全文获取类型
收费全文 | 67159篇 |
免费 | 1457篇 |
国内免费 | 405篇 |
专业分类
化学 | 30634篇 |
晶体学 | 460篇 |
力学 | 2406篇 |
综合类 | 16篇 |
数学 | 15489篇 |
物理学 | 20016篇 |
出版年
2021年 | 346篇 |
2020年 | 513篇 |
2019年 | 401篇 |
2018年 | 1680篇 |
2017年 | 1929篇 |
2016年 | 1747篇 |
2015年 | 1334篇 |
2014年 | 1375篇 |
2013年 | 2551篇 |
2012年 | 4742篇 |
2011年 | 4186篇 |
2010年 | 2991篇 |
2009年 | 2530篇 |
2008年 | 2348篇 |
2007年 | 2275篇 |
2006年 | 2171篇 |
2005年 | 5750篇 |
2004年 | 5058篇 |
2003年 | 3253篇 |
2002年 | 1363篇 |
2001年 | 1112篇 |
2000年 | 779篇 |
1999年 | 649篇 |
1998年 | 529篇 |
1997年 | 485篇 |
1996年 | 564篇 |
1995年 | 512篇 |
1994年 | 534篇 |
1993年 | 523篇 |
1992年 | 713篇 |
1991年 | 524篇 |
1990年 | 518篇 |
1989年 | 458篇 |
1988年 | 412篇 |
1987年 | 407篇 |
1986年 | 358篇 |
1985年 | 542篇 |
1984年 | 513篇 |
1983年 | 433篇 |
1982年 | 446篇 |
1981年 | 442篇 |
1980年 | 432篇 |
1979年 | 434篇 |
1978年 | 421篇 |
1977年 | 416篇 |
1976年 | 437篇 |
1975年 | 394篇 |
1974年 | 390篇 |
1973年 | 340篇 |
1967年 | 257篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
J. Abenojar F. Velasco J.M. Mota M.A. Mart?&#x;nez 《Journal of solid state chemistry》2004,177(2):382-388
Steels with a high boron content are valuable as a neutron shield in waste containers and as control absorbers in nuclear reactors. The purpose of this study was to obtain by mechanical alloying an iron powder with 50% boron (by weight) and then powder-metallurgy materials. The elementary powders were mixed in a high-energy mill for 36 h in an inert atmosphere. Samples were withdrawn at intervals, and the powder was characterized by differential thermal analysis, X-ray diffraction and electron microscopy. The Fe/B powders withdrawn at different intervals of milling were diluted with further additions of iron up to a final content of 10% boron. The mixtures were uniaxially compacted at 500 MPa; their green density was verified, and they were sintered in argon at 1150°C. Their physical properties (density and dimensional change) and bending strength were evaluated and microstructural studies and fracture tests were performed. 相似文献
972.
Manganese in vitamin-minerals tablets was determined by solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS) using three different calibration methods, namely calibration against aqueous standards, standard addition with aqueous standards on solid samples and calibration against solid certified standards. Samples were only finely ground and introduced directly into the furnace by means of solid autosampler system without any dissolving process. Effects of different calibration techniques, temperatures and heating rates of atomization and pyrolysis steps on the accuracy and precision of the analyte elements were investigated. After optimization of the experimental parameters, there is good agreement (at 95% confidence level) between the results obtained by solid sampling and those obtained by acid digestion of samples. 相似文献
973.
M.?Avramov Ivi?Email author J.?Popi? D.?Antonovi? 《Russian Journal of Electrochemistry》2005,41(3):270-274
Electrocatalytic properties of oxides formed at gold, platinum, and stainless steel electrodes in the malic acid electrooxidation in 0.1 M Na2SO4 are studied. Gas chromatographic analysis of the electrolyte after holding the potential at 1.0 V for 8 h shows that on platinum and gold electrodes 2 mmol of acetaldehyde are produced and on stainless steel, 45 mmol. The acetaldehyde yield is the highest on stainless steel.From Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 304–309.Original English Text Copyright © 2005 by Avramov Ivi, Popi, Antonovi.This article was submitted by the authors in English. 相似文献
974.
Wagner J Andres H Rohrbach S Wagner D Oberer L France J 《The Journal of organic chemistry》2005,70(23):9588-9590
[Reaction: see text]. Sanglifehrin A is a novel complex natural product showing strong immunosuppressive activity and remarkably high affinity for cyclophilin A. To assess its pharmacokinetic properties in vivo, an efficient synthetic route was developed to introduce a tritium label in position C35 of sangliferin A via an oxidation/reduction strategy. The synthetic approach is particularly attractive, because the C35-oxo intermediate 7 is available in good yield on large scale and the reducing agent, lithium tri-sec-butylborotritide, is readily available. An attempt to apply a similar strategy to the alcohol in position C31 led primarily to C31-epi-hydroxy sanglifehrin A under a variety of conditions. 相似文献
975.
Baier J Maier M Engl R Landthaler M Bäumler W 《The journal of physical chemistry. B》2005,109(7):3041-3046
Singlet oxygen was generated by energy transfer from the photoexcited sensitizer, Photofrin or 9-acetoxy-2,7,12,17-tetrakis-(beta-methoxyethyl)-porphycene (ATMPn), to molecular oxygen. Singlet oxygen was detected time-resolved by its luminescence at 1270 nm in an environment of increasing complexity, water (H2O), pure phosphatidylcholine, phosphatidylcholine in water (lipid suspensions), and aqueous suspensions of living cells. In the case of the lipid suspensions, the sensitizers accumulated in the lipids, whereas the localizations in the cells are the membranes containing phosphatidylcholine. By use of Photofrin, the measured luminescence decay times of singlet oxygen were 3.5 +/- 0.5 micros in water, 14 +/- 2 micros in lipid, 9 +/- 2 micros in aqueous suspensions of lipid droplets, and 10 +/- 3 micros in aqueous suspensions of human colonic cancer cells (HT29). The decay time in cell suspensions was much longer than in water and was comparable to the value in suspensions of phosphatidylcholine. That luminescence signal might be attributed to singlet oxygen decaying in the lipid areas of cellular membranes. The measured luminescence decay times of singlet oxygen excited by ATMPn in pure lipid and lipid suspensions were the same within the experimental error as for Photofrin. In contrast to experiments with Photofrin, the decay time in aqueous suspension of HT29 cells was 6 +/- 2 micros when using ATMPn. 相似文献
976.
Vijayasarathi Nagarajan Barbara Müller Oksana Storcheva Klaus Köhler Andreas Pöppl 《Research on Chemical Intermediates》2007,33(8):705-724
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin
echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data
of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental
and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands. 相似文献
977.
The monodisperse, macroporous poly(glycidyl methacrylate- co-ethylene dimethacrylate) beads were synthesized by a single-step swelling and polymerization method. Based on this media, a weak cation exchange (WCX) stationary phase for HPLC was synthesized by a new chemically modified method. The prepared resin has advantages for biopolymer separation, high column efficiency, low column backpressure, high protein mass recovery, and good resolution for proteins. The measured bioactivity recovery for lysozyme was 98+/-5%. The dynamic protein loading capacity of the WCX packings was 17.3 mg g(-1). The experimental results show that the synthesized WCX resin has very weak hydrophobicity. 相似文献
978.
Sonnenschein H Kreher T Gründemann E Krüger RP Kunath A Zabel V 《The Journal of organic chemistry》1996,61(2):710-714
The first compounds of a new series of redox-active cyclophanes were prepared by dehydrocyclization of bridged indolizines of type 1. The bridged dipyridino-compounds 2a and 2b obtained by reaction of 2 mol of lithiated alpha-picolines with dihalides were used as starting materials. Subsequent treatment of 2a,b with 2 mol of alpha-bromo ketones gave quaternary pyridinium halides. Ring closure in an alkaline medium (Chichibabin reaction) yielded the starting material for the synthesis of the macrocycles. Oxidative C-C coupling gave the diastereomeric cyclophanes of type 3. In all cases one pair of the enantiomers was obtained in excess. CV-investigations have shown that the main products are reversible redox systems. To clarify their conformations, compounds 3c, 3d/1, and3d/2 were subjected to X-ray analysis. 相似文献
979.
A normal-phase ion-pair chromatographic system has been developed for the high-performance liquid chromatographic investigation of pipecuronium bromide (2 beta,16 beta-bis-(N'-dimethyl-l-piperazinyl)-3 alpha,17 beta-diacetoxy-5 alpha-androstane dibromide) and related quaternary ammonium steroids. The use of silica as the stationary phase and a 96:4 mixture of acetonitrile and water containing 0.1 mol/dm3 sodium perchlorate as the eluent with detection at 213 nm enable the potential impurities as well as the hydrolytic and oxidative degradation products of pipecuronium bromide to be separated and detected down to the 0.01% level. The above system is also applicable to the high-performance liquid chromatographic investigation of other quaternary ammonium steroids (pancuronium bromide, vecuronium bromide). 相似文献
980.
Kraus RM Lagoudakis PG Müller J Rogach AL Lupton JM Feldmann J Talapin DV Weller H 《The journal of physical chemistry. B》2005,109(39):18214-18217
We study the interplay between Auger effects and ionization processes in the limit of strong electronic confinement in core/shell CdSe/ZnS semiconductor nanocrystal quantum dots. Spectrally resolved fluorescence decay measurements reveal a monotonic increase of the photoluminescence decay rate on excitation density. Our results suggest that Auger recombination accelerates ionization processes that lead to the occupation of dark, nonemissive nanocrystal states. A model is proposed in the quantized Auger regime describing these experimental observations and providing an estimate of the Auger assisted ionization rates. 相似文献