全文获取类型
收费全文 | 4058篇 |
免费 | 102篇 |
国内免费 | 31篇 |
专业分类
化学 | 3199篇 |
晶体学 | 53篇 |
力学 | 59篇 |
数学 | 184篇 |
物理学 | 696篇 |
出版年
2022年 | 23篇 |
2021年 | 33篇 |
2020年 | 33篇 |
2019年 | 41篇 |
2018年 | 24篇 |
2017年 | 32篇 |
2016年 | 44篇 |
2015年 | 76篇 |
2014年 | 90篇 |
2013年 | 277篇 |
2012年 | 179篇 |
2011年 | 239篇 |
2010年 | 136篇 |
2009年 | 122篇 |
2008年 | 206篇 |
2007年 | 207篇 |
2006年 | 233篇 |
2005年 | 215篇 |
2004年 | 193篇 |
2003年 | 215篇 |
2002年 | 197篇 |
2001年 | 52篇 |
2000年 | 60篇 |
1999年 | 58篇 |
1998年 | 41篇 |
1997年 | 41篇 |
1996年 | 61篇 |
1995年 | 54篇 |
1994年 | 50篇 |
1993年 | 37篇 |
1992年 | 31篇 |
1991年 | 34篇 |
1990年 | 34篇 |
1989年 | 40篇 |
1988年 | 38篇 |
1987年 | 31篇 |
1986年 | 37篇 |
1985年 | 61篇 |
1984年 | 55篇 |
1983年 | 35篇 |
1982年 | 63篇 |
1981年 | 54篇 |
1980年 | 70篇 |
1979年 | 67篇 |
1978年 | 48篇 |
1977年 | 35篇 |
1976年 | 28篇 |
1975年 | 27篇 |
1974年 | 33篇 |
1973年 | 25篇 |
排序方式: 共有4191条查询结果,搜索用时 265 毫秒
61.
Otaka A Watanabe J Yukimasa A Sasaki Y Watanabe H Kinoshita T Oishi S Tamamura H Fujii N 《The Journal of organic chemistry》2004,69(5):1634-1645
A samarium diiodide (SmI(2))-mediated reduction of gamma,gamma-difluoro-alpha,beta-enoates (15, 29, and 34) was successfully applied to the synthesis of (Z)-fluoroalkene dipeptide isosteres (23, 30, and 35), which have served as potential dipeptide mimetics. Reduction of the gamma,gamma-difluoro-alpha,beta-enoates by SmI(2) proceeded via successive two-electron transfers to form dienolate species which upon kinetically controlled trapping with t-BuOH yielded Xaa-Gly-type fluoroalkene isosteres exemplified by 23, 30, and 35. Replacement of the t-BuOH kinetic trapping agent with aldehydes or ketones provided access to alpha-substituted fluoroalkene isosteres (43 and 45) through aldol reactions of Sm-dienolates with the carbonyl compounds. Of particular note, the use of the SmI(2)-HCHO reagent system with chiral enoate 34 provided D-Phe-psi[(Z)-CF[double bond]CH]-D/L-Ser isosteres (45), which could be converted to enantiomerically pure isosteres (49-52) that bore a variety of side chain functionalities at the alpha-position. This was achieved by a sequence of manipulations consisting of beta-lactone formation followed by chromatographic separation and ring-opening with soft nucleophiles. Included in the present work is the first utilization of a Rh-catalyzed Reformatsky reaction of chiral imines for the stereoselective preparation of alpha,alpha-difluoro-beta-amino acid derivatives (28 and 33). The appropriate choice of reagents (carbonyl compounds for kinetic trapping or ring-opening nucleophiles and imines for Reformatsky reactions) allows the presented methodology to yield various fluoroalkene isosteres possessing a wide range of side chain functionalities. 相似文献
62.
Abe A Saito Y Imaizumi M Ogawa M Takeichi T Jinno K 《Journal of separation science》2005,28(17):2413-2418
The surface derivatization of poly(p-phenylene terephthalamide) fiber was studied. The obtained surface-derivatized filaments were packed into a fused-silica capillary to evaluate its surface characteristics by using GC. As the stationary phase for GC the surface-derivatized fibers showed higher retention for alkanes and alkylbenzenes than that with the untreated Kevlar fiber. The improvements on the retention power and the peak shape were observed on the benzyl-modified fibrous stationary phase. The derivatized fibrous materials were also evaluated as the extraction medium in fiber-in-tube SPE, and the effect of the surface modification on the extraction power was compared to the parent fiber. The results indicated that the modified fiber possessed a higher extraction power than the untreated fiber. Based on the facts, the successful modification of the fiber surface was estimated. 相似文献
63.
Tetsuji Ohata Akira Matsumoto Masayoshi Oiwa 《Journal of polymer science. Part A, Polymer chemistry》1980,18(2):467-475
In order to elucidate the effect of the hydroxyl group on the polymerization of diallyl hydroxydicarboxylates, we investigated in detail the radical polymerizations of diallyl succinate (DASu), diallyl malate (DAMa), and diallyl tartrate (DATa), each of which have similar structure differing only in the number of hydroxyl groups present. The rate of polymerization (Rp) was quite enhanced in the order DASu < DAMa < DATa, in accord with the increase in the number of hydroxyl groups within a monomer unit. The enhanced ability of the allylic monomer radical to reinitiate chain growth was also in the same order, as was clear from the dependence of Rp on the initiator concentration. The dependence of the residual unsaturation of the polymer on the monomer concentration in the polymerizations of DAMa and DATa was abnormal in terms of cyclopolymerization. These results are discussed in connection with the formation of the intermolecular hydrogen bond through the hydroxyl groups. 相似文献
64.
Toshiyuki Chikuma Yoko ShimabukuroTakeya Iguchi Akira TanakaKyoji Taguchi Takeshi KatoMitsune Yamaguchi Hiroshi Hojo 《Analytica chimica acta》2002,457(2):157-164
A rapid and sensitive assay for the determination of Dns-His-Lys-Arg-His-Lys cleaving enzyme activity is reported. This assay is based on fluorimetric detection of a dansylated dipeptide, 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys, enzymatically formed from the substrate 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys-Arg-His-d-Lys, after separation by high-performance liquid chromatography (HPLC) using a C-18 reversed-phase column by isocratic elution. This assay is sensitive enough to measure 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys at concentrations as low as 7 pmol, and yields highly reproducible results and requires less than 9.0 min per sample for separation and quantitation. The optimum pH for Dns-His-Lys-Arg-His-Lys cleaving enzyme activity was 7.5-8.0. The Michaelis constant (Km) and the maximum velocity (Vmax) values were 33.3 μM and 47.07 pmol/(μg h), respectively with the use of enzyme extract obtained from bovine pituitary. By using this assay, axonal transport of this enzyme activity was observed 48 h after double ligations of rat sciatic nerves. The high sensitivity and selectivity of this assay would be useful for clarification of the physiological role of this enzyme. 相似文献
65.
Six Sepharose derivatives, in which citrate was immobilized via methylene carbons, were prepared by coupling of the alpha- and beta-isomers of citrylpolymethylenediamine to Sepharose. The purification of fumarase from pig heart was dependent on the length of the spacer arm, but not on the isomeric configuration of the immobilized citrate. Gels having six methylene carbons had the largest adsorption capacity for the enzyme and therefore were the most suitable for use in affinity columns for its purification. Affinity chromatography with these gels was followed by hydrophobic interaction chromatography on an octamethylenediamine-Sepharose column. 相似文献
66.
Yoshihiro Yamauchi Takanori Okamoto Hiroshi Murayama Akira Nagara Tadashi Kashihara 《Applied biochemistry and biotechnology》1995,53(3):277-283
The characteristics of yeast sulfite metabolism in a multistage bioreactor system for beer fermentation were investigated. No sulfite was produced in the continuous stirred-tank reactor (CSTR). However, large amounts were produced in the packed-bed reactor (PBR). Production of sulfite in the PBR seems to be inevitable when it is operated continuously. In order to control the sulfite level in the young beer, the yeast needs to be reactivated into the growth phase. One possible strategy to achieve this is to aerate and periodically remove yeast clogged in the reactor once every 6–7 months before the sulfite level exceeds a given concentration (e.g., 20 mg/L). It was confirmed that sulfite production is closely related to the growth condition of the yeast and is therefore important to consider in the control strategy for sulfite when using the immobilized yeast reactor for beer production. 相似文献
67.
Simple and sensitive determination of methylglyoxal in biological samples by gas chromatography with electron-capture detection 总被引:1,自引:0,他引:1
Methylglyoxal was allowed to react with 4,5-dichloro-1,2-phenylenediamine, and the 6,7-dichloro-2-methylquinoxaline formed was determined by gas chromatography with electron-capture detection. The standard curve of the quinoxaline was linear up to 160 pmol/ml. The recoveries of methylglyoxal from coffee and rat liver homogenate were 84.1 and 77.6%, respectively. This procedure was very selective and so sensitive that as little as 9 fmol of the quinoxaline could be measured in biological and food samples. 相似文献
68.
Akira Yamasaki 《Analytica chimica acta》1981,133(4):741-746
The TOOL-IR. PDB and COOD systems are compared for the construction of data bases for 59Co-n.m.r. bibliographic and spectral data. The spectral data used are the chemical shifts from several different standards, and the line widths and coupling constants (if present). The PDB system is effective for storage and retrieval of bibliographic data, but the COOD system is better for the retrieval of spectral data, and for combination of data files on literature and chemical shifts. 相似文献
69.
Oishi S Kamano T Niida A Odagaki Y Tamamura H Otaka A Hamanaka N Fujii N 《Organic letters》2002,4(7):1051-1054
[reaction: see text] Acyclic psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type dipeptide isosteres were efficiently synthesized. In a key reaction, alpha-alkylation of gamma-mesyloxy-beta-methyl-alpha,beta-unsaturated esters with organocyanocuprates in diethyl ether or tetrahydrofuran preferentially afforded the psi[(E)-CH=CMe]- or psi[(Z)-CH=CMe]-isomer, respectively, via anti-S(N)2' mechanism. 相似文献
70.
Nakao Y Imanaka H Sahoo AK Yada A Hiyama T 《Journal of the American Chemical Society》2005,127(19):6952-6953
Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes, highly stable tetraorganosilicon reagents, are found to react with aryl and alkenyl iodides in the presence of a palladium catalyst and K2CO3 as a base, significantly milder conditions compared with those ever reported for the silicon-based cross-coupling reactions. The reaction tolerates a wide range of functional groups, including silyl protectors, and allows a gram-scale synthesis to recover and reuse the silicon residue. 相似文献