全文获取类型
收费全文 | 11016篇 |
免费 | 565篇 |
国内免费 | 349篇 |
专业分类
化学 | 7148篇 |
晶体学 | 124篇 |
力学 | 413篇 |
综合类 | 29篇 |
数学 | 1915篇 |
物理学 | 2301篇 |
出版年
2023年 | 73篇 |
2022年 | 94篇 |
2021年 | 180篇 |
2020年 | 212篇 |
2019年 | 168篇 |
2018年 | 167篇 |
2017年 | 155篇 |
2016年 | 267篇 |
2015年 | 258篇 |
2014年 | 295篇 |
2013年 | 684篇 |
2012年 | 557篇 |
2011年 | 651篇 |
2010年 | 410篇 |
2009年 | 352篇 |
2008年 | 622篇 |
2007年 | 586篇 |
2006年 | 531篇 |
2005年 | 503篇 |
2004年 | 387篇 |
2003年 | 363篇 |
2002年 | 401篇 |
2001年 | 190篇 |
2000年 | 176篇 |
1999年 | 135篇 |
1998年 | 116篇 |
1997年 | 126篇 |
1996年 | 155篇 |
1995年 | 91篇 |
1994年 | 111篇 |
1993年 | 116篇 |
1992年 | 113篇 |
1991年 | 106篇 |
1990年 | 102篇 |
1989年 | 84篇 |
1988年 | 96篇 |
1987年 | 94篇 |
1985年 | 151篇 |
1984年 | 146篇 |
1983年 | 122篇 |
1982年 | 136篇 |
1981年 | 149篇 |
1980年 | 148篇 |
1979年 | 126篇 |
1978年 | 132篇 |
1977年 | 127篇 |
1976年 | 117篇 |
1975年 | 104篇 |
1974年 | 106篇 |
1973年 | 105篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
111.
Ellen R. Goldman Igor L. Medintz George P. Anderson Brent L. Iverson George Georgiou Hedi Mattoussi 《Analytica chimica acta》2005,534(1):63-67
We report a simple and versatile approach for the conjugation of luminescent CdSe-ZnS core-shell quantum dots (QDs) to proteins through coordination of engineered C-terminal oligohistidine sequences. Several histidine tail containing proteins were self-assembled onto the QD surface using this method. A recombinant antibody specific for the high explosive 2,4,6-trinitrotoluene (TNT) was conjugated to QDs through a carboxy terminal histidine tail and the bioconjugate used to detect TNT by competitive immunoassay. TNT was detected over the range of 10 μg/ml down to 41 ng/ml using the scFv conjugated to QDs. These results open up the possibility to conjugate luminescent QDs to a whole range of proteins to form QD bioconjugates that can be effectively used in bio-oriented applications, such as sensing, imaging, immunoassay and other diagnostics. 相似文献
112.
Thomson RK Zahariev FE Zhang Z Patrick BO Wang YA Schafer LL 《Inorganic chemistry》2005,44(24):8680-8689
Easily prepared and highly modular organic amide proligands have been used to synthesize a series of new bis(amidate)-bis(amido) Ti and Zr complexes via protonolysis. These complexes have been structurally characterized by NMR spectroscopy and X-ray crystallography. The solid-state molecular structures of these complexes indicate that the amidate ligands bind to the metal centers in an exclusively bidentate fashion, resulting in discrete monomeric species. Geometric isomerism in these species is highly dependent upon the steric characteristics of the proligands utilized in the synthesis. In solution, these complexes are observed to isomerize on the NMR time scale, with one isomer being predominant. Bonding in the bis(amidate)-bis(amido) complexes was investigated by DFT calculations. The geometric isomers predicted by theory matched the experimentally observed results, within experimental error. The orbitals associated with amidate-metal bonding are energetically well below the frontier orbitals. The HOMO in these complexes is a pi orbital associated with amido ligand-to-metal bonding character, while the LUMO in all cases is a vacant d orbital on the metal center. 相似文献
113.
The growth of crystals in solution 总被引:3,自引:0,他引:3
George H. Nancollas 《Advances in colloid and interface science》1979,10(1):215-252
The crystallization of sparingly soluble salts from their aqueous supersaturated solutions is discussed from the standpoint of two important applications; scale formation and biological mineralization. Theories of crystal growth are outlined and the importance of kinetic factors in determining the nature of the growing phases is discussed. The kinetic factors can be studied by using a highly reproducible seeded growth technique and under certain conditions secondary nucleation can also be induced on the surface of the inoculating seed crystals. The kinetics of crystallization of the alkaline earth surfaces and the calcium phosphates is discussed. In the latter systems, temperature, supersaturation, surface concentration, pH, ionic strength and the presence of foreign ions are important in determining the nature of the phase which grows on the added seed crystals. The mechanism of the retardation of crystal growth by added crystallization inhibitors is illustrated by the influence of organic phosphonate molecules upon the precipitation of calcium carbonate. 相似文献
114.
建立了酱油中1,3-二氯-2-丙醇、2,3-二氯-1-丙醇、3-氯-1,2-丙二醇和2-氯-1,3-丙二醇的分散固相萃取-气相色谱-高分辨质谱快速筛查检测方法。样品采用乙酸乙酯提取,提取液浓缩后经N-丙基乙二胺净化,气相色谱-高分辨质谱测定,内标法定量。结果表明,该方法对于酱油中4种氯丙醇的定量限为0.5~10 μg/kg。在3个浓度水平下的加标回收率为78%~103%;相对标准偏差均不大于8.8%。该方法快速、简便、准确、灵敏,可作为酱油中4种氯丙醇的有效检测方法。 相似文献
115.
以高炉水淬渣合成的Ca-α-Sialon粉体为原料采用无压烧结技术制备了(Ca/Y)-α-Sialon陶瓷。通过用排水法、三点弯曲实验法、金相显微镜法、XRD法等手段研究了(Ca/Y)-α-Sialon陶瓷的烧结致密化过程、材料的力学性能、显微组织、相组成和材料的断裂特征。结果表明,适量的Y2O3促进材料的烧结致密化和提高材料的力学性能,但Y2O3过量(大于10%)时对材料的烧结和力学性能不利。掺杂Y^3+的(Ca/Y)-α-Sialon呈柱状晶,随着Y2O3含量的增加和烧结温度的提高,(Ca/Y)-α-Sialon呈柱状晶出现粗化和等轴化。含10%Y2O3的材料在1700℃烧结时可获得较高的力学性能。 相似文献
116.
Commodari F Sclavos G Ibrahimi S Khiat A Boulanger Y 《Magnetic resonance in chemistry : MRC》2005,43(6):444-450
The NMR-derived structure of estrogen (17beta-estradiol, E2), the drug of choice for postmenopausal women, was compared with a recent literature crystal x-ray structure of Fab-bound E2. 1H and 13C NMR spectra of E2 were acquired in DMSO-d6. Assignments were obtained from an analysis of DQF-COSY, TOCSY, HETCOR, HMQC and HMBC 2D NMR spectra. The 1H and 13C NMR assignments are the first reported for E2 in DMSO-d6. Two solution structures, S1 and S2, were obtained with molecular modeling using NOE constraints. S1 overlaps with the crystal structure for all rings. S2 shows prominent differences in the C-ring (C9--C11--C12--C13) segment, which deviates from a chair conformation, and excellent overlap in the A-, B- and D-rings of E2. The C-ring in S2 adopts a boat conformation as opposed to a chair conformation in the x-ray and S1 structures. The S2 structure is about 6 degrees more twisted than the bound x-ray and S1 models. The S1, S2 and x-ray structures had ring bowing values of 10.1 +/- 0.3, 11 +/- 1 and 10.37 degrees , respectively. Of the 100 solution conformers generated, 83 had S1 conformation and 17 had S2 conformation, with average internal energies of 112 +/- 2 and 141 +/- 2 kcal mol(-1), respectively. The 100 S1- and S2- derived conformers showed a r.m.s.d. of 0.72 A for all atoms. The x-ray, S1 and S2 C18--O17 distances were 2.93, 2.92 +/- 0.01 and 2.93 +/- 0.01 A, respectively, and the O3--O17 distances were 11.06, 11.18 +/- 0.12, and 10.89 +/- 0.05 A, respectively. 相似文献
117.
Henry DJ Yiapanis G Evans E Yarovsky I 《The journal of physical chemistry. B》2005,109(36):17224-17231
This study examines the adhesion of graphite to functionalized polyester surfaces using a range of qualitative and quantitative measures of theoretical adhesion. Modifications to the polyester surfaces include the addition of hydroxyl, carboxyl, or fluorine substituents with coverages of 0.4 and 0.9 groups per nm(2). In each case, the introduction of substituents to the surface of the polyester was calculated to lead to reduced adhesion to graphite. Effects of surface relaxation on adhesion are studied by employing different simulation protocols. The theoretical results suggest one mechanism to reduce adhesion to carbonaceous solids is to increase atomic roughness using strongly hydrophilic or alternatively strongly hydrophobic substituents. 相似文献
118.
Love JC Urbach AR Prentiss MG Whitesides GM 《Journal of the American Chemical Society》2003,125(42):12696-12697
Metallic rods with submicron diameters that contain disklike ferromagnetic sections self-assemble into highly stable, hexagonally close-packed arrays of rods. The rods were fabricated by electrodeposition in porous alumina membranes and comprised alternating sections of gold and nickel. The thicknesses of the ferromagnetic nickel sections were approximately one-half the diameter of the rods (400 nm); this geometry orients the "easy" axis of magnetization perpendicular to the long axis of the rod. After magnetization of the rods with a rare-earth magnet, followed by sonication of the suspension, the rods spontaneously assembled into three-dimensional (3D) bundles that, on average, contained 15-30 rods. A macroscopic model of the rods suggests that the most stable orientation of the magnetic dipoles for rods in a defect-free, hexagonally close-packed arrangement is in concentric rings with the dipoles oriented head-to-tail. This configuration minimizes the energy of the bundle and does not generate a net dipole for the structure. This work provides a simple demonstration that magnetic interactions between ferromagnetic objects can direct and stabilize the formation of ordered, 3D structures by self-assembly. 相似文献
119.
Akira Matsumoto Hisako Mano Masayoshi Oiwa George B. Butler 《Journal of polymer science. Part A, Polymer chemistry》1989,27(6):1811-1816
The radical polymerization of tetraallyl ammonium chloride (TAAC) was carried out in water using azo-initiator as compared to that of diallyl dimethyl ammonium chloride (DADMAC); the rate of polymerization was quite low for TAAC, around one-third of DADMAC. Kinetic discussion revealed the importance of degradative chain transfer in the polymerization of TAAC. The cyclopolymerizability of TAAC was estimated kinetically as the ability of 5-membered monocyclic radical to form a bicyclic ring, giving the cyclization constant of 21 mol/L at [M] = 2 mol/L. Gelation occurred at around 20% conversion. 相似文献
120.
The o-, m-, and p-phenylene bis(1,3-dioxolanium) dications (4-6) and 2,4,6-triphenylene tris(1,3-dioxolanium) trication (7) have been prepared by the ionization of the corresponding 2-methoxyethyl benzoates in FSO(3)H or CF(3)SO(3)H at 40 and 60 degrees C, respectively. The charge delocalization in these carbocations was probed by (13)C NMR chemical shifts and substantiated by GIAO/DFT calculations. Relatively less charge is delocalized into the aromatic ring of the carbotrication 7. The rotational barrier around the C(+)-Ar bond for carbodications 4 and 5 was also estimated to be 8-10 kcal/mol. 相似文献