全文获取类型
收费全文 | 2260篇 |
免费 | 57篇 |
国内免费 | 6篇 |
专业分类
化学 | 1600篇 |
晶体学 | 112篇 |
力学 | 57篇 |
数学 | 98篇 |
物理学 | 456篇 |
出版年
2023年 | 17篇 |
2022年 | 50篇 |
2021年 | 41篇 |
2020年 | 39篇 |
2019年 | 49篇 |
2018年 | 36篇 |
2017年 | 59篇 |
2016年 | 86篇 |
2015年 | 44篇 |
2014年 | 60篇 |
2013年 | 205篇 |
2012年 | 114篇 |
2011年 | 147篇 |
2010年 | 91篇 |
2009年 | 79篇 |
2008年 | 122篇 |
2007年 | 98篇 |
2006年 | 102篇 |
2005年 | 78篇 |
2004年 | 60篇 |
2003年 | 52篇 |
2002年 | 56篇 |
2001年 | 28篇 |
2000年 | 33篇 |
1999年 | 25篇 |
1998年 | 15篇 |
1997年 | 17篇 |
1996年 | 19篇 |
1995年 | 22篇 |
1994年 | 25篇 |
1993年 | 19篇 |
1992年 | 23篇 |
1991年 | 24篇 |
1990年 | 17篇 |
1989年 | 17篇 |
1988年 | 16篇 |
1987年 | 19篇 |
1986年 | 23篇 |
1985年 | 18篇 |
1984年 | 27篇 |
1983年 | 21篇 |
1982年 | 28篇 |
1981年 | 30篇 |
1980年 | 22篇 |
1979年 | 23篇 |
1978年 | 20篇 |
1977年 | 11篇 |
1976年 | 13篇 |
1975年 | 18篇 |
1973年 | 17篇 |
排序方式: 共有2323条查询结果,搜索用时 15 毫秒
111.
Himatkumar V. Patel Kavita A. Vyas Sudhanshu P. Pandey Peter S. Fernandes 《合成通讯》2013,43(21):3081-3087
A novel one-step synthesis of 4-arylazo-1H-1, 3, 5-trimethylpyrazoles is accomplished by reaction of N, N-dimethylhydrazine with 2, 3, 4-pentantrione-3-arylhydrazones via an unusual demethylation. 相似文献
112.
One of the key steps in the synthesis of ABT-431 is the diastereoselective cyclization of thieny alcohol 1 to trans amide 2. We report a detailed study of the influence of acids, solvents and temperature over the ratio of cis and trans diastereomers. 相似文献
113.
Do C Hatfield J Patel S Vasudevan D Tirla C Mills NS 《The Journal of organic chemistry》2011,76(1):181-187
Oxidation of m- and p-substituted benzylidene fluorenes to antiaromatic dications was attempted by electrochemical and chemical means. Electrochemical oxidation to dications was successful for benzylidene fluorenes with p-methoxy, p-methyl, p-fluoro, and unsubstituted phenyl rings in the 3-position; attempts to oxidize the m-substituted derivatives via electrochemistry were unsuccessful. Chemical oxidation with SbF(5)/SO(2)ClF gave the dication of 9-[(4-methoxyphenyl)methylene]-9H-fluorene cleanly; oxidation of all other substituted benzylidene fluorenes resulted in mixtures of products. The excellent linear relationship between the chemical shifts calculated by the GIAO method and the experimental shifts for the p-methoxy-substituted benzylidene fluorene dication suggests that the calculations satisfactorily reflect the magnetic properties of this dication and potentially those of the other dications studied. The redox potentials from electrochemical oxidation, a measure of the stability of the dications, showed a good linear relationship with another measure of stability, the calculated difference in energy between each dication and its neutral precursor. The dications of benzylidene fluorenes were less stable than the dications of diphenylmethylidene fluorenes; within each type of compound, dications with p-substituted phenyl rings were more stable than dications with m-substituted phenyl rings and dications with phenyl rings substituted with electron-donating groups were more stable than dications with phenyl rings substituted with electron-withdrawing groups. The antiaromaticity of the fluorenyl system was assessed through the nucleus-independent chemical shift (NICS) that was also calculated by the GIAO method. The plot of the NICS values per square area versus the calculated energy difference for the dications showed a moderate degree of linearity; the plot of NICS values per square area versus the oxidation potentials was less linear. Thus, a suggestive, but not conclusive, relationship between magnetic and energetic measures of antiaromaticity was observed. 相似文献
114.
Cimpoesu F Ito S Shimotani H Takagi H Dragoe N 《Physical chemistry chemical physics : PCCP》2011,13(20):9609-9615
Analysis of IR and Raman spectra of Ar@C(60) and Kr@C(60) shows that the incorporation of noble gas atoms causes a blue shift of low energy vibrations, which have radial character, and a red shift of higher energy ones which have a tangential character movement. The mechanism of these phenomena is explained on the basis of ab initio numerical experiments with DFT and MP2 procedures. Methodological discussions are advanced, altogether with a scheme for the estimation of the van der Waals interaction between fullerene and noble gas, based on the frequency shifts. 相似文献
115.
Bijay K. Mishra Partha Mukherjee Sukalyan Dash Sabita Patel Hari N. Pati 《合成通讯》2013,43(14):2529-2539
Some monomeric and dimeric surfactants with functional head groups have been synthesized from di- and triethanolamine synthons. The treatment of alkyl bromide with triethanolamine resulted in simultaneous N-alkylation and O-alkylation products. However, with diethanolamine, N-alkylated products were obtained, which were further used to synthesize various double-tailed surfactants and gemini surfactants. 相似文献
116.
4-Amino-, chloro-, and bromo-substituted salicylic acid-formaldehyde polymers and their metal chelates were screened for their antifungal activity. Various copolymers prepared from 4-chloro-(bromo)salicylic acid, formaldehyde, and other comonomers were also screened for their antifungal activity. All these polymers, copolymers, and polychelates were found active against several fungi Their fungicidal activities are compared with those of the corresponding monomers and monomeric chelates. 相似文献
117.
Some new biologically potent coumarin derivatives 7a–f, 8a–f, and 9a–f bearing modified pyridine moieties (indeno[1,2-b]pyridine, 4-azaphenanthrene and benzofuro [3,2-b]pyridine) at the sixth position were designed and synthesized. All the synthesized compounds were assayed for their antimicrobial efficiency against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Salmonella typhi, Candida albicans, and Aspergillus niger. Most of the compounds showed appreciable antimicrobial activity against the tested strains. Compounds 8b, 8c, 9b, 9d, and 9f emerged as most proficient members of the series. The antitubercular activity for all the synthesized compounds was performed against Mycobacterium tuberculosis H37Rv. Compounds 8f, 9b, and 9f exhibited promising antitubercular activity. Consequently, synthesized derivatives were found to be worthy of further investigation. 相似文献
118.
A general procedure using triphenylphosphine and diethylazodicarboxylate to prepare 2-oxazolines is described. 相似文献
119.
Shaginian A Patel M Li MH Flickinger ST Kim C Cerrina F Belshaw PJ 《Journal of the American Chemical Society》2004,126(51):16704-16705
We describe the development of photolabile protecting groups based on the 3,4,5-trimethoxyphenacyl group (TMP). Orthogonal safety-catches were created by introducing an acid-activatible dimethyl ketal (AA-TMP) and an oxidatively activatible 1,3-dithiane (OA-TMP) into the photolabile TMP group. We demonstrate the application of these protecting groups in light-directed synthesis of small molecule microarrays with diversity elements radially attached to a hydroxyproline scaffold. 相似文献
120.
Serganov A Yuan YR Pikovskaya O Polonskaia A Malinina L Phan AT Hobartner C Micura R Breaker RR Patel DJ 《Chemistry & biology》2004,11(12):1729-1741
Metabolite-sensing mRNAs, or "riboswitches," specifically interact with small ligands and direct expression of the genes involved in their metabolism. Riboswitches contain sensing "aptamer" modules, capable of ligand-induced structural changes, and downstream regions, harboring expression-controlling elements. We report the crystal structures of the add A-riboswitch and xpt G-riboswitch aptamer modules that distinguish between bound adenine and guanine with exquisite specificity and modulate expression of two different sets of genes. The riboswitches form tuning fork-like architectures, in which the prongs are held in parallel through hairpin loop interactions, and the internal bubble zippers up to form the purine binding pocket. The bound purines are held by hydrogen bonding interactions involving conserved nucleotides along their entire periphery. Recognition specificity is associated with Watson-Crick pairing of the encapsulated adenine and guanine ligands with uridine and cytosine, respectively. 相似文献