全文获取类型
收费全文 | 318篇 |
免费 | 13篇 |
国内免费 | 4篇 |
专业分类
化学 | 278篇 |
晶体学 | 1篇 |
力学 | 11篇 |
数学 | 14篇 |
物理学 | 31篇 |
出版年
2023年 | 5篇 |
2022年 | 5篇 |
2021年 | 4篇 |
2020年 | 6篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 10篇 |
2015年 | 5篇 |
2014年 | 9篇 |
2013年 | 17篇 |
2012年 | 21篇 |
2011年 | 33篇 |
2010年 | 11篇 |
2009年 | 9篇 |
2008年 | 19篇 |
2007年 | 24篇 |
2006年 | 29篇 |
2005年 | 23篇 |
2004年 | 22篇 |
2003年 | 14篇 |
2002年 | 10篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 8篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1971年 | 2篇 |
排序方式: 共有335条查询结果,搜索用时 62 毫秒
101.
102.
Dr. Pablo Labra-Vázquez Ricardo Flores-Cruz Aylin Galindo-Hernández Dr. Justo Cabrera-González Cristian Guzmán-Cedillo Dr. Arturo Jiménez-Sánchez Dr. Pascal G. Lacroix Dr. Rosa Santillan Dr. Norberto Farfán Dr. Rosario Núñez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16530-16540
A set of BODIPY-carboranyl dyads synthesized by a Sonogashira cross-coupling reaction, where different C-substituted ortho- and meta-carboranyl fragments have been linked to a BODIPY fluorophore is described. Chemical, photophysical and physicochemical analyses are presented, including NMR and single XRD experiments, optical absorption/emission studies and partition coefficient (log P) measurements. These studies, supported by DFT computations (M06-2X/6-31G**), provide an explanation to the largely divergent cell income that these fluorescent carboranyl-based fluorophores display, for which a structural or physicochemical explanation remains elusive. By studying the cell uptake efficiency and subcellular localization for our set of dyads on living HeLa cells, we tracked the origins of these differences to significant variations in their static dipole moments and partition coefficients, which tune their ability to interact with lipophilic microenvironments in cells. Remarkably, m-carboranyl-BODIPY derivatives with a higher lipophilicity are much better internalised by cells than their homologous with o-carborane, suggesting that m-isomers are potentially better theranostic agents for in vitro bioimaging and boron carriers for boron neutron capture therapy. 相似文献
103.
Daniel Silva Fátima Norberto Susana Santos Jim Iley 《Journal of Physical Organic Chemistry》2011,24(11):1081-1087
The reactivity of 6‐quinolinyl and 8‐quinolinyl N,N‐dimethylcarbamates was examined in several aqueous basic media. A quadratic dependence was observed for the constant rates upon hydroxide concentration for both compounds, which is a typical behaviour of a mechanism involving a base‐catalysed deprotonation of the tetrahedral intermediate with the formation of a dianion at high concentrations of hydroxide ion, while at lower concentrations a specific‐base catalysed addition–elimination mechanism seems to be predominant. The reactivity of 8‐quinolinyl N,N‐dimethylcarbamate was also studied in several amine buffers, showing specific base catalysis. The reactivity of 6‐quinolinyl N,N‐dimethylcarbamate was studied in H2O and in D2O and the solvent isotope effect supports the proposal of a mechanism involving a specific‐base hydrolysis. All results confirm the existence of a mechanism with a rate determining step involving the substrate anion and a second mole of hydroxide ion. This mechanism was so far unknown for carbamate reactivity, being only known to occur with amides. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
104.
105.
A system of ion implanted impurities in a semiconductor is described by a Monte Carlo simulation of a non-equilibrium system of random distributed hard spheres. The radial distribution function of this system is found. The comparison is made with the fluid hard sphere case. The assumption that the absence either of annealing or diffusion of the impurities after the implantation process is also made. 相似文献
106.
Macro‐hybrid penalized finite element approximations are studied for steady filtration problems with seawater intrusion. On the basis of nonoverlapping domain decompositions with vertical interfaces, sections of coastal aquifers are decomposed into subsystems with simpler geometries and small scales, interconnected via transmission conditions of pressure and flux continuity. Corresponding local penalized formulations are derived from the global penalized variational formulation of the two‐free boundary flow problem, with continuity transmission conditions modelled variationally in a dual sense. Then, macro‐hybrid finite element approximations are derived for the system, defined on independent subdomain grids. Parallel relaxation penalty‐duality algorithms are proposed from fixed‐point problem characterizations. Numerical experiments exemplify the macro‐hybrid penalized theory, showing a good agreement with previous primal conforming penalized finite element approximations (Comput. Methods Appl. Mech. Engng. 2000; 190 :609–624). Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
107.
Mariana Dennehy Ricardo M. Ferullo Oscar V. Quinzani Sandra D. Mandolesi Norberto Castellani Michael Jennings 《Polyhedron》2008
Treatment of Ag6(tsac)6 (tsac = thiosaccharinate anion) with pyridine (py) and 1,10-phenanthroline (o-phen) each affords two novel silver(I)-thiosaccharinate complexes: dinuclear [Ag2(tsac)2py] (1) and polynuclear [Ag(tsac)(o-phen)]n (2). Both crystal structures have been determined by X-ray diffraction and spectroscopic structural analysis (IR and Raman, UV–Vis, 1H and 13C NMR) have also been made for both compounds. Thermal stability analysis (TGA and DTA) of complex 1 are used to confirm the strength of the pyridine coordination to the silver ion. The molecular structure of complex 1 shows some astonishing characteristics. The two silver atoms are in different environments: one of them is surrounded by two S atoms, while the other completes its coordination sphere by three N atoms, two from the thiosaccharinate anions and the third from a pyridine molecule. The short Ag(1)–Ag(2) contact distance, 2.9681(8) Å, indicates an interaction between the two silver metal atoms exists. Complex 2 shows a thiosaccharinate molecule bridging two silver atoms through the exocyclic S atom while the o-phenanthroline ligand is coordinated as a bidentate N,N chelate, forming a polynuclear chain. Quantum chemical calculations confirm the argentophilic character of the Ag–Ag interaction in complex 1, and its structure and vibrational assignments were correlated and confirmed theoretically. 相似文献
108.
Galli S Masciocchi N Tagliabue G Sironi A Navarro JA Salas JM Mendez-Liñan L Domingo M Perez-Mendoza M Barea E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(32):9890-9901
The novel porous [{M(F-pymo)(2)}(n)]2.5n H(2)O coordination networks (M=Co, Zn; F-pymo=5-fluoropyrimidin-2-olate), possessing sodalitic topology, have been synthesised and structurally characterised by means of powder diffraction methods. Thermodiffractometry demonstrated their plasticity: when heated up to 363 K, they reversibly transform into three-dimensional dehydrated [{M(F-pymo)(2)}(n)] species, with significantly different lattice parameters. Further heating induces irreversible polymorphic transformations into layered phases, in which the original MN(4) coordination sphere changes into an MN(3)O one. A mixed-metal phase, [{Co(x)Zn(1-x)(F-pymo)(2)}(n)]2.5n H(2)O, was also prepared, showing that zinc is preferentially inserted, when starting from a Co/Zn reagent ratio of 1:1. The solid-gas adsorption properties of the anhydrous 3D frameworks have been explored towards N(2), H(2) (77 K) and CH(4), CO(2) (273 K). These results show that these materials permit the diffusion of CO(2) molecules only. Remarkably, the CO(2) adsorption process for the [{Co(F-pymo)(2)}(n)] network proceeds in two steps: the first step takes place at low pressures (<600 kPa) and the second one above a threshold pressure of 600 kPa. By contrast, the [{Zn(F-pymo)(2)}(n)] network only permits CO(2) diffusion by applying pressures above 900 kPa. This type of behaviour is typical of porous networks with gated channels. The high CO(2) selectivity of these systems over the rest of the essayed probe gases is explained in terms of flexibility and polarity of the porous network. Finally, the magnetic studies on the Co(II) systems reveal that the as synthesised [{Co(F-pymo)(2)}(n)]2.5n H(2)O material behaves as an antiferromagnet with a T(N) of about 29 K. At variance, the [{Co(F-pymo)(2)}(n)] layered phase shows an unusually weak ferromagnetic ordering below 17 K, arising from a spin-canting phenomenon. 相似文献
109.
Díaz-Moscoso A Balbuena P Gómez-García M Ortiz Mellet C Benito JM Le Gourriérec L Di Giorgio C Vierling P Mazzaglia A Micali N Defaye J García Fernández JM 《Chemical communications (Cambridge, England)》2008,(17):2001-2003
Self-assembled cyclodextrin (CD)-DNA nanoparticles (CDplexes) exhibiting transfection efficiencies significantly higher than PEI-based polyplexes have been prepared from homogeneous seven-fold symmetric polyaminothiourea amphiphiles constructed on a beta-cyclodextrin scaffold. 相似文献
110.
A high-performance liquid chromatographic method for the determination of atazanavir (ATV) in human plasma is developed and validated. The method involves a rapid and simple solid-phase extraction (SPE) of ATV using Bond-elut C18 3 mL cartridge. The separation of ATV from internal standard and endogenous components is achieved using an isocratic elution on an octyl column and an UV detector set at 260 nm. The method is linear from 20 to 10,000 ng/mL (mean r2 = 0.9991, n = 10). The observed intra- and inter-day assay precision ranged from 2.2% to 14.7%[at the lower limit of quantitation (LOQ)], whereas accuracy varies between 1.0% and 14% (at LOQ). Mean drug recovery is 80.5% for ATV and 78.4% for IS. The method is found to be precise and accurate, practical enough for therapeutic drug monitoring in routine clinical practice and is applied for the assessment of 24-h ATV plasma concentration-time profiles in HIV-infected pregnant women. 相似文献