
2014年 | 48篇 |
2013年 | 73篇 |
2012年 | 35篇 |
2011年 | 57篇 |
2010年 | 42篇 |
2009年 | 66篇 |
2008年 | 60篇 |
2007年 | 72篇 |
2006年 | 55篇 |
2005年 | 49篇 |
2004年 | 55篇 |
2003年 | 17篇 |
2002年 | 25篇 |
2001年 | 11篇 |
2000年 | 9篇 |
1999年 | 13篇 |
1998年 | 19篇 |
1997年 | 11篇 |
1996年 | 21篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1993年 | 11篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 5篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1970年 | 1篇 |
1968年 | 2篇 |
排序方式: 共有1189条查询结果,搜索用时 15 毫秒
1.
Antonio Guirado Enrique LópezSánchez Raquel Andreu Andrés Zapata 《Tetrahedron letters》2004,45(10):2075-2076
The first method for the synthesis of the title compounds has been established involving a stereoselective electrochemical diacylation process. The cathodic reductions of monothiobenzils in an aprotic medium, under constant potential, in the presence of twofold molecular amounts of aroyl chlorides provide previously unknown (Z)-α-benzoyloxy-β-benzoythiostilbenes in high to quantitative yields. 相似文献
2.
M. D. Warren 《国际流体数值方法杂志》1983,3(3):217-225
This paper derives the convection–diffusion-reaction equation governing the reaction between the dissolved oxygen in sea-water and the steel walls of a pulsating crack. By the neglect of the diffusion term it is shown that an exact solution of the convection-reaction equation can be obtained. A numerical method for the solution of the complete convection–diffusion-reaction equation is derived by the use of finite differences. The numerical computation of the initial transient and the final periodic steady-state values is also discussed. 相似文献
3.
The gene encoding a versatile biocatalyst that shows high enantioselectivity for a variety of ketones, SCR (Saccharomyces cerevisiae carbonyl reductase), has been identified, cloned, and expressed in Escherichia coli. Two types of expression systems with high NADPH-regenerating capacities have been constructed. One is the tandem system, where the genes encoding SCR and GDH (glucose dehydrogenase) are located in the same plasmid, and the other is the two-plasmid system, where each of the SCR and GDH genes is located in separate plasmids that can coexist in one E. coli cell. Asymmetric reduction of ketones with the recombinant E. coli cells gave synthetically useful 20 alcohols, 11 of which were enantiomerically pure. The productivity of one of these products was as high as 41 g/L. 相似文献
4.
P.Veeraraghavan Ramachandran Kamlesh J Padiya Vivek Rauniyar M.Venkat Ram Reddy Herbert C Brown 《Journal of fluorine chemistry》2004,125(4):615-620
Asymmetric “allyl”boration of pentafluorobenzaldehyde with various α-pinene based “allyl”boranes provides homoallylic alcohols in high de and ee; the alcohols have been converted into δ-lactones via acryloylation, ring-closing metathesis and hydrogenation. Pentafluorophenyl analog of key pharmacophore of statin drugs has been synthesized using diastereoselective epoxidation and regioselective reduction as key steps. 相似文献
5.
A new hydrophilic copolymer having three kinds of hydroxyl groups, i.e. primary OH on -hydroxy allyl alcohol component, secondary OH on cyclic hemiacetal component and tertiary OH on -hydroxy acrylate component, was prepared by reducing a ‘polylactone’, poly(1-oxa-2-oxobutane-1,4:3,3-tetrayl), with NaBH4 in mixed solvents containing an alcohol. The structural analyses were performed by the solution 1H NMR and the solid state 13C NMR spectroscopies of the reduced samples. The composition of the three components turned out to be variable to the alcohol species used for the mixed solvent. 相似文献
6.
Yanlin Huang Kiwan Jang Wanxue Zhao Eunjin Cho Ho Sueb Lee Xigang Wang Dake Qin Ying Zhang Chanfang Jiang Hyo Jin Seo 《Journal of solid state chemistry》2007,180(12):3325-3332
Usually, Sm2+ ions could be reduced by heating the materials in reducing atmospheres. Exposure to ionizing radiations is also known to cause Sm3+→Sm2+ conversion. In this work, BaBPO5 doped with the samarium ion was prepared by high temperature solid-state reaction. Sm2+ ions were obtained by two different reduction methods, i.e., heating in H2 reduced atmosphere and X-ray irradiation. The measurements of X-ray diffraction (XRD), and scanning electron microscope (SEM) were investigated. It is found that the conversion of Sm3+→Sm2+ is very efficient in BaBPO5 hosts after X-ray irradiation. Sm2+ ions under these two reduction methods exhibit different characteristics that were studied by measurements of luminescence and decay. The results showed that the luminescence properties of Sm2+ ions in BaBPO5 were highly dependent on the sample preparation conditions. 相似文献
7.
Shiori Hanada 《Tetrahedron letters》2006,47(35):6173-6177
Combination of commercially available platinum catalysts with siloxanes containing more than two Si-H groups is found to be an efficient catalyst system for the reduction of carboxamides to amines. In particular, facile removal of silicon and platinum residues from the product can be achieved by the use of polymethylhydrosiloxanes as reducing reagents. 相似文献
8.
使用TPR和H2-TPD技术对镍铝系催化剂的还原和氢脱附性能进行了研究,并与其催化性能相关联。结果发现,镍铝系催化剂的氢脱附能力与其催化性能之间有一定联系,脱附氢能力越强,催化剂的甲烷部分氧化反应性能就越好,但催化性能与还原性能无直接关联。 相似文献
9.
《Electroanalysis》2005,17(20):1886-1894
Lamivudine (LAM) is a synthetic nucleoside analogue with activity against human immunodeficiency virus‐type 1 (HIV‐1) and Hepatitis B virus (HBV). The aim of this study was to determine LAM levels in serum and pharmaceutical formulations, by means of electrochemical methods using hanging mercury drop electrode (HMDE). On this electrode, LAM undergoes irreversible reduction at the peak potential near Ep?1.26 V (vs. Ag/AgCl/3 M KCl). Reduction LAM signals were measured by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square‐wave voltammetry (OSW). DPV and OSW techniques for the determination of LAM in acetate buffer at pH 4.5, which allows quantitation over the 4×10?6 to 1×10?4 M range in supporting electrolyte for both methods, were proposed. The linear response was obtained in acetate buffer in the ranges of 2×10?6 to 2×10?4 M for spiked serum samples at pH 4.5 for both techniques. The repeatability and reproducibility of the methods for all media were determined. The standard addition method was used in serum. Precision and accuracy were also checked in all media. No electroactive interferences from the endogenous substances were found in serum. With respect to side effects of high doses and short half‐life of LAM, a fast and simple detection method is described in this study. 相似文献
10.
Ingrid M. M. Fussing Derek Pletcher Richard J. Whitby 《Journal of organometallic chemistry》1994,470(1-2):109-117
The syntheses of several new CpTiCl2(OR) (R = alkyl, aryl) complexes are described. It was possible to isolate pure product when the R group is substituted such as to cause steric crowding at the metal centre; for example, particularly good yields of the phenolate complexes were obtained when there were isopropyl substituents in the 2 and 6 positions of the phenolate. Electrochemical studies of the complexes in dry THF show that the TiIII complexes are relatively stable, but only a diol complex could be reduced further to a TiII species. In general, the TiIV complexes undergo a reversible 1e− reduction reaction. The chemistry is more complex if the electrolyte contains added water: both the TiIV and TiIII complexes can react with water, the OR group being replaced by OH. The reaction is particularly rapid for the TiIII alkoxide complexes. 相似文献