全文获取类型
收费全文 | 5512篇 |
免费 | 167篇 |
国内免费 | 12篇 |
专业分类
化学 | 4029篇 |
晶体学 | 51篇 |
力学 | 51篇 |
数学 | 778篇 |
物理学 | 602篇 |
无线电 | 180篇 |
出版年
2021年 | 55篇 |
2020年 | 63篇 |
2019年 | 60篇 |
2018年 | 37篇 |
2017年 | 40篇 |
2016年 | 111篇 |
2015年 | 125篇 |
2014年 | 135篇 |
2013年 | 213篇 |
2012年 | 265篇 |
2011年 | 293篇 |
2010年 | 205篇 |
2009年 | 197篇 |
2008年 | 289篇 |
2007年 | 223篇 |
2006年 | 255篇 |
2005年 | 221篇 |
2004年 | 234篇 |
2003年 | 177篇 |
2002年 | 163篇 |
2001年 | 93篇 |
2000年 | 82篇 |
1999年 | 80篇 |
1998年 | 72篇 |
1997年 | 78篇 |
1996年 | 85篇 |
1995年 | 72篇 |
1994年 | 76篇 |
1993年 | 68篇 |
1992年 | 68篇 |
1991年 | 76篇 |
1990年 | 57篇 |
1989年 | 58篇 |
1988年 | 57篇 |
1987年 | 55篇 |
1986年 | 66篇 |
1985年 | 85篇 |
1984年 | 97篇 |
1983年 | 52篇 |
1982年 | 74篇 |
1981年 | 95篇 |
1980年 | 75篇 |
1979年 | 67篇 |
1978年 | 78篇 |
1977年 | 46篇 |
1976年 | 68篇 |
1975年 | 53篇 |
1973年 | 52篇 |
1971年 | 41篇 |
1970年 | 35篇 |
排序方式: 共有5691条查询结果,搜索用时 15 毫秒
111.
A method for synthesizing multidentate thiol ligands on fused silica surfaces (e.g., optical fibers) was developed for the immobilization of CdSe/ZnS quantum dots (QDs) capped with hydrophilic or hydrophobic ligands. This work was motivated by the poor stability of QDs immobilized via monodentate thiol ligands and the need for stable immobilization strategies in the development of sensor technologies based on QDs. Multi-dentate immobilization was able to withstand washing protocols, and surface ligand exchange occurred via self-assembly through the zinc-metal affinity interaction. Atomic force and scanning electron microscopy images suggested that the QDs were immobilized at high density, approximately 2-4 x 10 (13) cm (-2). It was possible to immobilize one, two, or three colors of QD. Upon immobilization, 1-2 nm bathochromic shifts in the PL spectra were observed. This was attributed to both ligand exchange and the change in local environment. The change in environment was accompanied by a decrease in PL lifetime. Self-assembly of immobilized QD-oligonucleotide and QD-avidin conjugates was also demonstrated. These conjugates were able to hybridize with complementary oligonucleotide and bind biotin, respectively. This versatile immobilization chemistry is an important step in the development of surface-based QD nanosensors. Such technology requires QDs to be immobilized such that they remain accessible to target molecules in solution. 相似文献
112.
3,6-Di(pyridin-2-yl)pyridazines are an interesting class of compounds because of their metal-coordinating ability resulting in the self-assembly into [2x2] gridlike metal complexes with copper(I) or silver(I) ions. These and other substituted pyridazines can be prepared by the inverse-electron-demand Diels-Alder reactions between acetylenes and 1,2,4,5-tetrazines. In this contribution, the effect of (superheated) microwave conditions on these generally slow cycloadditions is described. The cycloaddition of acetylenes to 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine could be accelerated from several days reflux in toluene or N,N-dimethylformamide to several hours in dichloromethane at 150 degrees C. In addition, the unexpected cycloaddition of the enol tautomers of various ketones and aldehydes to 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine is described in detail providing an alternative route for the synthesis of (substituted) pyridazines. 相似文献
113.
114.
Hussain F Bassil BS Kortz U Kholdeeva OA Timofeeva MN de Oliveira P Keita B Nadjo L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(17):4733-4742
The dititanium-containing 19-tungstodiarsenate(III) [Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)](8-) (1) has been synthesized and characterized by IR, TGA, elemental analysis, electrochemistry, and catalytic studies. Single-crystal X-ray analysis was carried out on Cs(8)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)].2CsCl.12H(2)O (Cs-1), which crystallizes in the monoclinic system, space group P2(1)/m, with a=12.7764(19), b=19.425(3), c=18.149(3) A, beta=110.234(3) degrees, and Z=2. Polyanion 1 comprises two (B-alpha-As(III)W(9)O(33)) Keggin moieties linked through an octahedral {WO(5)(H(2)O)} fragment and two unprecedented square-pyramidal {TiO(4)(OH)} groups, leading to a sandwich-type structure with nominal C(2v) symmetry. Synthesis of 1 was accomplished by reaction of TiOSO(4) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous, acidic medium (pH 2). Polyanion 1 could also be isolated as a tetra-n-butyl ammonium (TBA) salt, {(n-C(4)H(9))(4)N}(5)H(3)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)] (TBA-1). TBA-1 was studied by cyclic voltammetry in acetonitrile (MeCN) solutions containing 0.1 M LiClO(4) and compared with the results obtained with Cs-1 in aqueous media. In MeCN, the Ti(IV) and W(VI) waves could not be separated distinctly. An important adsorption phenomenon on the glassy carbon working electrode was encountered both in cyclic voltammetry and in controlled potential electrolysis and was confirmed by Electrochemical Quartz Crystal Microbalance (EQCM) studies on a carbon film. TBA-1, dissolved in MeCN, reacts with H(2)O(2) to give peroxo complexes stable enough for characterization by UV-visible spectroscopy, cyclic voltammetry, and EQCM. TBA-1 shows high catalytic activity (TOF=11.3 h(-1)) in cyclohexene oxidation with aqueous H(2)O(2) producing products typical of a heterolytic oxidation mechanism. The stability of TBA-1 under turnover conditions was confirmed by using IR, UV-visible spectroscopy as well as cyclic voltammetry. 相似文献
115.
Trusch M Ehlert S Bertsch A Kohlbacher O Hildebrand D Schlüter H Tallarek U 《Journal of separation science》2010,33(21):3283-3291
The influence of packing process parameters (packing pressure, application of ultrasound) and the stationary phase particle size (3.5 and 5 μm) on the chromatographic performance of HPLC/MS chips was systematically investigated for proteomic samples. First, reproducibility and detection limits of the separation were evaluated with a low‐complexity sample of tryptic BSA peptides. The influence of adsorbent packing quality on protein identification was then tested with a typical proteomics sample of high complexity, a human plasma protein fraction (Cohn fraction IV‐4). All HPLC/MS chips provided highly reproducible separations of these proteomic samples, but improved packing conditions and smaller particle sizes resulted in chromatograms with narrower peaks and correspondingly higher signal intensities. Improved separation performance increased the peak capacity, the number of identified peptides, and thus the sequence coverage in the proteomic samples, particularly for low sample amounts. 相似文献
116.
117.
Janna Börner M. Sc. Ulrich Flörke Dr. Klaus Huber Prof. Dr. Artjom Döring Dipl.‐Chem. Dirk Kuckling Prof. Dr. Sonja Herres‐Pawlis Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(10):2362-2376
New class of air‐stable catalysts for lactide polymerisation: Guanidine–pyridine hybrid ligands (picture, left) were used to prepare a series of zinc complexes (e.g., depicted cation [ZnL2(CF3SO3)]+, where L is the quinoline‐containing ligand with R1=R2=R3=R4=Me), in which the ligand binds through two different N‐donor atoms. The zinc complexes show high activity in ring‐opening polymerisation of d,l ‐lactide (right), giving polylactide with molecular masses up to 176 000 g mol?1 and in high yield.
118.
The synthesis of well-defined block copolymers from styrene and methyl acrylate via ATRP is discussed in this contribution. Kinetic studies on these block copolymerizations as well as characterization studies were performed to investigate the monomer composition in the respective PS and PMA blocks. MALDI-TOF-MS was performed to clarify the exact number of repeating units of each block and the total number of units in the block copolymer. Block copolymers up to 22 kDa could be analyzed by MALDI-TOF-MS, whereby polymers with PMA as first block showed a large second distribution corresponding to PMA homopolymers. However, SEC demonstrated that only a small amount of homopolymer was present indicating that care needs to be taken with interpreting MALDI-TOF-MS data, which is a qualitative rather than a quantitative technique. 相似文献
119.
Silvia Dorn Peter Eggenberg Michael R. C. Gerstenberger Alois Haas Ulrich Niemann Peter Zobrist 《Helvetica chimica acta》1979,62(5):1442-1450
(Perhalomethylthio)heterocycles. X 1 IX. Mitt.: s. [1]. . Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activities In the presence of C4F9SO3H the (perhalomethylthio)pyrroles 1a–c react with Cl3?nFnCSCl (n = 1–3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a–f and 3a–h . 2a and 3a react with CF3SCl (catalyst CF3SO3H) yielding 2,3,5-tris (trifloromethylthio)pyrrole ( 4a ), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole ( 5 ). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole ( 4b ) is formed. The pyrroles 2a , 4a and 5 form the mercury salts 6a–c ; compound 5 yields also a silver salt 7 . The 1H- and 19F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated. 相似文献
120.
Ulrich Schwenk und Erhard Weber 《Fresenius' Journal of Analytical Chemistry》1958,164(1):159-164
Zusammenfassung An Stelle der Podbielniak-Analyse für Gasproben, die neben Inertgasen und leichten Kohlenwasserstoffen auch C5- und höhere Kohlenwasserstoffe enthalten, wird ein neues Verfahren vorgeschlagen. Die Inertgase und leichten Kohlenwasserstoffe werden wie üblich gaschromatographisch bestimmt. Zusätzlich trennt man aus einer zweiten Probe gaschromatographisch die leichten Anteile ab, spült durch Umkehr der Trägergasrichtung die Summe der schweren Kohlenwasserstoffe wieder aus der Säule und bestimmt ihre Menge durch Wägung. 相似文献