全文获取类型
收费全文 | 2225篇 |
免费 | 351篇 |
国内免费 | 152篇 |
专业分类
化学 | 1025篇 |
晶体学 | 35篇 |
力学 | 243篇 |
综合类 | 50篇 |
数学 | 428篇 |
物理学 | 947篇 |
出版年
2024年 | 4篇 |
2023年 | 25篇 |
2022年 | 58篇 |
2021年 | 65篇 |
2020年 | 67篇 |
2019年 | 65篇 |
2018年 | 68篇 |
2017年 | 86篇 |
2016年 | 116篇 |
2015年 | 72篇 |
2014年 | 108篇 |
2013年 | 240篇 |
2012年 | 137篇 |
2011年 | 138篇 |
2010年 | 122篇 |
2009年 | 139篇 |
2008年 | 123篇 |
2007年 | 142篇 |
2006年 | 104篇 |
2005年 | 120篇 |
2004年 | 93篇 |
2003年 | 83篇 |
2002年 | 78篇 |
2001年 | 73篇 |
2000年 | 55篇 |
1999年 | 48篇 |
1998年 | 33篇 |
1997年 | 29篇 |
1996年 | 34篇 |
1995年 | 26篇 |
1994年 | 22篇 |
1993年 | 21篇 |
1992年 | 20篇 |
1991年 | 16篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 13篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 5篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
排序方式: 共有2728条查询结果,搜索用时 187 毫秒
51.
52.
Maria Atanassova Victoria Lachkova Nikolay Vassilev Sabi Varbanov Ivan Dukov 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):173-179
The synergistic solvent extraction of five selected lanthanoid ions (La3+, Nd3+, Eu3+, Ho3+ and Lu3+) with a 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone(HP) and the 5,11,17,23-tert-butyl-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene, (S) in CHCl3 has been studied. It was found that in presence of this phosphorus-containing calix[4]arene the lanthanoids have been extracted
as LnP3 · S. On the basis of the experimental data, the values of the equilibrium constants have been calculated. The influence of
the synergistic agent on the extraction process has been discussed. A synergistic effect of almost three orders of magnitude
occurs in the extraction of Ln(III) with mixture of HP and S. The values of the separation factors (S.F.) between the adjacent
elements have been evaluated.
On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid complexes of Eu(III) with HP and Eu(III)
with HP and S were proposed. 相似文献
53.
E. Wünsch G. Wendlberger W. Göhring G. Hübener B. Traving 《Monatshefte für Chemie / Chemical Monthly》1993,124(5):577-586
Summary The synthesis of the heptacosapeptide amide with the primary structure of Human-secretin is described. For this purpose 7 fragments were designed, i.e. H-Gly-Leu-Val-NH2 25–27b,Z-Arg(Z
2)-Leu-Leu-Gln-OH 21–24,Z-Arg(Z
2)-Leu-Gln-OH 18–20,Z-Arg(Z
2)-Glu(OtBu)-Gly-Ala-OH 14–17,Z-Arg(Z
2)-Leu-OH 12–13,Z-Thr(tBu)-Ser(tBu)-Glu(OtBu)-Leu-Ser(tBu)-OH 7–11,Adoc-His(Adoc)-Ser(tBu)-Asp(OtBu)-Gly-Thr(tBu)-Phe-OH 1–6 these fragments were consequently assembled to the overall protected total sequence using the Wünsch/Weygand-method with dicyclohexylcarbodiimide. After deprotection by exposure to trifluoroacetic acid in presence of 1,2-ethanedithiol and water as scavenger, the isolated crude product was purified by column chromatography on CM-Sepharose, fast flow. This synthetized Human-secretin showed the full biological activity in comparison to Porcine-secretin.
Herrn Prof. Dr. E. Bayer zum 65. Geburtstag gewidmet. 相似文献
54.
Summary Computer-assisted procedures for the one-parameter optimization of the surfactant concentration and the concentration of urea or D-glucose as modifiers in micellar electrokinetic capillary chromatography have been developed. These procedures permit a rapid optimization of one parameter on the basis of only two experiments. Predicted values are compared to empirically obtained optimum values. The influence of the modifier concentration on the critical micelle concentration of sodium dodecyl sulfate was experimentally determined in buffers commonly employed in micellar electrokinetic chromatography. The alteration of retention factors of solutes caused by the influence of urea addition on the critical micelle concentration of sodium dodecyl sulfate was calculated under the assumption of constant distribution coefficients and compared to experimentally obtained values. It was demonstrated that the addition of urea or of D-glucose does not alter the phase ratio substantially. 相似文献
55.
DNA works as hereditary material and plays vital role in life science. The study of the binding of small molecules complex to DNA has been the focus of intense investigation, owning to their stereo and sequence specific interaction with the double helix1-… 相似文献
56.
Summary Pressure and temperature have significant influence on retention in HPLC. This study investigates the effect of pressure and
temperature on the retention behavior of aromatic hydrocarbons (toluene, ethyl benzene, butyl benzene, pentyl benzene) and
polar, acidic and basic samples (phenol, acetophenone, N,N-dimethyl aniline, benzophenone) on a reversed phase column. The
effect has been studied on non-porous, tetradecyl (C14) coated silica particles. We found that the adsorption-induced decrease of the partial molar volume of the solutes investigated
was between ΔV
m
=5–15 cm3 mol−1. The increment of the decrease of the partial molar volume due to the addition of one CH2 group, for the homologous series of the aromatic hydrocarbons is approximately ΔV
CH2
=2.3 cm3mol−1.
Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001. 相似文献
57.
Natalia V. Loginova Tat’yana V. Koval’chuk Rimma A. Zheldakova Anna A. Chernyavskaya Nikolai P. Osipovich Gennady K. Glushonok Henry I. Polozov Victor L. Sorokin Oleg I. Shadyro 《Central European Journal of Chemistry》2006,4(3):440-457
Cu (II) complexes with the sterically hindered diphenol derivatives 3,5-di(tert-butyl)-1,2-benzenediol (I), 4,6-di(tert-butyl)-1,2,3-benzenetriol (II) and the sulfur-containing 4,6-di(tert-butyl)-3-(2-hydroxyethylsulfanyl)-1,2-benzenediol (III) and 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid (IV) have been synthesized and characterized by elemental analysis, TG/DTA, FT-IR, ESR, XPS, XPD and conductivity measurements.
Compounds I–III can coordinate in their singly deprotonated forms and act as bidentate ligands. These compounds yield Cu (II) complexes of the stoichiometry Cu(L)2, which have square planar geometry (g| > g⊥ > ge). Unlike them, compound IV behaves as a terdentate ligand, and its complex Cu(LIV)2 has distorted octahedral geometry. According to ESR data, only the Cu(LII)2 complex contains a very small amount of phenoxyl radicals. Antimicrobial activities of these ligands and their respective
Cu (II) complexes have been determined with respect to Gram-positive and Gram-negative bacteria, as well as on yeasts. Their
phytotoxic properties against Chlorella vulgaris 157 were also examined. 相似文献
58.
This paper reports the results on a study of ion chromatography (IC) behaviour on strong cationic exchange column of CH3-(CH2)n−1-NH2 (n=1-6) type linear monoamines. The eluents were mixtures of HCl-NaCl, HNO3-NaNO3, HClO4-NaClO4, H2SO4-Na2SO4, HClO4-NaClO4-CH3CN. Amines were revealed with an amperometric detector. The influence of different counter-ions on retention factors, k′, is discussed. Relationships between k′ and pE (E=sum of Na+ and H+ concentrations), and length of alkylic chain, and sensitivity coefficient S, are reported and discussed. The addition of acetonitrile (ACN) in the eluent was also taken into account. Suitable considerations are derived from these data. An example of monoamines separation is given. 相似文献
59.
A biased bimetallic Fe-Fe complex Cp*Fe(dppe)(C≡CFc) (1) was synthesized from FcC≡CH (Fc=C5H4FeC5H5) and Cp*Fe(dppe)Cl (Cp*=C5Me5). Its one-electron oxidation species [Cp*Fe(dppe)(C≡CFc)][PF6] (1a) was also prepared and the spectroscopic properties of 1a was studied. The single-crystal X-ray diffraction analysis of 1 shows that ferrocenylacetylene is bonded at the terminal carbon to the iron center in the Cp*Fe(dppe) part. Crystallographic data for 1: monoclinic, space group C2/c, with a=4.067 65(14) nm, b=1.260 74(4) nm, c=1.649 89(5) nm, β=104.387(10)°, V=8.195 7(5) nm3, Z=8, Dc=1.354 g·cm-3, F(000)=3512, μ=0.822 mm-1. The structure was refined to R1=0.038 4, wR2=0.100 0. CCDC: 234893. 相似文献
60.