全文获取类型
收费全文 | 9060篇 |
免费 | 245篇 |
国内免费 | 20篇 |
专业分类
化学 | 5443篇 |
晶体学 | 175篇 |
力学 | 177篇 |
数学 | 1759篇 |
物理学 | 1771篇 |
出版年
2023年 | 44篇 |
2022年 | 87篇 |
2021年 | 100篇 |
2020年 | 144篇 |
2019年 | 195篇 |
2018年 | 211篇 |
2017年 | 240篇 |
2016年 | 448篇 |
2015年 | 326篇 |
2014年 | 417篇 |
2013年 | 782篇 |
2012年 | 484篇 |
2011年 | 522篇 |
2010年 | 386篇 |
2009年 | 352篇 |
2008年 | 544篇 |
2007年 | 480篇 |
2006年 | 427篇 |
2005年 | 339篇 |
2004年 | 302篇 |
2003年 | 215篇 |
2002年 | 192篇 |
2001年 | 132篇 |
2000年 | 134篇 |
1999年 | 80篇 |
1998年 | 92篇 |
1997年 | 66篇 |
1996年 | 79篇 |
1995年 | 75篇 |
1994年 | 49篇 |
1993年 | 45篇 |
1992年 | 53篇 |
1991年 | 67篇 |
1990年 | 59篇 |
1989年 | 62篇 |
1988年 | 57篇 |
1987年 | 55篇 |
1986年 | 56篇 |
1985年 | 112篇 |
1984年 | 114篇 |
1983年 | 79篇 |
1982年 | 71篇 |
1981年 | 80篇 |
1980年 | 71篇 |
1979年 | 58篇 |
1978年 | 41篇 |
1977年 | 38篇 |
1976年 | 47篇 |
1975年 | 39篇 |
1973年 | 36篇 |
排序方式: 共有9325条查询结果,搜索用时 0 毫秒
891.
Gabriela Wiosna Irina Petkova Maria S. Mudadu Randolph P. Thummel Jacek Waluk 《Chemical physics letters》2004,400(4-6):379-383
Three isomeric 7-(pyridyl)indoles reveal very different, solvent-dependent photophysical properties. Due to rapid excited state depopulation involving intramolecular hydrogen bonding, 7-(2′-pyridyl)indole is practically nonfluorescent at room temperature. In nonpolar and polar aprotic solvents, 7-(3′-pyridyl)indole and 7-(4′-pyridyl)indole fluorescence strongly, but the emission is quenched in alcohols. Syn and anti rotameric forms of 7-(3′-pyridyl)indole are detected, each quenched to a different degree. This differential quenching is interpreted as evidence of enhanced S1 → S0 internal conversion being more efficient in cyclic solvates, with alcohol molecules forming a bridge between the proton donor and acceptor groups of an excited chromophore. 相似文献
892.
NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl3 and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation. 相似文献
893.
Krystyna?Bogdanowicz-SzwedEmail author Jacek?Grochowski Ma?gorzata?Krasodomska Pawe??Serda 《Monatshefte für Chemie / Chemical Monthly》2004,135(2):201-209
Summary. The condensation of two molecules of 2-(2-thienylcarbonyl)thioacetanilides catalyzed by piperidine yielded thiazole derivatives as confirmed by X-ray crystal structure analysis. The reaction of malononitrile with 3-morpholino-3-(2-thienyl)acrylic acid thioanilides furnished 6-amino-1-aryl-4-(2-thienyl)-1,2-dihydro-2-thioxopyridine-5-carbonitriles. A similar reaction of malononitrile with 3-morpholino-3-(2-thienyl)acrylic acid anilides provided 2-oxopyridine-5-carbonitriles. 相似文献
894.
Ewa?Cholewa Ian?Burgess Julia?Kunze Jacek?LipkowskiEmail author 《Journal of Solid State Electrochemistry》2004,8(10):693-705
Electrochemical measurements including cyclic voltammetry, differential capacity, and chronocoulometry have been used to characterize the adsorption behaviors of the zwitterionic surfactant
N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDAPS) on the Au(111) electrode surface. The thermodynamics of the ideally polarized electrode have been employed to determine the Gibbs excess and the Gibbs energy of adsorption. The results show that the adsorption of DDAPS has a multistate character. The first two states are observed at potentials close to zero charge. At low bulk DDAPS concentrations, it corresponds to the formation of a film of nearly flat adsorbed molecules. At higher concentrations it is converted into a hemimicellar state. The second state is formed at negative potentials and charge densities close to 0 C cm–2. It corresponds to a film of tilted molecules oriented with the hydrocarbon tail towards the metal and the polar head toward the solution.Dedicated to Professor Zbigniew Galus on the occasion of his 70th birthday and in recognition of his many contributions to electrochemistry. 相似文献
895.
A novel silver nanoparticle-based (AgNP) method and two modified procedures, ferric reducing antioxidant power (FRAP) and 2,2'-diphenyl-1-picrylhydrazyl (DPPH), were used for determination of antioxidant capacities of the ethanolic, methanolic, methanolic-aqueous (1?:?1 v/v) and aqueous extracts of rapeseed and its products. The AgNP method based on the electron-transfer reaction between silver ions and antioxidants in an optimized ammonium buffer medium (pH = 8.4) and determination of silver nanoparticle formation has been elaborated. The novel AgNP method was validated using sinapic acid, gallic acid, caffeic acid, ascorbic acid and quercetin as standard antioxidant solutions in concentration ranges of 0.03-0.21 μmol mL(-1), 0.02-0.20 μmol mL(-1), 0.01-0.18 μmol mL(-1), 0.03-0.30 μmol mL(-1) and 0.001-0.009 μmol mL(-1). The calculated detection (DL = 0.01, 0.02, 0.009, 0.02 and 0.0004 μmol mL(-1) for sinapic, gallic, caffeic, ascorbic acids and quercetin, respectively) and quantification limits (QL = 0.04, 0.06, 0.03, 0.08 and 0.001 μmol mL(-1) for sinapic, gallic, caffeic, ascorbic acids and quercetin, respectively) confirm linearity concentration ranges for determination of antioxidant capacity by AgNP assay. The average antioxidant capacities of the studied rapeseed samples ranged between 14.7 and 126.2 μmol sinapic acid per gram for the proposed AgNP method, 7.4-112.7 μmol sinapic acid per gram for the FRAP method and 39.1-339.8 μmol sinapic acid per gram for DPPH assay. The methanol-water mixture (1:1 v/v) was the most efficient solvent for extraction of antioxidants from the studied rapeseed samples. There are significant, positive correlations between the novel AgNP and the modified FRAP, DPPH and FC methods for all extracts of the studied rapeseed samples (r = 0.7564-0.8516, p < 0.001). Satisfactory values of precision (RSD = 1.2-4.4%) and accuracy (recovery = 95.6-104.6%, except methanolic extracts) demonstrate the benefit of the proposed AgNP method for analysis of the antioxidant capacity of rapeseed samples. Results of the principal component analysis (PCA) indicate that there are differences between the total amounts of antioxidants in rapeseed samples extracted by different solvents. 相似文献
896.
The applications of spectroscopic methods in cancer detection open new possibilities in early stage diagnostics. Raman spectroscopy and Raman imaging represent novel and rapidly developing tools in cancer diagnosis. In the study described in this paper Raman spectroscopy has been employed to examine noncancerous and cancerous human breast tissues of the same patient. The most significant differences between noncancerous and cancerous tissues were found in regions characteristic for the vibrations of carotenoids, lipids and proteins. Particular attention was paid to the role played by unsaturated fatty acids in the differentiation between the noncancerous and the cancerous tissues. Comparison of Raman spectra of the noncancerous and the cancerous tissues with the spectra of oleic, linoleic, α-linolenic, γ-linolenic, docosahexaenoic and eicosapentaenoic acids has been presented. The role of sample preparation in the determination of cancer markers is also discussed in this study. 相似文献
897.
Błażej Gierczyk Wojciech Ostrowski Marcin Kaźmierczak 《Magnetic resonance in chemistry : MRC》2012,50(4):271-277
2‐Aryl‐1,3,4‐selenadiazoles were studied by 1H, 13C, 15N and 77Se NMR spectroscopy. The results (chemical shifts and coupling constants) were correlated with Hammett substituent parameters as well as calculated chemical shifts and bond lengths. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
898.
Agnieszka Ulanowska Ewa Trawińska Piotr Sawrycki Bogusław Buszewski 《Journal of separation science》2012,35(21):2908-2913
Chemotherapy used as a treatment against lung cancer has influence on metabolic processes occurring in healthy cells. The changes of biochemical pathways proceeded inside cells might be observed in expired air. In the experiment, breath analysis was carried out before and after anticancer therapy. Expired air samples were collected from 22 patients with a biopsy confirmed lung cancer. Volatile organic compounds present in breath were analyzed by gas chromatography/mass spectrometry. For enrichment of analytes solid‐phase microextraction technique was applied. Eight fibers covered by different sorbents were tested. Carboxen‐polydimethylsiloxane fiber revealed the highest extraction efficiency in relation to analytes in breath. The data showed that cytostatic drugs increase the concentration of acetone and isoprene in the breath collected after chemotherapy. Volatile metabolites of administrated drugs were not identified in expired air. 相似文献
899.
Tomasz Laskowski Zbigniew Rafiński Paweł Sowiński Jan Pawlak 《Magnetic resonance in chemistry : MRC》2012,50(5):347-349
The relative configurations of four stereogenic centers of the C33‐C42 fragment of niphimycin A were assigned as 2S*, 3R*, 4S* and 6S*, based upon 1H NMR analysis with double‐quantum filtered COSY and nuclear Overhauser spectroscopy experiments. These data were then correlated with absolute configurations at C36 and C38 of niphimycin A, which were declared previously as 36S and 38S [3]. This allowed for the assignment of the absolute configurations at C34 and C35 of niphimycin A as 34S and 35R. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
900.