全文获取类型
收费全文 | 1667篇 |
免费 | 98篇 |
国内免费 | 4篇 |
专业分类
化学 | 1258篇 |
晶体学 | 4篇 |
力学 | 63篇 |
数学 | 148篇 |
物理学 | 296篇 |
出版年
2023年 | 18篇 |
2022年 | 32篇 |
2021年 | 43篇 |
2020年 | 70篇 |
2019年 | 53篇 |
2018年 | 26篇 |
2017年 | 16篇 |
2016年 | 71篇 |
2015年 | 71篇 |
2014年 | 82篇 |
2013年 | 92篇 |
2012年 | 136篇 |
2011年 | 174篇 |
2010年 | 85篇 |
2009年 | 80篇 |
2008年 | 110篇 |
2007年 | 133篇 |
2006年 | 99篇 |
2005年 | 81篇 |
2004年 | 62篇 |
2003年 | 45篇 |
2002年 | 36篇 |
2001年 | 17篇 |
2000年 | 18篇 |
1999年 | 11篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1985年 | 4篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1970年 | 2篇 |
1917年 | 2篇 |
1910年 | 2篇 |
1895年 | 2篇 |
排序方式: 共有1769条查询结果,搜索用时 0 毫秒
71.
Whitfield TW Varma S Harder E Lamoureux G Rempe SB Roux B 《Journal of chemical theory and computation》2007,3(6):2068-2082
The hydration of K(+) is studied using a hierarchy of theoretical approaches, including ab initio Born-Oppenheimer molecular dynamics and Car-Parrinello molecular dynamics, a polarizable force field model based on classical Drude oscillators, and a nonpolarizable fixed-charge potential based on the TIP3P water model. While models based more directly on quantum mechanics offer the possibility to account for complex electronic effects, polarizable and fixed-charges force fields allow for simulations of large systems and the calculation of thermodynamic observables with relatively modest computational costs. A particular emphasis is placed on investigating the sensitivity of the polarizable model to reproduce key aspects of aqueous K(+), such as the coordination structure, the bulk hydration free energy, and the self diffusion of K(+). It is generally found that, while the simple functional form of the polarizable Drude model imposes some restrictions on the range of properties that can simultaneously be fitted, the resulting hydration structure for aqueous K(+) agrees well with experiment and with more sophisticated computational models. A counterintuitive result, seen in Car-Parrinello molecular dynamics and in simulations with the Drude polarizable force field, is that the average induced molecular dipole of the water molecules within the first hydration shell around K(+) is slightly smaller than the corresponding value in the bulk. In final analysis, the perspective of K(+) hydration emerging from the various computational models is broadly consistent with experimental data, though at a finer level there remain a number of issues that should be resolved to further our ability in modeling ion hydration accurately. 相似文献
72.
Segut O Lakard B Herlem G Rauch JY Jeannot JC Robert L Fahys B 《Analytica chimica acta》2007,597(2):313-321
A new type of pH biosensor was developed for biological applications. This biosensor was fabricated using silicon microsystem technology and consists in two platinum microelectrodes. The first microelectrode was coated by an electrosynthesized polymer and acted as the pH sensitive electrode when the second one was coated by a silver layer and was used as the reference electrode. Then, this potentiometric pH miniaturized biosensor based on electrosynthesized polypyrrole or electrosynthesized linear polyethylenimine films was tested. The potentiometric responses appeared reversible and linear to pH changes in the range from pH 4 to 9. More, the responses were fast (less than 1 min for all sensors), they were stable in time since PPy/PEI films were stable during more than 30 days, and no interference was observed. The influence of the polymer thickness was also studied. 相似文献
73.
Inside Back Cover: Self‐Assembly of Measles Virus Nucleocapsid‐like Particles: Kinetics and RNA Sequence Dependence (Angew. Chem. Int. Ed. 32/2016) 下载免费PDF全文
74.
Ghislaine Barouti Ali Khalil Clement Orione Kathleen Jarnouen Dr. Sandrine Cammas‐Marion Dr. Pascal Loyer Prof. Sophie M. Guillaume 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(8):2819-2830
Amphiphilic polycarbonate–poly(hydroxyalkanoate) diblock copolymers, namely, poly(trimethylene carbonate) (PTMC)‐b‐poly(β‐malic acid) (PMLA), are reported for the first time. The synthetic strategy relies on commercially available catalysts and initiator. The controlled ring‐opening polymerization (ROP) of trimethylene carbonate (TMC) catalyzed by the organic guanidine base 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), associated with iPrOH as an initiator, provided iPrO?PTMC?OH, which served as a macroinitiator in the controlled ROP of benzyl β‐malolactonate (MLABe) catalyzed by the neodymium triflate salt (Nd(OTf)3). The resulting hydrophobic iPrO?PTMC‐b‐PMLABe?OH copolymers were then hydrogenolyzed into the parent iPrO?PTMC‐b‐PMLA?OH copolymers. A range of well‐defined copolymers, featuring different sizes of segments (Mn,NMR up to 9300 g mol?1; ÐM=1.28–1.40), were thus isolated in gram quantities, as evidenced by NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry, and contact angle analyses. Subsequently, PTMC‐b‐PMLA copolymers with different hydrophilic weight fractions (11–75 %) self‐assembled in phosphate‐buffered saline upon nanoprecipitation into well‐defined nano‐objects with Dh=61–176 nm, a polydispersity index <0.25, and a negative surface charge, as characterized by dynamic light scattering and zeta‐potential analyses. In addition, these nanoparticles demonstrated no significant effect on cell viability at low concentrations, and a very low cytotoxicity at high concentrations only for PTMC‐b‐PMLA copolymers exhibiting hydrophilic fractions over 47 %, thus illustrating the potential of these copolymers as promising nanoparticles. 相似文献
75.
Dr. Gaëlle Charron Dr. Elena Malkin Dr. Guillaume Rogez Dr. Luke J. Batchelor Dr. Sandra Mazerat Dr. Régis Guillot Dr. Nathalie Guihéry Dr. Anne‐Laure Barra Dr. Talal Mallah Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16850-16862
By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy ( 1 ), (NCS?)2 ( 2 ), C2O42? ( 3 ), NO3? ( 4 )). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ ( 5 ; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3? and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. 相似文献
76.
Pramila Selvanathan Gang Huang Thierry Guizouarn Dr. Thierry Roisnel Dr. Guglielmo Fernandez‐Garcia Dr. Federico Totti Dr. Boris Le Guennic Dr. Guillaume Calvez Dr. Kévin Bernot Dr. Lucie Norel Prof. Stéphane Rigaut 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(43):15222-15226
A spiropyran‐based switchable ligand isomerizes upon reaction with lanthanide(III) precursors to generate complexes with an unusual N3O5 coordination sphere. The air‐stable dysprosium(III) complex shows a hysteresis loop at 2 K and a very strong axial magnetic anisotropy generated by the merocyanine phenolate donor. 相似文献
77.
Cover Picture: Fast‐Geomimicking using Chemistry in Supercritical Water (Angew. Chem. Int. Ed. 34/2016) 下载免费PDF全文
78.
Eva Montbarbon Dr. Fabien Sguerra Dr. Guillaume H. V. Bertrand Élodie Magnier Dr. Romain Coulon Dr. Robert B. Pansu Dr. Matthieu Hamel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):12074-12080
The synthesis, photophysical properties, and applications in scintillation counting of N‐(2‐ethylhexyl)carbazole (EHCz) are reported. This molecule displays all of the required characteristics for an efficient liquid scintillator (emission wavelength, scintillation yield), and can be used without any extra fluorophores. Thus, its scintillation properties are discussed, as well as its fast neutron/gamma discrimination. For the latter application, the material is compared with the traditional liquid scintillator BC‐501 A, and other liquid fluorescent molecules classically used as scintillation solvents, such as xylene, pseudocumene (PC), linear alkylbenzenes (LAB), diisopropylnaphthalene (DIN), 1‐methylnaphthalene (1‐MeNapht), and 4‐isopropylbiphenyl (iPrBiph). For the first time, an excimeric form of a molecule has been advantageously used in scintillation counting. A moderate discrimination between fast neutrons and gamma rays was observed in bulk EHCz, with an apparent neutron/gamma discrimination potential half of that of BC‐501 A. 相似文献
79.
Toquer G Porte G Nobili M Appell J Blanc C 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):4081-4087
We have investigated the nature of didodecyldimethylammonium bromide (DDAB)/water aggregates dispersed in 4-n-pentyl-4'-cyanobiphenyl thermotropic liquid crystal (5CB). The structure of this microemulsion has been probed by small-angle neutron and X-ray scattering experiments far above the nematic-to-isotropic phase transition temperature of the solvent. Our data show that the stability of this system is controlled by strong attractive van der Waals interactions between spherical inverted micelles. These interactions also explain why other swollen mesophases in related cosurfactant/DDAB/water/5CB phase diagrams are not observed. When approaching the isotropic-to-nematic phase transition, scattering experiments additionally confirm the predominance of an increasing attractive interaction due to the 5CB paranematic fluctuations. 相似文献
80.
Izzet G Zeng X Akdas H Marrot J Reinaud O 《Chemical communications (Cambridge, England)》2007,(8):810-812
A calix[6]arene capped by a tmpa unit provides Cu(ii) funnel complexes that, for the first time, accept not only neutral guest ligands but also anionic ones such as a hydroxide, which is due to a small conformational change in the calixarene cone. 相似文献