全文获取类型
收费全文 | 3947篇 |
免费 | 109篇 |
国内免费 | 10篇 |
专业分类
化学 | 3156篇 |
晶体学 | 99篇 |
力学 | 174篇 |
数学 | 113篇 |
物理学 | 524篇 |
出版年
2023年 | 25篇 |
2022年 | 49篇 |
2021年 | 55篇 |
2020年 | 72篇 |
2019年 | 93篇 |
2018年 | 97篇 |
2017年 | 76篇 |
2016年 | 127篇 |
2015年 | 90篇 |
2014年 | 170篇 |
2013年 | 429篇 |
2012年 | 263篇 |
2011年 | 234篇 |
2010年 | 146篇 |
2009年 | 138篇 |
2008年 | 223篇 |
2007年 | 216篇 |
2006年 | 160篇 |
2005年 | 161篇 |
2004年 | 153篇 |
2003年 | 132篇 |
2002年 | 132篇 |
2001年 | 47篇 |
2000年 | 43篇 |
1999年 | 35篇 |
1998年 | 21篇 |
1997年 | 24篇 |
1996年 | 42篇 |
1995年 | 25篇 |
1994年 | 32篇 |
1993年 | 30篇 |
1992年 | 29篇 |
1991年 | 25篇 |
1990年 | 38篇 |
1989年 | 30篇 |
1988年 | 26篇 |
1987年 | 29篇 |
1986年 | 28篇 |
1985年 | 37篇 |
1984年 | 40篇 |
1983年 | 29篇 |
1982年 | 26篇 |
1981年 | 24篇 |
1980年 | 24篇 |
1979年 | 19篇 |
1978年 | 13篇 |
1977年 | 21篇 |
1976年 | 16篇 |
1975年 | 18篇 |
1974年 | 9篇 |
排序方式: 共有4066条查询结果,搜索用时 15 毫秒
151.
An efficient and mild method for the reduction of aromatic nitro and azido groups on solid support using Al/NiCl2·6H2O and Al/NH4Cl is described. This solid phase reduction technique has been applied towards the synthesis of DNA binding pyrrolo[2,1-c][1,4]benzodiazepine antitumour antibiotics. 相似文献
152.
Venkatapuram Padmavathi Mudigonda Rajagopala Sarma Adivireddy Padmaja Dandu Bhaskar Reddy 《Journal of heterocyclic chemistry》2003,40(5):933-937
Novel 2‐pyrazolines were obtained by the cycloaddition of diazomethane to bis(arylsulfonylethenyl)‐sulfones ( 3 ) and 1‐arylsulfonyl‐2‐styrylsulfonylethenes (7). Dehydrogenation of 2‐pyrazolines with chloranil gave pyrazoles. 相似文献
153.
Cerium(IV) mediated grafting of polyacrylonitrile on to guar gum was studied. Grafting parameters were studied gravimetrically, as a function of temperature, initiator concentration and Guar to acrylonitrile ratio. Higher temperatures resulted in higher monomer conversion and homopolymer formation. Both monomer conversion and extent of grafting increased with increase in cerium ion concentration in the range studied (0.91–9.12 mmol/l). Similar results were obtained with increase in monomer to guar gum ratio from 1 to 5. Grafting with this initiator was found to be generally good with high grafting efficiencies and low homopolymer formation for most experiments. The copolymers obtained were subjected to alkaline hydrolysis to convert nitrile groups in to carboxylic acid groups and the water absorbency of the resulting anionic guar gum was studied. Materials with water absorption up to 300 g/g could be obtained from this study. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
154.
G. Venkataramana Reddy R. Chandraganthi K. Vasanthi R. Sriram 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):1997-2015
Abstract Polymerizations of methyl methacrylate (MMA) and acrylonitrile (AN) were carried out in aqueous nitric acid at 30°C with the redox initiator system ammonium ceric nitrate-ethyl cellosolve (EC). A short induction period was observed as well as the attainment of a limiting conversion for polymerization reactions. The consumption of ceric ion was first order with respect to Ce(IV) concentration in the concentration range (0.2–0.4) × 10?2 M, and the points at higher and lower concentrations show deviations from a linear fit. The plots of the inverse of pseudo-first-order rate constant for ceric ion consumption, (k 1)?1 vs [EC]?1, gave straight lines for both the monomer systems with nonzero intercepts supporting complex formation between Ce(IV) and EC. The rate of polymerization increases regularly with [Ce(IV)] up to 0.003 M, yielding an order of 0.41, then falls to 0.0055 M and again shows a rise at 0.00645 M for MMA polymerization. For AN polymerization, R p shows a steep rise with [Ce(IV)] up to 0.001 M, and beyond this concentration R p shows a regular increase with [Ce(IV)], yielding an order of 0.48. In the presence of constant [NO? 3], MMA and AN polymerizations yield orders of 0.36 and 0.58 for [Ce(IV)] variation, respectively. The rates of polymerization increased with an increase in EC and monomer concentrations: only at a higher concentration of EC (0.5 M) was a steep fall in R p observed for both monomer systems. The orders with respect to EC and monomer for MMA polymerization were 0.19 and 1.6, respectively. The orders with respect to EC and monomer for AN polymerization were 0.2 and 1.5, respectively. A kinetic scheme involving oxidation of EC by Ce(IV) via complex formation, whose decomposition gives rise to a primary radical, initiation, propagation, and termination of the polymeric radicals by biomolecular interaction is proposed. An oxidative termination of primary radicals by Ce(IV) is also included. 相似文献
155.
Homoallylic substrates such as (E)-6-arylhex-3-enyl alcohols, N-tosylamides, and thiols undergo smooth cross-coupling with various aldehydes in the presence of 10 mol % Sc(OTf)(3) and 30 mol % TsOH to afford the trans-fused hexahydro-1H-benzo[f]isochromenes, N-tosyloctahydrobenzo[f]isoquinolines, and hexahydro-1H-benzo[f]isothiochromenes, respectively. However, the cross-coupling of (Z)-olefins such as 6-arylhex-3-enyl alcohols, N-tosylamides, and thiols with aldehydes affords the corresponding hexahydro-1H-benzo[f]isochromenes, N-tosyloctahydrobenzo[f]isoquinolines, and hexahydro-1H-benzo[f]isothiochromenes with complete cis selectivity via intramolecular Prins-, aza-Prins-, and thia-Prins/Friedel-Crafts cyclizations, respectively. Though the Prins cyclization proceeds smoothly under the influence of Sc(OTf)(3), high conversions and enhanced reaction rates are achieved using a mixture of Sc(OTf)(3) and TsOH (1:3). 相似文献
156.
M. Sreenivasulu K. Arun KumarK. Sateesh Reddy K. Siva KumarP. Rajender Kumar K.B. ChandrasekharManojit Pal 《Tetrahedron letters》2011,52(6):727-732
A rapid, economic, and high yielding methodology has been developed for hydroacylation/reduction of activated ketones by using 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride as a catalyst in combination with triethylamine. The reaction proceeded at an ambient temperature via generating N-heterocyclic carbene in situ that interacted with the (hetero)aryl aldehyde employed. While the reduction of ketones takes place in MeOH, the hydroacylation process was found to be effective in THF for both electron rich and deficient aldehydes. 相似文献
157.
A highly efficient and stereoselective synthesis of (2R,3R,4R)-HMP is disclosed employing the sulfinyl group as an internal nucleophile to functionalize an olefin in the key step of the reaction sequence. The proline ring is elaborated by a (4C+N) cyclization. 相似文献
158.
Cladosporin, a secondary metabolite isolated from fungal sources like Cladosporium cladosporioides and Aspergillus flavus was found to exhibit selective nano-molar activity against malarial parasite Plasmodium falciparum by inhibiting parasitic protein biosynthesis. In addition, this natural product has a broad range of bioactivities including, antiparasitic, antifungal, antibacterial as well as plant growth inhibition. However, it has limited availability from the natural sources for further development. Herein, we report a modified and improved synthetic route which led us to produce this potent natural product in a gram scale. Conversion of the undesired diastereomer to desired one via Mitsunobu inversion of secondary alcohol and carbon monoxide insertion reaction towards the construction of isocoumarin unit are the key features of the present synthesis. 相似文献
159.
AbstractA convergent synthesis of the southern furan segment of novel furanocembranoids from Croton oblongifolius has been accomplished involving silver-catalyzed cyclization of alkynyl diol as the key step towards 2, 5-disubstituted furan ring formation. 相似文献
160.
Avula Krishna Kumari Vemulapati Hanuman Reddy Guda Mallikarjuna Reddy Yellala Venkata Rami Reddy Suddala Leelavathi 《Journal of heterocyclic chemistry》2019,56(5):1661-1666
In an effort for development of innovative biologically active agents, a sequence of 1,4‐dihydropyridine analogues was synthesized through the green synthetic method. In addition, all compounds were evaluated for their cytotoxic activities against three human cancer cell lines and mouse melanoma and figured out the most active compounds. Besides, promoter reusability, easy handling of the chemical reagent, simple reaction process, time minimization, ethanol–water solvent compatibility, and cost reduction reagent are key tools for this fruitful path. Thus, these examinations recommended that dihydropyridine and their derivatives are motivating moieties for the discovery of new anticancer drugs. 相似文献