全文获取类型
收费全文 | 2526篇 |
免费 | 63篇 |
国内免费 | 7篇 |
专业分类
化学 | 1656篇 |
晶体学 | 12篇 |
力学 | 59篇 |
数学 | 269篇 |
物理学 | 600篇 |
出版年
2021年 | 18篇 |
2020年 | 31篇 |
2019年 | 31篇 |
2017年 | 19篇 |
2016年 | 57篇 |
2015年 | 36篇 |
2014年 | 37篇 |
2013年 | 102篇 |
2012年 | 108篇 |
2011年 | 117篇 |
2010年 | 53篇 |
2009年 | 50篇 |
2008年 | 106篇 |
2007年 | 115篇 |
2006年 | 100篇 |
2005年 | 127篇 |
2004年 | 108篇 |
2003年 | 90篇 |
2002年 | 91篇 |
2001年 | 64篇 |
2000年 | 74篇 |
1999年 | 40篇 |
1998年 | 32篇 |
1997年 | 21篇 |
1996年 | 45篇 |
1995年 | 39篇 |
1994年 | 27篇 |
1993年 | 36篇 |
1992年 | 52篇 |
1991年 | 34篇 |
1990年 | 26篇 |
1989年 | 22篇 |
1988年 | 36篇 |
1987年 | 30篇 |
1986年 | 23篇 |
1985年 | 33篇 |
1984年 | 35篇 |
1983年 | 40篇 |
1982年 | 41篇 |
1981年 | 35篇 |
1980年 | 32篇 |
1979年 | 30篇 |
1978年 | 27篇 |
1977年 | 30篇 |
1976年 | 32篇 |
1975年 | 33篇 |
1974年 | 31篇 |
1973年 | 25篇 |
1972年 | 12篇 |
1970年 | 17篇 |
排序方式: 共有2596条查询结果,搜索用时 15 毫秒
91.
Crouse HF Potoma J Nejrabi F Snyder DL Chohan BS Basu S 《Dalton transactions (Cambridge, England : 2003)》2012,41(9):2720-2731
A series of twelve anionic, cationic, and neutral nickel(II) complexes have been synthesized and characterized. The interaction of these complexes with bovine serum albumin (BSA), human serum albumin (HSA), lysozyme (Lyso), and tryptophan (Trp) has been studied using steady-state fluorescence spectroscopy. Dynamic and static quenching constants have been calculated, and the role played in quenching by the ligand and complex charge investigated. The nickel complexes showed selectivity towards the different proteins based on the environment surrounding the Trp residue(s). Only small neutral complexes with hydrophobic ligands effectively quenched protein fluorescence via static quenching, with association constants ranging from 10(2) M(-1) (free Trp) to 10(10) M(-1) (lysozyme), indicating a spontaneous and thermodynamically favorable interaction. The number of binding sites, on average, was determined to be one in BSA, HSA and free Trp, and two in lysozyme. 相似文献
92.
93.
Robert G. Gilbert Alex C. Wu Mitchell A. Sullivan Gonzalo E. Sumarriva Natascha Ersch Jovin Hasjim 《Analytical and bioanalytical chemistry》2013,405(28):8969-8980
Two highly branched glucose polymers with similar structures—starch and glycogen—have important relations to human health. Slowly digestible and resistant starches have desirable health benefits, including the prevention and alleviation of metabolic diseases and prevention of colon cancer. Glycogen is important in regulating the use of glucose in the body, and diabetic subjects have an anomaly in their glycogen structure compared with that in healthy subjects. This paper reviews the biosynthesis–structure–property relations of these polymers, showing that polymer characterization produces knowledge which can be useful in producing healthier foods and new drug targets aimed at improving glucose storage in diabetic patients. Examples include mathematical modeling to design starch with better nutritional values, the effects of amylose fine structures on starch digestibility, the structure of slowly digested starch collected from in vitro and in vivo digestion, and the mechanism of the formation of glycogen α particles from β particles in healthy subjects. A new method to overcome a current problem in the structural characterization of these polymers using field-flow fractionation is also given, through a technique to calibrate evaporative light scattering detection with starch. Figure
? 相似文献
94.
Mahyar Nasabi Khashayar Khoshmanesh Francisco J. Tovar‐Lopez Kourosh Kalantar‐zadeh Arnan Mitchell 《Electrophoresis》2013,34(22-23):3150-3154
This paper demonstrates the utilization of 3D semispherical shaped microelectrodes for dielectrophoretic manipulation of yeast cells. The semispherical microelectrodes are capable of producing strong electric field gradients, and in turn dielectrophoretic forces across a large area of channel cross‐section. The semispherical shape of microelectrodes avoids the formation of undesired sharp electric fields along the structure and also minimizes the disturbance of the streamlines of nearby passing fluid. The advantage of semispherical microelectrodes over the planar microelectrodes is demonstrated in a series of numerical simulations and proof‐of‐concept experiments aimed toward immobilization of viable yeast cells. 相似文献
95.
A cotton cellulose derivative that forms charge-transfer complexes was prepared in yarn form. A charge-transfer complex is composed of two partners, one referred to as the donor and the other as an acceptor of electrical charge. In the present investigation, a donor was chemically bound to the cotton. It was shown that the modified donor cellulose adsorbs various acceptors from solution. Celluloses possessing donor or acceptor moieties are potentially useful as chromatographic agents and also in medicinal chemistry where a controlled release of a chemical agent is desired. 相似文献
96.
Dr. Carmine D'Agostino Dr. Tatyana Kotionova Dr. Jonathan Mitchell Dr. Peter J. Miedziak Prof. David W. Knight Dr. Stuart H. Taylor Prof. Graham J. Hutchings Prof. Lynn F. Gladden Dr. Mick D. Mantle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11725-11732
In recent work, it was reported that changes in solvent composition, precisely the addition of water, significantly inhibits the catalytic activity of Au/TiO2 catalyst in the aerobic oxidation of 1,4‐butanediol in methanol due to changes in diffusion and adsorption properties of the reactant. In order to understand whether the inhibition mechanism of water on diol oxidation in methanol is generally valid, the solvent effect on the aerobic catalytic oxidation of 1,3‐propanediol and its two methyl‐substituted homologues, 2‐methyl‐1,3‐propanediol and 2,2‐dimethyl‐1,3‐propanediol, over a Au/TiO2 catalyst has been studied here using conventional catalytic reaction monitoring in combination with pulsed‐field gradient nuclear magnetic resonance (PFG‐NMR) diffusion and NMR relaxation time measurements. Diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Combined NMR diffusion and relaxation time measurements suggest that molecular diffusion and, in particular, the relative strength of diol adsorption, are important factors in determining the conversion. These results highlight NMR diffusion and relaxation techniques as novel, non‐invasive characterisation tools for catalytic materials, which complement conventional reaction data. 相似文献
97.
Dr. Laia Vilà‐Nadal Dr. Scott G. Mitchell Dr. Stanislav Markov Dr. Christoph Busche Dr. Vihar Georgiev Prof. Asen Asenov Prof. Leroy Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16502-16511
We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO2, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom‐built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non‐volatile molecular memories (NVMM) or flash‐RAM. 相似文献
98.
G. A. Eiceman A. P. Snyder D. A. Blyth 《International journal of environmental analytical chemistry》2013,93(3):415-425
Abstract Automated, continuous monitoring of organic vapors in air under three field designs for plume drift was demonstrated using a hand-held ion mobility spectrometer (IMS) in characterizing IMS behavior as a point sensor. In one field study, the IMS was placed 50cm from a 9m2 grass plot contaminated with methylsalicylate and response to airborne vapors was recorded during a 13hr period of atmospheric turbulence to illustrate susceptibility of point sensors to wind direction. A similar study under near-quiescent atmospheric conditions was made using dimethylsulfoxide. In a third study, the plume from a point source of dipropyleneglycolmonomethylether was interrogated over a 25m × 12m grid downwind with windspeeds of 6–18km h?. Laboratory studies were used to measure instrumental response times and influences from potentially interfering atmospheric organic pollutants. 相似文献
99.
Vyskocil S Meca L Tislerová I Císarová I Polásek M Harutyunyan SR Belokon YN Stead RM Farrugia L Lockhart SC Mitchell WL Kocovský P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4633-4648
The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15-->18), followed by functional group transformations, involving C-P and C-N bond formation (18-->19 and 18-->23). Racemic intermediate 22 was resolved by co-crystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product). 相似文献
100.
Kimball DB Haley MM Mitchell RH Ward TR Bandyopadhyay S Williams RV Armantrout JR 《The Journal of organic chemistry》2002,67(25):8798-8811
The synthesis and study of dehydrobenzoannulene (DBA)-dimethyldihydropyrene (DDP) hybrids as models for the investigation of aromaticity in weakly diatropic systems is reported. Three new monofused DBA-DDP hybrids have been synthesized, and their NMR spectra are discussed with regard to quantifying the aromaticity remaining in multibenzene-fused DBAs. Nucleus-independent chemical shifts, determined at a series of locations for each compound, bond lengths, and (1)H and (13)C NMR chemical shifts were calculated and used to probe the aromaticity of these hybrids. Systems where more than one annulene/DBA is fused to the DDP core have also been obtained, and their potential use in photoinduced isomerization applications is discussed. 相似文献