全文获取类型
收费全文 | 1111篇 |
免费 | 42篇 |
专业分类
化学 | 797篇 |
晶体学 | 8篇 |
力学 | 34篇 |
数学 | 84篇 |
物理学 | 230篇 |
出版年
2023年 | 7篇 |
2022年 | 24篇 |
2021年 | 22篇 |
2020年 | 15篇 |
2019年 | 23篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 20篇 |
2015年 | 26篇 |
2014年 | 46篇 |
2013年 | 43篇 |
2012年 | 68篇 |
2011年 | 88篇 |
2010年 | 51篇 |
2009年 | 72篇 |
2008年 | 88篇 |
2007年 | 70篇 |
2006年 | 68篇 |
2005年 | 46篇 |
2004年 | 30篇 |
2003年 | 27篇 |
2002年 | 26篇 |
2001年 | 19篇 |
2000年 | 16篇 |
1999年 | 15篇 |
1998年 | 12篇 |
1997年 | 19篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 16篇 |
1993年 | 12篇 |
1992年 | 14篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 8篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1974年 | 12篇 |
1973年 | 17篇 |
1964年 | 2篇 |
排序方式: 共有1153条查询结果,搜索用时 31 毫秒
31.
Lee CM Hsieh CH Dutta A Lee GH Liaw WF 《Journal of the American Chemical Society》2003,125(38):11492-11493
Iron-nitrosyl complex containing S-bonded monosulfinate [PPN][(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (3) has been isolated from sulfur oxygenation of complex [PPN][(NO)Fe(S,S-C6H4)2] (2) which is obtained from addition of NO molecule to [PPN][(C4H8O)Fe(S,S-C6H4)2] (1) in organic solvents. This result reveals that binding of NO to the iron center promotes sulfur oxygenation of iron dithiolates by dioxygen and stabilizes the S-bonded sulfinate iron species. Analysis of the bond angles for complexes 2 and 3 reveals that iron is best described as existing in a distorted trigonal bipyramidal coordination environment surrounded by one NO, three thiolates, and one sulfinate in complex 3, whereas the distorted square pyramidal geometry is adopted in complex 2. Complex 3 further reacts in organic solvents with molecular oxygen in the presence of [PPN][NO2] to produce the dinuclear bis(sulfinate) complex [PPN]2[(NO)Fe(SO2,SO2-C6H4)(S,S-C6H4)]2 (4). Complex 3 showed reaction with PPh3 in THF/CH2Cl2 to yield complex 2 and Ph3PO. Upon photolysis of CH2Cl2 solution of complex 3 under N2 purge at ambient temperature, the UV-vis and IR spectra consistent with the formation of complex 2 demonstrate that complex 2 and 3 are photochemically interconvertible. Obviously, complex 3 is thermally quite stable but is photochemically active toward [O] release. Also described are the X-ray crystal structures of 3 and 4. 相似文献
32.
We report the separation of polycyclic aromatic hydrocarbons (PAHs) using 0.1% poly(ethylene oxide) (PEO) in micellar electrokinetic chromatography (MEKC). In the presence of PEO, adsorption of PAHs on the capillary wall was reduced, leading to better resolution and reproducibility. Effects of tetrapentylammonium iodide (TPAI), dextran sulfate (DS), methanol, and sodium lauryl sulfate (SDS) on the separation of PAHs were elucidated. In terms of resolution and speed, DS, compared to TPAI, is a better additive for separation of PAHs. When using 0.1% PEO solution containing 45% methanol, 50 mM SDS, and 0.02% DS, separation of 10 PAHs containing 2 to 5 benzene rings was accomplished in less than 12 min at 15 kV in a commercial CE system. The method has also been tested for separating seven PAHs with high quantum yields when excited at 325 nm using a He-Cd laser. Unfortunately, separation of the seven PAHs was not achieved and sensitivity diminished under the same conditions. To optimize sensitivity, resolution and speed, a stepwise technique in MEKC has been proposed. The seven PAHs were resolved in 35 min at 15 kV when separation was performed in 0.1% PEO solution containing 35 mM SDS, 40% methanol and 0.02% DS for 2 min, and subsequently in 0.1% PEO solution containing 20 mM SDS, 50% methanol, and 0.02% DS. 相似文献
33.
Bingham RJ Findlay JB Hsieh SY Kalverda AP Kjellberg A Perazzolo C Phillips SE Seshadri K Trinh CH Turnbull WB Bodenhausen G Homans SW 《Journal of the American Chemical Society》2004,126(6):1675-1681
In the present study we examine the thermodynamics of binding of two related pyrazine-derived ligands to the major urinary protein, MUP-I, using a combination of isothermal titration calorimetry (ITC), X-ray crystallography, and NMR backbone (15)N and methyl side-chain (2)H relaxation measurements. Global thermodynamics data derived from ITC indicate that binding is driven by favorable enthalpic contributions, rather than the classical entropy-driven hydrophobic effect. Unfavorable entropic contributions from the protein backbone and side-chain residues in the vicinity of the binding pocket are partially offset by favorable entropic contributions at adjacent positions, suggesting a "conformational relay" mechanism whereby increased rigidity of residues on ligand binding are accompanied by increased conformational freedom of side chains in adjacent positions. The principal driving force governing ligand affinity and specificity can be attributed to solvent-driven enthalpic effects from desolvation of the protein binding pocket. 相似文献
34.
35.
36.
37.
Ya‐Chu Hsieh Hau‐Yu Fang Yi‐Ting Chen Rong Yang Chen‐I Yang Pi‐Tai Chou Ming‐Yu Kuo Yao‐Ting Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(10):3112-3116
The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel‐catalyzed cyclodimerization of 9‐ethynyl‐1‐iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed‐shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open‐shell biradicals, which were studied by variable‐temperature 1H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π‐conjugation and biradical properties. Dibenzozethrenes have larger two‐photon absorption cross‐sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σmax=4323 GM at 530 nm]. 相似文献
38.
Y. J. Chang C. H. Chen B. T. Hsieh 《Journal of Radioanalytical and Nuclear Chemistry》2014,301(3):765-780
In this study, the detailed characteristics, including spatial uniformity, dose distributions, inter-batch variability, reproducibility, and long-term temporal stability, of N-isopropylacrylamide (NIPAM) polymer gel dosimeter were investigated. A commercial 10x fast optical computed tomography scanner (OCTOPUSTM-10×, MGS Research, Inc., Madison, CT, USA) was used to measure NIPAM polymer gel dosimeter. A cylindrical NIPAM gel phantom that measured 10 cm × 10 cm was irradiated via a single-field treatment plan with a field size of 4 cm × 4 cm. The maximum standard deviation of spatial uniformity for NIPAM gel was less than 0.29 %. The average standard deviation among the three batches of gel dosimeters was less than 1 %. The gamma pass rate could reach as high as 96.76 % when a 3 % dose difference and a 3 mm dose-to-agreement criteria were used. The long-term measurement of irradiated NIPAM gel dosimeter indicated that the dose maps attained a gradually stable value 15 h post-irradiation and remained stable until 72 h post-irradiation. The gamma pass rate could achieve a maximum value between 24 and 72 h post-irradiation. The edge enhancement effect that occurred around the irradiated region was observed 72 h post-irradiation. Thus, the results from this study suggest that NIPAM gel dosimeter should be measured approximately 24 h post-irradiation to reduce the occurrence of the edge enhancement effect. 相似文献
39.
Shin-Hun Juang Min-Tsang Hsieh Pei-Ling Hsu Ju-Ling Chen Hui-Kang Liu Fong-Pin Liang Sheng-Chu Kuo Chen-Yuan Chiu Shing-Hwa Liu Chen-Hsi Chou Tian-Shung Wu Hsin-Yi Hung 《Molecules (Basel, Switzerland)》2021,26(1)
Constitutive androstane receptor (CAR) activation has found to ameliorate diabetes in animal models. However, no CAR agonists are available clinically. Therefore, a safe and effective CAR activator would be an alternative option. In this study, sixty courmarin derivatives either synthesized or purified from Artemisia capillaris were screened for CAR activation activity. Chemical modifications were on position 5,6,7,8 with mono-, di-, tri-, or tetra-substitutions. Among all the compounds subjected for in vitro CAR activation screening, 6,7-diprenoxycoumarin was the most effective and was selected for further preclinical studies. Chemical modification on the 6 position and unsaturated chains were generally beneficial. Electron-withdrawn groups as well as long unsaturated chains were hazardous to the activity. Mechanism of action studies showed that CAR activation of 6,7-diprenoxycoumarin might be through the inhibition of EGFR signaling and upregulating PP2Ac methylation. To sum up, modification mimicking natural occurring coumarins shed light on CAR studies and the established screening system provides a rapid method for the discovery and development of CAR activators. In addition, one CAR activator, scoparone, did showed anti-diabetes effect in db/db mice without elevation of insulin levels. 相似文献
40.
Kai‐Hsuan Hsieh Chih‐Ying Hsu I‐Ju Hung Chih‐Ling Yeh Yau‐Hung Chen Chien‐Chung Cheng 《中国化学会会志》2021,68(1):34-38
Liposomes composed of cell‐penetrating peptide derivatives increased transport across the cell membrane. Conjugating rhodamine to a cell‐penetrating peptide increased the toxicity of rhodamine in E. coli and zebrafish embryos. A similar total protein inhibition pattern with different intensities, indicating that the interaction pathways of the rho‐KTTKS‐CONH2 monomer and liposomes were the same. It suggests that the rho‐KTTKS‐CONH2 liposomes showed higher toxicity because better transport across the cell membrane increased the effective concentration inside cells. The staining of zebrafish embryos using rho‐KTTKS‐CONH2 liposomes showed a longer retention time, suggesting that it can penetrate deeper tissues or organs in zebrafish. 相似文献