全文获取类型
收费全文 | 1341篇 |
免费 | 63篇 |
国内免费 | 3篇 |
专业分类
化学 | 1135篇 |
晶体学 | 10篇 |
力学 | 18篇 |
数学 | 109篇 |
物理学 | 135篇 |
出版年
2023年 | 24篇 |
2022年 | 25篇 |
2021年 | 36篇 |
2020年 | 41篇 |
2019年 | 33篇 |
2018年 | 18篇 |
2017年 | 15篇 |
2016年 | 43篇 |
2015年 | 42篇 |
2014年 | 43篇 |
2013年 | 60篇 |
2012年 | 105篇 |
2011年 | 128篇 |
2010年 | 67篇 |
2009年 | 53篇 |
2008年 | 101篇 |
2007年 | 94篇 |
2006年 | 82篇 |
2005年 | 91篇 |
2004年 | 76篇 |
2003年 | 71篇 |
2002年 | 48篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1992年 | 7篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1984年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1971年 | 1篇 |
1965年 | 1篇 |
1881年 | 1篇 |
1876年 | 1篇 |
排序方式: 共有1407条查询结果,搜索用时 15 毫秒
11.
David M. Rogers Claire Wells Melanie Joseph Vanessa J. Boddington Joseph J.W. McDouall 《Journal of Molecular Structure》1998,434(1-3):239-245
We describe a procedure which may be used to aid selection of the active space in multiconfigurational self-consistent field (MCSCF) calculations for general chemical systems. Starting from a restricted Hartree-Fock calculation, we define a hierarchy of interacting virtual orbitals for every occupied orbital. The most strongly interacting orbitals are then taken to constitute the active space in a configuration interaction (CI) calculation. The natural orbital occupation numbers obtained from the CI calculation are then used to choose the active space to be used in a subsequent MCSCF calculation. We illustrate our method on a number of systems (Li2, B2, C2, carbonyl oxide and the transition state for oxidation of H2S by dioxirane). In all these cases, ‘intuitive’ active spaces are inadequate, as are active spaces derived from the natural orbitals of unrestricted Hartree-Fock calculations. 相似文献
12.
Smain Bousalem Claire Mangeney Mohamed M. Chehimi Teresa Basinska Beata Miksa Stanislaw Slomkowski 《Colloid and polymer science》2004,282(12):1301-1307
N-Succinimidyl ester functionalized polypyrrole-coated polystyrene latex particles (PSE-PPyNSE) were prepared by the in situ copolymerization of pyrrole and the active ester-functionalized pyrrole (pyrrole-NSE) in the presence of polystyrene latex particles. Polystyrene microspheres were prepared by emulsion polymerization (PSE) leading to particles having a diameter of 450 nm. These PSE particles were precoated with poly(N-vinylpyrrolidone) prior to the in situ copolymerization of pyrrole and pyrrole-NSE. The initial comonomer concentration fractions were 25/75, 50/50 and 75/25 for pyrrole and pyrrole-NSE, respectively. The PPy-coated PSE particles were characterized in terms of morphology, particle size, electrophoretic mobility and chemical composition. The study of morphology by means of scanning electron microscopy showed roughening of the underlying PSE particles owing to the addition of PPyNSE, the overlayer thickness of which was estimated to be around 7 nm. Moreover, loading PPyNSE overlayers resulted in a shift of the electrophoretic mobility from –5.31 m cm/V s to a very small but positive value (0.082–0.112 m cm/V s). X-ray photoelectron spectroscopy and IR spectroscopy permitted the detection of pyrrole-NSE repeat units at the surface indicating that pyrrole and pyrrole-NSE did indeed copolymerize. The PSE-PPyNSE particles were further evaluated as bioadsorbents of human serum albumin used as a test protein. For this study, PSE-PPyNSE50 particles, synthesized from a comonomer feed ratio of 50/50 in pyrrole/pyrrole-NSE, were used and were shown to attach efficiently human serum albumin macromolecules with a maximum amount of 0.2 mg m–2.
相似文献
Mohamed M. ChehimiEmail: |
13.
Philippe Remuzon Daniel Bouzard Claire Clemencin Christian Dussy Munir Essiz Jean-Pierre Jacquet Jean Saint-Germain 《Journal of heterocyclic chemistry》1993,30(2):517-523
The synthesis of (1S,4S,7S)- and (1R,4R,7S)-2-(4-tolylsulfonyl>5-phenylmethyl-7-rnethyl-2,5-diazabicyclo-[2.2.1]heptanes ( 20 ) and ( 22 ) from trans 4-hydroxy-L-proline is described. 相似文献
14.
Kanony C Fabiano-Tixier AS Ravanat JL Vicendo P Paillous N 《Photochemistry and photobiology》2003,77(6):659-667
Pyropheophorbides are red-absorbing porphyrin-like photosensitizers that may interact with DNA either by intercalation or by external binding with self-stacking according to the value of the nucleotide to chromophore molar ratio (N/C). This article reports on the nature and sequence selectivity of the DNA damage photoinduced by a water-soluble chlorhydrate of aminopyropheophorbide. First, this pyropheophorbide is shown to induce on irradiation the cleavage of phiX174 DNA by both Type-I and -II mechanisms, suggested by scavengers and D2O effects. These conclusions are then improved by sequencing experiments performed on a 20-mer oligodeoxynucleotide (ODN) irradiated at wavelengths >345 nm in the presence of the dye, N/C varying from 2.5 to 0.5. Oxidation of all guanine residues to the same extent is observed after piperidine treatment on both single- and double-stranded ODN. Moreover, unexpectedly, a remarkable sequence-selective cleavage occurring at a 5'-CG-3' site is detected before alkali treatment. This frank break is clearly predominant for a low nucleotide to chromophore molar ratio, corresponding to a self-stacking of the dye along the DNA helix. The electrophoretic properties of the band suggest that this lesion results from a sugar oxidation, which leads via a base release to a ribonolactone residue. The proposal is supported by high-performance liquid chromatography-matrix-assisted laser desorption-ionization mass spectrometry experiments that also reveal other sequence-selective frank scissions of lower intensity at 5'-GC-3' or other 5'-CG-3' sites. This sequence selectivity is discussed with regard to the binding selectivity of cationic porphyrins. 相似文献
15.
Wipf P Coleman CM Janjic JM Iyer PS Fodor MD Shafer YA Stephenson CR Kendall C Day BW 《Journal of combinatorial chemistry》2005,7(2):322-330
Cascade reactions of internal and terminal alkynes, zirconocene hydrochloride, dimethylzinc, and phosphinoyl imines (prepared in one step from aldehydes and diphenylphosphinoyl amide) lead to allylic phosphinoyl amides after aqueous workup. Microwave acceleration allows the completion of this one-pot reaction sequence in 10 min. These allylic amides can be converted into a variety of derivatives, including carbamates and sulfonamides, or reacted prior to workup with diiodomethane to give novel C-cyclopropylalkylamides. A solution-phase "libraries from libraries" approach was used to generate an intermediate 20-member library which was subsequently expanded to a 100-member library by a series of N-functionalizations. The biological activity was evaluated in an assay for competitive binding to the estrogen receptor (ERalpha), revealing three potent lead compounds of a new structural type. 相似文献
16.
Khlobystov AN Brett MT Blake AJ Champness NR Gill PM O'Neill DP Teat SJ Wilson C Schröder M 《Journal of the American Chemical Society》2003,125(22):6753-6761
A series of structurally related binuclear metallacycles [Cd(NO(3))(2)L](2), where L is an angular exo-bidentate ligand, have been synthesized. Each metallacycle contains two coordinatively unsaturated, chiral metal centers within a single molecule, and the assembly of these metallacycles into polymeric framework structures has been studied systematically for the first time. Stereoselective homochiral association of [Cd(NO(3))(2)L](2) leads to the formation of helical coordination polymers, whereas meso type association results in nonhelical chain structures. The type of stereoselective aggregation depends on the conditions of self-assembly as well as on ligand functionality. Both helical and nonhelical polymeric complexes have been isolated for the metallacycle [Cd(NO(3))(2)(2,4'-pyacph)](2) (2,4'-pyacph = 2,4'-(4-ethynylphenyl)bipyridyl). Homochiral association results in the formation of helical [Cd(NO(3))]( infinity ) chains which link the binuclear [Cd(NO(3))(2)(2,4'-pyacph)](2) metallacycles into racemic two-dimensional sheets which contain both P and M [Cd(NO(3))]( infinity ) helices. In contrast, meso-association leads to the formation of nonhelical one-dimensional chains. It is shown that the product of homochiral association is predominately formed at room temperature and that of meso-association is generated at elevated temperatures. Thus, it may be concluded that the homochiral association appears to be energetically less favorable than the meso-association, a conclusion that has been confirmed by theoretical calculations of the crystal lattice energy. Several high-yield syntheses of bipyridyl-type ligands used for metallacyclic assembly are also reported. 相似文献
17.
J. Stephen Clark Rebecca P. Freeman Andrew W. Thomas Claire Wilson 《Tetrahedron letters》2004,45(47):8639-8642
A concise enantioselective synthesis of the cyclic ether core of the marine natural product (+)-laurenyne has been accomplished using ring-closing metathesis for medium-ring construction. 相似文献
18.
A concise synthesis of the complete tricyclic dibenzofuran-1,4-dione aromatic core of popolohuanone E has been demonstrated by mild base treatment of a biquinone intermediate, thus establishing a biomimetic route to this family of heterocyclic ring systems and the total synthesis of popolohuanone E. 相似文献
19.
The ionic Diels-Alder reaction, whereby an alpha,beta-unsaturated acetal in combination with a Lewis or Bronsted acid forms an equilibrium concentration of an activated dienophile, has been developed to provide an enantioselective synthesis of cis-decalins. Cyclohex-2-enone type chiral acetals of (2R,3R)-butane-2,3-diol have been screened against Lewis and Br?nsted acids with a variety of dienes and are efficient for the synthesis of a limited subset of cis-decalin structures. Diastereoselectivities of 73% and 82% have been found for the asymmetric ionic Diels-Alder reaction between the chiral acetal derivatives of cyclohex-2-enone (6) and 2-methylcyclohex-2-enone (18) with 2,3-dimethyl-1,3-butadiene (7). Terminal substituents on the diene partner in general render the system unreactive. However a synthetically useful cis-decalin 31, derived from the reaction of 2-methylcyclohex-2-enone and Z-3-t-butyldimethyl-silyloxypenta-1,3-diene has been prepared in enantiomerically pure form in 74% isolated yield using this asymmetric ionic Diels-Alder protocol. 相似文献
20.
Vidal-Madjar C Florentina CC Gherghi I Jaulmes A Pantazaki A Taverna M 《Journal of chromatography. A》2004,1042(1-2):15-22
The binding of an anticancer drug (actinomycin D or ACTD) to double-stranded DNA (dsDNA) was studied by means of high-performance liquid chromatography (HPLC). ACTD is an antitumor antibiotic containing one chromophore group and two pentapeptidic lactone cycles that binds dsDNA. Incubations of ACTD with DNA were performed at physiological pH. The complexed and free ligand concentrations of the mixture were quantified at 440 nm from their separation on a size-exclusion chromatographic (SEC) column using the same buffer for the elution and the sample incubation. The DNA and the ACTD-DNA complexes were eluted at the column exclusion volume while the ligand was retained on the support. An apparent binding curve was obtained by plotting the amount emerging at the exclusion column volume against that eluted at free ACTD retention volume. A dissociating effect was evidenced and the binding parameters were significantly different from those obtained at equilibrium by visible absorbance titration. The equilibrium binding parameters determined by absorption spectroscopy were used as starting data in the numerical simulations of the chromatographic process. The results showed a strong dependency of the apparent binding parameters on the reaction kinetics. Finally the comparison of the apparent binding curve obtained from the HPLC experiments and from the numerical simulations permitted an evaluation of the dissociation rate constant (kd = 0.004 s(-1)). 相似文献