全文获取类型
收费全文 | 1418篇 |
免费 | 81篇 |
国内免费 | 6篇 |
专业分类
化学 | 1154篇 |
晶体学 | 6篇 |
力学 | 21篇 |
数学 | 131篇 |
物理学 | 193篇 |
出版年
2023年 | 21篇 |
2022年 | 12篇 |
2021年 | 37篇 |
2020年 | 46篇 |
2019年 | 32篇 |
2018年 | 41篇 |
2017年 | 22篇 |
2016年 | 78篇 |
2015年 | 38篇 |
2014年 | 51篇 |
2013年 | 76篇 |
2012年 | 117篇 |
2011年 | 149篇 |
2010年 | 53篇 |
2009年 | 55篇 |
2008年 | 113篇 |
2007年 | 85篇 |
2006年 | 72篇 |
2005年 | 82篇 |
2004年 | 66篇 |
2003年 | 51篇 |
2002年 | 44篇 |
2001年 | 8篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 14篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1977年 | 5篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1971年 | 2篇 |
1968年 | 4篇 |
1960年 | 2篇 |
1957年 | 2篇 |
1935年 | 2篇 |
排序方式: 共有1505条查询结果,搜索用时 15 毫秒
21.
The introduction of quality standards for vegetable oil methyl esters is gaining in importance due to their increased use as diesel fuel substitutes and as technical products. Free and esterified sterols, the main constituents of the unsaponifiable matter in vegetable oils, are recovered in vegetable oil methyl esters and may influence the technical properties of vegetable oil methyl ester products. A rapid gas chromatographic method for the qualitative and quantitative determination of free and esterified sterols in vegetable oil methyl esters has therefore been developed. The concentration of the free sterols as well as their qualitative and quantitative composition and the concentration of the sterol esters have been determined in rape seed oil methyl ester samples by GC–FID. Prior to analysis, the free sterols were silylated with N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane; betulinol was used as an internal standard. Calibration was performed by analysis of standard solutions containing β-sitosterol, cholesteryl stearate, and betulinol. The reproducibility of the quantitative results has been evaluated by repeated injections of the same test solution and by repeated complete analysis of the same sample. 相似文献
22.
Thereza Christina Vessoni Penna Eb Chiarini Adalberto Pessoa Junior 《Applied biochemistry and biotechnology》2003,107(1-3):481-491
Transformed cells of Escherichia coli expressing recombinant green fluorescent protein (GFPuv) were subjected to two methods of extraction: (1) freezing/thawing/sonication
(FTS) cycles prior to the three-phase partitioning (TPP) method, or (2) directly to TPP extraction. The amount of GFPuv released
by the FTS plus TPP method varied: 374μg/mL (first cycle), 93–442 μg/mL (second cycle), 32–359 μg/mL (third cycle), 18–115
μg/mL (fourth cycle). The GFPuv yields by the second method (TPP only) were, 23–54 μg/mL for the first extract and 33–91 μg/mL
for the second. The FTS plus TPP method released similar amounts of GFPuv to that extracted by TPP; and provided a better
mixture elution through the hydrophobic interaction column: 13–63 μg/mL for FTS plus TPP methods, and 2.5–13 μg/mL for TPP.
The results showed that although selective permeation is a more laborious methodology, it was more efficient for obtaining
of GFPuv in relation to the direct extraction of the cells for TPP. 相似文献
23.
Hacker CA Anderson KA Richter LJ Richter CA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(3):882-889
Aliphatic alcohols and aldehydes were reacted with the Si(111)-H surface to form Si-O-C interfacial bonds from dilute solution by using ultraviolet light. The resulting monolayers were characterized by using transmission infrared spectroscopy, spectroscopic ellipsometry, and contact angle measurements. The effect of different solvents on monolayer quality is presented. The best monolayers were formed from CH(2)Cl(2). The optimized monolayers were thoroughly characterized to determine the film structure and monolayer stability. The UV-promoted, alcohol-functionalized, and aldehyde-functionalized monolayers are of comparable quality to those previously prepared by other means. Although both molecules are tethered through a Si-O-C bond, the film reactivity is distinctly different with the aldehyde films being more chemically resistant. The differences in chemical reactivity, vibrational spectra, hydrophobicity, and ellipsometric thickness between the alcohol and aldehyde monolayers are attributed to a difference in molecular coverage and monolayer formation. 相似文献
24.
25.
Tsamantakis C Masliyah J Yeung A Gentzis T 《Journal of colloid and interface science》2005,288(1):129-139
This study summarises the rheological behaviour of emulsion bitumen drops in the presence of aqueous solutions of de-ionised or process water (DIW or PW) containing montmorillonite clays (M) and/or calcium ions (Ca++). The presence of calcium ions and montmorillonite clays resulted in the plastic behaviour of bitumen drops. In a DIW+M+Ca++ system, increasing temperature and calcium ion concentration resulted in an increase in the number and degree of plastic bitumen drops. In the presence of considerable amounts of Ca++ ions and/or at higher experimental temperature, bitumen drops in a PW+M system exhibited no significant overall plasticity of their surfaces. Both calcium and sodium ions contained in process water compete with each other to occupy the montmorillonite clay surface. At the pH value of process water (pH congruent with8), increasing the temperature did not change the value of bitumen droplet zeta potential. Stability of bitumen-in-water emulsions at 22 degrees C showed that bitumen droplets coalesced upon contact in the DIW+M system. The addition of calcium ions (Ca++) led to the inhibition of coagulation and coalescence of bitumen droplets, which may indicate the formation of CaM aggregates at the bitumen-water interface. 相似文献
26.
The decomposition of η6-(2-lithiochlorobenzene)tricarbonylchromium(0) (I) was found to follow first order kinetics with kdec 5.1 x 10-3 min-1 at 0°C, the half life of I being 136 min at 0°C. While this dependence strongly suggests intermediacy of η6-(benzyne)tricarbonylchromium, trapping experiments were successful in only low yield. 相似文献
27.
Mild methods for controlled C- and N-alkylation of 3-benzyloxycarbonylpiperazine-2,5-diones are reported. The benzyloxylcarbonyl substituent can also serve as latent functionality for N-acyliminium ion formation and subsequent trapping enables installation of new carbon and/or heteroatom substituents. 相似文献
28.
Raska CS Parker CE Sunnarborg SW Pope RM Lee DC Glish GL Borchers CH 《Journal of the American Society for Mass Spectrometry》2003,14(10):1076-1085
A method has been developed for rapid and sensitive identification of epitope-containing peptides, based on direct MALDI-MS/MS analysis of epitope-containing peptides affinity bound to affinity beads. This technique provides sequence information of the epitope that allows unambiguous identification of the epitope either by database searching or de novo sequencing. With MALDI-MS, affinity beads with bound peptides can be placed directly on the MALDI target and analyzed. Coupling a MALDI source to an orthogonal injection quadrupole time-of-flight (QqTOF) mass spectrometer allows direct sequencing of the bound peptides. In contrast to ESI-MS/MS, elution of the affinity-bound peptides followed by additional concentration and purification steps is not required, thus reducing the potential for sample loss. Direct mass spectrometric sequencing of affinity-bound peptides eliminates the need for chemical or enzymatic sequencing. Other advantages of this direct MALDI-MS/MS analysis of epitope-containing peptides bound to the affinity beads include its sensitivity (femtomole levels) and speed. In addition, direct analysis of peptides on affinity beads does not adversely affect the high mass accuracy of a QqTOF, and database searching can be performed on the MS/MS spectra obtained. In proof-of-principle experiments, this method has been demonstrated on beads containing immobilized antibodies against phosphotyrosine, the c-myc epitope tag, as well as immobilized avidin. Furthermore, de novo sequencing of epitope-containing peptides is demonstrated. The first application of this method was with anti-FLAG-tag affinity beads, where direct MALDI MS/MS was used to determine an unexpected enzymatic cleavage site on a growth factor protein. 相似文献
29.
Wagner-Czauderna Elżbieta Boroń-Cegiełkowska Agata Orłowska Elżbieta Kalinowski Marek K. 《Transition Metal Chemistry》2004,29(1):61-65
The visible absorption spectra of CoCl2 in binary mixtures of acetone, dmf, dma and dmso with H2O show the existence of configuration equilibria between tetrahedral (T) and octahedral (O) species. Linear correlations between the values of log K (K = [O]/[T]) and the mole fraction of H2O,
w, have been observed in all the systems under study; their slopes decrease linearly with an increase of the donor number, DN, of the organic component of the mixture. The formation of octahedral species is enthalpy favoured but entropy disfavoured. It was found that both H and S values change linearly with
w and the slopes of these relationships depend clearly on the DN values. 相似文献
30.
Christina Moberg 《Journal of organometallic chemistry》1976,108(1):125-133
Reactions of trans-1-chloro-2-butene and of 3-chloro-1-butene with nickelocene give mixtures of (1-methyl-2-propenyl)-, (trans-2-butenyl)-, and (cis-2-butenyl)-cyclopentadienes. The reaction between π-crotyl-π-cyclopentadienylnickel and 5-chlorocyclopentadiene yields identical products. In the presence of tetrahcloromethane, 5-(trichloromethyl)cyclopentadiene is formed. Mechanisms involving oxidative addition and π-allylic nickel complexes are discussed. 相似文献