全文获取类型
收费全文 | 1853篇 |
免费 | 42篇 |
国内免费 | 8篇 |
专业分类
化学 | 1237篇 |
晶体学 | 25篇 |
力学 | 48篇 |
数学 | 248篇 |
物理学 | 345篇 |
出版年
2021年 | 13篇 |
2020年 | 9篇 |
2019年 | 16篇 |
2018年 | 21篇 |
2017年 | 18篇 |
2016年 | 27篇 |
2015年 | 33篇 |
2014年 | 34篇 |
2013年 | 71篇 |
2012年 | 71篇 |
2011年 | 109篇 |
2010年 | 82篇 |
2009年 | 70篇 |
2008年 | 99篇 |
2007年 | 95篇 |
2006年 | 83篇 |
2005年 | 88篇 |
2004年 | 85篇 |
2003年 | 98篇 |
2002年 | 79篇 |
2001年 | 42篇 |
2000年 | 47篇 |
1999年 | 28篇 |
1998年 | 27篇 |
1997年 | 21篇 |
1996年 | 22篇 |
1995年 | 17篇 |
1994年 | 19篇 |
1993年 | 14篇 |
1992年 | 13篇 |
1991年 | 17篇 |
1990年 | 10篇 |
1989年 | 19篇 |
1988年 | 13篇 |
1987年 | 16篇 |
1986年 | 16篇 |
1985年 | 26篇 |
1984年 | 22篇 |
1983年 | 13篇 |
1982年 | 24篇 |
1981年 | 26篇 |
1980年 | 23篇 |
1979年 | 20篇 |
1978年 | 22篇 |
1977年 | 28篇 |
1976年 | 16篇 |
1975年 | 14篇 |
1974年 | 16篇 |
1973年 | 16篇 |
1971年 | 6篇 |
排序方式: 共有1903条查询结果,搜索用时 23 毫秒
101.
This Note deals with the modeling of a structure made of straight elastic rods whose thickness tends to 0. We show that, upon an adequate scaling, the infimum of the total elastic energy tends to the minimum of a functional which depends on fields defined on the centerlines of the rods. 相似文献
102.
Yvon Pointud Anne-Gaelle Valade Christelle Pointon Georges Jeminet Jose-Luis Beltran 《Supramolecular chemistry》2013,25(4):261-269
The binding abilities of a new class of 14-membered ring ligands bearing diketal dilactam functions were explored by UV-visible spectrophotometry. Their formation constants, determined in THF solution, showed appreciable complexation with divalent cations (stability order: Sr2+≥Ca2+>Zn2+≥Mg2+>Ba2+) whereas no association was observed with monovalent cations. The stoichiometry of the complexes formed was essentially 1:1 although sometimes a low percentage (<10%) of 1:2 (cation–ligand) species was detected. The corresponding formation constants determined by computation (STAR program) were in the range 1.5<log?β 11<4.8 and 4.4<log?β 12<7.1. They depend significantly on the nature of the substituents. In addition, solvent extractions carried out in a water–chloroform system showed the highest constants (log K ex) for the most substituted macrocycles 7b and 7c (norephedrine series) with a lipophilic skeleton. 相似文献
103.
An efficient one-step synthesis of 1,1-dipfienyl-1-silacyclopent-3-ene 1 is reported. 相似文献
104.
Matthew P. Conley Murielle F. Delley Georges Siddiqi Giuseppe Lapadula Sébastien Norsic Vincent Monteil Olga V. Safonova Christophe Copéret 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(7):1903-1907
The insertion of an olefin into a preformed metal–carbon bond is a common mechanism for transition‐metal‐catalyzed olefin polymerization. However, in one important industrial catalyst, the Phillips catalyst, a metal–carbon bond is not present in the precatalyst. The Phillips catalyst, CrO3 dispersed on silica, polymerizes ethylene without an activator. Despite 60 years of intensive research, the active sites and the way the first Cr C bond is formed remain unknown. We synthesized well‐defined dinuclear CrII and CrIII sites on silica. Whereas the CrII material was a poor polymerization catalyst, the CrIII material was active. Poisoning studies showed that about 65 % of the CrIII sites were active, a far higher proportion than typically observed for the Phillips catalyst. Examination of the spent catalyst and isotope labeling experiments showed the formation of a Si–(μ‐OH)–CrIII species, consistent with an initiation mechanism involving the heterolytic activation of ethylene at CrIII O bonds. 相似文献
105.
D. Ragheb C. Koumeir V. Métivier J. Gaudillot A. Guertin F. Haddad N. Michel N. Servagent 《Journal of Radioanalytical and Nuclear Chemistry》2014,302(2):895-901
The high energy PIXE (HEPIXE) method is a multi-elemental non-destructive ion beam analysis technique. It is based on the detection of the X-ray emitted due to the interaction of high energy particle beam with a sample. This technique is fast and allows the analysis of heavy and medium elements in thin (μm), thick (mm) and multilayer samples. At the ARRONAX facility (Nantes, France), the HEPIXE method has been used to determine the composition of natural and synthetic sodalites. Photochromic properties of these samples are supposed to come from the trace elements (concentration in the ppm range) present in the samples. Taking advantage of the 70 MeV proton beam available at our facility, the HEPIXE method has been also used to study multilayer samples. It has been shown that it is possible to determine the composition of each layer, their thicknesses and their depth position by analyzing the recorded X-ray spectra. 相似文献
106.
Characterization and kinetic performance of 2.1 × 100 mm production columns packed with new 1.6 μm superficially porous particles 下载免费PDF全文
Fabrice Gritti Stephen Shiner Jacob N. Fairchild Georges Guiochon 《Journal of separation science》2014,37(23):3418-3425
The overall kinetic performance of three production columns (2.1 mm × 100 mm format) packed with 1.6 μm superficially porous CORTECS‐C18+ particles was assessed on a low‐dispersive I‐class ACQUITY instrument. The values of their minimum intrinsic reduced plate heights (hmin = 1.42, 1.57, and 1.75) were measured at room temperature (295 K) for a small molecule (naphthalene) with an acetonitrile/water eluent mixture (75:25, v/v). These narrow‐bore columns provide an average intrinsic efficiency of 395 000 plates per meter. The gradient separation of 14 small molecules shows that these columns have a peak capacity about 25% larger than similar ones packed with fully porous BEH‐C18 particles (1.7 μm) or shorter (50 mm) columns packed with smaller core–shell particles (1.3 μm) operated under very high pressure (>1000 bar) for steep gradient elution (analysis time 80 s). In contrast, because their permeabilities are lower than those of columns packed with larger core–shell particles, their peak capacities are 25% smaller than those of narrow‐bore columns packed with standard 2.7 μm core–shell particles. 相似文献
107.
Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents 下载免费PDF全文
Jules Zeuna Nguendia Weiheng Zhong Alexandre Fleury Guillaume De Grandpré Prof. Armand Soldera Prof. Ribal Georges Sabat Prof. Jerome P. Claverie 《化学:亚洲杂志》2014,9(5):1356-1364
Copolymers of 2‐ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl‐2‐hydroxymethacrylate (CEM) were prepared by reversible addition–fragmentation chain‐transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2–5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high‐power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2‐hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non‐polar organic solvents, without altering the fundamental properties of the CNTs. 相似文献
108.
Inside Cover: Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents (Chem. Asian J. 5/2014) 下载免费PDF全文
109.
Khaled A. Marghany Randa A. Abdelsalam Ghada M. Haddad 《Journal of separation science》2020,43(8):1398-1405
In this study, a sensitive high‐performance liquid chromatography method was developed and validated for the simultaneous determination of seven angiotensin II receptor blockers, namely, hydrochlorothiazide, chlorthalidone, eprosartan mesylate, valsartan, losartan potassium, irbesartan, and candesartan cilexetil. Different chromatographic parameters were tested and fully optimized. Best chromatographic separation was accomplished on a reversed‐phase octadecylsilyl column (250 × 4.6 mm id; 5 μm) under gradient elution using methanol/sodium phosphate monobasic buffer (0.01 M, pH 6.5) as mobile phase. The detection of target analytes was obtained at 254 nm. The pH of the buffer has been selected according to Marvin® sketch software. The proposed method was validated according to ICH guidelines and showed good precision (relative standard deviation < 1), good linearity (square of correlation coefficient ≥ 0.999), and high accuracy (between 98 and 102%) with detection limit and quantitation limit (40 and 160 ng/mL, respectively) for all the detected analytes. 相似文献
110.