全文获取类型
收费全文 | 723篇 |
免费 | 21篇 |
国内免费 | 2篇 |
专业分类
化学 | 531篇 |
晶体学 | 1篇 |
力学 | 18篇 |
数学 | 56篇 |
物理学 | 140篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 8篇 |
2020年 | 9篇 |
2019年 | 11篇 |
2018年 | 4篇 |
2017年 | 7篇 |
2016年 | 17篇 |
2015年 | 12篇 |
2014年 | 20篇 |
2013年 | 29篇 |
2012年 | 49篇 |
2011年 | 58篇 |
2010年 | 31篇 |
2009年 | 40篇 |
2008年 | 51篇 |
2007年 | 41篇 |
2006年 | 40篇 |
2005年 | 42篇 |
2004年 | 41篇 |
2003年 | 35篇 |
2002年 | 39篇 |
2001年 | 9篇 |
2000年 | 15篇 |
1999年 | 3篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 7篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 7篇 |
1987年 | 9篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1975年 | 2篇 |
1970年 | 2篇 |
1928年 | 2篇 |
1887年 | 2篇 |
1880年 | 2篇 |
排序方式: 共有746条查询结果,搜索用时 748 毫秒
71.
De Winter J Lemaur V Ballivian R Chirot F Coulembier O Antoine R Lemoine J Cornil J Dubois P Dugourd P Gerbaux P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9738-9745
Ion mobility spectrometry coupled with mass spectrometry was used to experimentally determine the three-dimensional structure of multiply charged sodium cationized polylactides (PLA). In particular, the experiments were conducted to evaluate the influence of the charge state and the size on the gas-phase conformation of cationized PLA. The measured collision cross sections were then compared to calculated values obtained by computational chemistry methods. The most striking feature was the experimental and theoretical observation of a breaking point in the quasilinear relationship between the average collision cross sections and the number of monomer units for the triply charged cations. This breaking point was theoretically demonstrated, for the doubly and triply charged cations, to be associated with a significant folding of the polymer chains around the cationizing agents. The occurrence of such breaking points could be exploited to correlate the charge state of the most intense ion series observed upon electrospray ionization with the number-average molecular mass of a polymer. 相似文献
72.
Elizabeth Renaud Christian Robelin Aïmen E. Gheribi Patrice Chartrand 《The Journal of chemical thermodynamics》2011,43(8):1286-1298
A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases of the (LiF + LiCl + NaF + NaCl + KF + KCl + MgF2 + MgCl2 + CaF2 + CaCl2 + SrF2 + SrCl2) system, and optimized model parameters have been found. The (LiCl + NaCl + KCl + MgCl2 + CaCl2 + SrCl2), (LiF + NaF + KF + MgF2 + CaF2 + SrF2), and (LiF + LiCl + NaF + NaCl + KF + KCl + MgF2 + MgCl2 + CaF2 + CaCl2) subsystems have been critically evaluated previously. The model parameters for the common-ion binary, common-anion ternary, and reciprocal ternary subsystems (i.e. systems with two cations and two anions) can be used to predict thermodynamic properties and phase equilibria for the multicomponent reciprocal system. The Modified Quasichemical Model in the Quadruplet Approximation was used for the molten salt phase. This model takes into account both first-nearest-neighbor (cation–anion) and second-nearest-neighbor (cation–cation and anion–anion) short-range ordering, and the coupling between them. Finally, the CaFCl–SrFCl solid solution was modeled using the Compound Energy Formalism. 相似文献
73.
Radical alkylation of 2-(tert-butyl)-2-methyldioxolan-4-one, a chiral equivalent of glycolic acid, occurs with good to high diastereoselectivity that compares favorably with the corresponding enolate alkylation. The importance of the position of the transition state position, early or late, is highlighted. 相似文献
74.
Okadaic acid (OA), responsible for gastrointestinal problems, inhibits protein phosphatase 2A (PP2A). Therefore, the inhibition exerted by the toxin on PP2A could be used to detect the presence of OA in aqueous solution and in shellfish sample.In this work, two commercial PP2As (from ZEU Immunotec and Millipore) and one produced by molecular engineering (from GTP Technology) were tested. Enzymes were used in solution and also immobilized within a polymeric gel. In solution, best performances were obtained using PP2A purchased from ZEU Immunotec (Spain). OA was detected in aqueous solution in concentration as low as 0.0124 μg L−1 using the enzyme from ZEU Immunotec whereas the detection limits were 0.47 μg L−1 and 0.123 μg L−1 with PP2As from Millipore and GTP Technology, respectively. Considering that the immobilization step contributes to stabilize the PP2A activity, enzymes were entrapped within a photopolymer and an agarose gel. These different polymeric matrices were optimized, tested and compared. Agarose gel seems to be a good alternative to the photopolymer largely used in our group. For instance, the IC50 value obtained with the test based on PP2A from ZEU Immunotec immobilized within an agarose gel was 1.98 μg L−1. This value was 1.8-fold lower than those obtained with the photopolymer test using the same enzyme. The proposed test is sensitive, fast and does not require expensive equipment. To evaluate the efficiency of the assay, PP inhibition tests based on PP2A from ZEU Immunotec in solution or immobilized within a gel were used for OA detection in contaminated shellfish. 相似文献
75.
Vial J Thiébaut D Marty F Guibal P Haudebourg R Nachef K Danaie K Bourlon B 《Journal of chromatography. A》2011,1218(21):3262-3266
Since the late 1970s, approaches have been proposed to replace conventional gas chromatography apparatus with silicon-based microfabricated separation systems. Performances are expected to be improved with miniaturization owing to the reduction of diffusion distances and better thermal management. However, one of the main challenges consists in the collective and reproducible fabrication of efficient microelectromechanical system (MEMS) gas chromatography (GC) columns. Indeed, usual coating processes or classical packing with particulate matters are not compatible with the requirements of collective MEMS production in clean room facilities. A new strategy based on the rerouting of conventional microfabrication techniques and widely used in electronics for metals and dielectrics deposition is presented. The originality lies in the sputtering techniques employed for the deposition of the stationary phase. The potential of these novel sputtered stationary phases is demonstrated with silica sputtering applied to the separation of light hydrocarbons and natural gases. If kinetic characteristics of the sputtered open tubular columns were acceptable with 2500 theoretical plates per meter, the limited retention and resolution of light hydrocarbons led us to consider semipacked sputtered columns with rectangular pillars allowing also significant reduction of typical diffusion distances. In that case separations were greatly improved because retention increased and efficiency was close to 5000 theoretical plates per meter. 相似文献
76.
Hoffer L Renaud JP Horvath D 《Combinatorial chemistry & high throughput screening》2011,14(6):500-520
Fragment-based screening is an emerging technology which is used as an alternative to high-throughput screening (HTS), and often in parallel. Fragment screening focuses on very small compounds. Because of their small size and simplicity, fragments exhibit a low to medium binding affinity (mM to μM) and must therefore be screened at high concentration in order to detect binding events. Since some issues are associated with high-concentration screening in biochemical assays, biophysical methods are generally employed in fragment screening campaigns. Moreover, these techniques are very sensitive and some of them can give precise information about the binding mode of fragments, which facilitates the mandatory hit-to-lead optimization. One of the main advantages of fragment-based screening is that fragment hits generally exhibit a strong binding with respect to their size, and their subsequent optimization should lead to compounds with better pharmacokinetic properties compared to molecules evolved from HTS hits. In other words, fragments are interesting starting points for drug discovery projects. Besides, the chemical space of low-complexity compounds is very limited in comparison to that of drug-like molecules, and thus easier to explore with a screening library of limited size. Furthermore, the "combinatorial explosion" effect ensures that the resulting combinations of interlinked binding fragments may cover a significant part of "drug-like" chemical space. In parallel to experimental screening, virtual screening techniques, dedicated to fragments or wider compounds, are gaining momentum in order to further reduce the number of compounds to test. This article is a review of the latest news in both experimental and in silico virtual screening in the fragment-based discovery field. Given the specificity of this journal, special attention will be given to fragment library design. 相似文献
77.
Buffi N Merulla D Beutier J Barbaud F Beggah S van Lintel H Renaud P van der Meer JR 《Lab on a chip》2011,11(14):2369-2377
Contamination with arsenic is a recurring problem in both industrialized and developing countries. Drinking water supplies for large populations can have concentrations much higher than the permissible levels (for most European countries and the United States, 10 μg As per L; elsewhere, 50 μg As per L). Arsenic analysis requires high-end instruments, which are largely unavailable in developing countries. Bioassays based on genetically engineered bacteria have been proposed as suitable alternatives but such tests would profit from better standardization and direct incorporation into sensing devices. The goal of this work was to develop and test microfluidic devices in which bacterial bioreporters could be embedded, exposed and reporter signals detected, as a further step towards a complete miniaturized bacterial biosensor. The signal element in the biosensor is a nonpathogenic laboratory strain of Escherichia coli, which produces a variant of the green fluorescent protein after contact to arsenite and arsenate. E. coli bioreporter cells were encapsulated in agarose beads and incorporated into a microfluidic device where they were captured in 500 × 500 μm(2) cages and exposed to aqueous samples containing arsenic. Cell-beads frozen at -20 °C in the microfluidic chip retained inducibility for up to a month and arsenic samples with 10 or 50 μg L(-1) could be reproducibly discriminated from the blank. In the 0-50 μg L(-1) range and with an exposure time of 200 minutes, the rate of signal increase was linearly proportional to the arsenic concentration. The time needed to reliably and reproducibly detect a concentration of 50 μg L(-1) was 75-120 minutes, and 120-180 minutes for a concentration of 10 μg L(-1). 相似文献
78.
Pentagalloyl Glucose (PGG) Partially Prevents Arterial Mechanical Changes Due to Elastin Degradation
Pavey S. N. Cocciolone A. J. Gutierrez Marty A. Ismail H. N. Hawes J. Z. Wagenseil J. E. 《Experimental Mechanics》2021,61(1):41-51
Experimental Mechanics - Elastic fibers are composed primarily of the protein elastin and they provide reversible elasticity to the large arteries. Degradation of elastic fibers is a common... 相似文献
79.
A practical synthesis of both enantiomers of 2-(tert-butyl)-2-methyl-1,3-dioxolan-4-one starting from D -mannitol is reported. These compounds are chiral equivalents of glycolic acid (= hydroxyacetic acid) which are configurationally stable and can be alkylated via their enolates. 相似文献
80.
Radical addition to 7-oxabicylco[2.2.1]hept-5-en-2-one ( 1 ) was examined from a regiochemical point of view, and despite the small electronic anisotropy of the double bond, electrophilic radicals were found to add preferentially at C(5) with selectivities of up to 5:1. We also report the first case of an inversion of the regioselectivity of a radical reaction using Lewis acids. 相似文献