全文获取类型
收费全文 | 5662篇 |
免费 | 176篇 |
国内免费 | 11篇 |
专业分类
化学 | 3089篇 |
晶体学 | 101篇 |
力学 | 169篇 |
综合类 | 1篇 |
数学 | 1170篇 |
物理学 | 1319篇 |
出版年
2023年 | 40篇 |
2022年 | 58篇 |
2021年 | 92篇 |
2020年 | 115篇 |
2019年 | 137篇 |
2018年 | 201篇 |
2017年 | 189篇 |
2016年 | 259篇 |
2015年 | 188篇 |
2014年 | 243篇 |
2013年 | 628篇 |
2012年 | 393篇 |
2011年 | 392篇 |
2010年 | 308篇 |
2009年 | 248篇 |
2008年 | 281篇 |
2007年 | 258篇 |
2006年 | 162篇 |
2005年 | 114篇 |
2004年 | 123篇 |
2003年 | 118篇 |
2002年 | 94篇 |
2001年 | 87篇 |
2000年 | 64篇 |
1999年 | 50篇 |
1998年 | 55篇 |
1997年 | 48篇 |
1996年 | 42篇 |
1995年 | 35篇 |
1994年 | 42篇 |
1993年 | 28篇 |
1992年 | 35篇 |
1991年 | 23篇 |
1990年 | 33篇 |
1989年 | 40篇 |
1988年 | 31篇 |
1987年 | 21篇 |
1985年 | 37篇 |
1984年 | 41篇 |
1983年 | 29篇 |
1982年 | 26篇 |
1981年 | 22篇 |
1980年 | 28篇 |
1979年 | 34篇 |
1978年 | 34篇 |
1977年 | 28篇 |
1976年 | 36篇 |
1975年 | 21篇 |
1974年 | 34篇 |
1973年 | 21篇 |
排序方式: 共有5849条查询结果,搜索用时 0 毫秒
81.
Jurij V. Brenčič Boris Čeh Ivan Leban 《Monatshefte für Chemie / Chemical Monthly》1981,112(12):1359-1368
Trans-[Cr(NH3)4F2]I·H2O (A) has monoclinic P2l/m (No. 11) space group witha=5.033 (3),b=16.333 (10),c=5.539 (3) Å and =98.47 (3)°,Z=2.Cis-[Cr(NH3)4F2]ClO4 (B) has tetragonal space group I4lmd (No. 109) witha=7.417 (1),c=16.610 (2) Å,Z=4. Cr–F and Cr–N bonding distances are 1.894 (3); 2.087 and 2.083 (5) Å for A and 1.887 (6); 2.062 (5) and 2.051 (7) Å for B. Octahedral angles within the cations are close to 90° for both compounds. Cr–N bondtrans to Cr–F bond in thecis compound is shorter. Structures were refined toR
2 values of 0.072 (A) and 0.058 (B).Trans-[Cr(NH3)4F2]I·H2O has weak N–H–F hydrogen bonds between the cations. None such interactions were found incis-[Cr(NH3)4F2]ClO4.
Fluorhältige Komplexe des Cr(III), 2. Mitt.: Kristall- und Molekülstruktur von trans-[Cr(NH3)4F2]I·H2O und cis-[Cr(NH3)4F2]ClO4
Zusammenfassung Trans-[Cr(NH3)4F2]I·H2O (A) kristallisiert in der Raumgruppe P2l/m (No. 11) mitZ=2 unda=5,033 (3),b=16,333 (10),c=5,539 (3) Å und =98,47 (3)°.Cis-[Cr(NH3)4F2]ClO4 (B) kristallisiert in der Raumgruppe I4lmd (No. 109) mitZ=4,a=7,417 (1) undc=16,610 (2) Å. Die Cr–F- und Cr–N-Abstände sind 1,894 (3); 2,087 (6), 2,083 (5) Å für A und 1,887 (6); 2,062 (5), 2,051 (7) Å für B. Die octaedrischen Bindungswinkel innerhalb der Kationen weichen nicht viel von 90° ab. Der Cr–N-Abstand intrans-Position der Cr–F-Bindung ist kürzer. Die Strukturen wurden bis zu GütefaktorenR 2 0,072 (A) und 0,058 (B) verfeinert. Bei der Verbindung A wurden schwache N–H ... F-Wasserstoff-Bindungen zwischen verschiedenen Kationen beobachtet, während bei der Verbindung B keine Wasserstoff-Bindungen vorhanden sind.相似文献
82.
Monooctyl--(4-carboxyanilino)benzylphosphonic acid (H2L) was investigated as a novel reagent for the extraction and separation of lead(II) and bismuth(III) from nitrate solutions. Stoichiometric ionization constants of H2L in ethanol — water mixtures determined by potentiometric NaOH titration had values pKa1 2.25 and pKa2 4.33. Ethanol and chloroform solutions of H2L followed Beer's law at 300 nm and 296 nm, molar absorptivities being 2.94·104 mol–1·l·cm–1 and 2.85·104 mol–1·l·cm–1, respectively. HNO3 and HCl were also extracted into chloroform solutions containing H2L. Bismuth(III) was quantitatively transferred into the chloroform H2L solution at pH 1, and lead(II) at 3.5. The value of the separation factor DBi/DPb is 160 at pH 1. 相似文献
83.
N. Filipović-Vinceković D. Barišić N. Mašić S. Lulić 《Journal of Radioanalytical and Nuclear Chemistry》1991,148(1):53-62
The distribution of137Cs through soil layers has been investigated by field sampling. The investigation deals with137Cs concentration found after the Chernobyl accident. The relationship between important soil characteristics, total precipitation and cesium distribution are analyzed. Cesium is strongly sorbed in the top soil layer and its migration downward is limited. Measurements performed over a 3-year period revealed that approximately 20–38 per cent of total137Cs is located in the upper soil layer. 相似文献
84.
Four 9H and four 7H tautomers of DNA base xanthine were studied by the ab initio LCAO-MO method at the MP2/6-311G**//HF/6-31G** and MP2/6-31G**//HF/6-31G** approximations. All calculated structures are minima at the HF/6-31G** potential energy surface with the dioxo 7H tautomer (A1) being the global minimum. The second most stable tautomer, dioxo-9H (B1) is by 9 kcal/mol less stable. For the A1 B1 transition the calculated MP2 energy gap corresponds to the equilibrium constant of 2 × 10–7. Therefore, only the major tautomeric form A1 is predicted to be detectable in the gas phase. The 7H and 9H groups of tautomers are discussed separately. Within both groups, the dioxo form (A1-7H, B1-9H) is the most stable one and is succeeded by the 2-dihydroxy (A2, B2) form. However, while the energy difference between A1 and A2 is 10 kcal/mol, the energy difference between B1 a B2 is only 2 kcal/mol. The effect of polar environment was estimated by the SCRF method, using a spherical cavity, at the HF/6-31G** level. These calculations did not change the gas phase stability order of the tautomers. However, the energy difference between A1 and B1 decreased from 9 kcal/mol at the HF/6-31G** level to 4 kcal/mol at the SCRF HF/6-31G** level. 相似文献
85.
Summary The aquation kinetics ofcis-[Co(NH3)Br(en)2]2+ were studied in aqueous and mixed aqueous-nonaqueous solvents in the presence of KBr, KCl, LiCl, NaNO3 and NaClO4 as supporting electrolytes. It was found that the association between the complex ion and Cl–, Br– and NO
3
–
ions takes place. The association constants, KIP, were evaluated from kinetic measurements. The kinetic parameters in the studied media are related to the influence of the cosolvents on the solvation spheres of the reactants and activated complex. 相似文献
86.
Naki Çolak Yılmaz Yıldırır Mustafa Kavutcu Nilhan Nurlu 《Monatshefte für Chemie / Chemical Monthly》2007,138(12):1283-1287
Summary. Methotrexate (MTX) is a folate antagonist used in treatment of several chronic inflammatory and neoplastic conditions. In this study, new MTX-like compounds that may-be potential anticancer agents were synthesized and their structures were determined by IR, UV, GC-MS,
1H NMR, and 13C NMR spectra. Also, in this study, a series structurally related to MTX or folate analogous compounds were evaluated whether they have inhibitory properties on the dihydrofolate reductase activity
(DHFR). 相似文献
87.
Zusammenfassung Es werden zwei neue Wege zur herstellung des 4,4-Äthinylendiphenols beschrieben. Der erste beruht auf der Entmethylierung des Bis-(4-methoxyphenyl)acetylens, der zweite auf der Oxydation des 4,4-Dihydroxybenzildihydrazons nach derCurtiusschen Methode.
Two new syntheses of 4.4-ethynylene diphenol
Two new syntheses of 4.4-ethynylene diphenol are described: demethylation of bis-(4-methoxyphenyl)-acetylene, and oxidation of 4.4-dihydroxybenzildihydrazone according toCurtius.相似文献
88.
Zusammenfassung 1,3-Dimethyl-4,5-diaminouracil (DAL) hat sich als sehr empfindliches Reagens zum selektiven Nachweis von Co2+-Ionen im stark alkalischen Medium einer Phosphatpufferlösung (pH=11,20) erwiesen. Es wurden vier Additionsverbindungen von DAL mit den Zentralatomen Cd(II), Pd(II), Ni(II) und Co(II) im Verhältnis Me DAL=1 2 hergestellt. Spektrophotometrische Untersuchungen weisen darauf hin, daß bei pH 6 bis 7 eine Komplexverbindung im Verhältnis CoDAL=12 gebildet wird.
Summary 1,3-dimethyl-4,5-diaminouracil (DAL) has been found to be a very sensitive reagent for the selective detection of Co2+ ions in strong alkaline medium of a phosphate buffer solution (pH=11.20). Four addition compounds of DAL with the central atoms Cd(II), Pd(II), Ni(II) and Co(II) with the ratio MeDal=12 have been prepared. Spectrophotometric studies indicate that at pH=6–7, complex compound is produced with the ratio CoDAL=12.相似文献
89.
Rotation matrices were expressed in terms of Gaunt coefficients and complex spherical harmonics. The rotation matrices were calculated using two different ways. In the first, Gaunt coefficients and normalized complex spherical harmonics were directly calculated using binomial coefficients; in the second, Gaunt coefficients and complex spherical harmonics were recursively calculated. The methods were compared with respect to accuracy and computation time (CPU) for low and very high quantum numbers. 相似文献
90.