全文获取类型
收费全文 | 1057篇 |
免费 | 42篇 |
国内免费 | 9篇 |
专业分类
化学 | 873篇 |
晶体学 | 12篇 |
力学 | 10篇 |
数学 | 80篇 |
物理学 | 133篇 |
出版年
2023年 | 8篇 |
2021年 | 18篇 |
2020年 | 26篇 |
2019年 | 25篇 |
2018年 | 11篇 |
2017年 | 10篇 |
2016年 | 30篇 |
2015年 | 21篇 |
2014年 | 19篇 |
2013年 | 57篇 |
2012年 | 69篇 |
2011年 | 71篇 |
2010年 | 47篇 |
2009年 | 34篇 |
2008年 | 67篇 |
2007年 | 57篇 |
2006年 | 55篇 |
2005年 | 72篇 |
2004年 | 59篇 |
2003年 | 53篇 |
2002年 | 42篇 |
2001年 | 8篇 |
2000年 | 17篇 |
1999年 | 9篇 |
1998年 | 13篇 |
1997年 | 12篇 |
1996年 | 11篇 |
1995年 | 6篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 7篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1987年 | 6篇 |
1986年 | 3篇 |
1985年 | 9篇 |
1984年 | 13篇 |
1983年 | 5篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 6篇 |
1975年 | 5篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1970年 | 4篇 |
1962年 | 3篇 |
排序方式: 共有1108条查询结果,搜索用时 31 毫秒
31.
Yoshida T Sakakibara K Asami M Chen KH Lii JH Allinger NL 《Journal of computational chemistry》2003,24(3):319-327
The MM3 force field has been extended to deal with the lithium amide molecules that are widely used as efficient catalysts for stereoselective asymmetric synthesis. The MM3 force field parameters have been determined on the basis of the ab initio MP2/6-31G* and/or DFT (B3LYP/6-31G*, B3-PW91/6-31G*) geometry optimization calculations. To evaluate the electronic interactions specific to the lithium amides derived from the diamine molecules properly, the Lewis bonding potential term for the interaction between the lithium atom and the nonbonded adjacent electronegative atom such as nitrogen was introduced into the MM3 force field. The bond dipoles were evaluated correctly from the electronic charges on the atoms calculated by fitting to the electrostatic potential at points selected. The MM3 results on the molecular structures, conformational energies, and vibrational spectra show good agreement with those from the quantum mechanical calculations. 相似文献
32.
Houjou H Kanesato M Hiratani K Mandon D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4576-4583
Novel diiron complexes with an Fe2(mu-OMe)2 core were studied as models of the active site of nonheme iron-containing enzymes. X-ray crystal structures of the complexes showed the existence of two types of ligand folding-parallel and twisted-both of which have four virtually equivalent phenolato groups sticking out from the Fe2O2 rhombic plane. Cyclic voltammetry measurements revealed two or more distinct redox waves in a region of relatively high potential, in addition to known Fe(II)/Fe(III) redox waves in a region of lower potential. These new peaks were assigned to the high-valence state of iron atoms, that is, Fe(III)Fe(IV) and Fe(IV)Fe(IV), resonating with the phenoxyl radical(s). The split width of the redox waves ranged from 0.14 to 0.20 eV, which may be a measure of the electronic interaction of the phenolate groups through the Fe2(mu-OMe)2 core. 相似文献
33.
Todoroki K Hayama T Ijiri S Kazuta A Yoshida H Nohta H Yamaguchi M 《Journal of chromatography. A》2004,1038(1-2):113-120
6-Rhodamine B amine functions as a highly sensitive fluorescence derivatization reagent for mono- and oligosaccharides; it reacts with the reducing end of saccharides under acidic conditions. The fluorescent derivatives of five monosaccharides can be separated within 25 min by reversed-phase liquid chromatography with isocratic elution. The detection limits (S/N = 3) for mono-, di-, and oligosaccharides are 7-51, 13, and 9-35 fmol/20 microl injection, which correspond to analyte concentrations of 35-255, 65, 45-175 nM, respectively. We have applied this derivatization method successfully to the analysis of the components of oligosaccharides in glycoproteins (ribonuclease B and fetuin) following their acidic or enzymatic hydrolysis. The results from these analyses are in good agreements with the reported values established previously. 相似文献
34.
Hideyuki Yoshida Junichiro Sonoda Junichi Ishida Masatoshi Yamaguchi 《Analytica chimica acta》2005,534(2):177-183
A simple screening method of organic aciduria by spectrofluorometric measurement of total dicarboxylic acids in human urine is described. This method is based on an intramolecular excimer-forming fluorescence derivatization with a pyrene reagent, 4-(1-pyrene)butanoic acid hydrazide (PBH). Dicarboxylic acids in urine were converted to the corresponding dipyrene-labeled derivatives by reaction with PBH in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and pyridine, and the derivatives afforded intramolecular excimer fluorescence (420-540 nm) which can clearly be discriminated from the normal fluorescence (360-420 nm) emitted from reagent blanks. The technique is so selective that it permits spectrofluorometric measurement of total amount of dicarboxylic acids by the direct derivatization of diluted urine samples. The same reaction mixture has also served as a liquid chromatographic (LC) sample for the separative determination of individual dicarboxylic acids. The spectrofluorometric data did not contradict with the LC data. These methods were usefully applied to preliminary screening test of glutaric aciduria. In conclusion, the present derivatization method allows rapid and direct determination of total amount of dicarboxylic acids in human urine samples. 相似文献
35.
Eiichi Kitazawa Akira Ogiso Shuji Takahashi Masaaki Kurabayashi Harumitsu Kuwano Tadashi Hata Chihiro Tamura 《Tetrahedron letters》1979,20(13):1117-1120
Two new diterpenelactones named plaunol A () and B () exhibiting anti-Shay ulcer activity were isolated from Thai medicinal plant, . Structure of was determined by X-ray analysis of its -bromobenzoate and structure of was deduced from the results of chemical correlation and the spectral data. 相似文献
36.
3,4-Dhydro-6,7-dimethoxy-4-methyl-3-oxo-quinoxaline-2-carbonyl azide is a highly senstive fluorescence derivatization reagent for primary, secondary and tertiary alcohols for high-performance liquid chromatography. Reaction conditions are optimized with benzyl alcohol, n-hexanol, cyclohexanol and 2-methyl-2-butanol. The reagent reacts with the alcohols in benzene to produce the corresponding fluorescent carbamic acid esters, which can be separated on a reversed-phase column YMC Pack C8 with aqueous methanol as eluent. the detection limits for the alchols are 2–5 fmol per 10-μl njection. The reagent also reacts with hydroxysteroids with primary, secondary and/or tertiary alcoholic group(s) to form fluorescent derivatives. Hydroxycarboxylic acids and phenols do not give any chromatographic peaks. 相似文献
37.
Masatoshi Taniguchi Ken-ichi SuzumuraKoji Nagai Tomihisa KawasakiTetsu Saito Jun TakasakiKen-ichi Suzuki Shigeo FujitaShin-ichi Tsukamoto 《Tetrahedron》2003,59(25):4533-4538
The isolation and structure elucidation of YM-254890, a novel Gq/11 inhibitor from Chromobacterium sp. QS3666, is described. The gross structure was determined by one- and two-dimensional NMR studies and mass spectrometry. YM-254890 is a cyclic depsipeptide containing uncommon amino acids; β-hydroxyleucine (two residues), N,O-dimethylthreonine and N-methyldehydroalanine. YM-254890 exists as a mixture of two conformers in a variety of NMR solvents, and the distinction between major and minor conformers appears to lie in the geometry of the amide bond between 3-phenyllactic acid and N-methyldehydroalanine. The absolute stereochemistery was elucidated by Marfey's analysis and chiral HPLC analysis of the acid hydrolysate of YM-254890. 相似文献
38.
We show that the mono-N-methylated and -ethylated derivatives of the achiral compound bisguanidinobenzene undergo spontaneous asymmetric crystallization into a chiral form with chiral space group P212121. The absolute configurations of the chiral crystals were determined by X-ray crystallography and correlated with circular dichroism (CD) spectra recorded in the solid state. The corresponding protonated and isopropylated derivatives, by contrast, afforded achiral crystals. 相似文献
39.
Chihiro Suetake 《Geometriae Dedicata》1992,42(2):163-185
A class of translation planes of order q
2m+1, where q is an odd prime power and m1, is constructed. If m=1, then this class is contained in the class of order q
3 constructed by Hiramine [5]. These planes of order q
2m+1 are of dimension 2m+1 over their kernels. If q
2m+133, then the linear translation complements of these planes have two orbits of length 2 and q
2m+1–1 on l
and this class contains many planes which are not generalized André planes. If q
2m+1= 33, then each plane of this class is isomorphic to the Hering plane of order 27.Dedicated to Professor Tuyosi Oyama on his 60th birthday 相似文献
40.
Huo SJ Li QX Yan YG Chen Y Cai WB Xu QJ Osawa M 《The journal of physical chemistry. B》2005,109(33):15985-15991
Au colloids were used to fabricate nanoscale-tunable Au nanofilms on silicon for surface-enhanced IR absorption bases in both ambient and electrochemical environments. This wet process incorporates the self-assembly of colloidal Au monolayer using 3-aminopropyl trimethoxysilane as the organic coupler with subsequent chemical plating in an Au(III)/hydroxylamine solution. FTIR spectroscopy in transmission mode of the probe species SCN- was used to evaluate the apparent surface enhancement in IR absorption of 2D Au colloid arrays and chemically plated Au particles. The nanostructure of Au films was examined by atomic force microscopy. The IR and AFM results show that the apparent surface enhancement factor (1-2 orders of magnitude) increases with increasing sizes and/or contact, and the severe aggregation of Au nanoparticles may cause the bipolar band shape. Cyclic voltammetry on the Au nanofilm obtained by the above nucleation and growth strategy exhibits a feasible electrochemical stability and behavior. In situ ATR-FTIR measurement of p-nitrobenzoic acid adsorption demonstrates that the as-grown Au film yields rather promising surface enhancement as well. 相似文献