全文获取类型
收费全文 | 382篇 |
免费 | 34篇 |
国内免费 | 1篇 |
专业分类
化学 | 360篇 |
晶体学 | 7篇 |
力学 | 7篇 |
数学 | 14篇 |
物理学 | 29篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 14篇 |
2020年 | 15篇 |
2019年 | 9篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 14篇 |
2015年 | 14篇 |
2014年 | 13篇 |
2013年 | 27篇 |
2012年 | 19篇 |
2011年 | 33篇 |
2010年 | 23篇 |
2009年 | 13篇 |
2008年 | 20篇 |
2007年 | 24篇 |
2006年 | 21篇 |
2005年 | 19篇 |
2004年 | 19篇 |
2003年 | 14篇 |
2002年 | 8篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1959年 | 1篇 |
1928年 | 2篇 |
1896年 | 1篇 |
1893年 | 2篇 |
排序方式: 共有417条查询结果,搜索用时 203 毫秒
321.
Hong Liu ShuFang Zheng Véronique Bellemare Georges Pelletier Fernand Labrie Van Luu-The 《BMC biochemistry》2007,8(1):2
Background
We have recently discovered that human type 12 17β-HSD (h17β-HSD12), a homolog of type 3 17β-HSD, is a new estrogen-specific 17β-hydroxysteroid dehydrogenase involved in the production of estradiol (E2). To further characterize this estradiol-producing enzyme, we have isolated the corresponding cDNA in the cynomolgus monkey (Macaca fascicularis), characterized its enzymatic activities and performed cellular localization using in situ hybridization. 相似文献322.
(–)-Butaclamol HCl, C25H31ONCl, crystallizes in the monoclinic space group P21 with cell dimensionsa=12.842(2),b=7.741(1),c=11.667(2)Å and=106.54(2)°,z=2. Refinement of nonhydrogen atoms with anisotropic thermal parameters and isotropic hydrogen atoms using 4381 observed reflections gaveR=5.4% for the (3R,4aR,13aR) enantiomorph, andR=6.6% for the other enantiomorph. The crystal structure shows that butaclamol has thetrans A conformer with respect to the rotation at C8-C9, as observed in other crystal structures of butaclamol and analogues. Conformational energy calculations were redone for butaclamol and isobutaclamol with the 1986 version of the MM2 program and parameter set with the result thattrans conformer A is now preferred for the protonated form of butaclamol, whereas thecis conformers continue to be preferred for the free base. The results for isobutaclamol are similar to those previously reported. 相似文献
323.
The molecular structure and conformational properties of structurally related oxo and thio heteroarotinoids have been calculated by employing AM1 molecular orbital and both MM2P and Chem-X “optimize” molecular mechanics methods, and the results have been compared with crystal structure data. For the cis and trans oxo heteroarotinoids, MM2P gives values of the bridge torsion angles ?1 and ?2 in closest agreement with the crystal structure, and all three computational methods yield values of ?1 and ?2 within about 10° of that found in the crystal structures. All three computational methods locate a minimum-energy conformation for the trans isomer corresponding to the two bridged aryl rings being mutually perpendicular, in agreement with the crystal structure and similar to that found for the structurally analogous trans-stilbene. The calculated heteroring geometries also reproduce the twist-sofa conformation observed for the crystal structure. Calculated conformational energies versus ?1 and ?2 indicate broad energy wells about the minimum-energy conformation with barriers to rotation at the planar and perpendicular conformations, and with higher barriers found for the more sterically congested cis isomer. The corresponding cis and trans thio heteroarotinoids exhibit conformational properties similar to their oxo analogues. Both AM1 and MM2P fare poorly in reproducing the crystal structure values of the sulfur-containing bond lengths and bond angles. The C-S bonds found in these thio heteroarotinoids may possess more double-bond character than accounted for in the calculations. Also, the results suggest that the MM2P sulfur-related force-field parameters adopted for these calculations may require further refinement. 相似文献
324.
325.
326.
Novel tricyclic heterocycles were prepared and evaluated for their affinity to the central benzodiazepine receptor. The most potent compounds with IC50's in the nanomolar range were; found among thienoquinolizines and benzo[a]quinolizines (cf. Tables 2–5). The central ring of the tricyclic ring system may be partially unsaturated (cf. Tables 2 and 4) or fully unsaturated (cf. Tables 3 and 5) without loss of the high affinity to the receptor. The position of the ester group in the pyridinone ring is crucial for good binding (cf. Tables 1 and 2). It may be replaced by a broad variety of functional groups, e.g. amides, alkyl carbamates, alkyl groups, and hydroxyalkyl groups (cf. Tables 2–5). In the benzo[a]quinolizines, shifting the halogen atom from C(10) to C(9) leads to complete loss of affinity to the benzodiazepine receptor (cf. Table 4). 相似文献
327.
A dramatic color change and tremendous emission enhancement have been "switched on" upon increasing diethyl ether ratio in acetonitrile or acetone solution of [Pt(tpy)(CC-CCH)]OTf, attributed to the formation of Pt...Pt and pi-pi interactions. Two crystal forms (dark-green and red) of [Pt(tpy)(CC-CCH)]OTf, together with [Pt(tBu3-tpy)(CC-CCH)]OTf, show different crystal-packing modes as revealed by X-ray crystallography. 相似文献
328.
Carlson JC Kanter A Thuduppathy GR Cody V Pineda PE McIvor RS Wagner CR 《Journal of the American Chemical Society》2003,125(6):1501-1507
In an effort to elucidate the role of ligand conformation in induced protein dimerization, we synthesized a flexible methotrexate (MTX) dimer, demonstrated its ability to selectively dimerize Escherichia coli dihydrofolate reductase (DHFR), and evaluated the factors regulating its ability to induce cooperative dimerization. Despite known entropic barriers, bis-MTX proved to possess substantial conformational stability in aqueous solution (-3.8 kcal/mol >/= DeltaG(fold) >/= -4.9 kcal/mol), exerting a dominant influence on the thermodynamics of dimerization. To dimerize DHFR, bis-MTX must shift from a folded to an extended conformation. From this conclusion, the strength of favorable protein-protein interactions in bis-MTX-E. coli DHFR dimers (-3.1 kcal/mol >/= DeltaG(c) >/= -4.2 kcal/mol), and the selectivity of dimerization for E. coli DHFR relative to mouse DHFR (>10(7)) could be determined. The crystal structure of bis-MTX in complex with E. coli DHFR confirms the feasibility of a close-packed dimerization interface and suggests a possible solution conformation for the induced protein dimers. Consequently, the secondary structure of this minimal foldamer regulates its ability to dimerize dihydrofolate reductase in solution, providing insight into the complex energy landscape of induced dimerization. 相似文献
329.
Photochromic and luminescence switching properties of a versatile diarylethene-containing 1,10-phenanthroline ligand and its rhenium(I) complex 总被引:1,自引:0,他引:1
A versatile bis(2,5-dimethyl-3-thienyl)-1,10-phenanthroline photochromic ligand has been successfully synthesized via a Suzuki cross-coupling reaction. The excitation wavelength for photochromic reaction of the dithienylphenanthroline could be extended from lambda = 340 nm in the UV region to ca. 480 nm in the visible region, corresponding to the MLCT excitation, through the incorporation into the rhenium(I) tricarbonyl system. Reversible switching of the emissive state by the photochromic reaction has also been demonstrated. 相似文献
330.
Yam VW Tang RP Wong KM Lu XX Cheung KK Zhu N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(17):4066-4076
A series of platinum (II) C empty set N empty set C complexes, [Pt(C empty set N empty set C) (L)] (HC empty set N empty set CH=2,6-diphenylpyridine (dppy); L=Ph(2)PB15C5 (1, B15C5=benzo[15]crown-5), Ph(2)PDMP (2, DMP=3,4-dimethoxyphenyl), pyCOA15C5 (3, A15C5=aza[15]crown-5), pyCON(CH(2)CH(2)OCH(3))(2) (4), pyC[triple bond]CB15C5 (5), pyC[triple bond]CDMP (6)) and terpyridyl complexes, [Pt(trpy)(L)](X)(2) (trpy=2,2':6',2'-terpyridine; L=Ph(2)PB15C5, X=OTf (7 a), PF(6) (7 b); X=PF(6), L=Ph(2)PDMP (8), pyC[triple bond]CB15C5 (9), and pyC[triple bond]CDMP (10)) have been successfully synthesized and characterized. The structures of 1, 3, and 7 a have been determined by X-ray crystallography. Excitation of complexes 1-6 in EtOH/MeOH (4:1 v/v) glass gave high-energy structured emission bands, assigned as derived from states of metal-perturbed intraligand (IL) origin. At higher concentrations, complexes 3-6 each displayed an additional, structureless emission band at 600-615 nm, with complexes 5 and 6 showing an obvious increase in the intensity of this emission band when the concentration was increased further. In dichloromethane at room temperature, complexes 3-6 showed, in addition to the high-energy emission at 490-505 nm, an extra, broad emission band at 620-625 nm when the concentration was increased. The emission origins of the low-energy band in glass and in fluid solutions are suggested to be derived from the ground-state oligomerization or aggregation process of the complexes. In the solid state at room temperature, complexes 1-6 each showed a broad, unstructured emission band at 560-600 nm, which was shifted to lower energy upon cooling to 77 K. On the other hand, the terpyridyl analogues 7-10 displayed intense vibronic-structured intraligand (IL) emissions at 460-472 nm in butyronitrile glass at 77 K. Solid-state samples of 9 and 10 displayed strong phosphorescence upon photoexcitation at 298 K and 77 K, tentatively assigned as derived from states of Pt(d pi)-->pi*(trpy) (3)MLCT origin(MLCT=metal-to-ligand charge transfer). The ion-binding properties of complexes 5 and 9 for Na(+), Ba(2+), and K(+) ions have been studied by UV/Vis spectrophotometric methods, and confirmed by ESI mass spectrometric studies. The ion-binding properties for Na(+) ions have also been probed by (1)H NMR experiments. For the same crown ether-containing ligand and the same metal ions, the neutral cyclometalated complexes gave larger binding constants than the positively charged terpyridyl analogues. 相似文献