全文获取类型
收费全文 | 666篇 |
免费 | 25篇 |
国内免费 | 2篇 |
专业分类
化学 | 465篇 |
晶体学 | 3篇 |
力学 | 13篇 |
数学 | 92篇 |
物理学 | 120篇 |
出版年
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 13篇 |
2020年 | 19篇 |
2019年 | 13篇 |
2018年 | 14篇 |
2017年 | 16篇 |
2016年 | 25篇 |
2015年 | 25篇 |
2014年 | 23篇 |
2013年 | 45篇 |
2012年 | 46篇 |
2011年 | 55篇 |
2010年 | 27篇 |
2009年 | 30篇 |
2008年 | 34篇 |
2007年 | 26篇 |
2006年 | 36篇 |
2005年 | 47篇 |
2004年 | 30篇 |
2003年 | 18篇 |
2002年 | 24篇 |
2001年 | 14篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 3篇 |
1984年 | 4篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1972年 | 1篇 |
1966年 | 2篇 |
1963年 | 2篇 |
1958年 | 2篇 |
1874年 | 1篇 |
排序方式: 共有693条查询结果,搜索用时 46 毫秒
101.
102.
103.
Mari S. Karthikeyan Bantwal S. Holla Shalini Shenoy 《Monatshefte für Chemie / Chemical Monthly》2008,139(6):707-716
2,4-Dichloro-5-fluorophenyl containing 7-arylidenetriazolothiadiazines were obtained by the reaction of 4-amino-3-(2,4-dichloro-5-fluorophenyl)-5-mercapto-1,2,4-triazole
with 2,3-dibromo-1,3-diarylpropan-1-ones, and also by the reaction of 4-amino-3-(2,4-dichloro-5-fluorophenyl)-5-mercapto-1,2,4-triazole
with α-bromopropenones in the presence of a base. The structure of the 7-arylidenetriazolothiadiazines was confirmed by an
alternative synthesis. A plausible mechanism for the formation of 7-arylidenetriazolothiadiazines is proposed. All newly synthesized
compounds were screened for their analgesic and antimicrobial activities. Compounds bearing 4-chlorophenyl or 3,4-methylenedioxyphenyl
moieties at position 7 of the arylidenetriazolothiadiazines showed excellent analgesic activity. Arylidenetriazolothiadiazines
carrying a phenyl, 4-chlorophenyl, 4-methylphenyl, 3,4-dimethoxyphenyl, and 2,4-dichlorophenyl moieties at position 7 showed
excellent antibacterial and antifungal activities.
Correspondence: Mari Sithambaram Karthikeyan, Department of Chemistry, Mangalore University, Mangalagangothri 574199, Karnataka,
India. 相似文献
104.
Frederick Trinh Tan Milan Mari? James A. Nicell 《Polymer Degradation and Stability》2008,93(8):1479-1485
The aerobic biological degradation of the synthetic aliphatic-aromatic co-polyester Ecoflex™ (BASF) by 29 strains of enzyme-producing soil bacteria, fungi and yeasts was investigated at moderate environmental conditions. Previous studies had shown that these materials could be degraded but these studies were done under thermophilic conditions. In this paper, a screening procedure was developed to assess the biodegradability of the co-polyester at ambient environmental conditions and to investigate the mechanism of biodegradation. Results showed that the aliphatic-aromatic co-polyester could be degraded by a number of different microorganisms. However, after 21 days exposure to even the most promising cultures of pure microorganisms, only partial degradation of the Ecoflex™ was accomplished and only a few samples showed visible signs of degradation as loosely defined by the mechanical weakening of the films. Weight loss was not as obvious as the visual degradation and suggested broader types of microbial attack. The bacteria studied preferentially degraded the bonds between aliphatic components of the copolymer and the rate of biodegradation of oligomers was appreciably faster than that for the polymer chains. Using GC-MS techniques, degradation intermediates were identified to be the monomers of the co-polyester. Gel permeation chromatography results suggested exo-enzyme type degradation, where the microbes hydrolysed the ester bonds at the termini of the polymeric chains preferentially. 相似文献
105.
Catherine P. Raptopoulou Athanassios K. Boudalis Katerina N. Lazarou Vassilis Psycharis Nikos Panopoulos Michael Fardis George Diamantopoulos Jean-Pierre Tuchagues Alain Mari George Papavassiliou 《Polyhedron》2008,27(18):3575-3586
The use of salicylaldehyde oxime (H2salox) in manganese(III) carboxylate chemistry has yielded new members of the family of hexanuclear compounds presenting the [Mn6(μ3-O)2(μ2-OR)2]12+ core, complexes [MnIII6(μ3-O)2(O2CPh)2(salox)6(L1)2(L2)2] (L1 = py, L2 = H2O (1); L1 = Me2CO, L2 = H2O (2); L1 = L2 = MeOH (3)). Addition of NaOMe to the acetonitrile reaction mixture, afforded the 1D complex [MnIII3Na(μ3-O)(O2CPh)2(salox)3(MeCN)]n (4), whereas addition of NaClO4 to the acetone reaction mixture afforded an analogous 1D complex [MnIII3Na(μ3-O)(O2CPh)2(salox)3(Me2CO)]n (5). The structures of 1–3 present the [Mn6(μ3-O)2(μ2-OR)2]12+ core and can be described as two [Mn3(μ3-O)]7+ triangular subunits linked by two μ2-oximato oxygen atoms of the salox2− ligands, which show the less common μ3-κ2O:κO′:κN coordination mode. The benzoato ligands are coordinated through the usual syn,syn-μ2-κO:κO′ mode. The 1D polymeric structures of 4 and 5 consist of alternating [Mn3(μ3-O)]7+ subunits and Na+ atoms linked through two μ3-κ2O:κO′:κN and one μ4-κ2O:κ2O′:κN salox2− ligands as well as one syn,anti-μ2-κO:κO′ benzoato ligand. DC and AC magnetic susceptibility studies on 1 revealed the stabilization of an S = 4 ground state, and indications of single-molecule magnetism behavior, whereas the DC experimental data from polycrystalline sample of 5 are indicative of antiferromagnetic interactions within the [Mn3] subunit. Solid state 1H NMR data of 1 were used to probe the spin-lattice relaxation of the system. 相似文献
106.
Beverina L Crippa M Landenna M Ruffo R Salice P Silvestri F Versari S Villa A Ciaffoni L Collini E Ferrante C Bradamante S Mari CM Bozio R Pagani GA 《Journal of the American Chemical Society》2008,130(6):1894-1902
Singlet oxygen sensitization by organic molecules is a topic of major interest in the development of both efficient photodynamic therapy (PDT) and aerobic oxidations under complete green chemistry conditions. We report on the design, synthesis, biology, and complete spectroscopic characterization (vis-NIR linear and two-photon absorption spectroscopy, singlet oxygen generation efficiencies for both one- and two-photon excitation, electrochemistry, intrinsic dark toxicity, cellular uptake, and subcellular localization) of three classes of innovative singlet oxygen sensitizers pertaining to the family of symmetric squaraine derivatives originating from pi-excessive heterocycles. The main advantage of pi-extended squaraine photosensitizers over the large number of other known photosensitizers is their exceedingly strong two-photon absorption enabling, together with sizable singlet oxygen sensitization capabilities, for their use at the clinical application relevant wavelength of 806 nm. We finally show encouraging results about the dark toxicity and cellular uptake capabilities of water-soluble squaraine photosensitizers, opening the way for clinical small animal PDT trials. 相似文献
107.
In this paper, we study a capacitated facility location problem with two decision makers. One (say, the leader) decides on which subset of facilities to open and the capacity to be installed in each facility with the goal of minimizing the overall costs; the second decision maker (say, the follower), once the facilities have been designed, aims at maximizing the profit deriving from satisfying the demands of a given set of clients beyond a certain threshold imposed by the leader. The leader can foresee but cannot control the follower’s behavior. The resulting mathematical formulation is a discrete–continuous bilevel optimization problem. We propose a decomposition approach to cope with the bilevel structure of the problem and the integrality of a subset of variables under the control of the leader. Such a proposal has been tested on a set of benchmark instances available in the literature. 相似文献
108.
A high‐speed DNA fragment separation system based on an on‐line combination of capillary ITP with CZE (CITP‐CZE) and using UV detection at 260 nm was developed. A novel CITP‐CZE buffer system of pH 6.1 was designed for the separation of ten DNA fragments with sizes ranging from 100 to 1000 bp. An effect of underivatized α‐, β‐ and γ‐cyclodextrins on the resolution of DNA fragments in the CZE step of the CITP‐CZE combination was systematically investigated. Methylhydroxyethylcellulose present in the BGE was used to eliminate the EOF. DNA ladder fragments were separated within 10 min with LODs in the range of 1–5 ng/μL (S/N = 3). The RSDs of the migration time and peak area of individual DNA fragments were in the range of 1–3 and 3–9%, respectively. The developed CITP‐CZE system was further applied to the analysis of digest plasmid DNA samples. 相似文献
109.
Stephan?Dahlke Filippo?De Mari Ernesto?De Vito S?ren?H?userEmail author Gabriele?Steidl Gerd?Teschke 《Journal of Geometric Analysis》2016,26(3):1693-1729
Recently, shearlet groups have received much attention in connection with shearlet transforms applied for orientation sensitive image analysis and restoration. The square integrable representations of the shearlet groups provide not only the basis for the shearlet transforms but also for a very natural definition of scales of smoothness spaces, called shearlet coorbit spaces. The aim of this paper is twofold: first we discover isomorphisms between shearlet groups and other well-known groups, namely extended Heisenberg groups and subgroups of the symplectic group. Interestingly, the connected shearlet group with positive dilations has an isomorphic copy in the symplectic group, while this is not true for the full shearlet group with all nonzero dilations. Indeed we prove the general result that there exist, up to adjoint action of the symplectic group, only one embedding of the extended Heisenberg algebra into the Lie algebra of the symplectic group. Having understood the various group isomorphisms it is natural to ask for the relations between coorbit spaces of isomorphic groups with equivalent representations. These connections are examined in the second part of the paper. We describe how isomorphic groups with equivalent representations lead to isomorphic coorbit spaces. In particular we apply this result to square integrable representations of the connected shearlet groups and metaplectic representations of subgroups of the symplectic group. This implies the definition of metaplectic coorbit spaces. Besides the usual full and connected shearlet groups we also deal with Toeplitz shearlet groups. 相似文献
110.
Total Synthesis of 11‐Saxitoxinethanoic Acid and Evaluation of its Inhibitory Activity on Voltage‐Gated Sodium Channels
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Chao Wang Mana Oki Toru Nishikawa Daisuke Harada Prof. Dr. Mari Yotsu‐Yamashita Prof. Dr. Kazuo Nagasawa 《Angewandte Chemie (International ed. in English)》2016,55(38):11600-11603
11‐Saxitoxinethanoic acid (SEA) is a member of the saxitoxin (STX) family of paralytic shellfish poisons, and contains an unusual C?C bond at the C11 position. Reported herein is a total synthesis of SEA. The key to our synthesis lies in a Mukaiyama aldol condensation reaction of silyl enol ether with glyoxylate in the presence of an anhydrous fluoride reagent, [Bu4N][Ph3SnF2], which directly constructs the crucial C?C bond at the C11 position in SEA. The NaVCh‐inhibitory activities of SEA and its derivatives were evaluated by means of cell‐based assay. SEA showed an IC50 value of (47±12) nm , which is approximately twice as potent as decarbamoyl‐STX (dcSTX). 相似文献