全文获取类型
收费全文 | 2294篇 |
免费 | 147篇 |
国内免费 | 184篇 |
专业分类
化学 | 1165篇 |
晶体学 | 6篇 |
力学 | 157篇 |
综合类 | 43篇 |
数学 | 848篇 |
物理学 | 406篇 |
出版年
2024年 | 3篇 |
2023年 | 12篇 |
2022年 | 24篇 |
2021年 | 45篇 |
2020年 | 45篇 |
2019年 | 49篇 |
2018年 | 52篇 |
2017年 | 57篇 |
2016年 | 64篇 |
2015年 | 46篇 |
2014年 | 129篇 |
2013年 | 194篇 |
2012年 | 107篇 |
2011年 | 102篇 |
2010年 | 84篇 |
2009年 | 114篇 |
2008年 | 134篇 |
2007年 | 115篇 |
2006年 | 125篇 |
2005年 | 141篇 |
2004年 | 103篇 |
2003年 | 106篇 |
2002年 | 109篇 |
2001年 | 82篇 |
2000年 | 64篇 |
1999年 | 68篇 |
1998年 | 63篇 |
1997年 | 42篇 |
1996年 | 48篇 |
1995年 | 35篇 |
1994年 | 38篇 |
1993年 | 30篇 |
1992年 | 34篇 |
1991年 | 21篇 |
1990年 | 22篇 |
1989年 | 18篇 |
1988年 | 18篇 |
1987年 | 11篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 10篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1973年 | 1篇 |
排序方式: 共有2625条查询结果,搜索用时 62 毫秒
101.
A.?R.?MustafinaEmail author L.?S.?Kuznetsova A.?S.?Michailov V.?E.?Kataev A.?I.?Konovalov W.?D.?Habicher 《Journal of solution chemistry》2004,33(10):1257-1276
The complexation of a macrocycle containing thiopyrimidine and uracil moieties (M) with amino acids and some dicarboxylic acids was studied by pH-metric, UV-VIS, 1H NMR spectroscopy methods in chloroform, methanol, aqueous 1,4-dioxane, and biphasic water–chloroform media. The complexation of M with acids is too weak to solubilize them from the solid state into chloroform solutions containing M. The 1H NMR spectra and pH-metric data of aqueous 1,4-dioxane (80 vol.%) reveal the pH-dependent 1:1 binding between M and the acids studied. The protonation of M is not a prerequisite for binding of fumaric, succinic, o-phtalic acids and the series of amino acids, whereas binding of maleic acid requires the protonation of both thiopyrimidine moieties of M. Therefore,M·(H+)2 exhibits strong selectivity towards maleic acid in aqueous 1,4-dioxane and in biphasic water–chloroform media. 相似文献
102.
S. Yordanova S. Miloshev I. Berlinova B. Diakovski 《Journal of inclusion phenomena and macrocyclic chemistry》2006,56(3-4):337-344
A novel two-step method was developed to prepare individual p-isopropenylcalix[n]arenes [n=4, 6, 8]. In the first step, linear phenolic oligomers were prepared in a basic medium from p-isopropenylphenol and paraformaldehyde. The second step, cyclization of the linear oligomers was carried out at higher temperatures.
Ethylene glycol was used as medium, and sodium tetraborate-decahydrate as the catalyst. O-Acetylated derivatives were obtained
by acetylation of the phenolic hydroxyl groups of p-isopropenylcalix[n]arenes [n=4, 6, 8]. The p-isopropenyl-calix[n]arenes and their acetylated derivatives were characterized by IR, 1H NMR and UV spectroscopy, and elemental analysis. Their ability to extract metal cations from aqueous solutions was evaluated
via metal picrate extraction experiments. A parallel investigation of the cation-binding ability of the p-tert-butylcalix[n]arenes [n=4, 6, 8] and their acetylated derivatives was also performed. The p-isopropenylcalix[6]arene hexaacetate is the most effective extracting agent for metal picrates, and shows strong affinity
towards Rb cation. 相似文献
103.
On-column complexation of Fe2+ and Fe3+ with 2,6-pyridinedicarboxylic acid (2,6-PDCA) formed anionic complexes, which were then separated by capillary zone electrophoresis with direct UV detection at 214 nm. To achieve reasonable separation selectivity and on-column complexation, the conditions such as pH, the concentration of 2,6-PCDA and the EOF modifiers in the electrolyte were examined. The electrolyte contained 5.0 mM 2,6-PDCA, 0.25 mM tetradecyltrimethlammonium bromide (TTAB) and 5% (v/v) acetonitrile at pH 4.0 was optimised for on-column complexation and the separation of Fe[PCDA]2(2-) and Fe[PCDA]2(-). To enhance the detection sensitivity, large-volume sample stacking (LVSS) was used for the on-line preconcentration of Fe[PCDA]2(2-) and Fe[PCDA]2(-). Under the optimised conditions, satisfactory working ranges (0.5-50 microM), lower detection limits (less than 0.1 microM) and good repeatability of the peak areas (R.S.D.: 5.2-7.8%, n = 5) was achieved using LVSS (300 s). With LVSS, the detection sensitivity was enhanced more than 50-fold compared to conventional hydrodynamic injection. The proposed method was used successfully for the determination of Fe2+ and Fe3+ in water samples. 相似文献
104.
The regions of variation of density, enthalpy of formation, and detonation velocity of all of the formally possible structual isomers were determined for several molecular formulas of C,H,N,O-containing explosives. The histograms of the distribution of the structual isomers over these parameters were constructed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 859–862, May, 1995.The authors are grateful to Mrs. I. D. Solodukhina for the design of the graphical material.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 94-03-09323). 相似文献
105.
Dao-Dao Zhang Yao-Jun Sun Li-Shan Zhao Yong-Ming Huang 《Journal of inclusion phenomena and macrocyclic chemistry》1992,14(2):113-118
Inclusion complexes of 7,7-dibromonorcarane (1) and 7,7-dichloronorcarane (2) with 2,6-dimethyl--cyclodextrin (DMCD) have been synthesized. Their structures have been studied by chemical analysis, thermal behavior, IR spectra, UV absorptions and13C NMR spectra in DMSO solutions. The studies show that the orientation of (1) is different from that of (2) in the DMCD cavity.Presented at the 6th International Symposium on Molecular Recognition and Inclusion, Berlin, Germany, 10–14 September 1990. 相似文献
106.
I. A. Tikhonova F. M. Dolgushin K. I. Tugashov P. V. Petrovskii M. Yu. Antipin V. B. Shur 《Russian Chemical Bulletin》2004,53(12):2871-2873
The first double-decker sandwich complex of a sandwich was synthesized and fully characterized. The complex was prepared by the reaction of cyclic trimeric perfluoro-o-phenylene-mercury (o-C6F4Hg)3 (1) with ferrocene in an ethereal solution at 20 °C and has the composition {[(o-C6F4Hg)3]2(Cp2Fe)} (2). The ferrocene sandwich in 2 is located between the planes of two mercury-containing macrocycles and is coordinated to each of them through donation of the -electrons of the 5-Cp ligands to vacant orbitals of the mercury atoms of the adjacent molecule 1. It was concluded that all carbon atoms of the 5-Cp rings in complex 2 are involved in the bonding to the macrocycles. Complexation with 1 leads to considerable shifts of the (C-H) and (C-H) bands of ferrocene in the IR spectrum to high frequencies. The structure of complex 2 was determined by X-ray diffraction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2754–2756, December, 2004. 相似文献
107.
Mahmoud M. Al Omari Mohammad B. Zughul J. Eric D. Davies Adnan A. Badwan 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):159-164
Ternary complexes exploiting solubility synergism (SSn) between basic drugs and β-cyclodextrin (β-CD) in the presence of an organic hydoxy acid have been reported to provide the pharmaceutical technology with highly soluble ternary complexes, even with the least soluble β-CD. In this work, phase solubility techniques were used to study factors affecting SSn in aqueous solution, which may help in understanding the mechanism involved in ternary complex formation in solution, under equilibrium conditions. The equilibrium solubility of both β-CD and each of 8 structurally unrelated drugs were measured in tandem in the presence of different acid types at low and high pHs, and at different time intervals over a period of 1–40 days. The results indicate that SSn is evident regardless of acid type (organic and inorganic) at low pH, but the extent of SSn is acid type dependant and is limited by the drug salt solubility product constant (pK
sp). Among different drugs, no apparent trend exists between drug salt solubility and the extent of SSn, but lowering drug salt solubility by increasing pH depresses SSn. The results also reveal no apparent trend between the magnitude of the complex formation constant (K
ij) and SSn. For example, drugs of low K
ij values such as astemizole, cisapride and sildenafil do not show any SSn, yet ketotifen and pizotifen, which also have low K
ij values, exhibit substantial SSn. However, the solublizing power of β-CD represented by the slope of phase solubility diagram can be used as a marker for SSn (slopes exceeding 0.4 induce SSn). 相似文献
108.
Crystalline [Y(OH2)3(NCMe)(benzo-15-crown-5)][ClO4]3·benzo-15-crown-5-CH3CN can be obtained by slowly cooling a reaction mixture of Y(ClO4)3·n H2O with benzo-15-crown-5 in a solution of acetonitrile and methanol (3 : 1) from 60°C to room temperature. The crystal structure of this complex has been determined at –150 and 20°C. The complex is triclinic,P
. At –150°C the cell parameters area = 11.986(4),b = 12.071(7),c = 16.364(5) Å, = 93.56(3), = 98.68(3), = 109.68(4)°, vol = 2187 Å3, andD
calc = 1.61 g cm–3 forZ = 2 formula units. 3633 independently observed [F
o 5(F
o)] reflections were used in the final least-squares refinement leading to an agreement index ofR = 0.048. The Y(III) ion coordination geometry approximates a tricapped trigonal prism with three water molecules and three benzo-15-crown-5 oxygen atoms forming the prism, with the two remaining benzo-15-crown-5 oxygen atoms and the acetonitrile molecule completing the coordination as capping atoms. The three water molecules hydrogen bond a second crown ether molecule and two of the perchlorate anions. The two acetonitrile molecules have contacts with perchlorate oxygen atoms close enough for some weak interaction. One perchlorate is ordered, one is partially disordered as is the coordinated solvent molecule, and the third anion is totally disordered. The two unique crown ether molecules have distinctively different conformations.For Part 20, see reference [1]. 相似文献
109.
Leonid M. Goldenberg Nikolai N Denisov Jan F. Biernat 《Journal of inclusion phenomena and macrocyclic chemistry》2000,38(1-4):171-186
The complexation of 13- and 16-memberedazo- and azoxycrowns with metal cations of similarionic diameter (Na+ and Ca2+; and K+,Ba2+, Ag+ and Pb2+) was studied byuv/visible spectroscopic titration in acetonitrile andMeOH. In MeOH the 13-membered azo- and azoxycrowns 1 and 2 are weakly and non-selectively bound tohard cations of similar ionic diameter, but differentcharge (Na+ and Ca2+). At the same time thebinding to the soft cation Ag+ of larger sizethan the macrocycle cavity is considerably stronger.In contrast to solutions in acetonitrile no bindingwith the small Li+ cation was found.The 16-membered azocrowns 3 and 4 alsodiscriminate silver cation in MeOH withlog K = 3.65 ± 0.1 for both compounds.Unexpectedly low bindingwith the hard barium divalent cation of similar size(log K = 1.55 ± 0.4 and 1.95 ± 0.2, respectively)was found for these compounds. Similarly to13-membered compounds no binding with the smallLi+ cation was detected. A reverse order ofselectivity was observed for these crowns inacetonitrile with binding constant for association of3 with Ba2+ (log K 5.3) considerablyhigher than for other cations. The previously observedstrong binding with the smaller Li+ and Na+cations is confirmed. 相似文献
110.
In an attempt to generate antibodies for the development of an immunoanalysis method for potassium and caesium ions, new 1,3-alternate calix[4]arenes-crown-5 and -6 bearing either carboxylic or hydroxyl functions were synthesized in good yields. Their complexation properties towards potassium and caesium ions were investigated using 1H NMR spectroscopy and the usual properties proved to be preserved in the presence of the anchoring arms. 相似文献