全文获取类型
收费全文 | 944篇 |
免费 | 38篇 |
国内免费 | 5篇 |
专业分类
化学 | 690篇 |
力学 | 37篇 |
综合类 | 1篇 |
数学 | 106篇 |
物理学 | 153篇 |
出版年
2023年 | 8篇 |
2022年 | 17篇 |
2021年 | 18篇 |
2020年 | 27篇 |
2019年 | 18篇 |
2018年 | 10篇 |
2017年 | 17篇 |
2016年 | 17篇 |
2015年 | 28篇 |
2014年 | 44篇 |
2013年 | 50篇 |
2012年 | 87篇 |
2011年 | 80篇 |
2010年 | 47篇 |
2009年 | 41篇 |
2008年 | 79篇 |
2007年 | 62篇 |
2006年 | 56篇 |
2005年 | 39篇 |
2004年 | 29篇 |
2003年 | 24篇 |
2002年 | 13篇 |
2001年 | 13篇 |
2000年 | 21篇 |
1999年 | 13篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1991年 | 11篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1971年 | 2篇 |
1958年 | 3篇 |
1956年 | 2篇 |
排序方式: 共有987条查询结果,搜索用时 15 毫秒
1.
2.
Jong Chan Lee Jin Young Park So Young Yoon Yong Hun Bae Seung Jun Lee 《Tetrahedron letters》2004,45(1):191-193
A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with [hydroxy(tosyloxy)iodo]benzene followed by magnesium halides under solvent-free microwave irradiation conditions is described. 相似文献
3.
Jacek Doskocz Jadwiga Sołoducho Joanna Cabaj Mieczysław Łapkowski Sylwia Golba Krystyna Palewska 《Electroanalysis》2007,19(13):1394-1401
A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique. 相似文献
4.
NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl3 and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation. 相似文献
5.
We present a short survey on the biological modeling, dynamics analysis, and numerical simulation of nonlocal spatial effects, induced by time delays, in diffusion models for a single species confined to either a finite or an infinite domain. The nonlocality, a weighted average in space, arises when account is taken of the fact that individuals have been at different points in space at previous times. We discuss and compare two existing approaches to correctly derive the spatial averaging kernels, and we summarize some of the recent developments in both qualitative and numerical analysis of the nonlinear dynamics, including the existence, uniqueness (up to a translation), and stability of traveling wave fronts and periodic spatio-temporal patterns of the model equations in unbounded domains and the linear stability, boundedness, global convergence of solutions and bifurcations of the model equations in finite domains. 相似文献
6.
In order to study cross flow induced vibration of heat exchanger tube bundles, a new fluid–structure interaction model based on surface vorticity method is proposed. With this model, the vibration of a flexible cylinder is simulated at Re=2.67 × 104, the computational results of the cylinder response, the fluid force, the vibration frequency, and the vorticity map are presented. The numerical results reproduce the amplitude‐limiting and non‐linear (lock‐in) characteristics of flow‐induced vibration. The maximum vibration amplitude as well as its corresponding lock‐in frequency is in good agreement with experimental results. The amplitude of vibration can be as high as 0.88D for the case investigated. As vibration amplitude increases, the amplitude of the lift force also increases. With enhancement of vibration amplitude, the vortex pattern in the near wake changes significantly. This fluid–structure interaction model is further applied to simulate flow‐induced vibration of two tandem cylinders and two side‐by‐side cylinders at similar Reynolds number. Promising and reasonable results and predictions are obtained. It is hopeful that with this relatively simple and computer time saving method, flow induced vibration of a large number of flexible tube bundles can be successfully simulated. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
7.
Ying‐Hung So Pamela Foster Jang‐Hi Im Philip Garrou Jack Hetzner Edmund Stark Kayla Baranek 《Journal of polymer science. Part A, Polymer chemistry》2006,44(5):1591-1599
Divinylsiloxane‐bisbenzocyclobutene (DVS‐bisBCB) polymer has very low dielectric constant and dissipation factor, good thermal stability, and high chemical resistance. The fracture toughness of the thermoset polymer is moderate due to its high crosslink density. A thermoplastic elastomer, polystyrene–polybutadiene–polystyrene triblock copolymer, was incorporated into the matrix to enhance its toughness. The cured thermoset matrix showed different morphology when the elastomer was added to the B‐staged prepolymer or when the elastomer was B‐staged with the DVS‐bisBCB monomer. Small and uniformly distributed elastomer domains were detected by transmission electron micrographs (TEM) in the former case, but TEM did not detect a separate domain in the latter case. A high percentage of the polystyrene–polybutadiene–polystyrene triblock copolymer could be incorporated into the DVS‐bisBCB thermoset matrix by B‐staging the triblock copolymer with the BCB monomer. The elastomer increased the fracture toughness of DVS‐bisBCB polymer as indicated by enhanced elongation at break and increased K1c values obtained by the modified edge‐lift‐off test. Elastomer modified DVS‐bisBCB maintained excellent electrical properties, high Tg and good thermal stability, but showed higher coefficient of linear thermal expansion values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1591–1599, 2006 相似文献
8.
An element σ of An, the Alternating group of degree n, is extendible in Sn, the Symmetric group of degree n, if there exists a subgroup H of Sn but not An whose intersection with An is the cyclic group generated by σ. A simple number-theoretic criterion, in terms of the cycle-decomposition, for an element of An to be extendible in Sn is given here. 相似文献
9.
The super-macromolecular complex, succinate:quinone oxidoreductase (SQR, Complex II, succinate dehydrogenase) couples the oxidation of succinate in the matrix / cytoplasm to the reduction of quinone in the membrane. This function directly connects the Krebs cycle and the aerobic respiratory chain. Until the recent first report of the structure of SQR from Escherichia coli (E. coli) the structure-function relationships in SQR have been inferred from the structures of the homologous QFR, which catalyses the same reaction in the opposite direction. The structure of SQR from E. coli, analogous to the mitochondrial respiratory Complex II, has provided new insight into SQR's molecular design and mechanism, revealing the electron transport pathway through the enzyme. Comparison of the structures of SQR, QFR and other related flavoproteins shows how common amino acid residues at the interface of two domains facilitate the inter-conversion of succinate and fumarate. Additionally, the structure has provided a possible explanation as to why certain organisms utilise both SQR and QFR despite the fact that both can catalyse the inter-conversion of succinate and fumarate, in vitro and in vivo. Here we review how this structure has advanced our knowledge of this important enzyme and compare the structural information to other members of the Complex II superfamily and related flavoproteins. 相似文献
10.
Riedl Z Kövér P Soós T Hajós G Egyed O Fábián L Messmer A 《The Journal of organic chemistry》2003,68(14):5652-5659
2-Arylsulfanyl and 2-benzylsulfanylpyridinium N-arylimides (2) easily prepared from 3-aryltetrazolopyridinium salts (1) with aryl and benzylthiolates, respectively, reacted with various dipolarophiles yielding cycloadducts that underwent transformation to give tetrahydropyrrolo[3,2-b]pyridines (5, 6, and 8) in good yields. A similar rearrangement (formation of 15) was also observed in the case of parent derivatives being unsubstituted in position 2 (12). The abscence of any significant solvent effect, comparison of the sulfur and non-sulfur analogues, as well as the stereoselective nature of the observed ring transformation seem to support a sigmatropic mechanism. Structure elucidation of the products has been carried out by single-crystal X-ray diffraction and (1)H NMR experiments. 相似文献