全文获取类型
收费全文 | 1511篇 |
免费 | 50篇 |
国内免费 | 7篇 |
专业分类
化学 | 1182篇 |
晶体学 | 9篇 |
力学 | 24篇 |
数学 | 184篇 |
物理学 | 169篇 |
出版年
2023年 | 8篇 |
2022年 | 22篇 |
2021年 | 22篇 |
2020年 | 31篇 |
2019年 | 22篇 |
2018年 | 20篇 |
2017年 | 22篇 |
2016年 | 32篇 |
2015年 | 40篇 |
2014年 | 44篇 |
2013年 | 100篇 |
2012年 | 104篇 |
2011年 | 98篇 |
2010年 | 58篇 |
2009年 | 33篇 |
2008年 | 91篇 |
2007年 | 90篇 |
2006年 | 85篇 |
2005年 | 74篇 |
2004年 | 79篇 |
2003年 | 74篇 |
2002年 | 58篇 |
2001年 | 16篇 |
2000年 | 20篇 |
1999年 | 11篇 |
1997年 | 16篇 |
1996年 | 21篇 |
1995年 | 17篇 |
1994年 | 15篇 |
1993年 | 8篇 |
1992年 | 11篇 |
1991年 | 13篇 |
1990年 | 13篇 |
1989年 | 7篇 |
1987年 | 10篇 |
1985年 | 8篇 |
1984年 | 15篇 |
1983年 | 7篇 |
1982年 | 8篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 16篇 |
1977年 | 10篇 |
1976年 | 12篇 |
1975年 | 13篇 |
1974年 | 8篇 |
1973年 | 11篇 |
1972年 | 7篇 |
1970年 | 7篇 |
排序方式: 共有1568条查询结果,搜索用时 62 毫秒
11.
Jocelyn Jalbert Roland Gilbert Pierre Tétreault Brigitte Morin Denise Lessard-Déziel 《Cellulose (London, England)》2007,14(4):295-309
In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by
the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative
conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture
of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the
number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded
(TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper
constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the
system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial
moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular
chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing
transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of
equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and
TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential
over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with
2-furfuraldehyde, which is the current reference in the domain. 相似文献
12.
13.
The molecular energy of the complex (η5-C5H5)2TiCl2 has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol?1. This difference is sufficiently high to explain the difficulty of the inversion process. 相似文献
14.
Multiple oxidants have been implicated as playing a role in cytochrome P450-mediated oxidations. Herein, we report results on N-dealkylation, one of the most facile reactions mediated by P450 enzymes. We have employed the N-oxides of a series of para-substituted 13C2H2-labeled N,N-dimethylanilines to function as both substrates and surrogate oxygen atom donors for P450cam and P4502E1. Kinetic isotope effect profiles obtained using the N-oxide system were found to closely match the profiles produced using the complete NAD(P)H/NAD(P)-P450 reductase/O2 system. The results are consistent with oxidation occurring solely through an iron-oxene species. 相似文献
15.
A systematic optimization strategy for reverse-phase h.p.l.c. is used to produce complete separation of all components of a mixture containing two coumarins, umbelliferone and scopoletin, and the cis-trans isomers of two cinnamic acids, p-coumaric and ferulic. A series of experiments gives retention time data for each of these substances in four citric acid-buffered mobile phases. A mathematical model fitted to this data gives model parameters that provide the basis for a window diagram of relative retentions vs. mobile phase pH. The window diagram gives an estimate of the mobile phase pH required for optimum separation. 相似文献
16.
Coates GW Hustad PD Reinartz S 《Angewandte Chemie (International ed. in English)》2002,41(13):2237-2257
Coordination-insertion polymerization systems have long been superior to their anionic, cationic, and radical polymerization counterparts with regard to stereochemical control. However, until five years ago, these metal-based insertion methods were inferior to ionic and radical mechanisms in the category of living polymerization, which is simply a polymerization that occurs with rapid initiation and negligible chain termination or transfer. In the last half decade, the living insertion polymerization of unactivated olefins has emerged as a powerful tool for the synthesis of new polymer architectures. Materials available today by this route range from simple homopolymers such as linear and branched polyethylene, to atactic or tactic poly(alpha-olefins), to end-functionalized polymers and block copolymers. This review article summarizes recent developments in this rapidly growing research area at the interface of synthetic and mechanistic organometallic chemistry, polymer chemistry, and materials science. While special emphasis is placed on polymer properties and novel polymeric architectures, most of which were inaccessible just a decade ago, important achievements with respect to ligand and catalyst design are also highlighted. 相似文献
17.
Christopher Irwin Angelit Barnes Denise Veres Kays Kaidbey 《Photochemistry and photobiology》1993,57(3):504-507
The wavelength dependence for immediate pigment darkening (IPD) was investigated by exposing the midback skin of volunteers to a series of incremental fluences of narrow waveband radiation isolated by band-pass filters in the310–400 nm region. The threshold IPD fluence for each waveband was determined by visual assessment of the skin responses immediately after each exposure. The action spectrum, constructed from the mean threshold fluences, was broad and extended from 320 nm to 400 nm with a peak at around 340 nm. No IPD could be evoked at 310 nm, even after erythemogenic fluences. The spectrum was similar in each of the three skin types investigated (III, IV, V). The broad nature of the action spectrum within the UVA region suggests that IPD may serve as an alternative endpoint for measuring photoprotection against these wavelengths. 相似文献
18.
Sonnenschein RN Farias JJ Tenney K Mooberry SL Lobkovsky E Clardy J Crews P 《Organic letters》2004,6(5):779-782
A reinvestigation of Auletta sp. yielded the novel compound milnamide C (3) plus the known compounds milnamide A (1), milnamide B (hemiasterlin) (2), jasplakinolide (5), and geodiamolides A (6), D (7), E (8), and G (9). The isolation work was guided by cytoskeletal bioactivity data. Compounds 2 and 3 were shown to cause microtubule depolymerization, and 6-9 were shown to cause microfilament disruption. This biological activity and the structural elucidation of 3, including X-ray analysis, are reported here. [structure: see text] 相似文献
19.
Using molecular dynamics simulations, we have determined that the nature of dynamical heterogeneity in jammed liquids is very sensitive to short-ranged attractions. Weakly attractive systems differ little from dense hard-sphere and Lennard-Jones fluids. Particle motion is punctuated and tends to proceed in steps of roughly a single particle diameter. Both of these basic features change in the presence of appreciable short-ranged attractions. Transient periods of particle mobility and immobility cannot be discerned at intermediate attraction strength, for which structural relaxation is greatly enhanced. Strong attractions, known to dramatically inhibit relaxation, restore bimodality of particle motion. But in this regime, transiently mobile particles move in steps that are significantly more biased toward large displacements than those in the case of weak attractions. This modified feature of dynamical heterogeneity, which cannot be captured by conventional mode coupling theory, verifies recent predictions from a model of spatially correlated facilitating defects. 相似文献
20.
B. S. Thyagarajan Phillip E. Glaspy Peter Brown 《Journal of mass spectrometry : JMS》1980,15(1):22-30
The title compounds display unusual modes of fragmentation under electron impact. One of the dominant modes is the concerted elimination of the two arylthio and arylsulfonyl moieties followed by further extrusion of the C6H4 unit as a cumulene. No elimination of SO2 is observed from any of the sulfones nor an expulsion of the C4H4 fragment. Such behavior contrasts strikingly with that of 1,4-diarylsulfonyl-2-butynes and of the 1,6-diarylsulfonyl-2,4-hexadiynes. 相似文献