全文获取类型
收费全文 | 5363篇 |
免费 | 684篇 |
国内免费 | 220篇 |
专业分类
化学 | 3634篇 |
晶体学 | 67篇 |
力学 | 390篇 |
综合类 | 49篇 |
数学 | 496篇 |
物理学 | 1631篇 |
出版年
2024年 | 14篇 |
2023年 | 32篇 |
2022年 | 118篇 |
2021年 | 104篇 |
2020年 | 179篇 |
2019年 | 117篇 |
2018年 | 137篇 |
2017年 | 147篇 |
2016年 | 219篇 |
2015年 | 190篇 |
2014年 | 246篇 |
2013年 | 502篇 |
2012年 | 370篇 |
2011年 | 354篇 |
2010年 | 296篇 |
2009年 | 318篇 |
2008年 | 331篇 |
2007年 | 327篇 |
2006年 | 275篇 |
2005年 | 263篇 |
2004年 | 240篇 |
2003年 | 194篇 |
2002年 | 121篇 |
2001年 | 127篇 |
2000年 | 103篇 |
1999年 | 131篇 |
1998年 | 98篇 |
1997年 | 85篇 |
1996年 | 59篇 |
1995年 | 79篇 |
1994年 | 51篇 |
1993年 | 54篇 |
1992年 | 57篇 |
1991年 | 36篇 |
1990年 | 29篇 |
1989年 | 24篇 |
1988年 | 38篇 |
1987年 | 23篇 |
1986年 | 23篇 |
1985年 | 28篇 |
1984年 | 13篇 |
1983年 | 11篇 |
1982年 | 30篇 |
1981年 | 16篇 |
1980年 | 17篇 |
1979年 | 14篇 |
1978年 | 6篇 |
1977年 | 12篇 |
1974年 | 4篇 |
1973年 | 2篇 |
排序方式: 共有6267条查询结果,搜索用时 15 毫秒
81.
I. Brandariz F. Arce X. L. Armesto F. Penedo M. Sastre de Vicente 《Monatshefte für Chemie / Chemical Monthly》1993,124(3):249-257
Summary A systematic study of the dependence of acid-base stoichiometric constants on the ionic strength has been carried out for the aminoacidL-valine in ClK and BrK solutions. The observed dependence has been interpreted by using Guggenheim, Scatchard and Pitzer models for the activity coefficients of the species involved in the equilibria.
Die Abhängigkeit von Gleichgewichtskonstanten desL-Valin von der Ionenstärke entsprechend den Modellen von Guggenheim, Scatchard und Pitzer
Zusammenfassung Es wurde anL-Valin in KCl- und KBr-Lösungen eine systematische Studie der Abhängigkeit der Säure-Base-Stöchiometrie von der Ionenstärke durchgeführt. Die beobachteten Abhängigkeiten wurden aufgrund der nach den Modellen von Guggenheim, Scatchard und Pitzer erhaltenen Aktivitätskoeffizienten der an den Gleichgewichten beteiligten Spezies interpretiert.相似文献
82.
Summary Diaromatics are geochemically significant constituents of crude oils. Their determination is usually achieved by elaborate prefractionation methods, such as medium pressure liquid chromatography and HPLC, prior to capillary gas chromatography. The present contribution describes the quantitative analysis of methylnaphthalenes, ethylnaphthalenes, and dimethylnaphthalenes in selected crude oils by two-dimensional capillary GC. Since the method does not comprise any work-up procedure the determination of geochemical parameters (alkylnaphthalene concentration ratios) is performed on the original, untreated crude oil samples. Accordingly, the analytical results reflect the original composition. The influence by evaporational losses in the laboratory is minimized. 相似文献
83.
A. A. El-Asmy 《中国化学会会志》1988,35(1):29-34
The preparation and characterization of a series of new coordination compounds of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) containing o-methyl- or o-chlorobenzoyl-4-phenyl-3-thiosemicarbazide (HMBPT, HCBPT=HL) are reported. The reaction products were investigated by analyses, electrolytic conductance, magnetic susceptibility, reflectance and IR spectral studies. The IR spectra show that HMBPT and HCBPT coordinate with the metal ions via different coordination sites (NS and/or NO). The spectral data support the suggestion that the ligands form his-chelates with Ni(II) and Cu(II) of square planar stereochemistry and of general formulae ML2·H2O, where L is the uninegatively charged bidentate ligand. The Co(II) ion forms octahedral and tetrahedral structures with HMBPT and HCBPT, respectively. The ligand field parameters (D4, B and β) for the Co(II) chelates were calculated using the averaged-ligand-field approximation. The influence of the benzene ring substituents (o-chloro or o-methyl) on the stereochemistry are discussed. Also, the formation of the complexes in solution was tested by the pH-metric method. 相似文献
84.
S. V. Galushko 《Chromatographia》1993,36(1):39-42
Summary To calculate retention in reversed-phase, high-performance liquid chromatography a method based on the molecular structure of the analyte and the characteristics of sorbents and mobile phases has been employed. Characteristics of different ODS-columns in water-methanol eluents have been determined. 相似文献
85.
86.
Information content of data and variables and types of weighting in least-squares regression methods
Algorithms are given for evaluating the relative amount of useful information related to a particular parameter which is carried by individual data points and intervals of the variables. The algorithms provide an efficient means of using the information contained in a set of data. Applications to the optimization of weighting in regression methods are described. Several informational and combined informational-statistical types of weighting are studied as a means of improving the accuracy and precision of the parameters obtained by non-linear regression. 相似文献
87.
E. L. Anderson M. M. Thomason H. T. Mayfield W. Bertsch 《Journal of separation science》1979,2(6):335-342
A versatile two-dimensional gas chromatograph is described, consisting of 2 separate ovens, one intermediate trap, an auxiliary inlet, and the necessary hardware to effect off-line switching according to the principle of Deans. The unit has been designed for use with high resolution glass capillary columns. The performance of individual instrumental components was critically evaluated. Results showed that low dead volume glass to metal connections were required in the manifold and detector lines to minimize extra-column effects. The mass of the intermediate trap must be low to allow rapid heating. Operational parameters are discussed and examples of some applications are shown. 相似文献
88.
An automated on-line method for the determination of the isoflavones, daidzein and genistein, was developed using in-tube solid-phase microextraction coupled to high-performance liquid chromatography (in-tube SPME-HPLC). In-tube SPME is a new extraction technique for organic compounds in aqueous samples, in which analytes are extracted from the sample directly into an open tubular capillary by repeated draw/eject cycles of sample solution. Daidzein, genistein and their glucosides tested in this study were clearly separated within 8 min by HPLC using an XDB-C8 column with diode array detection. In order to optimize the extraction of these compounds, several in-tube SPME parameters were examined. The glucosides daidzin and genistin were analyzed as aglycones after hydrolysis because the glucosides were not concentrated by in-tube SPME. The optimum extraction conditions for daidzein and genistein were obtained with 20 draw/eject cycles of 40 microl of sample using a Supel-Q porous layer open tubular capillary column. The extracted compounds were easily desorbed from the capillary by mobile phase flow, and carryover was not observed. Using the in-tube SPME-HPLC method, the calibration curves of these compounds were linear in the range 5-200 ng/ml, with a correlation coefficient above 0.9999 (n = 18), and the detection limits (S/N = 3) were 0.4-0.5 ng/ml. This method was successfully applied to the analysis of soybean foods without interference peaks. The recoveries of aglycones and glucosides spiked into food samples were above 97%. 相似文献
89.
Moon Hwan Cho Seung Chang Yang Nam Keun Yang Yongjin Kang Jaejung Ko 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(4):279-287
The thermodynamic parameters for the interaction of Cu2+, Ni2+, Co2+, Cd2+, andAg+ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag+ exhibited remarkably higher complexation selectivity.Ag+ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg+–M2+ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag+ was observed in both single and competitiveAg+–M2+ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2) with silver,[Ag(P2N2)] (NO3), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P21/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) 3 and Z = 4. 相似文献
90.
蛋白质变性机理与变性时的热力学参数研究进展 总被引:7,自引:0,他引:7
生物大分子是近年来生命科学的研究热点和难点之一,而对蛋白质变性的研究有助于深刻揭示生命现象的机理.利用光谱学和热力学可以分别从微观和宏观角度对蛋白质变性进行研究,并由此得到表征蛋白质变性的热力学参数.这对深入了解蛋白质的折叠与伸展、变性机理、结构稳定性及生命体的新陈代谢等问题具有很大意义.近年来,国内外学者在此方面做了大量的工作,主要涉及蛋白质在水溶液中的变性机理、在有变性剂存在下水溶液中的变性机理及在含有其它物质水溶液中的变性机理.用来表征蛋白质变性的热力学参数有热容、变性自由能、变性焓和变性熵等.本文对这些研究进行了概述. 相似文献