全文获取类型
收费全文 | 6092篇 |
免费 | 159篇 |
国内免费 | 11篇 |
专业分类
化学 | 3770篇 |
晶体学 | 117篇 |
力学 | 190篇 |
数学 | 423篇 |
物理学 | 1762篇 |
出版年
2023年 | 37篇 |
2022年 | 81篇 |
2021年 | 129篇 |
2020年 | 135篇 |
2019年 | 152篇 |
2018年 | 154篇 |
2017年 | 194篇 |
2016年 | 237篇 |
2015年 | 163篇 |
2014年 | 224篇 |
2013年 | 491篇 |
2012年 | 378篇 |
2011年 | 391篇 |
2010年 | 268篇 |
2009年 | 247篇 |
2008年 | 317篇 |
2007年 | 276篇 |
2006年 | 192篇 |
2005年 | 191篇 |
2004年 | 151篇 |
2003年 | 126篇 |
2002年 | 131篇 |
2001年 | 69篇 |
2000年 | 59篇 |
1999年 | 43篇 |
1998年 | 35篇 |
1997年 | 44篇 |
1996年 | 50篇 |
1995年 | 34篇 |
1994年 | 43篇 |
1993年 | 52篇 |
1992年 | 57篇 |
1991年 | 42篇 |
1990年 | 45篇 |
1989年 | 56篇 |
1988年 | 50篇 |
1987年 | 50篇 |
1986年 | 37篇 |
1985年 | 74篇 |
1984年 | 62篇 |
1983年 | 44篇 |
1982年 | 54篇 |
1981年 | 60篇 |
1980年 | 52篇 |
1979年 | 58篇 |
1978年 | 47篇 |
1977年 | 56篇 |
1976年 | 56篇 |
1975年 | 47篇 |
1974年 | 45篇 |
排序方式: 共有6262条查询结果,搜索用时 135 毫秒
91.
A fibre-optic sensor for continuous measurement of sulphur dioxide is described. It is based on the dynamic quenching of the fluorescence of a polynuclear aromatic hydrocarbon [benzo(b)fluoranthene] which is immobilized in silicone polymer. Sulphur dioxide is shown to be an efficient quencher; Stern-Volmer graphs are given which describe the relation between SO2 concentration and relative fluorescence. Detection limits are about 0.01% (v/v) SO2 in air; the useful range is from 0.01–6% (v/v). Other gases likely to occur in air were found to be inert, except for oxygen which also acts as a dynamic quencher. Its interference is negligible for SO2 levels below 6% in air at constant oxygen pressure, because the quenching efficiency of SO2 is about 26 times higher than that of oxygen. For varying oxygen levels, a two-sensor technique is suggested. 相似文献
92.
Cabeza A Ouyang X Sharma CV Aranda MA Bruque S Clearfield A 《Inorganic chemistry》2002,41(9):2325-2333
Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation. 相似文献
93.
94.
95.
96.
97.
Junquera E Laynez J Menéndez M Sharma S Penadés S 《The Journal of organic chemistry》1996,61(20):6790-6798
Thermodynamic studies of the binding of a series of p-nitrophenyl glycosides (PNPGly) of varying stereochemistry to alpha-cyclodextrin (alpha-CD) were performed at three different temperatures (25, 35, and 42 degrees C) using a microcalorimetric technique. The system p-nitrophenol (PNP) at pH = 3 and alpha-CD was also studied for the sake of comparison. All these complexes were found to be enthalpy driven with a favorable enthalpic term clearly dominant over an unfavorable entropic term. A clear enthalpy-entropy compensation effect was observed at all the temperatures, with a slope close to unity (alpha = 1.02) and an intercept TDeltaS degrees (o) = 2.91 kcal mol(-)(1). This thermodynamic pattern is in agreement with those usually found for lectin-carbohydrate associations and for the binding processes of several host-guest systems. This pattern is explained in terms of the contribution of primarily two driving forces: the van der Waals interactions between the host and the guest, and the solvation/desolvation processes which accompany the association reaction. The presence of the carbohydrate molecule in the PNP ring causes a slight destabilization of the complex at 25 degrees C with respect to the alpha-CD-PNP (pH = 3) complex, although a different behavior has been observed depending on the axial/equatorial configuration of the glycoside and the temperature. This behavior is modulated by the stereochemistry of the glycoside. Differences were observed between the deoxy-derivatives (LAra and LFuc) and those derivatives with a hydroxymethyl group (Glc, Gal, Man). DeltaC(p) degrees values were obtained from the dependency of DeltaH degrees on temperature (=( partial differentialDeltaH degrees / partial differentialT)(p)). These values are small and negative except for alphaMan complex. For the latter complex, discrepancy between the calorimetric and the calculated van't Hoff enthalpies was observed. Parallels are drawn between the thermodynamics of our model and those proposed for carbohydrate-protein associations. 相似文献
98.
Arun K. Sinha Vinod Kumar Abhishek Sharma Anuj Sharma Rakesh Kumar 《Tetrahedron》2007,63(45):11070-11077
A mild and convenient one-pot two-step synthesis of hydroxystilbenes with trans selectivity has been developed through a modified Perkin reaction between benzaldehydes and phenylacetic acids bearing 4- or 2-hydroxy substitution at the aromatic ring, in the presence of piperidine-methylimidazole and polyethylene glycol under microwave irradiation. The observation of a simultaneous condensation-decarboxylation leading to the unusual formation of hydroxystilbenes in lieu of α-phenylcinnamic acid reveals an interesting facet to the classical Perkin reaction. The developed protocol provides a green alternative to the prevalent methods employing a toxic decarboxylating agent in the form of quinoline/Cu salt, and the requirement for harsh protection-deprotection steps for the synthesis of hydroxylated stilbenes. 相似文献
99.
Validation of LC/MS electrospray ionisation method for the estimation of ursodiol in human plasma and its application in bioequivalence study 总被引:1,自引:0,他引:1
Sundd Singh S Shah H Gupta S Jain M Sharma K Patel H Shah B Thakkar P Patel N Shah R Bhushan Lohary B 《Annali di chimica》2004,94(12):951-959
A novel High Performance Liquid Chromatography-electrospray mass spectrometric method has been developed for the estimation of Ursodiol (Ursodeoxycholic acid)--a bile acid, in human plasma using Ornidazole as internal standard. The methodology involved solid phase extraction of the analyte from human plasma matrix. The chromatographic separation was achieved within seven minutes by an isocratic mobile phase containing 1.0 mM ammonium acetate and Acetonitrile (65:35, v/v), flowing through XTerra MS C18, 100 x 2.1, 3.5 microm analytical column, at a flow rate of 0.2 ml/min. Ion signals were measured in negative mode for Ursodiol and internal standard at m/z 391.3 and 278.1, respectively. A detailed validation of the method was performed as per USFDA guidelines and the standard curves were found to be linear in the range 50.0 ng/ml to 3000.0 ng/ml with the mean correlation coefficient more than 0.99. The absolute recovery was more than 54.90% for Ursodiol and 76.51% for internal standard. Ursodiol was stable for sixty-nine days at -70 degrees C and for eight hours at ambient temperature. After extraction from plasma, the reconstituted samples of Ursodiol were stable in autosampler at 10 degrees C for forty-eight hours. Upon subjecting to three freeze thaw cycles, there was no change in the recovery of the analyte. The integrity of the plasma samples remained unaffected even upon four-fold dilution with drug free human plasma. The method was simple, specific, sensitive, precise, accurate and suitable for bioequivalence and pharmacokinetic studies. It was successfully applied to the pilot bioequivalence study of Ursodiol in male human subjects. 相似文献
100.
Hiremath Siddalingaiah A. Dodamani Ashok F. Naik Sunil G. 《Transition Metal Chemistry》2002,27(1):47-51
The title complex was prepared and characterized by elemental and spectral analyses. The formation constants of various heterocyclic nitrogen base adducts with the NiII–di(2,4-dibromophenyl)carbazonate have been determined in a monophase by spectrophotometry at 25 ± 0.1 °C. The monodenatate and bidentate bases form penta- and hexa-coordinated adducts respectively with 1:1 stoichiometry for the metal chelate-base, whereas the unsaturated monodentate bases form hexa-coordinated adducts with 1:2 stoichiometry. The behaviour of saturated heterocyclic bases such as pyrrolidine, piperidine, hexamethyleneimine and morpholine towards the metal chelate has been studied, and the results are discussed in terms of steric hindrance, basicity and ring structure. 相似文献