全文获取类型
收费全文 | 596篇 |
免费 | 44篇 |
国内免费 | 2篇 |
专业分类
化学 | 421篇 |
晶体学 | 5篇 |
力学 | 32篇 |
数学 | 40篇 |
物理学 | 144篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 22篇 |
2021年 | 33篇 |
2020年 | 26篇 |
2019年 | 26篇 |
2018年 | 34篇 |
2017年 | 12篇 |
2016年 | 29篇 |
2015年 | 19篇 |
2014年 | 27篇 |
2013年 | 22篇 |
2012年 | 33篇 |
2011年 | 36篇 |
2010年 | 37篇 |
2009年 | 19篇 |
2008年 | 49篇 |
2007年 | 35篇 |
2006年 | 40篇 |
2005年 | 29篇 |
2004年 | 19篇 |
2003年 | 15篇 |
2002年 | 18篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1972年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有642条查询结果,搜索用时 15 毫秒
101.
Kirill Tsiberkin 《Transport in Porous Media》2018,121(1):109-120
The study considers an effect of the nonlinear inertial terms in the Brinkman filtration equation on the characteristics of coupled flows in a pure fluid and porous medium in the frameworks of two independent problems. The first problem is the forced boundary-layer flow overlying the Darcy–Brinkman porous medium. The Prandtl theory is used, and the self-similar equations are built to describe it. It is shown that the inertial terms have a valuable effect on the boundary-layer structure because of the large velocity gradient in the transition zone. The boundary-layer thickness in a porous medium rapidly grows at large Reynolds numbers. The velocity magnitude and gradient at the interface also change. The second independent problem is an analysis of the inertial terms effect on the flow stability. The neutral curves of the full and linearized flow models are built using the shooting method. They have different short-wave asymptotic, but there are no significant changes in the critical Reynolds numbers and corresponding wave numbers. 相似文献
102.
Kirill Tsiberkin 《Transport in Porous Media》2018,125(2):259-269
The study considers the forced boundary-layer flow overlying the Darcy–Brinkman porous medium and gives a quantitative analysis of the nonlinear inertial terms in the Brinkman filtration equation. The inertial terms are shown to be larger than the Darcy’s drag near the porous medium interface. The applicability range of boundary-layer approach is determined. It is suitable in high-permeable media with moderate velocities of an external flow. If it is slow enough, the inertial terms can be omitted in spite of interface effect. On the other hand, fast external flow produces the filtration with large pore-scale Reynolds number; therefore, the Forchheimer’s drag should be taken into account. It is shown the Brinkman term as well as inertial terms have a significant role in boundary-layer formation within the porous medium. 相似文献
103.
Diels-Alder ligation of peptides and proteins 总被引:2,自引:0,他引:2
de Araújo AD Palomo JM Cramer J Seitz O Alexandrov K Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(23):6095-6109
The development of the Diels-Alder cycloaddition as a new method for the site-specific chemoselective ligation of peptides and proteins under mild conditions is reported. Peptides equipped with a 2,4-hexadienyl ester and an N-terminal maleimide react in aqueous media to give cycloadducts in high yields and depending on the amino acid sequence with high stereoselectivity. Except for the cysteine SH group the transformation is compatible with all amino acid side chain functional groups. For ligation to proteins the hexadienyl group was attached to avidin and streptavidin noncovalently by means of complex formation with a biotinylated peptide or by covalent attachment of a hexadienyl ester-containing label to lysine side chains incorporated into the proteins. Site-specific attachment of the hexadienyl unit into a Rab protein was achieved by means of expressed protein ligation followed by protection of the generated cysteine SH by means of Ellman's reagent. The protein reacted with different maleimido-modified peptides under mild conditions to give the fully functional cycloadducts in high yield. The results demonstrate that the Diels-Alder ligation offers an advantageous and technically straightforward new opportunity for the site-specific equipment of peptides and proteins with further functional groups and labels. It proceeds under very mild conditions and is compatible with most functional groups found in proteins. Its combination with other ligation methods, in particular expressed protein ligation is feasible. 相似文献
104.
Genzer J Efimenko K Fischer DA 《Langmuir : the ACS journal of surfaces and colloids》2006,22(20):8532-8541
The goal of this study is to elucidate the formation of molecular gradients made of semifluorinated organosilanes (SFOs) on flat substrates by using a methodology developed by Chaudhury and Whitesides (Science 1992, 256, 1539). We use surface-sensitive combinatorial near-edge X-ray absorption fine structure (combi-NEXAFS) spectroscopy to measure the position-dependent concentration and orientation of SFO molecules in SFO molecular gradients on flat silica surfaces. Using the combi-NEXAFS data, we establish the correlation between the fraction of the F(CF(2))(8)(CH(2))(2)- species on the substrate and the average tilt angle of the -(CF(2))(8)F group in the SFO as a function of the deposition gas medium (air vs nitrogen) and the end group around the silicon atom (monofunctional vs trifunctional). In addition, we utilize the gradient geometry to comprehend the mechanism of formation of SFO self-assembled monolayers (SAMs). Specifically, we provide evidence that depending on the nature of the end group in the SFO and the vapor phase the SFO molecules add themselves into the existing SAMs either as individual molecules or as multimolecular complexes. 相似文献
105.
Krivdin LB Larina LI Chernyshev KA Rulev AY 《Magnetic resonance in chemistry : MRC》2006,44(2):178-187
Configurational assignment of seven azomethines obtained from the alpha-functionally substituted and nonsubstituted alpha,beta-unsaturated aldehydes has been performed on the basis of experimental measurements and the high-level ab initio calculations of their 1J(C,C) and 1J(C,H), involving the alpha-imino carbon that demonstrated the marked stereochemical dependence of both coupling constants upon the orientation of the nitrogen lone pair in the diverse isomers of the title azomethines. 相似文献
106.
GOMON Daniel SEDYKH Egor RODRíGUEZ Sebastin IDELFONSO Tafur Monroy ZAITSEV Kirill VOZIANOVA Anna KHODZITSKY Mikhail 《中国光学》2018,11(1):47-59
本文分析了电环形谐振腔的几何参数对超材料吸收体吸收率的影响。文中详细分析了电环形谐振腔参数、介电层(间隔物)厚度和电环形谐振腔厚度对超材料吸收体的影响,在此基础上,设置正交实验分析了几种参数的综合影响,最终获得超材料的理论吸收率。根据上述结果,制备了2个超材料吸收体的原理样机,经实验测得,原理样机的窄带吸收率高于98%。本文的研究成果为高性能吸收器的设计提供了指导。 相似文献
107.
Oleg?G.?Salnikov Danila?A.?Barskiy Dudari?B.?Burueva Yulia?K.?Gulyaeva Bair?S.?Balzhinimaev Kirill?V.?Kovtunov Igor?V.?KoptyugEmail author 《Applied magnetic resonance》2014,45(10):1051-1061
Hydrogenation of propyne to propene over Pd/aluminosilicate fiberglass catalyst in the temperature range 175–350 °C was investigated with the use of parahydrogen-induced polarization (PHIP) technique. Activation energies for both pairwise and non-pairwise H2 addition routes were estimated. It was found that at 175–275 °C the activation energies for hydrogen addition to the triple bond of propyne have similar values (about 60–70 kJ/mol) for both routes of hydrogen addition. At higher temperatures (275–350 °C), the rate constant for pairwise hydrogen addition reaches a maximum value while the rate constant for non-pairwise hydrogen addition continues to increase with increasing temperature. 相似文献
108.
Deraeve C Guo Z Bon RS Blankenfeldt W DiLucrezia R Wolf A Menninger S Stigter EA Wetzel S Choidas A Alexandrov K Waldmann H Goody RS Wu YW 《Journal of the American Chemical Society》2012,134(17):7384-7391
Post-translational attachment of geranylgeranyl isoprenoids to Rab GTPases, the key organizers of intracellular vesicular transport, is essential for their function. Rab geranylgeranyl transferase (RabGGTase) is responsible for prenylation of Rab proteins. Recently, RabGGTase inhibitors have been proposed to be potential therapeutics for treatment of cancer and osteoporosis. However, the development of RabGGTase selective inhibitors is complicated by its structural and functional similarity to other protein prenyltransferases. Herein we report identification of the natural product psoromic acid (PA) that potently and selectively inhibits RabGGTase with an IC(50) of 1.3 μM. Structure-activity relationship analysis suggested a minimal structure involving the depsidone core with a 3-hydroxyl and 4-aldehyde motif for binding to RabGGTase. Analysis of the crystal structure of the RabGGTase:PA complex revealed that PA forms largely hydrophobic interactions with the isoprenoid binding site of RabGGTase and that it attaches covalently to the N-terminus of the α subunit. We found that in contrast to other protein prenyltransferases, RabGGTase is autoinhibited through N-terminal (α)His2 coordination with the catalytic zinc ion. Mutation of (α)His dramatically enhances the reaction rate, indicating that the activity of RabGGTase is likely regulated in vivo. The covalent binding of PA to the N-terminus of the RabGGTase α subunit seems to potentiate its interaction with the active site and explains the selectivity of PA for RabGGTase. Therefore, psoromic acid provides a new starting point for the development of selective RabGGTase inhibitors. 相似文献
109.
Hoa V. Phan Pradip Chakraborty Meimei Chen Yitzi M. Calm Dr. Kirill Kovnir Lawrence K. Keniley Jr. Jordan M. Hoyt Elisabeth S. Knowles Dr. Céline Besnard Prof. Mark W. Meisel Prof. Andreas Hauser Prof. Catalina Achim Prof. Michael Shatruk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(49):15805-15815
Three iron(II) complexes, [Fe(TPMA)(BIM)](ClO4)2?0.5H2O ( 1 ), [Fe(TPMA)(XBIM)](ClO4)2 ( 2 ), and [Fe(TPMA)(XBBIM)](ClO4)2 ?0.75CH3OH ( 3 ), were prepared by reactions of FeII perchlorate and the corresponding ligands (TPMA=tris(2‐pyridylmethyl)amine, BIM=2,2′‐biimidazole, XBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐biimidazole, XBBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐bibenzimidazole). The compounds were investigated by a combination of X‐ray crystallography, magnetic and photomagnetic measurements, and Mössbauer and optical absorption spectroscopy. Complex 1 exhibits a gradual spin crossover (SCO) with T1/2=190 K, whereas 2 exhibits an abrupt SCO with approximately 7 K thermal hysteresis (T1/2=196 K on cooling and 203 K on heating). Complex 3 is in the high‐spin state in the 2–300 K range. The difference in the magnetic behavior was traced to differences between the inter‐ and intramolecular interactions in 1 and 2 . The crystal packing of 2 features a hierarchy of intermolecular interactions that result in increased cooperativity and abruptness of the spin transition. In 3 , steric repulsion between H atoms of one of the pyridyl substituents of TPMA and one of the benzene rings of XBBIM results in a strong distortion of the FeII coordination environment, which stabilizes the high‐spin state of the complex. Both 1 and 2 exhibit a photoinduced low‐spin to high‐spin transition (LIESST effect) at 5 K. The difference in the character of intermolecular interactions of 1 and 2 also manifests in the kinetics of the decay of the photoinduced high‐spin state. For 1 , the decay rate constant follows the single‐exponential law, whereas for 2 it is a stretched exponential, reflecting the hierarchical nature of intermolecular contacts. The structural parameters of the photoinduced high‐spin state at 50 K are similar to those determined for the high‐spin state at 295 K. This study shows that N‐alkylation of BIM has a negligible effect on the ligand field strength. Therefore, the combination of TPMA and BIM offers a promising ligand platform for the design of functionalized SCO complexes. 相似文献
110.
Li G Ray L Glass EN Kovnir K Khoroshutin A Gorelsky SI Shatruk M 《Inorganic chemistry》2012,51(3):1614-1624
Ru(II) complexes with 5-(3-thienyl)-4,6-dipyrrin (3-TDP), containing 2,2'-bipyridine (bpy) or 4,4'-bis(methoxycarbonyl)-2,2'-bipyridine (dcmb) as coligands, have been prepared and extensively characterized. Crystal structure determination of [Ru(bpy)(2)(3-TDP)]PF(6) (1a) and [Ru(bpy)(3-TDP)(2)] (2) reveals that the 3-thienyl substituent is rotated with respect to the plane of the dipyrrinato moiety. These complexes, as well as [Ru(dcmb)(2)(3-TDP)]PF(6) (1b), act as panchromatic light absorbers in the visible range, with two strong absorption bands observable in each case. A comparison to known Ru(II) complexes and quantum-chemical calculations at the density functional theory (DFT) level indicate that the lower-energy band is due to metal-to-ligand charge transfer (MLCT) excitation, although the frontier occupied metal-based molecular orbitals (MOs) contain significant contributions from the 3-TDP moiety. The higher energy band is assigned to the π-π* transition of the 3-TDP ligand. Each complex exhibits an easily accessible one-electron oxidation. According to DFT calculations and spectroelectrochemical experiments, the first oxidation takes place at the Ru(II) center in 1a, but is shifted to the 3-TDP ligand in 1b. An analysis of MO energy diagrams suggests that complex 1b has potential to be used for light harvesting in the dye-sensitized (Gr?tzel) solar cell. 相似文献