全文获取类型
收费全文 | 1206篇 |
免费 | 28篇 |
国内免费 | 10篇 |
专业分类
化学 | 857篇 |
晶体学 | 17篇 |
力学 | 18篇 |
数学 | 83篇 |
物理学 | 269篇 |
出版年
2023年 | 6篇 |
2022年 | 7篇 |
2021年 | 8篇 |
2020年 | 11篇 |
2019年 | 23篇 |
2018年 | 18篇 |
2017年 | 11篇 |
2016年 | 14篇 |
2015年 | 21篇 |
2014年 | 29篇 |
2013年 | 79篇 |
2012年 | 60篇 |
2011年 | 69篇 |
2010年 | 37篇 |
2009年 | 35篇 |
2008年 | 103篇 |
2007年 | 86篇 |
2006年 | 62篇 |
2005年 | 70篇 |
2004年 | 51篇 |
2003年 | 48篇 |
2002年 | 52篇 |
2001年 | 19篇 |
2000年 | 19篇 |
1999年 | 16篇 |
1998年 | 15篇 |
1997年 | 17篇 |
1996年 | 22篇 |
1995年 | 15篇 |
1994年 | 15篇 |
1993年 | 15篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 7篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 11篇 |
1984年 | 11篇 |
1983年 | 8篇 |
1982年 | 8篇 |
1981年 | 17篇 |
1980年 | 10篇 |
1979年 | 19篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1973年 | 8篇 |
1971年 | 5篇 |
排序方式: 共有1244条查询结果,搜索用时 0 毫秒
1.
A method for the determination of 5 triazine herbicides and 12 degradation products in environmental water samples using liquid chromatography-electrospray ionization mass spectrometry (LC/ESI/MS) has been developed. The pesticides in water were extracted with two types of solid phase: a styrene-divinylbenzene copolymer and a graphitized carbon black. Desorption solvents for the extracted compounds were acetone for the styrene-divinylbenzene copolymer and methanol for the graphitized carbon black. Overall recoveries from ground water and river water ranged from 73% to 111%. The limits of detection (LODs) were 0.2 to 28 ng l(-1). This method was applied to several ground water samples. 相似文献
2.
3.
In the recycling of poly(vinyl chloride) (PVC), it is required to discriminate every plasticizer for quality control. For this purpose, the near-infrared spectra were measured for 41 kinds of PVC samples with different plasticizers (DINP, DOP, DOA, TOTM and Polyester) and different plasticizer contents (0-49%). A neural-network analysis was applied to the near-infrared spectra pretreated by second-derivative processing. They were discriminated from one another. The neural-network analysis also allowed us to propose a calibration model which predicts the contents of plasticizers in PVC. The correlation coefficient (R) and the root-mean-square error of prediction (RMSEP) for the DINP calibration model were found to be 0.999 and 0.41 wt%, respectively. In comparison, a partial least-squares regression analysis was carried out. The R and RMSEP of the DINP calibration model were calculated to be 0.993 and 1.27 wt%, respectively. It is found that a near-infrared spectra measurement combined with a neural-network analysis is useful for plastic recycling. 相似文献
4.
We have developed a sensitive method for the measurement of rhodanese activity in human serum which is based on the colorimetric method for the determination of thiocyanate produced from methanethiosulfonate and cyanide as substrates. Thiocyanate gives a red complex with ferric ion in an acidic condition. The present method is about 70-fold more sensitive than the conventional method using cyanide and thiosulfate as substrates and correlates well (r = 0.997) with the conventional method in bovine liver rhodanese. Within-run precision of the method is 0.91% for 420 units/l serum and the calibration curve is linear up to 1850 units/l. The normal value for human serum, determined by the present method on 31 healthy persons, was 20.9 +/- 20.0 units/l (mean +/- 2S.D.). Rhodanese activity was clearly elevated in some serum samples which were observed at abnormal values in some biochemical diagnostic tests and showed significant positive correlations with guanase activity (r = 0.728, p less than 0.01) and glutamic-oxalacetic transaminase activity (r = 0.625, p less than 0.01). 相似文献
5.
Hirokazu Tezuka 《Zeitschrift fur Physik C Particles and Fields》1995,65(1):101-104
It is shown that the Dirac equation with attractive monomial vector potential cannot confine a particle. General polynomial type vector potential cannot confine a particle, either. This condition is not changed by a scalar potential smaller than the vector one. 相似文献
6.
Oishi S Kamano T Niida A Odagaki Y Hamanaka N Yamamoto M Ajito K Tamamura H Otaka A Fujii N 《The Journal of organic chemistry》2002,67(17):6162-6173
Diastereoselective synthesis of new psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type alkene dipeptide isosteres corresponding to dipeptides having one N-methylamino acid, and application to bioactive peptides, are described. In a key reaction introducing the chiral alpha-alkyl group of the isosteres, organocopper-mediated alkylation of syn-beta-methylated gamma-mesyloxy-alpha,beta-enoate 26a afforded E- and Z-isomers of anti-S(N)2' products in a solvent-dependent manner. The resulting two isosteres, D-Phe-psi[(E)-CH=CMe]-L-Val 27a and D-Phe-psi[(Z)-CH=CMe]-L-Val 28b, which corresponded to trans- and cis-conformers of D-Phe-L-MeVal, respectively, were utilized in a structure-activity relationship study on cyclic RGD peptides 1 and 2, in company with a psi[(E)-CH=CH]-type alkene dipeptide isostere, D-Phe-psi[(E)-CH=CH]-L-Val. The cyclic isostere-containing pseudopeptides 3, 4, and 40 were synthesized and biological activity against integrin alpha(V)beta(3) and alpha(IIb)beta(3) receptors were also evaluated. 相似文献
7.
Infrared and Raman spectra of 1,2-dibromoethane CH2BrCH2Br and CD2BrCD2Br were observed in the liquid state, and the fundamental frequencies were determined by comparison with those of related molecules. Infrared absorption intensities of fundament bands were measured in the liquid state, and the intensity data were interpreted on the basis of the valence-optical theory. From the converged value of a population ratio, the energy difference between the trans and gauche isomers was determined, which was in good agreement with the value obtained from the temperature effect of the IR spectrum. 相似文献
8.
Isotropie Raman spectra of the symmetric C—H stretching bands of several organic molecules are measured in the neat liquid and in solvents including water. The linewidths are interpreted on the basis of the vibrational dephasing model, and intermolecular interactions between the solutes and solvents are discussed. 相似文献
9.
Otaka A Yukimasa A Watanabe J Sasaki Y Oishi S Tamamura H Fujii N 《Chemical communications (Cambridge, England)》2003,(15):1834-1835
Gamma-acetoxy-alpha,beta-enoates were easily reduced by samarium diiodide (SmI2) in THF to generate samarium dienolates which were kinetically trapped with ease at their alpha-positions by electrophiles (proton, aldehydes or ketones) to yield (E)-alkene dipeptide isosteres or gamma-amino acid derivatives in high chemical yields. 相似文献
10.
Otaka A Watanabe J Yukimasa A Sasaki Y Watanabe H Kinoshita T Oishi S Tamamura H Fujii N 《The Journal of organic chemistry》2004,69(5):1634-1645
A samarium diiodide (SmI(2))-mediated reduction of gamma,gamma-difluoro-alpha,beta-enoates (15, 29, and 34) was successfully applied to the synthesis of (Z)-fluoroalkene dipeptide isosteres (23, 30, and 35), which have served as potential dipeptide mimetics. Reduction of the gamma,gamma-difluoro-alpha,beta-enoates by SmI(2) proceeded via successive two-electron transfers to form dienolate species which upon kinetically controlled trapping with t-BuOH yielded Xaa-Gly-type fluoroalkene isosteres exemplified by 23, 30, and 35. Replacement of the t-BuOH kinetic trapping agent with aldehydes or ketones provided access to alpha-substituted fluoroalkene isosteres (43 and 45) through aldol reactions of Sm-dienolates with the carbonyl compounds. Of particular note, the use of the SmI(2)-HCHO reagent system with chiral enoate 34 provided D-Phe-psi[(Z)-CF[double bond]CH]-D/L-Ser isosteres (45), which could be converted to enantiomerically pure isosteres (49-52) that bore a variety of side chain functionalities at the alpha-position. This was achieved by a sequence of manipulations consisting of beta-lactone formation followed by chromatographic separation and ring-opening with soft nucleophiles. Included in the present work is the first utilization of a Rh-catalyzed Reformatsky reaction of chiral imines for the stereoselective preparation of alpha,alpha-difluoro-beta-amino acid derivatives (28 and 33). The appropriate choice of reagents (carbonyl compounds for kinetic trapping or ring-opening nucleophiles and imines for Reformatsky reactions) allows the presented methodology to yield various fluoroalkene isosteres possessing a wide range of side chain functionalities. 相似文献