全文获取类型
收费全文 | 1632篇 |
免费 | 42篇 |
国内免费 | 2篇 |
专业分类
化学 | 1030篇 |
晶体学 | 17篇 |
力学 | 50篇 |
数学 | 143篇 |
物理学 | 436篇 |
出版年
2023年 | 13篇 |
2022年 | 24篇 |
2021年 | 29篇 |
2020年 | 30篇 |
2019年 | 35篇 |
2018年 | 25篇 |
2017年 | 26篇 |
2016年 | 47篇 |
2015年 | 41篇 |
2014年 | 38篇 |
2013年 | 125篇 |
2012年 | 83篇 |
2011年 | 110篇 |
2010年 | 76篇 |
2009年 | 63篇 |
2008年 | 86篇 |
2007年 | 72篇 |
2006年 | 87篇 |
2005年 | 55篇 |
2004年 | 44篇 |
2003年 | 57篇 |
2002年 | 48篇 |
2001年 | 36篇 |
2000年 | 15篇 |
1999年 | 21篇 |
1998年 | 13篇 |
1997年 | 11篇 |
1996年 | 16篇 |
1995年 | 18篇 |
1994年 | 19篇 |
1993年 | 22篇 |
1992年 | 17篇 |
1991年 | 16篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 8篇 |
1985年 | 10篇 |
1984年 | 17篇 |
1983年 | 16篇 |
1982年 | 18篇 |
1981年 | 16篇 |
1980年 | 18篇 |
1979年 | 11篇 |
1978年 | 10篇 |
1977年 | 15篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1973年 | 6篇 |
排序方式: 共有1676条查询结果,搜索用时 15 毫秒
41.
Pronoy K. Chatterjee Carl M. Conrad 《Journal of polymer science. Part A, Polymer chemistry》1966,4(3):459-474
Sakurada's equation and fundamental kinetic laws were applied to the heterogeneous cyanoethylation of cellulose, performed by reacting fiber with liquid acrylonitrile, with sodium hydroxide as the catalyst. The data fit Sakurada's equation better at higher temperatures; deviation occurs at the initial stage, and the rate of reaction falls abruptly at a later stage. The degree of substitution at which the abrupt rate change occurred decreased as the temperature increased from 31 to 60°C. and also as the crystallinity of the fiber decreased. Diluting the reagent with different solvents decreased the rate of reaction and changed its transition points, but did not change the essential nature of the reaction, each segment of which fits Sakurada's equation very well. A uniform distribution of the catalyst (sodium hydroxide) throughout the fiber was attempted, and then the reaction was studied at 50°C. Diffractograms of the samples provided further evidence that the position of the rate change is associated with the change of cellulose (I) crystalline structure. Approximate energy of activation has been calculated, from the specific rate constants, between 31 and 40°C. as 10.6 kcal. and between 45 and 50°C. as 16.7 kcal. At other temperatures the determination was handicapped, due to temperature dependence of the order of reaction. An empirical relation between the constants of Sakurada's equation and the reaction temperature has been sought and correlated with the Arrhenius equation. Energies of activation, determined from this relationship, have been found to be very close to the above values. The change of order of reaction with temperature suggests that the reaction is affected by diffusion and the mechanism is interpreted as a diffusion-controlled reaction where hydrogen bonds play a significant role in diffusion. 相似文献
42.
β-Cyclodextrin-polyurethane polymer as solid phase extraction material for the analysis of carcinogenic aromatic amines 总被引:1,自引:0,他引:1
β-Cyclodextrin-polyurethane (β-CDPU) polymer was synthesized by the reaction of β-cyclodextrin with hexamethylene diisocyanate in dry dimethylformamide and used as a sorbent for the solid phase extraction (SPE) of carcinogenic aromatic amines from water. The polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and particle size analysis. The separation and quantification was performed by Liquid chromatography with RP-C18 column and diode array detection using standard arylamines for quantification. When compared with commercially available sorbents, β-CDPU gave better recovery for the aromatic amines. From the variation of pH of the extractant from 4.0 to 8.5 recovery was highest at pH 8.5. The breakthrough volume has been ascertained to be 100 ml for 200 mg of the resin. The new SPE material offers better recovery and estimation of banned arylamines. 相似文献
43.
44.
Bhaskar Dhotare 《Tetrahedron letters》2005,46(17):3103-3105
(R)-2,3-Cyclohexylideneglyceraldehyde 1 has been used in a simple and efficient synthesis of (−)-muricatacin 10. The required chiron, syn-alkanetriol 2a was prepared by the reduction of a ketone 3 derived from 1. 相似文献
45.
A highly sensitive spectrophotometric method for the determination of nitrite in water and soil has been developed. The reaction of nitrite with acidified potassium iodide to liberate iodine which oxidizes leuco‐crystal violet (LCV) to form crystal violet having absorption maxima at 590 nm forms the bases of this method. In aqueous medium the system obeys Beer's law in the range of 0.1 to 1.0 μg per 25 mL (0.004–0.04 ppm), while in an extractive system the range is 0.025–0.25 μg in 100 mL (0.00025–0.0025 ppm). The molar absorptivity and Sandell's sensitivity were found to be 1.54 × 106 1 mol?1 cm?1 and 44 pg cm?2, respectively. 相似文献
46.
A guanine-rich PNA dodecamer having the sequence H-G4T4G4-Lys-NH2 (G-PNA) hybridizes with a DNA dodecamer of homologous sequence to form a four-stranded quadruplex (Datta, B.; Schmitt, C.; Armitage, B. A. J. Am. Chem. Soc. 2003, 125, 4111-4118). This report describes quadruplex formation by the PNA alone. UV melting curves and fluorescence resonance energy transfer experiments reveal formation of a multistranded structure stabilized by guanine tetrads. The ion dependency of these structures is analogous to that reported for DNA quadruplexes. Electrospray ionization mass spectrometry indicates that both dimeric and tetrameric quadruplexes are formed by G4-PNA, with the dimeric form being preferred. These results have implications for the use of G-rich PNA for homologous hybridization to G-rich targets in chromosomal DNA and suggest additional applications in assembling quadruplex structures within lipid bilayer environments. 相似文献
47.
Mukhopadhyay S Chatterjee PB Mandal D Mostafa G Caneschi A van Slageren J Weakley TJ Chaudhury M 《Inorganic chemistry》2004,43(11):3413-3420
Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds. 相似文献
48.
Trans‐1,2‐cyclohexanediol and trans‐2‐aminocycloxexanol are useful chiral auxiliaries. Simple chemical resolution procedures for these molecules are presented. 相似文献
49.
Vijaya Bhaskar Reddy Ambavaram Venugopal Nandigam Madhavi Vemula Gangadhara Reddy Kalluru Madhavi Gajulapalle 《Biomedical chromatography : BMC》2013,27(7):916-923
A sensitive and selective liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was developed and validated for simultaneous determination of urapidil and aripiprazole in human plasma. A simple liquid–liquid extraction with ethyl acetate was used for the sample preparation. Chromatographic separation was achieved on a Phenomenex C18 (4.6 × 50 mm, 5 µm) column with 0.1% formic acid–acetonitrile (10:90, v/v) as the mobile phase with flow rate of 0.6 mL/min. The quantitation of the target compounds was determined in a positive ion multiple reaction monitoring mode. Calibration plots were linear over the range of 2.0–2503.95 ng/mL for urapidil and 1.0–500.19 ng/mL for aripiprazole. The lower limit of quantitation for urapidil and aripiprazole was 2.0 and 1.0 ng/mL, respectively. Mean recovery was in the range of 69.94–75.62% for both analytes and internal standards. Intra‐day and inter‐day precisions of the assay at three concentrations were 2.56–5.89% with accuracy of 92.31–97.83% for urapidil, and 3.14–6.84% with accuracy of 91.38–94.42% for aripiprazole. The method was successfully applied to human pharmacokinetic study of urapidil and aripiprazole in healthy human male volunteers. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
50.
V. Padmavathi T. V. Ramana Reddy A. Balaiah K. Audisesha Reddy D. Bhaskar Reddy 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):1223-1235
Some new heterocyclic compounds containing selenadiazole, thiadiazole and diazaphosphole fused to cyclohexanones have been prepared and characterized by spectral data. 相似文献