全文获取类型
收费全文 | 5883篇 |
免费 | 238篇 |
国内免费 | 28篇 |
专业分类
化学 | 3949篇 |
晶体学 | 71篇 |
力学 | 161篇 |
数学 | 444篇 |
物理学 | 1524篇 |
出版年
2024年 | 4篇 |
2023年 | 30篇 |
2022年 | 119篇 |
2021年 | 154篇 |
2020年 | 104篇 |
2019年 | 106篇 |
2018年 | 86篇 |
2017年 | 93篇 |
2016年 | 149篇 |
2015年 | 170篇 |
2014年 | 219篇 |
2013年 | 378篇 |
2012年 | 425篇 |
2011年 | 460篇 |
2010年 | 294篇 |
2009年 | 244篇 |
2008年 | 426篇 |
2007年 | 365篇 |
2006年 | 375篇 |
2005年 | 308篇 |
2004年 | 290篇 |
2003年 | 238篇 |
2002年 | 234篇 |
2001年 | 169篇 |
2000年 | 113篇 |
1999年 | 97篇 |
1998年 | 54篇 |
1997年 | 29篇 |
1996年 | 45篇 |
1995年 | 56篇 |
1994年 | 34篇 |
1993年 | 38篇 |
1992年 | 29篇 |
1991年 | 15篇 |
1990年 | 31篇 |
1989年 | 29篇 |
1988年 | 14篇 |
1987年 | 15篇 |
1985年 | 22篇 |
1984年 | 10篇 |
1983年 | 11篇 |
1982年 | 14篇 |
1981年 | 13篇 |
1980年 | 10篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1969年 | 3篇 |
排序方式: 共有6149条查询结果,搜索用时 15 毫秒
901.
Cryptophane-A was synthesized from vanillin by a three-step method and its spectroscopic properties in different organic solvents were determined. Two absorption bands at about 240-250 and 280-290 nm were observed for cryptophane-A. A fluorescence emission peak was obtained at 320-330 nm using a solution of approximately 10(-5)M cryptophane-A. The interaction of cryptophane-A with chlorinated compounds CH(n)Cl(4 - n) (n=0, 1, 2) in dioxane and ethyl acetate solvents were studied in detail by fluorescence spectroscopy, respectively. The results show that cryptophane-A is well suited for inclusion of CH(2)Cl(2) to form a stable 1:1 complex and the binding constant was estimated to be 19+/-2M(-1). These results were also confirmed by (1)H NMR and CPK models. Larger similar molecules such as CHCl(3) and CCl(4) are unable to enter the cavity of cryptophane-A because of their bigger sizes. However, the fluorescence emission of cryptophane-A can be efficiently quenched by CHCl(3) and CCl(4), following the Stern-Volmer relationship. 相似文献
902.
Eui Ta Choi 《Tetrahedron》2008,64(7):1515-1522
Catalytic asymmetric dehydration of β-aryl or alkyl substituted β-hydroxy esters via kinetic resolution has been investigated. A brief survey of 10 different chiral ligands is conducted to examine the effects of chiral ligand structure on selectivity of the dehydration. The kinetic resolution of a variety of rac-β-hydroxy tert-butyl esters in the presence of prolinol chiral ligand 2 and BrZnCH2CO2-t-Bu can provide highly enantioenriched β-hydroxy esters 14-21 with selectivity factors ranging from 11 to 66. Also, application of this asymmetric synthetic methodology to the preparation of enantioenriched flavane derivatives 25-29 is demonstrated. 相似文献
903.
I. S. Al’tman I. E. Agranovskii M. Choi V. A. Zagainov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2008,82(12):2097-2102
An attempt is made to critically analyze the modern state of the theory of homogeneous nucleation as concerns its ability to describe experiments with high accuracy. An analysis of the experimental data led us to conclude that the dependence of the nucleation rate on supersaturation and temperature T was not described by the theory, which underestimates the critical cluster size compared with the Gibbs-Thomson equation. The possibility of applying density functional theory (one of the latest achievements in the theory of homogeneous nucleation) was questioned. Within this theory, the Gibbs-Thomson equation remains valid even outside the classic capillary approximation. It is suggested that, to bring theory in consistency with experiment, certain fundamental propositions of the theory of nucleation should be revised. The inclusion of an additional contribution to the Gibbs energy of a cluster caused by the size dependence of the specific heat capacity of the cluster decreases the critical cluster size compared with the value calculated by the Gibbs-Thomson equation. The calculated dependence of nucleation rate on supersaturation was in agreement with the experimental results. 相似文献
904.
Kunyong Yang Xiaohui He Ha-soon Choi Zhicheng Wang David H. Woodmansee Hong Liu 《Tetrahedron letters》2008,49(11):1725-1728
An expedient one-pot synthesis of fused bicyclic 2,3-diaryl-pyrimidin-4(3H)-ones from three readily available components is described. The key step is a Lewis acid assisted cyclization reaction. 相似文献
905.
Bond length and the electron density at the bond critical point: X--X, Z--Z, and C--Z bonds (X = Li-F, Z = Na-Cl) 总被引:1,自引:0,他引:1
Castillo N Robertson KN Choi SC Boyd RJ Knop O 《Journal of computational chemistry》2008,29(3):367-379
The aim was to investigate the relationship between the bond length and the electron density at the bond critical point in homonuclear X--X and Z--Z and heteronuclear C--Z bonds (X = Li-F, Z = Na-Cl). The d,rho(c) pairs were obtained from 472 target bonds in DFT-optimized (B3LYP/6-311+G(d,p)) small molecular species. These species were selected arbitrarily but with a view to maximize the range widths WR for each atom combination. It was found that (i) with one clear exception, the d(A - A) means (A = X or Z) correlate linearly with the bond lengths d(A(2)) of the respective diatomic molecules; (ii) the d(A - A) means correlate parabolically with n, the formal number of valence electrons in the atoms of the bond; and (iii) with increasing sample size N the ratio WR(rho(c))/WR(d) appears to converge toward a representation f [WR(rho(c))/WR(d)](N-->infinity) characteristic of A. Detailed analysis of the d,rho(c) relationship has shown that by and large simple power regression accounts best for the DFT data. The regression coefficients of d = arho(c) (-b) and rho(c) = alphad(-beta) (b, beta > 0) vary with n in a seemingly irregular manner but one that is consistent with simple chemical notions. The d(A(2)) can be approximated in terms of multilinear MO electron occupancies. 相似文献
906.
Khay S Abd El-Aty AM Cho SK Choi JH Mamun MI Goudah A Shin HC Shim JH 《Biomedical chromatography : BMC》2008,22(6):581-589
This study was undertaken to investigate whether an additional column clean-up procedure can affect the accuracy of an analytical method developed for the determination of imidacloprid residues in Chinese cabbage. Thereafter, the residue levels and the degradation rates of imidacloprid were investigated in experimental Chinese cabbage plots after treatment with two different commercial formulations: emulsifiable concentrate (EC) and wettable powder (WP). The analyte was determined using high-performance liquid chromatography-ultraviolet detection (HPLC-UVD) and confirmed by high-performance liquid chromatography-mass spectrometry (HPLC-MS) in the select ion-monitoring mode. The mean recoveries ranged from 75.34 to 98.00% and 96.95 to 100.97%, with relative standard deviations of 0.86-4.14 and 1.22-3.52%, in samples treated with and without additional column clean-up procedures, respectively. The minimum detectable amount of imidacloprid was 4 ng, while the limits of detection and quantitation were 0.2 and 0.5 ppm, respectively. The degradation of pesticide was monitored throughout a period of 13 days under greenhouse conditions. Although the behaviors of the EC and WP formulations appear to be similar, the absolute residue levels obtained with EC and WP treatments differed slightly. When imidacloprid formulations were applied (as foliar treatments) according to the recommended rate, the final residues (13 days post-treatment) in Chinese cabbage were much lower than the maximum residue limit (MRL = 3.5 ppm) established by the Korean Food and Drug Administration. Taken together, our study suggests that the analysis of imidacloprid can be performed without an additional column clean-up procedure, and the decline curve and the residue levels in Chinese cabbage could change if the same active ingredient is used in different formulations. 相似文献
907.
Two new liquid chromatographic chiral stationary phases based on diastereomeric chiral crown ethers incorporating two different chiral units such as optically active 3,3'-diphenyl-1,1'-binaphthyl and tartaric acid unit were prepared. Between the two CSPs, one was much superior to the other especially in the resolution of tocainide and its analogues (for example, in the resolution of tocainide the separation factor, alpha, was 4.26 vs. 1.00 on the two CSPs). From these results, the two chiral units composing the two diastereomeric chiral crown ether moieties of the stationary phases were expected to show "matched" or "mismatched" effect on the chiral recognition according to their stereochemistry. The different chiral recognition abilities of the two CSPs were rationalized by the different three-dimensional structures of the two diastereomeric chiral crown ethers. 相似文献
908.
Kim C Choi H Kim S Baik C Song K Kang MS Kang SO Ko J 《The Journal of organic chemistry》2008,73(18):7072-7079
Three organic sensitizers containing bis-dimethylfluorenyl amino donor and a cyanoacrylic acid acceptor bridged by p-phenylene vinylene unit were synthesized. The power conversion efficiency was quite sensitive to the length of bridged phenylene vinylene groups. A nanocrystalline TiO2 dye-sensitized solar cell was fabricated using three sensitizers. The maximum power conversion efficiency of JK-59 reached 7.02%. 相似文献
909.
Ju-Hyung Chae Minyeong Choi Semin Son Su-Min Ko Prof. In-Hwan Lee 《Angewandte Chemie (International ed. in English)》2023,62(31):e202305414
Precise control of multiple structural parameters associated with vinyl polymers is important for producing materials with the desired properties and functions. While the development of living polymerization methods has provided a way to control the various structural parameters of vinyl polymers, the concomitant control of their sequence and regioregularity remains a challenging task. To overcome this challenge, herein, we report the living cationic ring-opening polymerization of hetero Diels–Alder adducts. The scalable and modular synthesis of the cyclic monomers was achieved by a one-step protocol using readily available vinyl precursors. Subsequently, living polymerization of the cyclic monomers was examined, allowing the synthesis of vinyl polymers while controlling multiple factors, including molecular weight, dispersity, alternating sequence, head-to-head regioregularity, and end-group functionality. The living characteristics of the developed method were further demonstrated by block copolymerization. The synthesized vinyl polymers exhibited unique thermal properties and underwent fast photodegradation even under sunlight. 相似文献
910.
Hongmin Wang Shuting Fu Bo Shang Sungho Jeon Yiren Zhong Nia J. Harmon Chungseok Choi Eric A. Stach Hailiang Wang 《Angewandte Chemie (International ed. in English)》2023,62(30):e202305251
Photothermal CO2 reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K+−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K+−Co−C catalyst shows a record-high photothermal CO2 hydrogenation rate of 758 mmol gcat−1 h−1 (2871 mmol gCo−1 h−1) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO2 reduction reactions. We further demonstrate with this catalyst effective CO2 conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production. 相似文献