全文获取类型
收费全文 | 106193篇 |
免费 | 1580篇 |
国内免费 | 386篇 |
专业分类
化学 | 44229篇 |
晶体学 | 988篇 |
力学 | 7207篇 |
数学 | 35387篇 |
物理学 | 20348篇 |
出版年
2023年 | 257篇 |
2022年 | 171篇 |
2021年 | 344篇 |
2020年 | 528篇 |
2019年 | 471篇 |
2018年 | 10845篇 |
2017年 | 10656篇 |
2016年 | 7094篇 |
2015年 | 1764篇 |
2014年 | 1237篇 |
2013年 | 2298篇 |
2012年 | 5880篇 |
2011年 | 12546篇 |
2010年 | 6781篇 |
2009年 | 6937篇 |
2008年 | 8386篇 |
2007年 | 10494篇 |
2006年 | 1916篇 |
2005年 | 2800篇 |
2004年 | 2725篇 |
2003年 | 2890篇 |
2002年 | 1825篇 |
2001年 | 884篇 |
2000年 | 836篇 |
1999年 | 557篇 |
1998年 | 482篇 |
1997年 | 358篇 |
1996年 | 523篇 |
1995年 | 335篇 |
1994年 | 288篇 |
1993年 | 353篇 |
1992年 | 286篇 |
1991年 | 217篇 |
1990年 | 188篇 |
1989年 | 176篇 |
1988年 | 177篇 |
1987年 | 175篇 |
1986年 | 174篇 |
1985年 | 224篇 |
1984年 | 182篇 |
1983年 | 155篇 |
1982年 | 144篇 |
1981年 | 137篇 |
1980年 | 125篇 |
1979年 | 137篇 |
1978年 | 115篇 |
1977年 | 91篇 |
1976年 | 94篇 |
1975年 | 86篇 |
1973年 | 106篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
992.
M.P. Sánchez-Sánchez J.M. Salas-Peregrín M.A. Romero-Molina A. Mata-Arjona 《Thermochimica Acta》1985,88(2):355-361
The thermodynamic protonation constants of 4-amino-1,6-dihydro-2-methylthio-5-nitroso-6-oxo-pyrimidine (MTH), 4-amino-5-nitroso-6-oxo-1,2,3,6,-tetrahydro-2-thiopyrimidine (TANH) and 2-thioxanthine (TXH) in aqueous media at 25, 30, 40 and 50 ± 0.1°C, have been determined potentiometrically by Bjerrum and Robinson's methods. The ionic strength was maintained constant by using 0.1 M NaNO3 as the supporting electrolyte.The stability constants and thermodynamic functions for Zn(II) and Cd(II) complexes of MTH and TXH, at different ionic strengths and temperatures, have been calculated. 相似文献
993.
The rapid gas chromatographic detection and determination of ethylene glycol in biological fluids is described. Phenylboronic acid in acetone was used for the esterification of glycol. The phenylboronates of ethylene glycol and 1,2-propylene glycol are not separated on a packed column of medium polarity (OV-17), but they can be separated on a non-polar column (OV-101). In both instances, 1,3-propylene glycol can be used as an internal standard. The method requires only 100 microliters of serum or urine and is suitable for trace analysis in an emergency toxicological laboratory. The utility of the method is demonstrated on two cases of human intoxication with ethylene glycol. 相似文献
994.
Oleg V. Mikhailov Marina A. Kazymova Tatyana A. Shumilova Galina A. Chmutova Svetlana E. Solovieva 《Transition Metal Chemistry》2005,30(3):299-304
The complexing process proceeding in the NiII–thiocarbohydrazide (H2N–H–NC(=S)–NH–NH2)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of NiII with (N,N,S,S)-donor tetradentate ligands having NiL1, NiL2 and NiL3compositions where L1 is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L2 is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L3 is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur. 相似文献
995.
The influence of the buffering medium on the reaction of Hg(II) with Xylenol Orange has been studied. Amine-type compounds are complexed by Hg(II)/Xylenol Orange with a sharp hyperchromic effect on the reagent itself, at 590 nm, but complex formation of Hg(II)/Xylenol Orange in non-amine-type buffer, such as citric acid-phosphate, gives a hypochromic effect on Xylenol Orange at 580 nm. Hg(II) is determined at pH 7.5 in two ranges of concentration, 2-9 ppm in citrate buffer, measured at 580 nm ( = 2.50 x 10(4)), and 6-11 ppm in hexamine buffer, at 590 nm ( = 4.18 x 10(4)). 相似文献
996.
M. Galán López A. Martín Sánchez V. Gómez Escobar 《Journal of Radioanalytical and Nuclear Chemistry》2004,261(3):631-636
A procedure for the determination of 222Rn in environmental water samples using liquid scintillation counting (LSC) was applied. The extractive scintillator RADONSÒ and an ultra-low background 1220 QuantulusÔ were used. A minimum detectable activity of 0.1 Bq·l?1 in 20 ml was found with low-diffusion polyethylene vials and 200 minute measurement time. Quenching effects and possible interferences due to the existence of other radionuclides in the extraction process were studied. The procedure was controlled by gamma-ray spectrometry of the 222Rn daughters. Applications to environmental samples collected from spas, wells, and public springs in Extremadura (Spain) are presented. 相似文献
997.
Cuadros-Rodríguez L Almansa-López EM García-Campaña AM González-Casado A Egea-González FJ Garrido-Frenich A Martínez-Vidal JL 《Talanta》2005,66(4):1063-1072
The use of the recovery term has presented some confusion in Analytical Chemistry. Recent IUPAC recommendations propose to distinguish between two terms: recovery or recovery factor, ℜ, and apparent recovery, ℜ*. Apparent recovery includes recovery factor and a new recovery term proposed in this paper, named calibration recovery, ℜC, which depends of the type of systematic error due to the matrix effect (constant and/or proportional) and is related to the applied calibration methodology. This paper highlights the dependence of the calibration recovery on the sample analyte concentration and, for extension, of the apparent recovery, defines the recovery profile, and makes evident the need to determine a “fit for purpose” analyte concentration interval to comply with a regulated recovery requirements. An approach to estimate the calibration recovery and its associated uncertainty in relation to the above-mentioned dependence is presented. The usefulness of the proposed methodology has been shown in the quantification of a pesticide by GC-ECD for assessing dermal exposure. 相似文献
998.
Yuan Ruo Cao ShuRui Chai YaQin Gao FengXian Zhao Qing Tang MingYu Tong ZhongQiang Xie Yi 《中国科学B辑(英文版)》2007,50(5):620-628
Alternate adsorption of positively charged colloid-Au nanoparticles (nano-Au⊕) and negatively charged hemoglobin (Hb) on L-cysteine (L-cys) modified gold electrode resulted in the assembly of {Hb/nano-Au⊕}n layer-by-layer films/L-cys modified gold electrode. The nano-Au⊕ was characterized by transmission electron micrograph (TEM) and microelectrophoresis. The modified electrode interface morphology was characterized by electrochemical impedance spectroscopy (EIS), atomic force mi- croscopy (AFM), cyclic voltammograms (CV) and chronoamperometry. Direct electron transfer between hemoglobin and gold electrodes was studied, and the apparent Michaelis-Menten constant ( km app) of the modified electrode was evaluated to be 0.10 mmol·L?1. Moreover, the higher activity of proteins in the nano-Au⊕ films could be retained compared with the electropolymerization membrane, since the pro- teins in nano-Au⊕ films retained their near-native structure. Direct electron transfer between hemoglo- bin and electrode and electrochemically catalyzed reduction of hydrogen peroxide on a modified elec- trode was studied, and the linear range was from 2.1×10-8 to 1.2 ×10?3 mol·L-1 (r = 0.994) with a detection limit of 1.1×10-8 mol·L-1 H2O2. 相似文献
999.
Iannucci NB Navarro del Cañizo AA Cascone O 《Applied biochemistry and biotechnology》2003,104(3):173-183
Twenty triazinic dyes were assayed as ligands for the chromatographic affinity purification of a neutral protease from Flavourzyme™, a commercial preparation. Screening at pH 4.0 allowed the selection of eight dyes on the basis of their high protease adsorption.
When the pH was set to 5.0 in order to increase selectivity, only Yellow HE-4R, Red HE-3B, and Cibacron Blue F3G-A maintained
protease adsorption at high values. Neither maximum capacities nor dissociation constants calculated from isotherms measured
at 8 and 25°C showed great differences. By contrast, a strong temperature effect was evidenced in the elution step: elution
at 8°C allowed 70, 81, and 98% recovery of adsorbed protease with Yellow HE-4R, Red HE-3B, and Cibacron Blue F3G-A, respectively,
whereas only 20% recovery was attained at 25°C. Based on the results obtained, a purification process for the neutral protease
contained in Flavourzyme with Cibacron Blue F3G-A as the affinity ligand was developed, yielding 96% of electrophoretically
pure enzyme in a single step, the specific activity rising from 850 to 3650 U/mg. 相似文献
1000.
Complexes of TiCl4, VCl4 and SnX4 (X = Cl or Br) with Schiff bases derived from 2-aminobenzimidazole
Agueda Arquero Pilar Souza José A. García-Vázquez José R. Masaguer 《Transition Metal Chemistry》1985,10(11):424-426
Summary The reactions of anhydrous titanium(IV), tin(IV) and vanadium(IV) halides with Schiff bases derived from 2-aminobenzimidazole and 4-methylbenzaldehyde (abimbz) and salicylaldehyde (abisal), yield hexacoordinated complexes M(abimbz)Cl4 and M(abisal)2X4 (M = Ti, Sn or V; X = Cl or Br).The compounds have been characterized by elemental analyses, magnetic measurements, e.p.r., electronic and i.r. spectral studies. I.r. spectra suggest that the Schiff base (abimbz) is coordinated as a bidentate ligand with the metal ion and the (abisal) base acts as a monodentate ligand. 相似文献