全文获取类型
收费全文 | 6133篇 |
免费 | 196篇 |
专业分类
化学 | 3873篇 |
晶体学 | 25篇 |
力学 | 207篇 |
数学 | 804篇 |
物理学 | 1420篇 |
出版年
2023年 | 28篇 |
2022年 | 36篇 |
2021年 | 48篇 |
2020年 | 74篇 |
2019年 | 74篇 |
2018年 | 100篇 |
2017年 | 68篇 |
2016年 | 148篇 |
2015年 | 183篇 |
2014年 | 153篇 |
2013年 | 348篇 |
2012年 | 394篇 |
2011年 | 388篇 |
2010年 | 264篇 |
2009年 | 157篇 |
2008年 | 391篇 |
2007年 | 348篇 |
2006年 | 327篇 |
2005年 | 301篇 |
2004年 | 257篇 |
2003年 | 244篇 |
2002年 | 205篇 |
2001年 | 125篇 |
2000年 | 141篇 |
1999年 | 61篇 |
1998年 | 88篇 |
1997年 | 57篇 |
1996年 | 100篇 |
1995年 | 59篇 |
1994年 | 50篇 |
1993年 | 45篇 |
1992年 | 54篇 |
1991年 | 32篇 |
1990年 | 47篇 |
1989年 | 36篇 |
1988年 | 48篇 |
1986年 | 31篇 |
1985年 | 49篇 |
1984年 | 62篇 |
1983年 | 28篇 |
1982年 | 39篇 |
1981年 | 47篇 |
1980年 | 42篇 |
1979年 | 36篇 |
1978年 | 43篇 |
1977年 | 40篇 |
1976年 | 52篇 |
1975年 | 33篇 |
1974年 | 26篇 |
1973年 | 29篇 |
排序方式: 共有6329条查询结果,搜索用时 258 毫秒
171.
172.
Jossang A Cavé A Saez J Bartoli MH Cavé A Jossang P 《The Journal of organic chemistry》1996,61(9):3023-3030
Monterine 1 as well as granjine 3, 1R,1'S configured biphenylic bisbenzylisoquinoline alkaloids, generate two highly populated conformers. The interconversion of two forms was detected by saturation tranfer in (1)H NMR NOEs experiments. Tridimensional structure of the conformers was determined on the basis of (1)H NMR analysis of anisotropic shielding protons, by NOEs measurements and vicinal proton coupling constants of CH1-CH(2)alpha and CH1'-CH(2)alpha'. The structures established from NMR data were further refined to observe the mobility of 3D conformations by molecular dynamics simulation in vacuo. The highly populated conformers, monterine 1a and 1b, as well as granjine 3a and 3b, are interconvertible by rotation about the C1'-Calpha', Calpha'-C9', and C11'-C11 bonds and inversion of the benzyl D ring by reference to CH(2)alpha'. The slow exchange system was investigated by dynamic NMR spectroscopy: DeltaG()(c) 77.9 KJ/mol and k(c) 200 s(-)(1) for monterine 1; DeltaG()(c) 77.7 KJ/mol and k(c) 211 s(-)(1) for granjine 3. Natural and synthetic biphenylic bisbenzylisoquinolines displayed, in vitro, cytotoxic activities against human prostate and breast cancer cell lines. 相似文献
173.
Andrejevic Blant S Grosjean P Ballini JP Wagnières G van den Bergh H Fontolliet C Monnier P 《Journal of photochemistry and photobiology. B, Biology》2001,61(1-2):1-9
To date, little is known about precise time-dependent distribution and histological localization of tetra(m-hydroxyphenyl)chlorin (mTHPC) in human healthy tissues and squamous cell malignancies in the upper aero-digestive tract. A fluorescence microscopy study was performed on 50 healthy tissue biopsies and on 13 tumors (graded from Tis to T1 SCC) from 30 patients. Tissue samples were taken between 4 h and 11 days following injection of 0.15 mg/kg mTHPC. A fairly comparable distribution pattern in various tissues was observed over time in different patients. Vascular localization of mTHPC fluorescence predominates at a short delay, whereas the dye is essentially located in the tumoral and healthy mucosa after longer delays. A much lower uptake and retention of mTHPC fluorescence was noted in striated muscle and cartilage as compared to neoplastic lesions. No significant selectivity was found between healthy and tumoral mucosa. The obtained data are important to confirm drug-light interval that have been selected for effective PDT for early SCC malignancies while minimizing the risks of over- or under-treatment. The low fluorescence level in striated muscle provides the opportunity to develop interstitial PDT as a treatment modality for invasive SCC of unfavorable locations in the oral cavity or pharynx, such as the base of the tongue. 相似文献
174.
Nowaczyk S Alayrac C Metzner P Averbuch-Pouchot MT 《The Journal of organic chemistry》2002,67(19):6852-6855
The alkylation of the lithium enolate of enantiopure alpha-cyclohexylsulfinyl thioacetamide 1 with allyl bromides 5 possessing an electron-withdrawing group at the vinylic position does not occur at the sulfur center - as expected in the sulfur series - but at the carbon center through conjugate addition followed by bromide elimination. The modest to excellent 1,2-asymmetric induction achieved by the alkylsulfinyl group (dr up to 100:0) is explained by an electronic model. 相似文献
175.
Ronald A. Buono Nathalie Kucharczyk Magrit Neuenschwander Johan Kemmink Lih-Yueh Hwang Jean-Luc Fauchère Carol A. Venanzi 《Journal of computer-aided molecular design》1996,10(3):213-232
Summary The design of enzyme mimics with therapeutic and industrial applications has interested both experimental and computational chemists for several decades. Recent advances in the computational methodology of restrained molecular dynamics, used in conjunction with data obtained from two-dimensional 1H NMR spectroscopy, make it a promising method to study peptide and protein structure and function. Several issues, however, need to be addressed in order to assess the validity of this method for its explanatory and predictive value. Among the issues addressed in this study are: the accuracy and generizability of the GROMOS peptide molecular mechanics force field; the effect of inclusion of solvent on the simulations; and the effect of different types of restraining algorithms on the computational results. The decapeptide Ser-Tyr-Ser-Met-Glu-His-Phe-Arg-Trp-Gly, which corresponds to the sequence of ACTH1–10, has been synthesized, cyclized, and studied by two-dimensional 1H NMR spectroscopy. Restrained molecular dynamics (RMD) and time-averaged restrained molecular dynamics (TARMD) simulations were carried out on four different distance-geometry starting structures in order to determine and contrast the behavior of cyclic ACTH1–10 in vacuum and in solution. For the RMD simulations, the structures did not fit the NOE data well, even at high values of the restraining potential. The TARMD simulation method, however, was able to give structures that fit the NOE data at high values of the restraining potential. In both cases, inclusion of explicit solvent molecules in the simulation had little effect on the quality of the fit, although it was found to dampen the motion of the cyclic peptide. For both simulation techniques, the number and size of the NOE violations increased as the restraining potential approached zero. This is due, presumably, to inadequacies in the force field. Additional TARMD vacuum-phase simulations, run with a larger memory length or with a larger sampling size (16 additional distance-geometry structures), yielded no significantly different results. The computed data were then analyzed to help explain the sparse NOE data and poor chymotryptic activity of the cyclic peptide. Cyclic ACTH1–10, which contains the functional moieties of the catalytic triad of chymotrypsin, was evaluated as a potential mimic of chymotrypsin by measurement of the rate of hydrolysis of esters of L-and d-phenylalanine. The poor rate of hydrolysis is attributed to the flexibility of the decapeptide, the motion of the side chains, which result in the absence of long-range NOEs, the small size of the macrocycle relative to that of the substrate, and the inappropriate orientation of the Gly, His, and Ser residues. The results demonstrate the utility of this method in computer-aided molecular design of cyclic peptides and suggest structural modifications for future work based on a larger and more rigid peptide framework. 相似文献
176.
The thermal condensation of functional phosphonates bearing strongly withdrawing groups (RO)2P(O)CH2Z1 with dimethylformamide dimethyl acetal gives corresponding β-functional, β-phosphonic enamines (RO)2P(O)C(Z)=CHNMe22. Acid or basic hydrolysis of the enamines frequently gives the free aldehyde (RO)2P(O)CH(Z)—CHO 3. We show that the enamines can be used with success for the synthesis of heterocycles like, pyrazoles 4, pyrimidines 5, benzodiazepine 6 or indole 7, all of them substituted with a phosphonate group. 相似文献
177.
M. C. Bergère C. de Calan A. P. C. Malbouisson 《Communications in Mathematical Physics》1978,62(2):137-158
For any Feynman amplitude, where any subset of invariants and/or squared masses is scaled by a real parameter going to zero or infinity, the existence of an expansion in powers of and ln is proved, and a method is given for determining such an expansion. This is shown quite generally in euclidean metric, whatever the external momenta (exceptional or not) and the internal masses (vanishing or not) may be, and for some simple cases in minkowskian metric, assuming only finiteness of the — eventually renormalized — amplitude before scaling. The method uses what is called Multiple Mellin representation, the validity of which is related to a generalized power-counting theorem.On leave of absence from University of Bahia (Brazil). Fellow of CAPES, Brazil 相似文献
178.
Turbiez M Frère P Allain M Videlot C Ackermann J Roncali J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3742-3752
Hybrid oligothiophenes based on a various combinations of thiophene and 3,4-ethylenedioxythiophene (EDOT) groups have been synthesized. UV/Vis absorption spectra show that the number and relative positions of the EDOT groups considerably affect the width of the HOMO-LUMO gap and the rigidity of the conjugated system. Analysis of the crystallographic structure of two hybrid quaterthiophenes confirms that insertion of two adjacent EDOT units in the middle of the molecule leads to a self-rigidification of the conjugated systems by intramolecular SO interactions. Cyclic voltammetry data shows that the first oxidation potential of the oligomers decreases with increasing chain length and increasing number of EDOT groups for a given chain length. Electrochemical studies and theoretical calculations show that the positions of the EDOT units in the conjugated chain control the potential difference (DeltaE(p)) between the first and second oxidation steps. Moving the EDOT groups from the outer to the inner positions of the conjugated system increases DeltaE(p). Theoretical calculations confirm that this phenomenon reflects an increase of the intramolecular coulombic repulsion between positive charges in the dication. A thin-film field-effect transistor was fabricated by vacuum sublimation of a pentamer with alternating thiophene-EDOT structure, and the hole mobility was determined. 相似文献
179.
Michèle Decouzon Jean-Fraçois Gal Jérôme Gayraud Pierre-Charles Maria Gian-Angelo Vaglio Paolo Volpe 《Journal of the American Society for Mass Spectrometry》1993,4(1):54-57
An accurate gas-phase acidity for germane (enthalpy scale, equivalent to the proton affinity of GeH3 ?), ΔH acid o(GeH4) = 1502.0 ± 5.1 kJ mol?1, is obtained by constructing a consistent acidity ladder between GeH4, and H2S by using Fourier transform-ion cyclotron resonance spectrometry, and 0 and 298.15 K values for the first bond dissociation energy of GeH4 are proposed: D0 o(H3Ge-H) = 352 ± 9 kJ mol?1; D o(H3Ge-H) = 358 ± 9 kJ mol?1, respectively. These results are compared with experimental and theoretical data reported in the literature. Methylgermane was found to be a weaker acid than germane by approximately 35 kJ mol?1: ΔH acid o = 1536.6 kJ mol?1. 相似文献
180.
Bacillus subtilis pyrrolidone carboxyl peptidase (Pcp) overexpressed in Escherichia coli was purified to homogeneity in less than 12 h using ammonium sulphate precipitation and hydrophobic interaction chromatography. The enzyme, which removes amino-terminal L-pyroglutamic acid from peptides, appears to be a tetramer of 25,200 molecular mass subunits. The protein cross-reacted with polyclonal antibodies raised against Pcp from Streptococcus pyogenes. The overexpressed enzyme exhibits an absolute substrate specificity towards N-terminal pyroglutamyl residues with a Michaelis constant of 1.04 mM for L-pyroglutamyl-beta-naphthylamide. The enzyme could be used for the removal of pyroglutamyl residues that block amino termini of proteins and peptides before performing Edman sequential degradation. 相似文献