全文获取类型
收费全文 | 5956篇 |
免费 | 153篇 |
国内免费 | 46篇 |
专业分类
化学 | 3722篇 |
晶体学 | 35篇 |
力学 | 208篇 |
数学 | 1275篇 |
物理学 | 915篇 |
出版年
2022年 | 54篇 |
2021年 | 57篇 |
2020年 | 65篇 |
2019年 | 67篇 |
2018年 | 58篇 |
2017年 | 49篇 |
2016年 | 96篇 |
2015年 | 116篇 |
2014年 | 135篇 |
2013年 | 311篇 |
2012年 | 294篇 |
2011年 | 325篇 |
2010年 | 222篇 |
2009年 | 207篇 |
2008年 | 305篇 |
2007年 | 315篇 |
2006年 | 306篇 |
2005年 | 272篇 |
2004年 | 268篇 |
2003年 | 216篇 |
2002年 | 210篇 |
2001年 | 100篇 |
2000年 | 91篇 |
1999年 | 98篇 |
1998年 | 73篇 |
1997年 | 66篇 |
1996年 | 90篇 |
1995年 | 66篇 |
1994年 | 73篇 |
1993年 | 81篇 |
1992年 | 65篇 |
1991年 | 43篇 |
1990年 | 75篇 |
1989年 | 59篇 |
1988年 | 47篇 |
1987年 | 53篇 |
1986年 | 47篇 |
1985年 | 68篇 |
1984年 | 81篇 |
1983年 | 51篇 |
1982年 | 78篇 |
1981年 | 79篇 |
1980年 | 95篇 |
1979年 | 75篇 |
1978年 | 80篇 |
1977年 | 76篇 |
1976年 | 71篇 |
1975年 | 51篇 |
1974年 | 38篇 |
1973年 | 58篇 |
排序方式: 共有6155条查询结果,搜索用时 15 毫秒
91.
Elizabeth Dinand Michel Vignon Henri Chanzy Laurent Heux 《Cellulose (London, England)》2002,9(1):7-18
The mercerization of homogenized primary wall cellulose extracted fromsugar beet pulp was investigated by transmission electron microscopy (TEM),X-ray diffraction together with 13C CP-MAS NMR, and FT-IR spectroscopy.For samples resulting from acid extraction, mercerization began at 9% NaOH, whereasfor samples purified by alkaline treatment, the mercerization started at 10%NaOH. The change in morphology when going from cellulose I to cellulose II wasspectacular, as all the microfibrillar cellulose morphology disappeared duringthe treatment. This change in morphology was very drastic as soon as the NaOHconcentrations were increased beyond 8 and 9% for the acid and alkalinepreparedsamples, respectively. On the other hand, the conversion was found to be moreprogressive in terms of increasing NaOH concentration when the transformationwas analyzed by X-ray diffraction or spectroscopy. Our observations of themercerization of isolated cellulose microfibrils are consistent with theconceptof cellulose microfibrils made of parallel chains in cellulose I and crystalsofcellulose II consisting of antiparallel chains. 相似文献
92.
Laser Raman spectrometry with a fibre-optic system is used to monitor the concentrations of ethanol, glucose and fructose at various stages of an alcoholic fermentation process. For evaluation of the data, cross-correlation and multivariate least-squares procedures are compared; the latter gives the best results. Ethanol, glucose and fructose can be determined remotely with a precision of ca. 10 g l?1 (10–15%). 相似文献
93.
Rogers PH Michel E Bauer CA Vanderet S Hansen D Roberts BK Calvez A Crews JB Lau KO Wood A Pine DJ Schwartz PV 《Langmuir : the ACS journal of surfaces and colloids》2005,21(12):5562-5569
The directed three-dimensional self-assembly of microstructures and nanostructures through the selective hybridization of DNA is the focus of great interest toward the fabrication of new materials. Single-stranded DNA is covalently attached to polystyrene latex microspheres. Single-stranded DNA can function as a sequence-selective Velcro by only bonding to another strand of DNA that has a complementary sequence. The attachment of the DNA increases the charge stabilization of the microspheres and allows controllable aggregation of microspheres by hybridization of complementary DNA sequences. In a mixture of microspheres derivatized with different sequences of DNA, microspheres with complementary DNA form aggregates, while microspheres with noncomplementary sequences remain suspended. The process is reversible by heating, with a characteristic "aggregate dissociation temperature" that is predictably dependent on salt concentration, and the evolution of aggregate dissociation with temperature is observed with optical microscopy. 相似文献
94.
Cvetovich RJ Chartrain M Hartner FW Roberge C Amato JS Grabowski EJ 《The Journal of organic chemistry》1996,61(19):6575-6580
A convergent synthesis of [S-(R,S)]-2-[4-[(4-methylpiperazin-1-yl)carbonyl]phenoxy]-3,3-diethyl-N-[1-[3,4-(methylenedioxy)phenyl]butyl]-4-oxo-1-azetidinecarboxamide (L-694,458, 1), a potent human leukocyte elastase inhibitor, was achieved via chiral synthesis of key intermediates: (S)-3,3-diethyl-4-[4'-[(N-methylpiperazin-1-yl)carbonylphenoxy]-2-azetidinone (2) and (R)-alpha-propylpiperonyl isocyanate (3). Synthesis of beta-lactam 2 was achieved by a novel enantioselective lipase hydrolysis of ester 5 to produce (S)-3,3-diethyl-4-(4'-carboxyphenoxy)-2-azetidinone (6) (60% yield, three cycles, 93% ee) with isolation, epimerization, and recycling of the undesired (R)-ester 5. Isocyanate 3 was prepared by chiral addition of Zn(n-Pr)(2) to piperonal (98% yield, 99.2% ee), azide displacement and reduction to (R)-alpha-propylpiperonylamine (11) (58% yield, 85% ee), crystallization as the D-pyroglutamic acid salt (92% yield, 98.2% ee), and isocyanate formation (98% yield) with phosgene. 相似文献
95.
Development and validation of methods for the trace determination of phthalates in sludge and vegetables 总被引:1,自引:0,他引:1
Sablayrolles C Montréjaud-Vignoles M Benanou D Patria L Treilhou M 《Journal of chromatography. A》2005,1072(2):233-242
A routine method which is simple, quick and precise has been set up and validated for phthalate analysis in environmental samples (tomato plants and sewage sludges). Six phthalates have been studied simultaneously: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethyl-hexyl phthalate (DEHP) and di-n-octylphthalate. Optimization of sample, solvent extraction uses a Soxtec apparatus and extract purification with an a solid-phase extraction cartridge allows between 90 and 110% recovery of phthalates. Precise, sensitive and selective identification and quantifying of analytes is by GC-MS in the single ion monitoring mode. This protocol allows analytes with concentrations as low as 10 microg/kg dry matter (DM) to be determined from small (1-2 g DM) samples. This analytical method has been applied to the phthalate transfer study for agricultural recycling of sludges, where phthalate bioavailability has been studied in aquiculture using two types of experiments. Tomatoes have been grown in containers where the trace organics have been directly introduced as pure substances, and in a second experiment under the same growth conditions, sewage sludge has replaced the pure substances. Transfer of these trace organics has been followed into the various parts of the tomato plant and in general only the DEHP is worthy of note although its percentage transfer remains very low even in an experiment designed to maximize this. 相似文献
96.
Supercritical fluid chromatography of carbohydrates 总被引:1,自引:0,他引:1
Michel Lafosse Bernard Herbreteau Luc Morin-Allory 《Journal of chromatography. A》1996,720(1-2):61-73
Supercritical fluid chromatography (SFC) is a relatively new technique applied to polar solutes such as carbohydrates about 10 years ago. The developments in the SFC of carbohydrates are summarized and a comparison between capillary and packed column SFC is presented. High-efficiency capillary columns are suitable only for derivatized carbohydrates since various packed columns are well adapted for non derivatized mono-, di- and trisaccharides and provide complementary selectivities. 相似文献
97.
The kinetics of radical telomerization of VDF at 141 °C, initiated by ditertbutylperoxide, in the presence of three chain transfer agents (CTAs), HCCl3, CCl4 and CCl3Br, are presented. The values of the chain transfer constants were assessed as 35, 0.25 and 0.06 at 141 °C for CCl3Br, CCl4 and HCCl3, respectively. The values of the degree of polymerization (DPn) were obtained for each CTA and were compared for the same CTA concentration. Hence, CCl3Br behaved as an efficient CTA towards VDF and usually afforded the monoadduct selectively, but in certain conditions the VDF diadduct can also be produced. In contrast, HCCl3 was not so efficient since a polymeric structure was identified as the major product. 相似文献
98.
In order to analyse metal complexation with polyfunctional phenolic compounds as ligand models of natural substances, a detailed examination is described for five simple binary complexes and three ternary mixed ligand complexes at 25°C (μ = 0.1 M NaClO4). The ligands are tyrosine, 4,5-dihydroxy-1,3-benzene disulfonic acid, disodium salt (tiron), 3,4-dihydroxycinnamic acid (caffeic acid), 3,4,5-trihydroxy-1 -cyclohexene-1 -carboxylic acid (shikimic acid) and 1,3,4,5-tetrahydroxycyclohexanecarboxylic acid 3-(3,4-dihydroxycinnamate) (chlorogenic acid). The ternary systems are Cu(II)/HqA/tiron, where HqA is tyrosine, caffeic or chlorogenic acids. Potentiometric data were used successively to evaluate the protonation of each individual ligand, to detect simple and mixed complexes (including protonated species) and to determine their stability constants (a set of 33 values of constants with several original data is provided). The calculated distribution (speciation) of each species as a function of pH is indicated. Mixed coordination enhances the stability of complexes and the stabilization is expressed in terms of various parameters. The results emphasize that mixed ligand complex formation is essential to studies of multiple equilibria. 相似文献
99.
Abdallah Aissa Michel Gruselle René Thouvenot Rainer Traksmaa 《Journal of solid state chemistry》2007,180(8):2273-2278
The reaction between phenyl phosphonic dichloride (C6H5P(O)Cl2) and synthetic calcium hydroxy- and fluorapatite has been investigated. The presence of mono- or polymeric (C6H5PO) fragment bound to hydroxyapatite was evidenced by IR, and solid-state 31P NMR spectroscopy. X-ray powder analysis has shown that the apatitic structure remains unchanged during the reaction. In contrast, no reaction was found using fluorapatite. According to the results found for these two different apatites a mechanism was proposed for the formation of covalent P-O-P bonds as the result of a reaction between the C6H5P(O)Cl2 organic reagent and (HPO4)− and/or OH− ions of the hydroxyapatite. 相似文献
100.
Cianetti S Négrerie M Vos MH Martin JL Kruglik SG 《Journal of the American Chemical Society》2004,126(43):13932-13933
Cytochrome c (cyt c) is an electron-transfer heme protein that also binds nitric oxide (NO). In resting cyt c, two endogenous ligands of the heme iron are histidine-18 (His) and methionine-80 (Met) side chains, and NO binding requires the cleavage of one of the axial bonds. Previous femtosecond transient absorption studies suggested the photolysis of either Fe-His or Fe-Met bonds. We aimed at unequivocally identifying the internal side chain that is photodissociated in ferrous cyt c and at monitoring heme structural dynamics, by means of time-resolved resonance Raman (TR3) spectroscopy with approximately 0.6 ps time resolution. The Fe-His stretching mode at 216 cm-1 has been observed in photoproduct TR3 spectra for the first time for a c-type heme. The same transient mode was observed for a model ferrous cyt c N-fragment (residues 1-56) ligated with two His in the resting state. Our TR3 data reveal that upon ferrous cyt c photoexcitation, (i) distal Met side chain is instantly released, producing a five-coordinated domed heme structure, (ii) proximal His side chain, coupled to the heme, exhibits distortion due to strain exerted by the protein, and (iii) alteration in heme-cysteine coupling takes place along with the relaxation of the protein-induced deformations of the heme macrocycle. 相似文献