全文获取类型
收费全文 | 69654篇 |
免费 | 3907篇 |
国内免费 | 3756篇 |
专业分类
化学 | 25375篇 |
晶体学 | 660篇 |
力学 | 4418篇 |
综合类 | 550篇 |
数学 | 19601篇 |
物理学 | 26713篇 |
出版年
2023年 | 515篇 |
2022年 | 1213篇 |
2021年 | 1153篇 |
2020年 | 1240篇 |
2019年 | 1515篇 |
2018年 | 1257篇 |
2017年 | 1395篇 |
2016年 | 1423篇 |
2015年 | 1147篇 |
2014年 | 1774篇 |
2013年 | 3919篇 |
2012年 | 2337篇 |
2011年 | 3025篇 |
2010年 | 2191篇 |
2009年 | 3469篇 |
2008年 | 3798篇 |
2007年 | 4157篇 |
2006年 | 3643篇 |
2005年 | 2791篇 |
2004年 | 2830篇 |
2003年 | 3212篇 |
2002年 | 4142篇 |
2001年 | 3553篇 |
2000年 | 3298篇 |
1999年 | 3166篇 |
1998年 | 2853篇 |
1997年 | 1754篇 |
1996年 | 1268篇 |
1995年 | 930篇 |
1994年 | 957篇 |
1993年 | 647篇 |
1992年 | 721篇 |
1991年 | 494篇 |
1990年 | 560篇 |
1989年 | 455篇 |
1988年 | 373篇 |
1987年 | 356篇 |
1986年 | 368篇 |
1985年 | 403篇 |
1984年 | 393篇 |
1983年 | 209篇 |
1982年 | 310篇 |
1981年 | 394篇 |
1980年 | 342篇 |
1979年 | 246篇 |
1978年 | 283篇 |
1977年 | 214篇 |
1976年 | 140篇 |
1975年 | 114篇 |
1974年 | 109篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
931.
Synthesis and binding studies of new bis-calix[4]arenes containing aromatic and heteroaromatic units
A series of new bis-calix[4]arenes containing different aromatic and heteroaromatic moieties have been synthesized. The complexing behavior of these bis-calix[4]arenes have been studied towards different metal ions and it has been found that these bis-calix[4]arenes bind silver ions selectively over other metal ions. The complexation has been studied by liquid-liquid extraction and by NMR and IR spectroscopy. 相似文献
932.
Yoshida H. Yang M. Masaka K. Houshito Y. Mashiko K. Nakamura S. 《Journal of Thermal Analysis and Calorimetry》2002,70(3):703-711
Phase transition behavior of polyesters derived from 2,7-phenanthrene dicarbonic acid diethylester and alkanediols with even
methylene carbon number was investigated by the simultaneous DSC-XRD method. The smectic A phase was observed on cooling from
the molten state. The transition entropy from the isotropic state to the smectic A phase was about 9.0 J mol-1 K-1, which depended on the methylene carbon number. The linear expansion coefficients, based on the (001) spacing of the crystalline
phase at room temperature, were 1.3·10-4 K-1 (crystalline phase), 5.7·10-4 K-1 (crystallization region), 1.7·10-3 K-1 (smectic A phase) during cooling, and 1.5·10-4 K-1 (crystalline phase), and 1.0·10-3K-1(melting region) on heating.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
933.
V. Slavinska Dz. Sile G. Rozenthal G. Maurops J. Popelis M. Katkevich V. Stonkus E. Lukevics 《Chemistry of Heterocyclic Compounds》2006,42(5):570-573
The hydrogenation of ethyl 4-R-2,4-dioxobutyrates (R = phenyl, 2-furyl) at 5% Pt/Al2O3 catalyst, modified with cinchonidine, and at palladium black was investigated. The former had low activity under the conditions
we tested. The main products during the hydrogenation of these compounds at palladium black are ethyl 4-R-2-hydroxy-4-oxobutyrates.
The yield of the phenyl derivative amounts to 68.5%, while the yield of the corresponding 2-furyl derivative amounts to 97%.
In the last case ethyl 2-hydroxy-4-oxo-4-(2-tetrahydrofuryl)butyrate was detected as impurity. The optimum conditions for
the formation of ethyl 2-hydroxy-4-phenylbutyrate (yield 88.2%) were determined.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 655–659, May, 2006. 相似文献
934.
F. Buiarelli F. Coccioli R. Jasionowska M. Merolle A. Terracciano 《Chromatographia》2006,64(7-8):475-481
Resveratrol (3,5,4′-trihydroxystilbene) is a phytoalexin that belongs to the group of stilbenes, known to occur in grapes and consequently in grape products. Its presence in wine is an important qualitative parameter because of the several beneficial effects on human health. The aim of this work is the development of a high-performance liquid chromatographic (HPLC) method for the determination of trans resveratrol in wines, and comparisons between the results obtained by different detection techniques: UV-vis spectroscopy, fluorescence spectroscopy and mass spectrometry. Resveratrol is analysed on a C-18 column using gradient elution. The method permits direct injection of sample, revealing to be time-saving, overcoming the need of sample pre-treatment steps. Detection limits were 154.8 ng mL−1 by HPLC-UV, 118.0 ng mL−1 by HPLC-FL and 48.0 ng mL−1 by HPLC-MS. Trans resveratrol has been then quantified in a group of 52 wines derived from different Italian regions, cultivars and winemaking technologies by HPLC-UV. 相似文献
935.
Yunhui Zhai Xijun Chang Yuemei Cui Ning Lian Shoujun Lai Hong Zhen Qun He 《Mikrochimica acta》2006,154(3-4):253-259
A rapid, selective method that utilize 4-(2-Pyridylazo)-resorcinol (PAR)-modified nanometer SiO2 (nanometer SiO2–PAR) as a new solid-phase extractant for preconcentration of trace mercury (II) has been developed. The adsorption property
of nanometer SiO2–PAR for metal ions was studied by selectively extracting different metal ions from aqueous solutions. The results revealed
an excellent affinity of the nanometer SiO2–PAR for mercury (II) in presence of interfering metal ions at pH 4. The main parameters of solid-phase extraction such as
shaking time, elution and sample dilution effect were studied. The extractant shows rapid kinetic sorption, and the adsorption
equilibrium of mercury (II) on nanometer SiO2–PAR was achieved in less than 2 min. The adsorbed mercury (II) was easily eluted by 4 mL of 6 mol L−1 HCl. The maximum preconcentration factor was 50. The maximum static adsorption capacity was 276 μmol g−1 at pH 4. The detection limit (3σ) was 0.43 μg L−1 for cold vapor atomic absorption spectrometry (CVAAS), and the relative standard deviation of the eight replicate determinations
was 2.4% for the determination of 2.0 μg of Hg(II) in 100 mL water sample. The method was applied to the determination of
trace mercury (II) in sample solutions with satisfactory results. 相似文献
936.
A. I. Ilovaisky V. M. Merkulova Yu. N. Ogibin G. I. Nikishin 《Russian Chemical Bulletin》2005,54(7):1585-1592
Electrolysis of salts of primary and secondary nitro compounds (nitroethane, 1- and 2-nitropropanes, nitrocyclohexane, and
nitrocycloheptane) in the presence of excess halide, nitrite, cyanide, and phenylsulfinate anions under undivided and divided
amperostatic electrolysis conditions in a two-phase medium (CH2Cl2/H2O) produces geminal nitrohalides (35–85% yields), dinitro compounds (15–51%), nitronitriles (6–27%), and nitrosulfones (50–70%).
The salts of secondary nitro compounds form the products of oxidative coupling with halide and phenylsulfinate anions under
the undivided electrolysis conditions. In all other cases, divided electrolysis is required.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1539–1546, July, 2005. 相似文献
937.
HUA Er-BingCoordination Chemistry Institute State Key Laboratory of Coordination Chemistry Nanjing University Nanjing Jiangsu ChinaYANG Pin LI Qing-Shan YANG Bin-ShengInstitute of Molecular Science Shanxi University Taiyuan Shanxi China 《中国化学》1996,14(4):297-302
The effect of Cu2+ on the triple-stranded helical structure of poly(A:2I) was studied by means of circular dichroism spectral method with the help of ultraviolet spectral and ethidium bromide fluorescence probe methods. It was found that Cu2+ destabilizes the structure of the triple helix poly(A:2I) and induces its structural transformations, meanwhile, the transformations can be partially reversed by a higher NaCl concentration. The structural transformations may be expressed by the following scheme: poly(A:2I) - poly(A:I) + poly(I)- poly(A) + 2poly(I) 相似文献
938.
In our former investigations, the phenomenon high temperature corrosion (HTC) was described exemplarily on selected materialcoating combinations for blades of stationary gas turbines, mainly in the temperature region of up to 750° C. To answer the question, in which manner higher gas inlet and/or higher material surface temperature would influence the HTC behaviour, a special analytical technique—the integral layer profile analysis—was introduced to ameliorate concentration profile methods. By examining IN 738 LC specimens with CoCrAlY plasma spray coating, stressed by hot gas at 900° C, the limits of this system are shown by explaining the corrosion mechanism; the method is also used for other systems, e.g. U 520 with NiCrAlY coating at 750° C. 相似文献
939.
Rashid A. Zeineh George Kyriakidis Roger Acey Christopher Smith 《Applied biochemistry and biotechnology》1986,13(2):119-125
Citrus tristeza virus (CTV) extracted from Etrog citron (C.medica L.) was immunoprecipitated. The immunoprecipitate was fractionated by SDS-PAGE and western blotted onto nitrocellulose. The CTV
antigens were determined by immunoblot analysis using rabbit anti-CTV IgG, and the protein-band pattern exhibited on the nitrocellulose
was assessed by soft-laser scanning densitometry. The densitometric tracing revealed the presence of bands that were not visible
to the naked eye. Using the superimposition mode of the instrument, it was also revealed that the protein-band patterns of
different CTV samples were not identical. Computer-aided soft-laser scanning densitometry proved to be a powerful approach
in the detection and assessment of protein bands revealed on nitrocellulose immunoblots, which we were previously unable to
do employing conventional methods. 相似文献
940.
3-O-Acetyl-1,2-O-isopropylidene--D-allofuranose (2 b) was prepared from 1,2:5,6-di-O-isopropylidene--D-allofuranose (1 b). Treatment of2 b with triphenylphosphine-diethyl azodicarboxylate afforded regio- and stereospecifically the 5,6-epoxy--D-allo derivative (3). The other diastereomeric compound, 5,6-epoxy-1,2-O-isopropylidene--L-talofuranose (6) was also prepared stereoselectively from2 b
via the intermediates5 a and5 b. The epoxy sugars3 and6 were converted with lithium aluminum hydride to the corresponding 6-deoxy-1,2-O-isopropylidene--D-allofuranose (4 a) and --L-talofuranose (7 a) derivatives. Hydrolysis of4 a and7 a afforded 6-deoxy-D-allose and 6-deoxy-L-talose, respectively. The corresponding 3,5-di-O-acetyl- (4 b and7 b) and the 3,5-O-(tetraisopropyldisiloxane-1,3-diyl) derivatives (4 c and7 c) are also described. Selective removal of the isopropylidene group and subsequent acetylation offers a convenient route to prepare sugar derivatives containing furanose ring, like8 b, as a suitable precursor for nucleoside analogs.Herrn Prof. Dr.K. Komarek mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献