全文获取类型
收费全文 | 1785篇 |
免费 | 62篇 |
国内免费 | 11篇 |
专业分类
化学 | 1398篇 |
晶体学 | 21篇 |
力学 | 60篇 |
数学 | 112篇 |
物理学 | 267篇 |
出版年
2023年 | 8篇 |
2022年 | 20篇 |
2021年 | 50篇 |
2020年 | 39篇 |
2019年 | 47篇 |
2018年 | 45篇 |
2017年 | 44篇 |
2016年 | 82篇 |
2015年 | 60篇 |
2014年 | 109篇 |
2013年 | 157篇 |
2012年 | 136篇 |
2011年 | 153篇 |
2010年 | 83篇 |
2009年 | 62篇 |
2008年 | 107篇 |
2007年 | 112篇 |
2006年 | 89篇 |
2005年 | 89篇 |
2004年 | 53篇 |
2003年 | 47篇 |
2002年 | 44篇 |
2001年 | 12篇 |
2000年 | 16篇 |
1999年 | 10篇 |
1998年 | 19篇 |
1997年 | 12篇 |
1996年 | 15篇 |
1995年 | 12篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1991年 | 12篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1969年 | 2篇 |
1964年 | 5篇 |
排序方式: 共有1858条查询结果,搜索用时 15 毫秒
41.
[structures: see text] A range of cis-fused hexahydro-1-benzofuran-3(2H)-one or tetrahydro-2H-cyclopenta[b]furan-3(3aH)-one ring systems was synthesized by the rhodium(II) acetate catalyzed reaction of alpha-diazo carbonyl compounds in the presence of various oxygen, nitrogen, and sulfur nucleophiles. A double-nucleophilic addition was possible by using an excess of alpha-diazo ketone. These reactions proceeded with complete diastereoselectivity, and the stereochemistry was confirmed by the single-crystal X-ray analysis. This process discloses the first example of tandem cyclization-nucleophilic addition reaction. 相似文献
42.
43.
The ab initio calculation of the title compound was carried out at HF as well as DFT level of theory. The full geometry optimization of the ligand was carried out using 6-31G(d) basis set. The results obtained were correlated with the single crystal X-ray data, also reported in this paper, shows close resemblance between these two. The influence of electron correlation effects also was studied by carrying out geometry optimization at the MP2 level. The attempts were also made to ascertain the most stable tautomer of the said compound. 相似文献
44.
KailasaSuresh Kumar Kanchi Suvardhan Dasari Rekha B. Jayaraj Pattium Chiranjeevi 《Helvetica chimica acta》2005,88(5):1022-1027
A facile, rapid, and sensitive spectrophotometric method for the determination of propoxur in insecticidal formulations, fortified water, vegetables, agricultural wastewater, and agricultural soil samples has been elaborated. The proposed method is based on the hydrolysis of propoxur under basic conditions, followed by instantaneous azo coupling of the resulting 2‐isopropoxyphenol with the anilines 2a – c . This yielded the orange‐red chromophore 3a (λmax=at 470 nm), the pale‐red coupling product 3b (490 nm), or the red derivative 3c (478 nm), which are stable for 46 h, 38 h, and 24 h, respectively, and could be readily analyzed spectrophotometrically. 相似文献
45.
Devendra K. Rastogi Suresh K. Sahni Vidya B. Rana Satendra K. Dua 《Transition Metal Chemistry》1978,3(1):56-60
Summary Dimeric manganese(II)and iron(II)complexes, (ML)2, derived from benzoyl hydrazones ofo-hydroxyaryl aldehydes and ketones arc described and characterised by elemental analyses and by conductance, molecular weight, magnetic, electronic and i.r. spectral measurements. The dimeric nature of the complexes is revealed by i.r. spectra which show bands atca. 885 Mn2+ and 820 cm–1 Fe2+, characteristic of ring vibrations. The i.r. spectra reveal the terdentate nature of the ligands. The electronic spectra in dimethylformamide are consistent with the tetrahedral nature of the complexes. The appreciable lowering in
eff is attributed to the presence of exchange interactions between two paramagnetic atomsvia oxygen bridges.Reprints of this article are not available. 相似文献
46.
D'Souza F Chitta R Gadde S Zandler ME McCarty AL Sandanayaka AS Araki Y Ito O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(15):4416-4428
Two types of structurally well-defined, self-assembled zinc porphyrin-fullerene conjugates were formed by "two-point" binding strategies to probe the effect of axial ligation or pi-pi-type interactions on the photochemical charge stabilization in the supramolecular dyads. To achieve this, meso-tetraphenylporphyrin was functionalized to possess one or four [18]crown-6 moieties at different locations on the porphyrin macrocycle while fullerene was functionalized to possess an alkyl ammonium cation, and a pyridine or phenyl entities. As a result of the crown ether-ammonium cation complexation, and zinc-pyridine coordination or pi-pi-type interactions, stable zinc porphyrin-fullerene conjugates with defined distance and orientation were formed. Evidence for the zinc-pyridine complexation or pi-pi-type interactions was obtained from the spectral and computational studies. Steady-state and time-resolved emission studies revealed efficient quenching of the zinc-porphyrin singlet excited state in these dyads, and the measured rates of charge separation, k(CS) were found to be slightly better in the case of the dyads held by axial coordination and crown ether-cation complexation. Nanosecond transient absorption studies provided evidence for the electron transfer reactions, and these studies also revealed charge stabilization in these dyads. The lifetimes of the radical ion pairs were found to depend upon the type of porphyrins utilized to form the dyads, that is, porphyrin possessing the crown ether moiety at the ortho position of one of the phenyl rings yielded prolonged charge stabilized states. Addition of pyridine to the supramolecular dyads eliminated the zinc-pyridine coordination or pi-pi-type interactions of the "two-point" bound systems due to the formation of a new zinc-pyridine axial bond thus giving a unique opportunity to probe the effect of axial coordination or pi-pi interactions on k(CS) and k(CR). Under these conditions, the measured electron transfer rates revealed faster k(CS) and slower k(CR) as compared to those obtained in the absence of added pyridine. The evaluated lifetimes of the radical ion-pairs were found to be hundreds of nanoseconds and were longer in the presence of pyridine. 相似文献
47.
Suresh Chandra Rastogi 《Journal of separation science》1995,18(10):653-658
A gas chromatographic (GC)-mass spectrometric (GC-MS) method has been developed for the routine analysis of 11 fragrance substances in cosmetics: cinnamic alcohol, cinnamic aldehyde, eugenol, hydroxy citronellal, α-amyl cinnamic aldehyde, geraniol, isoeugenol, coumarin, dihydrocoumarin, citronellal and citral. Methods for sample preparation of various types of cosmetic products, prior to GC analysis, have also been developed and proved to be rugged. Detection limits of all of target fragrance substances were approximately 1 ppm. Calibration curves of the target fragrance substances analyzed by GC were found to be linear in the investigated concentration range, 0.005% – 0.50%. The recoveries of the target fragrances from various types of cosmetic products were 80% – 116% and the relative standard deviations of the quantitative analysis of the target fragrance substances were within 5%. 相似文献
48.
Pure silicon tetrafluoride can be prepared in 66% yield from silicon tetrachloride by refluxing with lead fluoride in acetonitrile. The gas can be reduced to pure silane by lithium aluminum hydride in diethyl ether. 相似文献
49.
Nithyanandhan J Jayaraman N Davis R Das S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):689-698
A series of azobenzene-functionalized poly(alkyl aryl ether) dendrimers have been synthesized and their photochemical and photophysical properties in solution and as thin films have been investigated. Although the photochemical behavior of the azodendrimers in solution indicated that the azobenzene units behave independently, very similar to the constituent monomer azobenzene unit, the properties of thin solid films of the dendrimers were distinctly different. The azodendrimers, AzoG1, AzoG2, and AzoG3 were observed to form stable supercooled glasses, which showed long-wavelength absorption and red emission characteristics of J-aggregates of the azobenzene chromophores. Reversible photoinduced isomerization of the azodendrimers in the glassy state is described. 相似文献
50.
A Pyrex glass capillary (0.4 mm internal diameter) microreactor was developed and used for Suzuki coupling reactions. Capillary-microreactors are more attractive than photolithographic microfluidic devices in terms of simplicity, low cost and ease of handling. Compared with the conventional synthesis procedure, our approach of using a capillary-microreactor offers a convenient and highly efficient means to optimize reaction conditions and the performance of catalysts. The procedure exhibits good precision, reproducibility and high reaction yield for a range of reactants investigated. 相似文献