全文获取类型
收费全文 | 1621篇 |
免费 | 99篇 |
国内免费 | 6篇 |
专业分类
化学 | 1259篇 |
晶体学 | 6篇 |
力学 | 17篇 |
数学 | 233篇 |
物理学 | 211篇 |
出版年
2023年 | 23篇 |
2022年 | 14篇 |
2021年 | 38篇 |
2020年 | 50篇 |
2019年 | 31篇 |
2018年 | 41篇 |
2017年 | 23篇 |
2016年 | 93篇 |
2015年 | 47篇 |
2014年 | 62篇 |
2013年 | 100篇 |
2012年 | 132篇 |
2011年 | 170篇 |
2010年 | 62篇 |
2009年 | 64篇 |
2008年 | 111篇 |
2007年 | 79篇 |
2006年 | 77篇 |
2005年 | 87篇 |
2004年 | 69篇 |
2003年 | 55篇 |
2002年 | 47篇 |
2001年 | 11篇 |
2000年 | 9篇 |
1999年 | 12篇 |
1998年 | 19篇 |
1997年 | 13篇 |
1996年 | 22篇 |
1995年 | 16篇 |
1994年 | 12篇 |
1993年 | 13篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1986年 | 9篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1982年 | 13篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 9篇 |
1976年 | 6篇 |
1968年 | 4篇 |
1957年 | 2篇 |
1935年 | 2篇 |
排序方式: 共有1726条查询结果,搜索用时 109 毫秒
21.
Thiele CM 《The Journal of organic chemistry》2004,69(22):7403-7413
The concept of using residual dipolar couplings (RDCs) for the structure determination of organic molecules is applied to the simultaneous assignment of all diastereotopic protons in strychnine. To use this important NMR parameter the molecule has to be aligned in the magnetic field. Here we present a new alignment medium for organic substrates. The optimization of the alignment properties of mixtures of poly-gamma-ethyl-L-glutamate (PELG) and CDCl(3) are described and the alignment properties of PELG at different concentrations are evaluated. A comparison of PELG with poly-gamma-benzyl-L-glutamate (PBLG) shows considerable differences in the magnitude of alignment for strychnine in the two alignment media. PELG induces a lower degree of order and makes the measurement of residual dipolar couplings (RDCs) in strychnine possible. All one-bond C-H RDCs of strychnine in PELG were determined by using 2D heteronuclear single quantum coherence (HSQC) spectroscopy. The strategy for the extraction of RDCs for methylene groups is described in detail. The RDCs and order parameters are used to assign pairs of diastereotopic protons. This methodology can distinguish not only one pair of diastereotopic protons but it can be used to assign all pairs of diastereotopic protons simultaneously. Two different calculation approaches to achieve this task are described in detail. 相似文献
22.
Vasse JL Stranne R Zalubovskis R Gayet C Moberg C 《The Journal of organic chemistry》2003,68(8):3258-3270
Chiral P,N-ligands with pseudo-C2 and pseudo-Cs symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C2-symmetric ligands based on the binaphthyl skeleton than with the analogous C2-symmetric P,P- and N,N-analogues. Pseudo-C2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands. 相似文献
23.
Thereza Christina Vessoni Penna Marina Ishii Adalberto Pessoa Junior Laura de Oliveira Nascimento Luciana Cambricoli de Souza Olivia Cholewa 《Applied biochemistry and biotechnology》2004,114(1-3):453-468
To determine the influence of various culture conditions, transformed cells of Escherichia coli expressing recombinant green fluorescent protein (GFPuv) were grown in nine cultures with four variable conditions (storage
of inoculated broth at 4°C prior to incubation, agitation speed, isopropyl-β-d-thiogalactopyranoside [IPTG] concentration, and induction time). The pelleted cells were resuspended in extraction buffer
and subjected to the three-phase partitioning (TPP) extraction method. To determine the most appropriate purification resin,
protein extracts were eluted through one of four types of HiTrap hydrophobic interaction chromatography (HIC) columns prepacked
with methyl, butyl, octyl, or phenyl resins and analyzed further on a 12% sodium dodecylsulfatepolyacrylamidegel. With Coomassie
staining, a single band between 27 (standard GFPuv) and 29 kDa (molecular weight standard) was visualized for every HIC column
sample. TPP extraction with HIC elution provided about 90% of the GFPuv recovered and eight-fold GFPuv enrichment related
to the specific mass. Rotary speed and IPTG concentration showed, respectively, greater negative and positive influences on
GFPuv expression at the beginning of the logarithmic phase for the set culture conditions (37°C, 24-h incubation). 相似文献
24.
A method for semi-automatic background estimation in energy-dispersive x-ray fluorescence spectra is outlined. Two cubic splines were investigated and the spline called the Butland interpolant was chosen for further investigation. Prior to the calculation of the spline, peak regions are set up, and suitable knots are defined outside the peak regions. To set up the peak regions, an automatic peak-search routine and a calibration equation are used. For a given peak, the latter relates the full width at half maximum (FWHM) to the peak centre. In turn, the size of the peak regions are defined by the FWHM multiplied by a constant given by the user. The method was tested on several types of spectra. It was found that the optimal size of the peak region decreased with increasing peak density. Reproducibility tests showed that the standard deviation of the summation of counts within a peak region and after background subtraction was less than would be expected from the counting statistics. 相似文献
25.
A dimethylsiloxane diluted polysiloxane side chain co-polymer with non-chiral banana-shaped mesogenic units shows an optically isotropic ferroelectric switching polar smectic C phase (SmCPF) consisting of a conglomerate of homogeneously chiral domains with opposite handedness. 相似文献
26.
The infrared spectra of maleimide as a vapour (160°C), melt (100°C), oriented polycrystalline film, pellet and when dissolved in various solvents were recorded between 4000 and 400 cm?1. Also certain spectra in the far infrared region 400-40 cm?1 were obtained. Raman spectra of the crystalline solid, melt and as a saturated solution in acetonitrile were recorded and semiquantitative polarization measurements carried out. For N-D maleimide infrared and Raman spectra of the solid compound were recorded.The fundamental frequencies have been assigned in terms of C2v, symmetry on the basis of infrared vapour contours and dichroism of the oriented film as well as on Raman polarization data. A force field was derived for maleimide, by initially transferring force constants from maleic anhydride and subsequent refinement of the force constants. The agreement between observed and calculated frequencies for the in-plane modes was satisfactory whereas certain large discrepancies remained for the out-of-plane vibrations. 相似文献
27.
Metabolic profiling of normal and hypertensive rat kidney tissues by hrMAS-NMR spectroscopy 总被引:5,自引:0,他引:5
Intact kidney tissue samples of normal and spontaneously hypertensive rats (SHRs) were analyzed by hrMAS-NMR spectroscopy and principal component analysis (PCA). Radial components (cortex, outer stripe of the outer medulla, inner stripe of the outer medulla, and papilla) were sampled from various regions across the kidney from multiple animals in order to establish inter- and intra-animal variability. The effects of temperature were also measured. Papilla was differentiated from the other tissue types, and this variation by tissue type was greater than the effect of temperature on the samples (spectra were compared from samples at 2 and 30 °C). This study also revealed long term stability issues of tissue storage at -80 °C. The PCA showed that the greatest differentiation between normal rats and SHRs was found in the cortex and the regions in the NMR spectra that were correlated with this variation were identified.Abbreviations hrMAS High-resolution magic angle spinning - NMR Nuclear magnetic resonance - PCA Principal component analysis - CSA Chemical shift anisotropy - DD Dipolar coupling - SHR Spontaneously hypertensive rat 相似文献
28.
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
29.
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
30.
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