全文获取类型
收费全文 | 849篇 |
免费 | 70篇 |
国内免费 | 1篇 |
专业分类
化学 | 578篇 |
晶体学 | 4篇 |
力学 | 21篇 |
数学 | 80篇 |
物理学 | 169篇 |
无线电 | 68篇 |
出版年
2023年 | 9篇 |
2022年 | 21篇 |
2021年 | 24篇 |
2020年 | 30篇 |
2019年 | 28篇 |
2018年 | 18篇 |
2017年 | 13篇 |
2016年 | 45篇 |
2015年 | 26篇 |
2014年 | 25篇 |
2013年 | 40篇 |
2012年 | 55篇 |
2011年 | 74篇 |
2010年 | 33篇 |
2009年 | 28篇 |
2008年 | 46篇 |
2007年 | 46篇 |
2006年 | 36篇 |
2005年 | 37篇 |
2004年 | 34篇 |
2003年 | 28篇 |
2002年 | 17篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 16篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 17篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 4篇 |
1983年 | 8篇 |
1982年 | 3篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1968年 | 4篇 |
1967年 | 5篇 |
1966年 | 3篇 |
1960年 | 4篇 |
1958年 | 4篇 |
排序方式: 共有920条查询结果,搜索用时 15 毫秒
891.
Vladimir Sladek Kraiwan Punyain Michal Ilčin Vladimír Lukeš 《International journal of quantum chemistry》2014,114(13):869-878
Optimal structures, electronic and thermodynamic properties of the title complexes are presented. The stability of the hydrogen bonded systems is enhanced by the increasing dipole moments whereas in the halogen bonded systems it is also affected by the atom size in the diatomics. The consecutive addition of fluorine atoms to the pyridine moiety results in the decrease of the interaction energy for both types of the investigated bonds. The substitution on the meta sites in pyridine leads to more stable complexes than the substitution in the ortho position. The role of substitution on electric polarization and electrostatic forces is estimated by the symmetry‐adapted perturbation theory energy decomposition. The predicted Gibbs free energies of the complexes of mono fluorinated pyridines with HCl, HF, and ClF are from ?12 to ?22 kJ mol?1 at 200 K. The possible experimental identification of the complexes with respect to the vibrational modes is discussed. © 2014 Wiley Periodicals, Inc. 相似文献
892.
Mechanism of Alkyne Alkoxycarbonylation at a Pd Catalyst with P,N Hemilabile Ligands: A Density Functional Study
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Luke Crawford Prof. David J. Cole‐Hamilton Prof. Eite Drent Prof. Michael Bühl 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):13923-13926
A detailed mechanism for alkyne alkoxycarbonylation mediated by a palladium catalyst has been characterised at the B3PW91‐D3/PCM level of density functional theory (including bulk solvation and dispersion corrections). This transformation, investigated via the methoxycarbonylation of propyne, involves a uniquely dual role for the P,N hemilabile ligand acting co‐catalytically as both an in situ base and proton relay coupled with a Pd0 centre, allowing for surmountable barriers (highest ΔG≠ of 22.9 kcal mol?1 for alcoholysis). This proton‐shuffle between methanol and coordinated propyne accounts for experimental requirements (high acid concentration) and reproduces observed regioselectivities as a function of ligand structure. A simple ligand modification is proposed, which is predicted to improve catalytic turnover by three orders of magnitude. 相似文献
893.
All‐Inorganic Nanocrystals as a Glue for BiSbTe Grains: Design of Interfaces in Mesostructured Thermoelectric Materials
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)
Dr. Jae Sung Son Hao Zhang Dr. Jaeyoung Jang Dr. Bed Poudel Al Waring Luke Nally Prof. Dr. Dmitri V. Talapin 《Angewandte Chemie (International ed. in English)》2014,53(29):7466-7470
Nano‐ and mesostructuring is widely used in thermoelectric (TE) materials. It introduces numerous interfaces and grain boundaries that scatter phonons and decrease thermal conductivity. A new approach has been developed for the rational design of the interfaces in TE materials by using all‐inorganic nanocrystals (NCs) that serve as a “glue” for mesoscopic grains. For example, circa 10 nm Bi NCs capped with (N2H5)4Sb2Te7 chalcogenidometallate ligands can be used as an additive to BiSbTe particles. During heat treatment, NCs fill up the voids between particles and act as a “glue”, joining grains in hot‐pressed pellets or solution‐processed films. The chemical design of NC glue allowed the selective enhancement or decrease of the majority‐carrier concentration near the grain boundaries, and thus resulted in doped or de‐doped interfaces in granular TE material. Chemically engineered interfaces can be used as to optimize power factor and thermal conductivity. 相似文献
894.
Hadler KS Tanifum EA Yip SH Mitić N Guddat LW Jackson CJ Gahan LR Nguyen K Carr PD Ollis DL Hengge AC Larrabee JA Schenk G 《Journal of the American Chemical Society》2008,130(43):14129-14138
The glycerophosphodiesterase (GpdQ) from Enterobacter aerogenes is a promiscuous binuclear metallohydrolase that catalyzes the hydrolysis of mono-, di-, and triester substrates, including some organophosphate pesticides and products of the degradation of nerve agents. GpdQ has attracted recent attention as a promising enzymatic bioremediator. Here, we have investigated the catalytic mechanism of this versatile enzyme using a range of techniques. An improved crystal structure (1.9 A resolution) illustrates the presence of (i) an extended hydrogen bond network in the active site, and (ii) two possible nucleophiles, i.e., water/hydroxide ligands, coordinated to one or both metal ions. While it is at present not possible to unambiguously distinguish between these two possibilities, a reaction mechanism is proposed whereby the terminally bound H2O/OH(-) acts as the nucleophile, activated via hydrogen bonding by the bridging water molecule. Furthermore, the presence of substrate promotes the formation of a catalytically competent binuclear center by significantly enhancing the binding affinity of one of the metal ions in the active site. Asn80 appears to display coordination flexibility that may modulate enzyme activity. Kinetic data suggest that the rate-limiting step occurs after hydrolysis, i.e., the release of the phosphate moiety and the concomitant dissociation of one of the metal ions and/or associated conformational changes. Thus, it is proposed that GpdQ employs an intricate regulatory mechanism for catalysis, where coordination flexibility in one of the two metal binding sites is essential for optimal activity. 相似文献
895.
Careful analysis of Pt L3-edge extended X-ray absorption fine structure (EXAFS) spectra shows that the hydrated platinum(II) ion in acidic (HClO 4) aqueous solution binds four water molecules with the Pt-O bond distance 2.01(2) A and one (or two) in the axial position at 2.39(2) A. The weak axial water coordination is in accordance with the unexpectedly small activation volume previously reported for water exchange in an interchange mechanism with associative character. The hydrated cis-diammineplatinum(II) complex has a similar coordination environment with two ammine and two aqua ligands strongly bound with Pt-O/N bond distances of 2.01(2) A and, in addition, one (or two) axial water molecule at 2.37(2) A. This result provides a new basis for theoretical computational studies aiming to connect the function of the anticancer drug cis-platin to its ligand exchange reactions, where usually four-coordinated square planar platinum(II) species are considered as the reactant and product. (195)Pt NMR spectroscopy has been used to characterize the Pt(II) complexes. 相似文献
896.
Loughlin WA Jenkins ID Henderson LC Campitelli MR Healy PC 《The Journal of organic chemistry》2008,73(9):3435-3440
An efficient formal synthesis of (+/-)-hyphodermins A and D, metabolites of Hyphoderma radula, has been completed in 12 and 11 steps, respectively. The tricyclic carbon skeleton of enone 6 was rapidly assembled from diester 11 via an alpha brominationn-elimination sequence followed by anhydride formation. Regioselective reduction of the lactone group of enone 6 with LiAlH(t-BuO) 3 gave lactol 15. Lactol 15 was converted in two steps to (+/-)-hyphodermin D, without the need for complex protection-deprotection strategies. Lactol 15 was converted in three steps to (+/-)-hyphodermin A, via the key step of epoxidation of an enone in the presence of a THP lactol. A combination of NMR and ab initio studies suggests that the structures of hyphodermin C and D should be interchanged. 相似文献
897.
We present a novel approach for the ultra-rapid direct patterning of complex three-dimensional, stacked polystyrene (PS) microfluidic chips. By leveraging the inherent shrinkage properties of biaxially pre-stressed thermoplastic sheets, microfluidic channels become thinner and deeper upon heating. Design conception to fully functional chips can thus be completed within minutes. 相似文献
898.
Parvanov VM Schenter GK Hess NJ Daemen LL Hartl M Stowe AC Camaioni DM Autrey T 《Dalton transactions (Cambridge, England : 2003)》2008,(33):4514-4522
The activation energies for rotations in low-temperature orthorhombic ammonia borane were analyzed and characterized in terms of electronic structure theory. The perdeuterated (11)B-enriched ammonia borane, (11)BD(3)ND(3), sample was synthesized, and the structure was refined from neutron powder diffraction data at 175 K. This temperature has been chosen as median of the range of previously reported nuclear magnetic resonance spectroscopy measurements of these rotations. A representative molecular cluster model was assembled from the refined geometry, and the activation energies were calculated and characterized by analysis of the environmental factors that control the rotational dynamics. The barrier for independent NH(3) rotation, E(a) = 12.7 kJ mol(-1), largely depends on the molecular conformational torsion in the solid-state geometry. The barrier for independent BH(3) rotation, E(a) = 38.3 kJ mol(-1), results from the summation of the effect of molecular torsion and large repulsive intermolecular hydrogen-hydrogen interactions. However, a barrier of E(a) = 31.1 kJ mol(-1) was calculated for internally correlated rotation with preserved molecular conformation. Analysis of the barrier heights and the corresponding rotational pathways shows that rotation of the BH(3) group involves strongly correlated rotation of the NH(3) end of the molecule. This observation suggests that the barrier from previously reported measurement of BH(3) rotation corresponds to H(3)B-NH(3) correlated rotation. 相似文献
899.
Powell LH Docherty PH Hulcoop DG Kemmitt PD Burton JW 《Chemical communications (Cambridge, England)》2008,(22):2559-2561
The use of manganese(III) acetate in combination with copper(II) triflate allows the synthesis of [3.3.0]-bicyclic gamma-lactones from 4-pentenylmalonates in excellent yields. 相似文献
900.
Dr. Peter Rapta Dr. Vladimír Lukeš Dr. Krzysztof R. Idzik Prof. Rainer Beckert Prof. Lothar Dunsch 《Chemphyschem》2012,13(9):2322-2330
Model structures of 1,3,5‐triarylbenzenes with a substituted benzene core linked to thienyl or 3,4‐ethylenedioxythienyl (EDOT) terminal groups are studied by electrochemical and in situ ESR/UV/Vis/NIR spectroelectrochemical techniques. Oxidative polymerization of the monomers results in C? C coupling of the thiophene moieties in the 5‐position, forming dimeric structures with bithiophene linkers as the first step. Both the doubly charged protonated dimer and the new dimer formed after proton release are studied in detail for 2,4,6‐tris[2‐(3,4‐ethylenedioxythienyl)]‐1‐methoxybenzene. Quite high stability of the doubly charged σ dimer formed on oxidation with unusual redox behavior at the electrode is observed. Density functional calculations of the molecular structure as well as spectroscopic and electronic properties of charged states in 1,3,5‐triarylbenzene derivatives in the monomeric, dimeric, and oligomeric form are presented. The complex spectroelectrochemical response of a thin solid film formed on the electrode surface upon potentiodynamic polymerization indicates the existence of different charge states of oligomeric structures within the solid matrix. 相似文献