全文获取类型
收费全文 | 3667篇 |
免费 | 156篇 |
国内免费 | 19篇 |
专业分类
化学 | 2614篇 |
晶体学 | 24篇 |
力学 | 55篇 |
数学 | 414篇 |
物理学 | 735篇 |
出版年
2023年 | 21篇 |
2022年 | 16篇 |
2021年 | 72篇 |
2020年 | 64篇 |
2019年 | 79篇 |
2018年 | 56篇 |
2017年 | 48篇 |
2016年 | 119篇 |
2015年 | 116篇 |
2014年 | 123篇 |
2013年 | 239篇 |
2012年 | 228篇 |
2011年 | 279篇 |
2010年 | 174篇 |
2009年 | 175篇 |
2008年 | 246篇 |
2007年 | 214篇 |
2006年 | 189篇 |
2005年 | 162篇 |
2004年 | 149篇 |
2003年 | 101篇 |
2002年 | 122篇 |
2001年 | 63篇 |
2000年 | 80篇 |
1999年 | 41篇 |
1998年 | 47篇 |
1997年 | 37篇 |
1996年 | 39篇 |
1995年 | 47篇 |
1994年 | 33篇 |
1993年 | 42篇 |
1992年 | 39篇 |
1991年 | 40篇 |
1990年 | 35篇 |
1989年 | 25篇 |
1988年 | 25篇 |
1987年 | 24篇 |
1986年 | 22篇 |
1985年 | 30篇 |
1984年 | 28篇 |
1983年 | 19篇 |
1982年 | 24篇 |
1981年 | 17篇 |
1980年 | 15篇 |
1978年 | 11篇 |
1977年 | 11篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 7篇 |
1970年 | 8篇 |
排序方式: 共有3842条查询结果,搜索用时 15 毫秒
71.
Authentic samples of whisky produced in Scotland and USA and counterfeit whisky samples commercialized in Brazil have been directly submitted to electrospray ionization mass spectrometry (ESI-MS) analysis in both the negative and positive ion modes to assess the potential of this technique for simple and rapid quality control and proof of authenticity of whisky samples. ESI in the negative ion mode yields the most characteristic whisky fingerprinting mass spectra in just a few seconds by direct infusion of the samples, detecting the most polar or acidic components of each sample in their deprotonated anionic forms. No pre-treatment of the sample, such as extraction or derivatization or even dilution, is required. The analysis of the ESI(-)-MS data both by simple visual inspection but more particularly by chemometric data treatment enables separation of the whisky samples into three unequivocally distinct groups: Scotch, American and counterfeit whisky, whereas single malt and blended Scotch whiskies are also distinguished to some extent. As indicated by ESI-MS/MS analysis, the diagnostic anions are simple sugars, disaccharides and phenolic compounds. Direct infusion ESI-MS therefore provides immediate chemical fingerprinting of whisky samples for type, origin and quality control, as demonstrated herein for American, Scottish and counterfeit samples, whereas ESI-MS/MS analysis of diagnostic ions adds a second dimension of fingerprinting characterization when improved selectivity is desired. 相似文献
72.
The preparation of 2-amino-5-nitrothiophene, 2-formamido-5-nitrothiophene, 2-acetamido-5-nitrothiophene and 2-t-butyloxycarbonylamino-5-nitrothiophene are described. Abnormal values of the coupling constants J3.4 had been observed in the 1H-nmr spectra of compounds obtained. 相似文献
73.
Urones JG Sexmero MJ Hernandez FA Basabe AB Diez D Marcos IS 《Natural product letters》2001,15(6):387-391
Two new diterpenic acids with an ent-halimane skeleton have been isolated from the aerial parts of Halimium viscosum (Villarino de los Aires chemotype) and separated as methyl esters. These diterpenes were 13-oxo-14, 15-dinor-1(10),11E-ent-halimadien-18-oic acid and 15-hydroxy-1(10),13Z-ent-halimadien-18-oic acid. 相似文献
74.
Recently, a new and efficient method for total homocysteine (tHcy) quantitation in plasma using trap and release membrane introduction mass spectrometry (T&R-MIMS) with a versatile removable direct introduction membrane probe (DIMP) was described [R. Haddad, M. A. Mendes, N. F. Hoehr and M. N. Eberlin, Analyst, 2001, 126, 1212]. Herein we report on the use of the DIMP-T&R-MIMS technique for total cysteine (tCys) quantitation; hence combined tCys and tHcy quantitation in plasma or serum can be achieved. The method employs Cys and Hcy derivatization with ethyl chloroformate (after disulfide bond reduction with dithiothreitol and protein precipitation with trichloroacetic acid), preconcentration in a capillary silicone membrane, and their thermal desorption to the gas phase inside the ion source region of a mass spectrometer, at a point exactly between the two ionization filaments. Thermal desorption uses the uniform heat radiation provided by the two ionization filaments. The analytes are then ionized by electron ionization and both Cys and Hcy are quantitated by mass spectrometry using selected ion monitoring. For tCys quantitation, good linearity and reproducibility was observed for concentrations ranging from 5 to 350 microM, recovery was near 95%, and the limit of detection (LOD) was of 2 microM. This LOD is well below the mean Cys concentration in plasma, and serum samples from a large group of healthy people showed a mean tCys concentration of 132 +/- 45 microM. 相似文献
75.
Kumar K Michalik D Garcia Castro I Tillack A Zapf A Arlt M Heinrich T Böttcher H Beller M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):746-757
A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals. 相似文献
76.
Araúzo-Bravo MJ Fujii S Kono H Ahmad S Sarai A 《Journal of the American Chemical Society》2005,127(46):16074-16089
Sequence dependence of DNA conformation plays a crucial role in its recognition by proteins and ligands. To clarify the relationship between sequence and conformation, it is necessary to quantify the conformational energy and specificity of DNA. Here, we make a systematic analysis of dodecamer DNA structures including all the 136 unique tetranucleotide sequences at the center by molecular dynamics simulations. Using a simplified conformational model with six parameters to describe the geometry of adjacent base pairs and harmonic potentials along these coordinates, we estimated the equilibrium conformational parameters and the harmonic potentials of mean force for the central base-pair steps from many trajectories of the simulations. This enabled us to estimate the conformational energy and the specificity for any given DNA sequence and structure. We tested our method by using sequence-structure threading to estimate the conformational energy and the Z-score as a measure of specificity for many B-DNA and A-DNA crystal structures. The average Z-scores were negative for both kinds of structures, indicating that the potential of mean force from the simulation is capable of predicting sequence specificity for the crystal structures and that it may be used to study the sequence specificity of both types of DNA. We also estimated the positional distribution of conformational energy and Z-score within DNA and showed that they are strongly position dependent. This analysis enabled us to identify particular conformations responsible for the specificity. The presented results will provide an insight into the mechanisms of DNA sequence recognition by proteins and ligands. 相似文献
77.
Eimer GA Gómez Costa MB Pierella LB Anunziata OA 《Journal of colloid and interface science》2003,263(2):400-407
The adsorption of aniline on Na-AlMCM-41 synthesized by us has been characterized by infrared spectroscopy, temperature programmed desorption (TPD), and differential thermal analysis methods. Aniline would be mostly bound to the mesostructure through weak pi interactions. On the mesostructure containing adsorbed water, the co-adsorption of aniline could occur by weak hydrogen bonding through surface water molecules. For water, two possible modes of adsorption have been identified. Different associations between aniline and hydrated and nonhydrated mesostructures have been evaluated in order to favor the posterior in situ polymerization of adsorbed aniline. 相似文献
78.
79.
Rezende MC Flores P Guerrero J Villarroel L 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(7):1637-1640
The 13C NMR of two solvatochromic dyes derived from a barbituric acid acceptor and dimethylaminophenyl donor fragments, compound 1 and the related merocyanine 2, were recorded in various solvents. The observed chemical-shift variations were used to interpret their structural differences and solvatochromic behavior in solution. 相似文献
80.
A new kinetic method for determination of selenium is based on its inhibitory effect on the Pd(II)-catalysed reaction between Pyronine G and hypophosphite. Under the optimum experimental conditions (6 x 10(-5)M Pyronine G, 0.4M hypophosphite, 0.4 mug/ml Pd(II), pH 2.8, temperature 22.0 +/- 0.2 degrees ), Se can be determined in the concentration range 0.033-0.50 mug/ml. The method suffers from numerous interferences and is thus limited in application. It has been applied to the determination of selenium in spring waters and pharmaceutical preparations. 相似文献