全文获取类型
收费全文 | 29945篇 |
免费 | 4246篇 |
国内免费 | 2730篇 |
专业分类
化学 | 20475篇 |
晶体学 | 284篇 |
力学 | 1944篇 |
综合类 | 273篇 |
数学 | 3284篇 |
物理学 | 10661篇 |
出版年
2024年 | 106篇 |
2023年 | 590篇 |
2022年 | 909篇 |
2021年 | 957篇 |
2020年 | 1112篇 |
2019年 | 1082篇 |
2018年 | 912篇 |
2017年 | 814篇 |
2016年 | 1282篇 |
2015年 | 1270篇 |
2014年 | 1539篇 |
2013年 | 2055篇 |
2012年 | 2633篇 |
2011年 | 2662篇 |
2010年 | 1648篇 |
2009年 | 1635篇 |
2008年 | 1743篇 |
2007年 | 1662篇 |
2006年 | 1494篇 |
2005年 | 1231篇 |
2004年 | 945篇 |
2003年 | 789篇 |
2002年 | 752篇 |
2001年 | 562篇 |
2000年 | 559篇 |
1999年 | 651篇 |
1998年 | 578篇 |
1997年 | 574篇 |
1996年 | 659篇 |
1995年 | 506篇 |
1994年 | 467篇 |
1993年 | 389篇 |
1992年 | 373篇 |
1991年 | 324篇 |
1990年 | 256篇 |
1989年 | 203篇 |
1988年 | 158篇 |
1987年 | 136篇 |
1986年 | 129篇 |
1985年 | 118篇 |
1984年 | 88篇 |
1983年 | 61篇 |
1982年 | 41篇 |
1981年 | 36篇 |
1980年 | 18篇 |
1978年 | 19篇 |
1977年 | 23篇 |
1976年 | 20篇 |
1975年 | 28篇 |
1974年 | 27篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Caignan GA Deshmukh R Wilks A Zeng Y Huang HW Moënne-Loccoz P Bunce RA Eastman MA Rivera M 《Journal of the American Chemical Society》2002,124(50):14879-14892
The origin of the unusual regioselectivity of heme oxygenation, i.e. the oxidation of heme to delta-biliverdin (70%) and beta-biliverdin (30%), that is exhibited by heme oxygenase from Pseudomonas aeruginosa (pa-HO) has been studied by (1)H NMR, (13)C NMR, and resonance Raman spectroscopies. Whereas resonance Raman indicates that the heme-iron ligation in pa-HO is homologous to that observed in previously studied alpha-hydroxylating heme oxygenases, the NMR spectroscopic studies suggest that the heme in this enzyme is seated in a manner that is distinct from that observed for all other alpha-hydroxylating heme oxygenase enzymes for which a structure is known. In pa-HO, the heme is rotated in-plane approximately 110 degrees, so the delta-meso-carbon of the major orientational isomer is located within the HO-fold in the place where the alpha-hydroxylating enzymes typically place the alpha-meso-carbon. The unusual heme seating displayed by pa-HO places the heme propionates so that these groups point in the direction of the solvent-exposed heme edge and appears to originate in large part from the absence of stabilizing interactions between the polypeptide and the heme propionates, which are typically found in alpha-hydroxylating heme oxygenase enzymes. These interactions typically involve Lys-16 and Tyr-112, in Neisseriae meningitidis HO, and Lys-16 and Tyr-134, in human and rat HO-1. The corresponding residues in pa-HO are Asn-19 and Phe-117, respectively. In agreement with this hypothesis, we found that the Asn-19 Lys/Phe-117 Tyr double mutant of pa-HO exists as a mixture of molecules exhibiting two distinct heme seatings; one seating is identical to that exhibited by wild-type pa-HO, whereas the alternative seating is very similar to that typical of alpha-hydroxylating heme oxygenase enzymes and is related to the wild-type seating by approximately 110 degrees in-plane rotation of the heme. Furthermore, each of these heme seatings in the pa-HO double mutant gives rise to a subset of two heme isomeric orientations that are related to each other by 180 degrees rotation about the alpha-gamma-meso-axis. The coexistence of these molecules in solution, in the proportions suggested by the corresponding area under the peaks in the (1)H NMR spectrum, explains the unusual regioselectivity of heme oxygenation observed with the double mutant, which we found produces alpha- (55%), delta- (35%), and beta-biliverdin (10%). Alpha-biliverdin is obtained by oxidation of the heme seated similar to that of alpha-hydroxylating enzymes, whereas beta- and delta-biliverdin are formed from the oxidation of heme seated as in wild-type pa-HO. 相似文献
942.
Huang SJ Huh S Lo PS Liu SH Lin VS Liu SB 《Physical chemistry chemical physics : PCCP》2005,7(16):3080-3087
An extensive study has been made on a series of multifunctional mesoporous silica materials, prepared by introducing two different organoalkoxysilanes, namely 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEPTMS) and 3-cyanopropyltriethoxysilane (CPTES) during the base-catalyzed condensation of tetraethoxysilane (TEOS), using the variable-temperature (VT) hyperpolarized (HP) 129Xe NMR technique. VT HP-129Xe NMR chemical shift measurements of adsorbed xenon revealed that surface properties as well as functionality of these AEP/CP-functionalized microparticles (MP) could be controlled by varying the AEPTMS/CPTES ratio in the starting solution during synthesis. Additional chemical shift contribution due to Xe-moiety interactions was observed for monofunctional AEP-MP and CP-MP as well as for bifunctional AEP/CP-MP samples. In particular, unlike CP-MP that has a shorter organic backbone on the silica surface, the amino groups in the AEP chain tends to interact with the silanol groups on the silica surface causing backbone bending and hence formation of secondary pores in AEP-MP, as indicated by additional shoulder peak at lower field in the room-temperature 129Xe NMR spectrum. The exchange processes of xenon in different adsorption regions were also verified by 2D EXSY HP-129Xe NMR spectroscopy. It is also found that subsequent removal of functional moieties by calcination treatment tends to result in a more severe surface roughness on the pore walls in bifunctional samples compared to monofunctional ones. The effect of hydrophobicity/hydrophilicity of the organoalkoxysilanes on the formation, pore structure and surface property of these functionalized mesoporous silica materials are also discussed. 相似文献
943.
A series of poly(o-hydroxy amide)s having both ether and ortho-catenated phenylene unit in the main chain were synthesized via the low-temperature solution polycondensation of 4,4′-(1,2-phenylenedioxy)dibenzoyl chloride and 4,4′-(4-tert-butyl-1,2-phenylenedioxy)dibenzoyl chloride with three bis(o-aminophenol)s including 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The poly(o-hydroxy amide)s exhibited inherent viscosities in the range of 0.23-0.96 dl/g. Most of the poly(o-hydroxy amide)s were soluble in polar organic solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) and could afford flexible and tough films by solution casting. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s afforded polybenzoxazoles. However, the polybenzoxazoles were organic-insoluble except for those with the hexafluoroisopropylidene group. The polybenzoxazoles exhibited glass-transition temperatures (Tg) in the range of 200-232 °C by DSC and softening temperatures (Ts) of 250-256 °C by thermomechanical analysis. Thermogravimetric analyses indicated that most polybenzoxazoles were stable up to 500 °C in air or nitrogen. The 10% weight loss temperatures were recorded in the ranges of 546-606 °C in air and 574-631 °C in nitrogen. 相似文献
944.
Shui W Yu Y Xu X Huang Z Xu G Yang P 《Rapid communications in mass spectrometry : RCM》2003,17(14):1541-1547
The physical processes underlying micro-electrospray (micro-ES) performance were investigated using a stainless steel (SS) emitter with a blunt tip. Sheathless micro-ES could be generated at a blunt SS tip without any tapering or sanding if ESI conditions were optimized. The Taylor cone was found to shrink around the inner diameter of the SS tubing, which permitted a low flow rate of 150 nL/min for sheathless microspray on the blunt tip (100 microm i.d. x 400 microm o.d.). It is believed that the wettability and/or hydrophobicity of SS tips are responsible for their micro-ES performance. The outlet orifice was further nipped to reduce the size of the spray cone and limit the flow rate to 50-150 nL/min, resulting in peptide detection down to attomole quantities consumed per spectrum. The SS emitter was also integrated into a polymethylmethacrylate microchip and demonstrated satisfactory performance in the analysis and identification of a myoglobin digest. 相似文献
945.
Efficient resolution of racemic 1,1'-bi-2-naphthol, a well-studied analyte in chiral separation, was achieved using selectors developed from a small library. Separation factors (up to 7.2) obtained are significantly higher than the ones reported previously for this analyte. The library consists of 121 members and it does not contain the pi deficient 3,5-dinitrobenzoyl (Dnb) group. These highly efficient stationary phases may lead to the practical large-scale chromatographic resolution of enantiomers of 1,1'-bi-2-naphthol, which are widely used as chiral auxiliaries and ligands in asymmetric synthesis. 相似文献
946.
Sem DS Bertolaet B Baker B Chang E Costache AD Coutts S Dong Q Hansen M Hong V Huang X Jack RM Kho R Lang H Ma CT Meininger D Pellecchia M Pierre F Villar H Yu L 《Chemistry & biology》2004,11(2):185-194
Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases. 相似文献
947.
测定核黄素的化学发光新方法 总被引:4,自引:0,他引:4
研究了核黄素的化学发光性质,建立了一种测定核黄素的化学发光新方法,并应用于实际样品中核黄素的测定,与文献相比,本方法无需避光,而且分析体系和样品处理简单;干扰小,牛血清白蛋白、抗坏血酸、天冬氨酸等8种生物有机物质和 Cu(Ⅱ)、Zn(Ⅱ)、Fe(Ⅲ)等15种常见金属离子的允许量较大;核黄素溶液浓度在0. 10~50 mg/L范围内,与化学发光强度成正比,方法线性范围宽;测定1.0mg/L核黄素溶液12次,求得相对标准偏差为2.9%,方法精密度高;方法的检测限为0.075 mg/L,灵敏度高。 相似文献
948.
949.
950.
[reaction: see text] A convenient synthesis of monodendrons whose conformation is restricted through the intervention of intramolecular hydrogen bonding and repulsive electrostatic interactions is described. X-ray crystal structure analysis of the second generation dendron shows the presence of a propeller-type secondary structure and indicates that the dendrons have assembled into a symmetrically interdigitated dimer in the solid state. 1H NMR and IR spectral data are in agreement with the presence of intramolecular hydrogen bonding between the amides and the pyridine N throughout the dendron structure in solution. 相似文献