全文获取类型
收费全文 | 281篇 |
免费 | 25篇 |
专业分类
化学 | 217篇 |
力学 | 13篇 |
数学 | 30篇 |
物理学 | 46篇 |
出版年
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 5篇 |
2017年 | 3篇 |
2016年 | 14篇 |
2015年 | 13篇 |
2014年 | 8篇 |
2013年 | 13篇 |
2012年 | 26篇 |
2011年 | 15篇 |
2010年 | 14篇 |
2009年 | 5篇 |
2008年 | 17篇 |
2007年 | 14篇 |
2006年 | 13篇 |
2005年 | 7篇 |
2004年 | 4篇 |
2003年 | 14篇 |
2002年 | 7篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1991年 | 2篇 |
1989年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1976年 | 6篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
1932年 | 2篇 |
1923年 | 1篇 |
排序方式: 共有306条查询结果,搜索用时 15 毫秒
301.
Remi A. Momo Jane F. Povey C. Mark Smales Christopher J. O’Malley Gary A. Montague Elaine B. Martin 《Analytical and bioanalytical chemistry》2013,405(25):8251-8265
Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF MS) has been exploited extensively in the field of microbiology for the characterisation of bacterial species, the detection of biomarkers for early disease diagnosis and bacterial identification. Here, the multivariate data analysis technique of partial least squares-discriminant analysis (PLS-DA) was applied to ‘intact cell’ MALDI-ToF MS data obtained from Escherichia coli cell samples to determine if such an approach could be used to distinguish between, and characterise, different growth phases. PLS-DA is a technique that has the potential to extract systematic variation from large and noisy data sets by identifying a lower-dimensional subspace that contains latent information. The application of PLS-DA to the MALDI-ToF data obtained from cells at different stages of growth resulted in the successful classification of the samples according to the growth phase of the bacteria cultures. A further outcome of the analysis was that it was possible to identify the mass-to-charge (m/z) ratio peaks or ion signals that contributed to the classification of the samples. The Swiss-Prot/TrEMBL database and primary literature were then used to provisionally assign a small number of these m/z ion signals to proteins, and these tentative assignments revealed that the major contributors from the exponential phase were ribosomal proteins. Additional assignments were possible for the stationary phase and the decline phase cultures where the proteins identified were consistent with previously observed biological interpretation. In summary, the results show that MALDI-ToF MS, PLS-DA and a protein database search can be used in combination to discriminate between ‘intact cell’ E. coli cell samples in different growth phases and thus could potentially be used as a tool in process development in the bioprocessing industry to enhance cell growth and cell engineering strategies. 相似文献
302.
Kévin Cocq Nathalie Saffon‐Merceron Yannick Coppel Corentin Poidevin Valérie Maraval Remi Chauvin 《Angewandte Chemie (International ed. in English)》2016,55(48):15133-15136
A ring carbo‐mer of naphthalene, C32Ar8 (Ar=p‐n‐pentylphenyl), has been obtained as a stable blue chromophore, after a 19‐step synthetic route involving methods inspired from those used in the synthesis of carbo‐benzenes, or specifically devised for the present target, like a double Sonogashira‐type coupling reaction. The last step is a SnCl2/HCl‐mediated reduction of a decaoxy‐carbo‐decalin, which is prepared through successive [8+10] macrocyclization steps. Two carbo‐benzene references are also described, C18Ar6 and o‐C18Ar4(C≡C‐SiiPr3)2. The carbo‐naphthalene bicycle is locally aromatic according to structural and magnetic criteria, as revealed by strong diatropic ring current effects on the deshielding of 1H nuclei of the Ar groups and on the negative value of the DFT‐calculated NICS at the center of the C18 rings (?12.8 ppm). The stability and aromaticity of this smallest fused molecular fragment of α‐graphyne allows prediction of the same properties for the carbon allotrope itself. 相似文献
303.
A series of 1-(2,3-dihydro-5H-4,1-benzoxathiepin-3-yl)pyrimidine derivatives were synthesized and two of them (8 and 9) showed a modest antiproliferative activity against the MCF-7 breast cancer cell line. We then decided to change the pyrimidine base for the more lipophilic 6′-chloropurine, and the N-9′ purine (15) and N-7′ purine (17) were obtained. The sulfone N-7′-alkylated-6-chloropurine 18 was the most active derivative. Compound 17 was found to be slightly more active than its regioisomer 15, with an activity similar to that of 5-fluorouracil as a reference drug. Encouraged by these values, we tested these compounds against both the HT-29 human colon cancer cell line and the IEC-6 normal rat intestinal epithelial cell line, and 15 was found to be 12.7-fold more active against HT-29 than versus IEC-6. 相似文献
304.
We consider the Hartree equation with a smooth kernel and an external potential, in the semiclassical regime. We analyze the
propagation of two initial wave packets and show different possible effects of the interaction, according to the size of the
nonlinearity in terms of the semiclassical parameter. We show three different sorts of nonlinear phenomena. In each case,
the structure of the wave as a sum of two coherent states is preserved. However, the envelope and the center (in phase space)
of these two wave packets are affected by nonlinear interferences, which are described precisely. 相似文献
305.
Difluorenyl carbo‐Benzenes: Synthesis,Electronic Structure,and Two‐Photon Absorption Properties of Hydrocarbon Quadrupolar Chromophores
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Iaroslav Baglai Manuel de Anda‐Villa Rodrigo M. Barba‐Barba Corentin Poidevin Dr. Gabriel Ramos‐Ortíz Dr. Valérie Maraval Dr. Christine Lepetit Dr. Nathalie Saffon‐Merceron Dr. José‐Luis Maldonado Prof. Dr. Remi Chauvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):14186-14195
The synthesis, crystal and electronic structures, and one‐ and two‐photon absorption properties of two quadrupolar fluorenyl‐substituted tetraphenyl carbo‐benzenes are described. These all‐hydrocarbon chromophores, differing in the nature of the linkers between the fluorenyl substituents and the carbo‐benzene core (C?C bonds for 3 a , C?C?C?C expanders for 3 b ), exhibit quasi–superimposable one‐photon absorption (1PA) spectra but different two‐photon absorption (2PA) cross‐sections σ2PA. Z‐scan measurements (under NIR femtosecond excitation) indeed showed that the C?C expansion results in an approximately twofold increase in the σ2PA value, from 336 to 656 GM (1 GM=10?50 cm4 s molecule?1 photon?1) at λ=800 nm. The first excited states of Au and Ag symmetry accounting for 1PA and 2PA, respectively, were calculated at the TDDFT level of theory and used for sum‐over‐state estimations of σ2PA(λi), in which λi=2 hc/Ei, h is Planck’s constant, c is the speed of light, and Ei is the energy of the 2PA‐allowed transition. The calculated σ2PA values of 227 GM at 687 nm for 3 a and 349 GM at 708 nm for 3 b are in agreement with the Z‐scan results. 相似文献
306.
Soncini A Fowler PW Lepetit C Chauvin R 《Physical chemistry chemical physics : PCCP》2008,10(7):957-964
Maps of current density induced by a perpendicular external magnetic field are calculated at the ipsocentric CTOCD-DZ/6-31G**//B3PW91/6-31G** level for ring carbo-mers of [N]-annulenes (closed-shell singlet states of C(3N)H, N = 3 to 7, with q = -1, 0, +1, 0, -1, respectively, and also the triplet ground state for N = 4) and of [N]-cycloalkanes (C(3N)H(qN), N = 3, 4, 5). Strong four-electron diatropic ring currents indicate conventional pi aromaticity for all the singlet and triplet carbo-[N]annulenes studied, with the exception of C(12)H(4), where instead the strong two-electron paratropic ring current is the signature of pi antiaromaticity. The carbo-[N]cycloalkanes (also known as [N]pericyclynes) show only localized pi currents, consistent with non-aromaticity. There is no indication of a 'homo-aromatic' ring current attributable to the in-plane pi orbitals of the inserted C2 units in any of the maps. Consequences for the interpretation of ELF (electron localisation function) populations are discussed. 相似文献