全文获取类型
收费全文 | 1158篇 |
免费 | 53篇 |
专业分类
化学 | 902篇 |
晶体学 | 5篇 |
力学 | 22篇 |
数学 | 135篇 |
物理学 | 147篇 |
出版年
2023年 | 15篇 |
2022年 | 42篇 |
2021年 | 57篇 |
2020年 | 39篇 |
2019年 | 42篇 |
2018年 | 20篇 |
2017年 | 33篇 |
2016年 | 57篇 |
2015年 | 45篇 |
2014年 | 43篇 |
2013年 | 91篇 |
2012年 | 101篇 |
2011年 | 100篇 |
2010年 | 45篇 |
2009年 | 42篇 |
2008年 | 62篇 |
2007年 | 63篇 |
2006年 | 42篇 |
2005年 | 43篇 |
2004年 | 31篇 |
2003年 | 29篇 |
2002年 | 27篇 |
2001年 | 11篇 |
2000年 | 9篇 |
1999年 | 4篇 |
1998年 | 9篇 |
1997年 | 3篇 |
1996年 | 17篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 7篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 7篇 |
1975年 | 2篇 |
1972年 | 3篇 |
1971年 | 2篇 |
1967年 | 2篇 |
1966年 | 1篇 |
1937年 | 1篇 |
排序方式: 共有1211条查询结果,搜索用时 781 毫秒
141.
Moinuddin SG Youn B Bedgar DL Costa MA Helms GL Kang C Davin LB Lewis NG 《Organic & biomolecular chemistry》2006,4(5):808-816
Secoisolariciresinol dehydrogenase (SDH) catalyzes the NAD+ dependent enantiospecific conversion of secoisolariciresinol into matairesinol. In Podophyllum species, (-)-matairesinol is metabolized into the antiviral compound, podophyllotoxin, which can be semi-synthetically converted into the anticancer agents, etoposide, teniposide and Etopophos. Matairesinol is also a precursor of the cancer-preventative "mammalian" lignan, enterolactone, formed in the gut following ingestion of, for example, various high fiber dietary foods, as well as being an intermediate to numerous defense compounds in vascular plants. This study investigated the mode of enantiospecific Podophyllum SDH catalysis, the order of binding, and the stereospecificity of hydride abstraction/transfer from secoisolariciresinol to NAD+. SDH contains a highly conserved catalytic triad (Ser153, Tyr167 and Lys171), whose activity was abolished with site-directed mutagenesis of Tyr167Ala and Lys171Ala, whereas mutagenesis of Ser153Ala only resulted in a much reduced catalytic activity. Isothermal titration calorimetry measurements indicated that NAD+ binds first followed by the substrate, (-)-secoisolariciresinol. Additionally, for hydride transfer, the incoming hydride abstracted from the substrate takes up the pro-S position in the NADH formed. Taken together, a catalytic mechanism for the overall enantiospecific conversion of (-)-secoisolariciresinol into (-)-matairesinol is proposed. 相似文献
142.
Diana Q. L. Oliveira Luiz C. A. Oliveira Enver Murad José D. Fabris Adilson C. Silva Lucas Morais de Menezes 《Hyperfine Interactions》2010,195(1-3):27-34
Heterogeneous Fenton or Fenton-like reagents consist of a mixture of an iron-containing solid matrix and a liquid medium with H2O2. The Fenton system is based on the reaction between Fe2?+? and H2O2 to produce highly reactive intermediate hydroxyl radicals (???OH), which are able to oxidize organic contaminants, whereas the Fenton-like reaction is based on the reaction between Fe3?+? and H2O2. These heterogeneous systems offer several advantages over their homogeneous counterparts, such as no sludge formation, operation at near-neutral pH and the possibility of recycling the iron promoter. Some doping transition cations in the iron oxide structure are believed to enhance the catalytic efficiency for the oxidation of organic substrates in water. In this work, goethites synthesized in presence of niobium served as precursors for the preparation of magnetites (niobian magnetites) via chemical reduction with hydrogen at 400°C. These materials were used as Fenton-like catalysts. Both groups of (Nb, Fe)-oxide samples were characterized by 57Fe Mössbauer spectroscopy at 298 K. The results show that increasing niobium contents raise the catalytic potential for decomposition of methylene blue, which was, in this work, used as a model molecule for organic substrates in water. 相似文献
143.
Computational Management Science - We propose asset and liability management models in which the risk of underfunding is modelled based on the concept of stochastic dominance. Investment decisions... 相似文献
144.
This contribution studies the effects of credit contagion on the credit risk of a portfolio of bank loans. To this aim we introduce a model that takes into account the counterparty risk in a network of interdependent firms that describes the presence of business relations among different firms. The location of the firms is simulated with probabilities computed using an entropy spatial interaction model. By means of a wide simulation analysis we investigate the behavior of the model proposed and study the effects of default contagion on the loss distribution of a portfolio of bank loans. 相似文献
145.
Combinatorial library screening offers a rapid process for identifying potential therapies to toxins. Hinge peptide libraries,
which rely on conformational diversity rather than traditional molecular diversity, reduce the need for huge numbers of syntheses
and screening steps and greatly expedite the discovery process of active molecules. Hinge peptide libraries having the structures:
Acetyl-X1–X2–hinge–X3–X4–NH2 (capped) and X1–hinge–X2–X3 (uncapped), where X1 through X4 are near-equimolar mixtures of twelve L-amino acids and hinge = 4-aminobutyric acid, were screened for inhibitory activity in bioassays for botulinum neurotoxins
A and B (BoNT/A, BoNT/B) and saxitoxin. The zinc protease activity of the reduced light chains of BoNT/A and /B was assayed
by measuring the cleavage of synthetic substrates. Saxitoxin activity was measured by the restoration of the viability of
neuroblastoma cells treated with ouabain and veratridine. Deconvolution of libraries was accomplished by fixing one position
at a time beginning with the C-terminus. Primary library subsets in which position 4 was fixed showed moderate levels of inhibition
for BoNT/A. Secondary library subsets showed stronger inhibition in the bioassays. In each of the bioassays, inhibitory potency
was stronger when the second position to be fixed was on the opposite side of the hinge, rather than on the same side with
respect to the C-terminus, suggesting that the hinge facilitates the interaction of side chains. Inhibitors for all three
of the toxins studied were discovered within library subsets, although not necessarily in primary subsets. These studies demonstrate
that (1) the best strategy for deconvoluting hinge peptide libraries is by fixing residues alternately on each side of the
hinge moiety, and (2) it is essential to investigate secondary subsets even when primary subsets are inactive. The present
findings support the concept that the increased flexibility imposed by the inclusion of a central hinge residue in small peptides
increases the opportunity for side chain interactions, providing a distinct advantage for hinge peptide libraries over conventional
peptide libraries. Hinge peptide libraries are a rich source of novel ligands for modulation of biomechanisms. The library
subsets uncovered in this study may possess peptides that will lead to effective therapies to neurotoxin poisoning. 相似文献
146.
A general procedure for creating Markovian interest rate models is presented. The models created by this procedure automatically fit within the HJM framework and fit the initial term structure exactly. Therefore they are arbitrage free. Because the models created by this procedure have only one state variable per factor, twoand even three-factor models can be computed efficiently, without resorting to Monte Carlo techniques. This computational efficiency makes calibration of the new models to market prices straightforward. Extended Hull- White, extended CIR, Black-Karasinski, Jamshidian's Brownian path independent models, and Flesaker and Hughston's rational log normal models are one-state variable models which fit naturally within this theoretical framework. The ‘separable’ n-factor models of Cheyette and Li, Ritchken, and Sankarasubramanian - which require n(n + 3)/2 state variables - are degenerate members of the new class of models with n(n + 3)/2 factors. The procedure is used to create a new class of one-factor models, the ‘β-η models.’ These models can match the implied volatility smiles of swaptions and caplets, and thus enable one to eliminate smile error. The β-η models are also exactly solvable in that their transition densities can be written explicitly. For these models accurate - but not exact - formulas are presented for caplet and swaption prices, and it is indicated how these closed form expressions can be used to efficiently calibrate the models to market prices. 相似文献
147.
148.
Aggregation-induced emission (AIE) compounds display a photophysical phenomenon in which the aggregate state exhibits stronger emission than the isolated units. The common term of “AIEgens” was coined to describe compounds undergoing the AIE effect. Due to the recent interest in AIEgens, the search for novel hybrid organic–inorganic compounds with unique luminescence properties in the aggregate phase is a relevant goal. In this perspective, the abundant, inexpensive, and nontoxic d10 zinc cation offers unique opportunities for building AIE active fluorophores, sensing probes, and bioimaging tools. Considering the novelty of the topic, relevant examples collected in the last 5 years (2016–2021) through scientific production can be considered fully representative of the state-of-the-art. Starting from the simple phenomenological approach and considering different typological and chemical units and structures, we focused on zinc-based AIEgens offering synthetic novelty, research completeness, and relevant applications. A special section was devoted to Zn(II)-based AIEgens for living cell imaging as the novel technological frontier in biology and medicine. 相似文献
149.
150.
Diana B. Muñiz-Márquez Guillermo C. Martínez-Ávila Jorge E. Wong-Paz Ruth Belmares-Cerda Raúl Rodríguez-Herrera Cristóbal N. Aguilar 《Ultrasonics sonochemistry》2013,20(5):1149-1154
Bay leaves (BL) (Laurus nobilis L., Family: Laureceae) are traditionally used to treat some symptoms of gastrointestinal problems, such as epigastric bloating, impaired digestion, eructing and flatulence. These biological properties are mainly attributed to its phenolic compounds. In this paper, ultrasound-assisted extraction of phenolic compounds from Laurus nobilis L. (Laureceae) was studied.Effects of several experimental factors, such as sonication time, solid/liquid ratio and concentration of solvent on extraction of phenolic compounds were evaluated through a randomized complete block design with factorial treatment arrangement (33). The best extraction conditions were: 1 g plant sample with 12 mL of 35% ethanol, for 40 min, obtaining a yield of phenolic compounds of 17.32 ± 1.52 mg g?1 of plant. In addition, free radical-scavenging potential of DPPH and lipid oxidation inhibition, by linoleic acid peroxidation of the selected extract was measured in order to evidence their antioxidant properties. Results indicated that high amounts of phenolic compounds can be extracted from L. nobilis by ultrasound-assisted extraction technology. 相似文献