全文获取类型
收费全文 | 3928篇 |
免费 | 227篇 |
国内免费 | 4篇 |
专业分类
化学 | 2923篇 |
晶体学 | 14篇 |
力学 | 131篇 |
数学 | 558篇 |
物理学 | 533篇 |
出版年
2023年 | 42篇 |
2022年 | 51篇 |
2021年 | 73篇 |
2020年 | 77篇 |
2019年 | 79篇 |
2018年 | 71篇 |
2017年 | 66篇 |
2016年 | 135篇 |
2015年 | 136篇 |
2014年 | 143篇 |
2013年 | 237篇 |
2012年 | 303篇 |
2011年 | 363篇 |
2010年 | 160篇 |
2009年 | 126篇 |
2008年 | 267篇 |
2007年 | 235篇 |
2006年 | 236篇 |
2005年 | 223篇 |
2004年 | 202篇 |
2003年 | 155篇 |
2002年 | 118篇 |
2001年 | 37篇 |
2000年 | 47篇 |
1999年 | 40篇 |
1998年 | 27篇 |
1997年 | 18篇 |
1996年 | 30篇 |
1995年 | 24篇 |
1994年 | 21篇 |
1993年 | 20篇 |
1992年 | 17篇 |
1991年 | 20篇 |
1990年 | 25篇 |
1989年 | 17篇 |
1988年 | 17篇 |
1987年 | 14篇 |
1986年 | 9篇 |
1985年 | 19篇 |
1984年 | 21篇 |
1983年 | 11篇 |
1982年 | 27篇 |
1981年 | 17篇 |
1980年 | 23篇 |
1979年 | 27篇 |
1978年 | 17篇 |
1977年 | 21篇 |
1976年 | 19篇 |
1975年 | 12篇 |
1974年 | 12篇 |
排序方式: 共有4159条查询结果,搜索用时 15 毫秒
51.
Ernest Wenkert Edward W. Hagaman Nicole Kunesch Nai-yi Wang Bla Zsadon 《Helvetica chimica acta》1976,59(8):2711-2723
The 13C shifts of 16α- and 16β-substituted derivatives of quebrachamine, 14,15-dehydroquebrachamine, cleavamine, 15,20α-dihydrocleavamine and 15,20β-dihydrocleavamine are determined and correlated with possible conformations of these tetracycles. The method of analysis of the C(16) configuration of these compounds, which emanated from this study, is used for the determination of the configuration of the site of coupling of vindoline and cleavamine β-chloroindolenine. 相似文献
52.
Nicole M. Brunkan 《Journal of organometallic chemistry》2003,683(1):77-82
The complex (dippe)Ni(η3-allyl)(CN) has been prepared and fully characterized (dippe=bis-(diisopropylphosphino)ethane), including X-ray diffraction studies, as a square pyramidal structure. The complex shows dynamic 1H-NMR behavior consistent with substantial structural rearrangements upon π to σ allyl interconversion. A comparison is made with (dippe)Ni(η3-allyl)Br, which also displays a square pyramidal structure. 相似文献
53.
Reactivities of homogeneous series of ethylenic compounds R1CHCH21, trans R1CHCHMe 2, R1MeCCH23 and R1CHCMe24 have been measured in methanol at 25°C (R1 Me, Et, n-Pr, -CH2C6H5-CH2OCOCH3, -CH2Cl). The criterion developed to decide between a bridged and a carbonium ion-like transition state is based on an internal comparison of the series and avoids resorting to external structural scales. Even in the case of alkenes 3 and 4 which are very dissymmetric with respect to polarity, the sensitivity to polar effects remains constant and the transition state behaves like a symmetric entity; only a slight secondary effect, attributed to hyperconjugation, is detectable. 相似文献
54.
Milen Raytchev Elke Mayer Nicole Amann Hans-Achim Wagenknecht Torsten Fiebig 《Chemphyschem》2004,5(5):706-712
5-(Pyren-1-yl)-2'-deoxyuridine (PydU) and 5-(Pyren-1-yl)-2'-deoxycytidine (PydC) were used as model nucleosides for DNA-mediated reductive electron transport (ET) in steady-state fluorescence and femtosecond time-resolved transient absorption spectroscopy studies. Excitation of the pyrene moiety in PydU and PydC leads to an intramolecular electron transfer that yields the pyrenyl radical cation and the corresponding pyrimidine radical anion (dU.- and dC.-. By comparing the excited state dynamics of PydC and PydU, we derived information about the energy difference between the two pyrimidine radical anion states. To determine the influence of protonation on the rates of photoinduced intramolecular ET, the spectroscopic investigations were performed in acetonitrile, MeCN, and in water at different pH values. The results show a significant difference in the basicity of the generated pyrimidine radical anions and imply an involvement of proton transfer during electron hopping in DNA. Our studies revealed that the radical anion dC.- is being protonated even in basic aqueous solution on a picosecond time scale (or faster). These results suggest that protonation of dC.- may also occur in DNA. In contrast, efficient ET in PydU could only be observed at low pH values (< 5). In conclusion, we propose--based on the free energy differences and the different basicities--that only dT.- but not dC.- can participate as an intermediate charge carrier for excess electron migration in DNA. 相似文献
55.
[reaction: see text] The regioselectivity of the Birch reductive alkylation of polysubstituted biaryls has been investigated. Results indicate that regioselectivity is affected by the electronic nature of substituents on both aromatic rings. The electron-rich 3,5-dimethoxyphenyl moiety is selectively reduced and then alkylated, while phenols and aniline are not dearomatized under these conditions. Biaryls possessing a phenol moiety are alkylated on the second ring, providing that the acidic proton has been removed prior to the Li/NH3 reduction. 相似文献
56.
Marie-Noelle Avettand-Fènoël N. David G. Reumont J. -M. Fiorani M. Vilasi P. Perrot 《Journal of Thermal Analysis and Calorimetry》2007,90(2):329-332
The Fe-Sn-Zn system is of interest because Sn is one element added to the Zn galvanizing bath to overcome the drawbacks due
to the presence of Si in semi-killed steels. This work has been undertaken with the aim to understand the tin effect on the
microstructure and the layers growth in batch galvanized coatings on low alloyed steels.
Various experimental techniques such as metallography, scanning electron microscopy (SEM) coupled with X-ray energy dispersive
spectroscopy (EDX) are used in order to characterize the microstructure and the properties of such coatings elaborated in
a zinc bath enriched with tin.
Solidification phenomena and layers growth mechanisms during galvanization are explained by means of the ternary phase diagram
Fe-Sn-Zn at 450°C. The Calphad method allows to obtain this phase diagram from the three optimized binary phase diagrams Fe-Sn,
Fe-Zn and Sn-Zn and some experimental data inside the ternary Fe-Sn-Zn system. 相似文献
57.
Rondelez Y Rager MN Duprat A Reinaud O 《Journal of the American Chemical Society》2002,124(7):1334-1340
Two calixarene-based model systems (a and b) for monocopper enzymes are compared. Both present a tris(pyridine) coordination site for Cu that mimics the imidazole-rich neutral binding site in enzymes. Upon reaction with 1 equiv of copper(I), the tridentate ligands gave rise to ill-defined unsymmetrical complexes. However, in the presence of an organonitrile RCN (R = Me, Et, Ph), tetrahedral species were obtained, with the nitrilo ligand included in the calixarene hydrophobic cone. System b presents a larger cavity than system a, with a wider opening thanks to the removal of three tBu groups from the calixarene structure. As a result, the recognition pattern for MeCN vs PhCN is inverted, and the relative affinity constants differ by 3 orders of magnitude. The mechanism of the acetonitrile exchange at the cuprous centers was studied by (1)H NMR spectroscopy. Thermodynamic and kinetic data show that it follows a dissociative pathway in both cases. The main differences between systems a and b stem from the presence of a door that entraps the guest in case a. In system b indeed, the removal of three calixarene tBu groups led to a 100-fold acceleration of the MeCN exchange rate. Hence, these supramolecular systems provide a rare and interesting model for the hydrophobic substrate channel giving access to a metalloenzyme active site. 相似文献
58.
Cremer GA Bureaud N Lelièvre D Piller V Piller F Delmas A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6353-6360
Our goal was to develop mimics of MUC1, highly immunogenic to induce an efficient immune response against the tumor-associated form of MUC1, and sufficiently different from the natural antigen to bypass the tolerance barrier in humans. With the aim of obtaining a well-defined peptide construct as a means of evoking the precise immune responses required in immunotherapy, we synthesized artificial mimics of the MUC1 protein composed of two MUC1 repeat units of inverse orientation and a universal T-helper epitope. To synthesize these heteromeric peptide constructs, we followed a convergent approach using chemoselective ligation based on oxime chemistry. A stem peptide was first synthesized bearing two orthogonally masked aldehydes. After successive deprotection, two oxime bonds can be specifically generated. The proposed strategy proved to be concise and robust, and allowed the synthesis of the tri-branched protein in a very satisfactory yield. The different constructs were tested for their ability to generate antibodies able to recognize the MUC1 protein. 相似文献
59.
60.
Cyrille Ceugniet Ltitia Lepetit Nancy Lauth De Viguerie Henry Jammes Nicole Peyrot Monique Rivire 《Journal of chromatography. A》1998,810(1-2):237-240
A high-performance liquid chromatographic (HPLC) procedure was developed to allow the rapid separation, in a single run, of a mixture of the main retinal isomers (all-trans, 13-cis, 9-cis), all-trans-retinol, and of the two major photooxygenated photoproducts (5,8-peroxyretinal and 5,6-epoxyretinal). The mixture was separated by HPLC on an octadecyl (ODS) column with 16% (v/v) diethyl ether in hexane as mobile phase and anthracene as the internal standard. A commercial type cosmetic formulation containing 0.05% all-trans-retinal was analyzed successfully for this analyte. 相似文献