全文获取类型
收费全文 | 19795篇 |
免费 | 634篇 |
国内免费 | 113篇 |
专业分类
化学 | 14181篇 |
晶体学 | 195篇 |
力学 | 382篇 |
综合类 | 1篇 |
数学 | 2973篇 |
物理学 | 2810篇 |
出版年
2022年 | 149篇 |
2021年 | 199篇 |
2020年 | 295篇 |
2019年 | 290篇 |
2018年 | 187篇 |
2017年 | 181篇 |
2016年 | 408篇 |
2015年 | 361篇 |
2014年 | 453篇 |
2013年 | 934篇 |
2012年 | 993篇 |
2011年 | 1275篇 |
2010年 | 630篇 |
2009年 | 529篇 |
2008年 | 1019篇 |
2007年 | 1097篇 |
2006年 | 1077篇 |
2005年 | 1046篇 |
2004年 | 884篇 |
2003年 | 752篇 |
2002年 | 735篇 |
2001年 | 252篇 |
2000年 | 258篇 |
1999年 | 231篇 |
1998年 | 225篇 |
1997年 | 259篇 |
1996年 | 288篇 |
1995年 | 230篇 |
1994年 | 215篇 |
1993年 | 249篇 |
1992年 | 208篇 |
1991年 | 186篇 |
1990年 | 164篇 |
1989年 | 141篇 |
1988年 | 140篇 |
1987年 | 159篇 |
1986年 | 136篇 |
1985年 | 203篇 |
1984年 | 249篇 |
1983年 | 178篇 |
1982年 | 220篇 |
1981年 | 241篇 |
1980年 | 180篇 |
1979年 | 181篇 |
1978年 | 214篇 |
1977年 | 163篇 |
1976年 | 157篇 |
1975年 | 150篇 |
1974年 | 168篇 |
1973年 | 142篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
The completely conjugated polymer, polyethynylferrocene, was prepared by heating ethynylferrocene with catalytic amounts of azobisisobutyronitrile to 180-240[ddot] under nitrogen in bulk. Cyclotrimerization competes with polymerization under these conditions. Pure low molecular weight polyethynylferrocene was isolated and characterized by IR and NMR spectroscopy and by a gel permeation chromatography. The pure polymer exhibits a conductivity of 2 × 10?14 ?1 cm?1. Attempts to prepare polyethynylferrocene by heating acetylferrocene in molten zinc chloride were, contrary to literature reports, unsuccessful. A polymer containing hydroxyl and keto groups was obtained, and extensive degradation of the ferrocene groups occurred. The general reaction scheme is discussed. It includes cleavage of cyclopentadienyl rings from ferrocene and the incorporation of cyclopentane rings into the polymer structure. 相似文献
992.
Yannick Weesepoel Jean‐Paul Vincken Raluca Maria Pop Kun Liu Harry Gruppen 《Journal of mass spectrometry : JMS》2013,48(7):862-874
The microalga Haematococcus pluvialis produces the pigment astaxanthin mainly in esterified form with a multitude of fatty acids, which results in a complex mixture of carotenol mono‐ and diesters. For rapid fingerprinting of these esters, matrix‐assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF/TOF‐MS) might be an alternative to traditional chromatographic separation combined with MS. Investigation of ionization and fragmentation of astaxanthin mono‐ and diester palmitate standards in MALDI‐TOF/TOF‐MS showed that sodium adduct parent masses [M + Na]+ gave much simpler MS2 spectra than radical / protonated [M]+● / [M + H]+ parents. [M + Na]+ fragments yielded diagnostic polyene‐specific eliminations and fatty acid neutral losses, whereas [M]+● / [M + H]+ fragmentation resulted in a multitude of non‐diagnostic daughters. For diesters, a benzonium fragment, formed by polyene elimination, was required for identification of the second fatty acid attached to the astaxanthin backbone. Parents were forced into [M + Na]+ ionization by addition of sodium acetate, and best signal‐to‐noise ratios were obtained in the 0.1 to 1.0 mM range. This method was applied to fingerprinting astaxanthin esters in a crude H. pluvialis extract. Prior to MALDI‐TOF/TOF‐MS, the extract was fractionated by normal phase Flash chromatography to obtain fractions enriched in mono‐ and diesters and to remove pheophytin a, which compromised monoester signals. All 12 types of all‐trans esterified esters found in LC were identified with MALDI‐TOF/TOF‐MS, with the exception of two minor monoesters. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
993.
Mircea Ştefănescu Mirela Barbu Paul Barvinschi Oana Ştefănescu 《Journal of Thermal Analysis and Calorimetry》2013,111(2):1121-1127
This paper presents a study regarding the obtaining of NiCr2O4 by two new unconventional synthesis methods: (i) the first method is based on the formation of Cr(III) and Ni(II) carboxylate-type precursors in the redox reaction between the nitrate ion and 1,3-propanediol. The thermal decomposition of these complex combinations, at ~300 °C, leads to an oxide mixture of Cr2O3+x and NiO, with advanced homogeneity, small particles and high reactivity. On heating this mixture at 500 °C, Cr2O3 reacts with NiO to form NiCr2O4, which was evidenced by FT-IR and X-ray diffractometry (XRD) analysis; (ii) the second method starts from a mechanical mixture of (NH4)2Cr2O7 and Ni(NO3)2·6H2O. On heating this mixture, a violent decomposition at 240 °C with formation of an oxides mixture (Cr2O3 + CrO3) and NiO takes place. On thermal treatment up to 500 °C, an intermediary phase NiCrO4 is formed, which by decomposition at ~700 °C leads to NiCr2O4, evidenced by FT-IR and XRD analysis. NiCr2O4 is formed, in both cases, starting with a temperature higher than 400 °C, when the non-stoichiometric chromium oxide (Cr2O3+x ) loses the oxygen excess and turns to stoichiometric chromium oxide (Cr2O3), which further reacts with NiO. 相似文献
994.
Paul Barvinschi Oana Stefanescu Thomas Dippong Simona Sorescu Mircea Stefanescu 《Journal of Thermal Analysis and Calorimetry》2013,112(1):447-453
The study reports the preparation of CoFe2O4/SiO2 nanocomposites by a new modified sol–gel method starting from cobalt nitrate, iron nitrate, and diols: 1,2-ethanediol (EG), 1,3-propanediol (1,3PG), and tetraethylorthosilicate (TEOS), for final compositions of 30 %CoFe2O4/70 %SiO2 and 50 %CoFe2O4/50 %SiO2. The method is based on the formation of a Co(II), Fe(III)—carboxylate precursors mixture, during the redox reaction between the NO 3 ? ion and the diol (~140 °C) within the silica gels. The thermal decomposition of these complex combinations takes place at ~300 °C leading to the corresponding amorphous metal oxides within the pores of the hybrid gels. Depending on the subsequent thermal treatment, CoFe2O4 can be obtained as single phase or in a mixture with Co2SiO4. The CoFe2O4 crystallites sizes are in the nanometer range (3–10 nm). The obtained nanocomposites have a hard magnet behavior, as a result of the high anisotropy of CoFe2O4 having large hysteresis cycles. 相似文献
995.
996.
Peter C. Griffiths Nicolo Mauro Damien M. Murphy Emma Carter Simon C. W. Richardson Paul Dyer Paolo Ferruti 《Macromolecular bioscience》2013,13(5):641-649
A series of nanoparticles is prepared via layer‐by‐layer assembly of oppositely charged, synthetic biocompatible polyamidoamine polymers as potential carriers. Particle size, surface charge and internal chain mobility are quantified as a function of the polymer type and number of layers. The effect of addition of surfactant is examined to simulate the effects of nanoparticle dissolution. The cyctotoxicity of these particles (in epithelia and murine cell lines) are orders of magnitude lower than polyethyleneimine controls. Stable nanoparticles may be prepared from mixtures of strongly, oppositely charged polymers, but less successfully from weakly charged polymers, and, given their acceptable toxicity characteristics, such modularly designed constructs show promise for drug and gene delivery.
997.
Paul Bendig Florian Hägele Walter Vetter 《Analytical and bioanalytical chemistry》2013,405(23):7485-7496
Food and contaminated indoor environments are the most relevant sources of human exposure to polyhalogenated chemicals. This study analyzed for the first time fat residues in kitchen hoods for contaminations with polyhalogenated compounds. A wide range of contaminants was detected in all kitchen hoods (n?=?15) and most of them could be quantified. Between 0.2 and 18 μg polyhalogenated chemicals/g fat were detected, with chlorinated paraffins being the most relevant contaminant group. Aside from the chlorinated paraffins, each kitchen hood fat sample showed a distinct fingerprint. A wide range of old and current-use brominated flame retardants were also detected in the samples. In addition to these contaminants originating from their use in indoor equipment, residues of organochlorine pesticides and semi-volatile halogenated natural products verified that cooking of food, accompanied with the release of contaminants from the heated food, was another relevant source of contamination. Re-analyses of two samples after 3 months only resulted in small variations in contaminant pattern and concentrations. Therefore, fat from kitchen hoods is proposed as an easily accessible matrix to assess contamination of these hazardous polyhalogenated chemicals. Figure
Picture of a kitchen hood and its filter. The fat collected from kitchen hood filters contained plenty of polyhalogenated chemicals 相似文献
998.
Peter Ó Conghaile Sirisha Kamireddy Domhnall MacAodha Paul Kavanagh Dónal Leech 《Analytical and bioanalytical chemistry》2013,405(11):3807-3812
Here, we report on a novel, versatile approach for the preparation of mediated enzyme electrodes, demonstrated using cross-linked films of glucose oxidase and a range of functionalised osmium complexes on graphite electrodes. Response of enzyme electrodes are optimised by evaluation of glucose response as a function of variation in ratios of [Os(2,2′-bipyridine)2(4-aminomethyl pyridine)Cl]+ redox mediator, polyallylamine support and glucose oxidase enzyme cross-linked using a di-epoxide reagent in films on graphite. Lowering of the redox potential required to mediate glucose oxidation is achieved by synthesis of complexes using (4,4′-dimethyl-2,2′-bipyridine) or (4,4′-dimethoxy-2,2′-bipyridine) as a ligand instead of (2,2′-bipyridine). Enzyme electrodes prepared using the complexes based on dimethoxy- or dimethyl-substituted bipyridines provide glucose oxidation current densities of 30 and 70 μA?cm?2 at 0.2 and 0.35 V applied potential compared to 120 μA?cm?2 at 0.45 V for the initial enzyme electrode, under pseudo-physiological conditions in 5 mM glucose, with stability of signals proving inadequate for long-term operation. Current output and stability may be improved by selection of alternate anchoring and cross-linking methodology, to provide enzyme electrodes capable for application to long-term glucose biosensors and anodes in enzymatic fuel cells. Figure
Glucose enzyme electrodes for application as biosensors or anodes in enzymatic fuel cells prepared by crosslinking films of osmium complex, glucose oxidase and polymer support on graphite electrodes. 相似文献
999.
Vera A. Schulte Dora F. Alves Paul P. Dalton Martin Moeller Marga C. Lensen Petra Mela 《Macromolecular bioscience》2013,13(5):562-572
Designing three‐dimensional (3D) scaffolds for selective manipulation of cell growth is of high relevance for applications in regenerative medicine. Especially, scaffolds with oriented morphologies bear high potential to guide the restoration of specific tissues. The fabrication of hydrogel scaffolds that support long‐term survival, proliferation, and unidirectional growth of embedded cells is presented here. Parallel channel structures are introduced into the bulk hydrogels by uniaxial freezing, providing stable, and uniform porosity suitable for cell invasion (pore diameters of 5–15 µm). In vitro assessment of the scaffolds with murine fibroblasts (NIH L929) shows a remarkable unidirectional movement along the channels, with the cells traveling several millimeters through the hydrogel.
1000.
Dr. Xuecheng Chen Dr. Krzysztof Kierzek Karolina Wenelska Krzystof Cendrowski Jiang Gong Dr. Xin Wen Prof. Tao Tang Prof. Paul K. Chu Prof. Ewa Mijowska 《化学:亚洲杂志》2013,8(11):2627-2633
Core–shell‐structured mesoporous silica spheres were prepared by using n‐octadecyltrimethoxysilane (C18TMS) as the surfactant. Hollow mesoporous carbon spheres with controllable diameters were fabricated from core–shell‐structured mesoporous silica sphere templates by chemical vapor deposition (CVD). By controlling the thickness of the silica shell, hollow carbon spheres (HCSs) with different diameters can be obtained. The use of ethylene as the carbon precursor in the CVD process produces the materials in a single step without the need to remove the surfactant. The mechanism of formation and the role played by the surfactant, C18TMS, are investigated. The materials have large potential in double‐layer supercapacitors, and their electrochemical properties were determined. HCSs with thicker mesoporous shells possess a larger surface area, which in turn increases their electrochemical capacitance. The samples prepared at a lower temperature also exhibit increased capacitance as a result of the Brunauer–Emmett–Teller (BET) area and larger pore size. 相似文献