全文获取类型
收费全文 | 5132篇 |
免费 | 135篇 |
国内免费 | 7篇 |
专业分类
化学 | 3030篇 |
晶体学 | 128篇 |
力学 | 173篇 |
数学 | 403篇 |
物理学 | 1540篇 |
出版年
2023年 | 37篇 |
2022年 | 115篇 |
2021年 | 109篇 |
2020年 | 117篇 |
2019年 | 132篇 |
2018年 | 121篇 |
2017年 | 160篇 |
2016年 | 194篇 |
2015年 | 141篇 |
2014年 | 189篇 |
2013年 | 401篇 |
2012年 | 309篇 |
2011年 | 326篇 |
2010年 | 221篇 |
2009年 | 193篇 |
2008年 | 250篇 |
2007年 | 216篇 |
2006年 | 147篇 |
2005年 | 150篇 |
2004年 | 118篇 |
2003年 | 102篇 |
2002年 | 112篇 |
2001年 | 62篇 |
2000年 | 54篇 |
1999年 | 35篇 |
1998年 | 34篇 |
1997年 | 38篇 |
1996年 | 43篇 |
1995年 | 31篇 |
1994年 | 34篇 |
1993年 | 42篇 |
1992年 | 51篇 |
1991年 | 37篇 |
1990年 | 41篇 |
1989年 | 49篇 |
1988年 | 44篇 |
1987年 | 42篇 |
1986年 | 32篇 |
1985年 | 61篇 |
1984年 | 57篇 |
1983年 | 40篇 |
1982年 | 44篇 |
1981年 | 51篇 |
1980年 | 45篇 |
1979年 | 46篇 |
1978年 | 43篇 |
1977年 | 51篇 |
1976年 | 54篇 |
1975年 | 44篇 |
1974年 | 38篇 |
排序方式: 共有5274条查询结果,搜索用时 31 毫秒
81.
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
82.
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
83.
The unrestricted Hartree-Fock (UHF) method of Snyder and Amos is used to calculate, in the -electron approximation, the spin density distributions in radical anions of heterocyclic amine N-oxides. The computed spin densities are observed to be in good agreement with the experimental values. The computed spin density distribution of the radical anion of pyridine N-oxide is consistent with the greater susceptibility of pyridine N-oxide relative to pyridine to electrophilic nitration. Also, the calculations are consistent with the lower basicity of the N-oxides relative to the parent bases. 相似文献
84.
Sharma M Sahu K Dube A Gupta PK 《Journal of photochemistry and photobiology. B, Biology》2005,81(2):107-113
Effect of varying extracellular pH on mode of cell death induced by photodynamic action of chlorin p6 was investigated in human colon carcinoma (Colo-205) cells. At an extracellular pH of 7.4, compared to cells treated with chlorin p6 in dark, the photodynamically treated cells showed reduction in mitochondrial membrane potential, an increase in ADP/ATP ratio (1:2) and a large percentage of cells with chromatin condensation. In contrast, when photodynamic treatment and post irradiation incubation was carried out in acidic medium (pH 6.5), total loss of mitochondrial membrane potential, a marked increase in ADP/ATP ratio (1:33) and increased damage to plasma membrane were observed. Further, cells subjected to photodynamic treatment in a medium of pH 7.4 showed twofold increase in caspase-3 activity as compared to photodynamic treatment at pH 6.5. These results suggest that chlorin p6 mediated photodynamic action induces apoptotic cell death when extracellular pH is 7.4 whereas necrosis is more predominant under condition when extracellular pH is 6.5. 相似文献
85.
The structure of the abnormal product 1a formed in the Knoevenagel condensation of 2-carbethoxycyclohexanone and malononitrile has been further confirmed. Oxidation of the tetrahydroisoquinoline 3b using Na2Cr2O-AcOH-H2SO4 gave the keto isoquinoline 3d and the isoquinoline-1-carboxylic acid 5a. The acid chloride of 5a was condensed with diethyl ethoxymagnesiomalonate to afford after decarbethoxylation the methyl ketone 5d which on Baeyer-Villiger oxidation gave a mixture of the acetate 1g and the title compound 1b. The unambiguous synthesis of 1b confirms the structure assigned earlier to the title compound also formed during the partial hydrolysis of the diethoxy compound 1c. Condensation of 2-acetylcyclohexane-1,3-dione with malononitrile gave the quinoline derivative 4c which on ethylation yielded the ketoquinoline 4d. The present studies have confirmed that the quinoline compound 4a is also formed in the condensation of 2-acetylcyclohexanone and cyanoacetamide. 相似文献
86.
R. Singh R. M. Misra D. C. Gupta D. D. Shukla M. N. Sharma M. P. Madan 《Zeitschrift für Physik B Condensed Matter》1985,58(2):83-89
The parameterC
1=[(1/K
T
)/P]
T
, which describes the pressure variation of the compressibility, has been examined correlating the thermodynamical and interatomic potential approaches employing fewer approximations than has been usual heretofore. General expressions have been derived forC
1 by including the thermal correction terms, which have generally been ignored in previous studies concerning thermal properties of ionic crystals. The parameterC
1 has also been related to the Grüneisen parameter, , using a relation given earlier. The applicability of the derived equations is investigated and discussed for alkali halides employing few realistic potential forms. A good general accord is found with the available experimental data, which exhibits an essential improvement over other theoretical determinations. 相似文献
87.
1. Contrary to the observations of earlier workers, it has been shown that formic acid can be quantitatively oxidixed by ceric sulphate in the presence of concentrated sulphuric acid. 2. Tartaric, malonic, malic and glycolic acids can also be oxidized completely to carbon dioxide and water by the following general procedure : to a known amount of the organic acid is added ceric sulphate (excess) solution in dilute sulphuric acid and the mixed solution refluxed for ten to fifteen minutes. Concentrated sulphuric acid (double the volume of the reaction mixture) is then added taking care that formic acid is not lost during the addition, and the mixture again refluxed for 45 to 50 minutes. The excess ceric sulphate is determined by titrating against ferrous ammonium sulphate. 3. The complete oxidation of the above acids provides satisfactory methods for their quantitative estimation. 相似文献
88.
New PNA analogues derived from aminoethylpyrrolidin-5-one backbone show stabilization of aepone-PNA:DNA hybrids and destabilization of the corresponding RNA hybrids compared to unmodified PNA. 相似文献
89.
Misra AK Sharma SK Chio CH Lucey PG Lienert B 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(10):2281-2287
A remote Raman system has been developed utilizing a 532nm pulsed laser and gated intensified charged couple device (ICCD) detector in the oblique geometry. When the system is set for 50m sample distance it is capable of measuring Raman spectra of minerals located at distances in the range of 10-65m from the telescope. Both daytime and nighttime operations are feasible and the spectra of minerals can be measured in a short period of time, of the order of a few seconds. In oblique geometry, measured sampling depth is more than 30m, during which the system maintains very high performance without any adjustments. Much longer sampling depth (0.1-120m) has been observed when the system is configured in the coaxial geometry. Clear advantages of using a gated detection mode over the continuous (CW) mode of operation in reducing the background signal and eliminating long-lived fluorescence signals from the Raman spectra are presented. The performance of the pulsed Raman system is demonstrated by measuring spectra of Raman standards including benzene (C(6)H(6)) and naphthalene (C(10)H(8)), a low Raman cross section silicate mineral muscovite (KAl(2)(Si(3)Al)O(10)(OH)(2)), and a medium Raman cross section mineral calcite (CaCO(3)). 相似文献
90.
Molar excess volumes, VE, for pyridine (A) + α-picoline (B), + β-picoline (B) and + γ-picoline (B) and benzene (A) + toluene (B), + o-xylene (B) and + p-xylene (B) and carbon tetrachloride (A) + n-heptane (B) have been measured dilatometrically as a function of temperature and composition and have been utilized to study B—B and B—B—B interactions in the presence of A via the Mayer—McMillan approach. A model has also been presented to account for these B—B and B—B—B interactions. The VE data at 308.15 K have also been analysed in terms of the “graph theoretical” approach which describes the VE data well for all these mixtures at 308.15 K. The “graph theoretical” approach has further been extended to successfully evaluate VE data for a mixture at any temperature, T2, when the VE data at T1 are known. 相似文献