全文获取类型
收费全文 | 3841篇 |
免费 | 155篇 |
国内免费 | 25篇 |
专业分类
化学 | 2623篇 |
晶体学 | 30篇 |
力学 | 73篇 |
数学 | 646篇 |
物理学 | 649篇 |
出版年
2023年 | 29篇 |
2022年 | 61篇 |
2021年 | 126篇 |
2020年 | 82篇 |
2019年 | 85篇 |
2018年 | 71篇 |
2017年 | 65篇 |
2016年 | 132篇 |
2015年 | 122篇 |
2014年 | 148篇 |
2013年 | 239篇 |
2012年 | 247篇 |
2011年 | 312篇 |
2010年 | 190篇 |
2009年 | 182篇 |
2008年 | 257篇 |
2007年 | 246篇 |
2006年 | 188篇 |
2005年 | 162篇 |
2004年 | 159篇 |
2003年 | 118篇 |
2002年 | 128篇 |
2001年 | 57篇 |
2000年 | 54篇 |
1999年 | 49篇 |
1998年 | 32篇 |
1997年 | 29篇 |
1996年 | 38篇 |
1995年 | 30篇 |
1994年 | 35篇 |
1993年 | 31篇 |
1992年 | 27篇 |
1991年 | 22篇 |
1990年 | 26篇 |
1989年 | 16篇 |
1988年 | 16篇 |
1987年 | 18篇 |
1986年 | 17篇 |
1985年 | 26篇 |
1984年 | 21篇 |
1983年 | 18篇 |
1982年 | 23篇 |
1981年 | 15篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 9篇 |
1976年 | 6篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 6篇 |
排序方式: 共有4021条查询结果,搜索用时 203 毫秒
31.
A. González Arias C. Torres C. de
Francisco J. M. Muñoz P. Hernández
Gómez O. Alejos O. Montero J. I. Iñiguez 《Journal of Thermal Analysis and Calorimetry》2006,86(1):195-198
The article discusses theory and experiment about the measurement of
defect concentration in Ti-substituted yttrium iron garnet by means of thermogravimetry
techniques. The two possible cases arising from oxygen interchange with atmosphere,
oxygen vacancies and interstitial cations, may be analyzed quantitatively
from the derived expressions. The possibility of another type of defects being
present in the samples, not associated to oxygen evolution, is not excluded.
Measurements were carried out in air and CO2 for different
Ti contents. The substitution tends to increase slightly the defect parameter
θ in YIG, while a CO2 reducing atmosphere is
much more effective than the Ti substitution for increasing θ. Calculations
for a given single-phased sample sintered in air show two possibilities: a
deficit of one oxygen atom for every 2.5 unit cells of 96 atoms, or one excess
cation for every 3.5 cells. Other samples show very similar results. The accuracy
involved in the measurements is about 2–3%. 相似文献
32.
33.
Maria do Carmo B. Pimentel Eduardo Henrique M. Melo José Luiz Lima Filho William M. Ledingham Nelson Durán 《Applied biochemistry and biotechnology》1997,66(2):185-195
This work is a study of lipase production by a Brazilian strain ofPenicillium citrinum using an inexpensive and simple medium without organic nitrogen sources and of some important industrial properties, including
thermostability in relation to ionic strength. The maximal lipase activity (1585 U/L) was obtained whenPenicillium citrinum was cultured on 0.75% ammonium sulfate complemented with minerals salts instead of yeast extract. Although this activity
was about 55% lower than that produced in medium with yeast extract (2850 U/L), the specific activity (7.8 U/mg proteins)
was higher than that obtained with the yeast extract (4.9 U/mg proteins). The morphology of fungus changed totally, with yeast
extract there are smooth, solid, and spherical pellets whereas on ammonium sulfate there are small “hairy” pellets uniformly
suspended in the medium. The effect of ferrous (Fe++) ions was carried out using medium MA with and without Fe++ ions. Lipase production byPenicillium citrinum in medium MA requires Fe++ ions, the absence of which caused a decreased of about 50% in the specific activity (3.5 U/mg proteins). The utilization
of commercial, locally available oils as carbon sources, such as soybean oil (236 U/L) and corn oil (74 U/L) resulted in lower
activity compared to olive oil, showing that lipase production byPenicillium citrinum is specifically induced by olive oil. Potassium concentration in the medium can effects the production of lipase (1 mM (1585
U/L), 10 mM (1290 U/L), and 30 mM (1238 U/L), 50 mM (195 U/L), and 100 mM (2 U/L). The crude culture filtered was susceptable
to thermal deactivation. It was stable at pH 6.0, but was not stable at the optimum pH (8.0-8.5) at 50 mM. At the low ionic
concentration (1-25 mM) this lipase was stable at low pH (3.5-4.0). The activation energy was 22.4 ±2.2 Kcal. mol 1. 相似文献
34.
Chemical, structural, and thermal properties of Zn(II)-Cr(III) layered double hydroxides intercalated with sulfated and sulfonated surfactants 总被引:1,自引:0,他引:1
Crepaldi EL Pavan PC Tronto J Valim JB 《Journal of colloid and interface science》2002,248(2):429-442
Zn(II)-Cr(III)-LDHs (layered double hydroxides) containing sulfated or sulfonated surfactants as the interlamellar anion were synthesized by the coprecipitation method. The syntheses were conducted under various different experimental conditions, such as the Zn : Cr ratio, pH, and aging time. In each of the prepared materials, unlike previously reported data, the interlayer anion arrangement did not change, being consistent with a perpendicular monolayer. The thermal decomposition process of the prepared materials was studied by a set of analysis methods, such as TG/DTA, TG/MS, PXRD, and FT-IR. From the results obtained it was possible to conclude that, in an air atmosphere, the anions decomposed by a partial combustion, leading to the formation of sulfide. The results also showed that sulfonated surfactants containing LDHs are much more stable than those containing sulfated surfactants. A mechanism was proposed for the thermal decomposition of such LDHs based on the experimental results. 相似文献
35.
VISIBLE CHEMILUMINESCENCE ASSOCIATED WITH THE REACTION BETWEEN METHEMOGLOBIN OR OXYHEMOGLOBIN WITH HYDROGEN PEROXIDE 总被引:1,自引:0,他引:1
Eduardo A. Lissi Jorge Escobar Carlos Pascual Maria del Castillo Tais H. Schmitt Paolo Di Mascio 《Photochemistry and photobiology》1994,60(5):405-411
Abstract Visible chemiluminescence is emitted in the irreversible deactivation of hemoglobin or methemoglobin with excess H2 O2 . The emission takes place in two phases. The most intense one lasts a few seconds and is followed by a second phase of lower intensity that remains for longer periods. This second phase presents chaotic or sustained oscillations. Free radicals are implicated in the luminescent process since the emission can be reduced by free radical scavengers such as 6-hydroxy-2,5,7,8,-tetramethylchroman-2-carboxylic acid (Trolox) or ascorbic acid. These additives lead to a delay in reaching the maximum intensity, which can be related to their consumption, implying substantial recycling of the hemoprotein. Chemiluminescence is also observed in the oxidation of hemin by H2 O2 , suggesting a role for the heme group in the processes leading to the excited state production. The lower intensity observed in the presence of hemin can be related to the contribution of the globin chains. 相似文献
36.
Oscar E. Piro Eduardo E. Castellano Roberto C. V. Piatti Agustín E. Bolzn Alejandro J. Arvia 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m252-m255
The crystal structures of two salts of bis(thiourea)gold(I) complexes, namely bis(thiourea‐κS)gold(I) chloride, [Au(CH4N2S)2]Cl, (I), and bis[bis(thiourea‐κS)gold(I)] sulfate, [Au(CH4N2S)2]2SO4, (II), have been determined. The chloride salt, (I), is isomorphous with the corresponding bromide salt, although there are differences in the bonding. The AuI ion is located on an inversion centre and coordinated by two symmetry‐related thiourea ligands through the lone pairs on their S atoms [Au—S 2.278 (2) Å and Au—S—C 105.3 (2)°]. The sulfate salt, (II), crystallizes with four independent [Au(CH4N2S)2]+ cations per asymmetric unit, all with nearly linear S—Au—S bonding. The cations in (II) have similar conformations to that found for (I). The Au—S distances range from 2.276 (3) to 2.287 (3) Å and the Au—S—C angles from 173.5 (1) to 177.7 (1)°. These data are relevant in interpreting different electrochemical processes where gold–thiourea species are formed. 相似文献
37.
Summary The generator contains diffusion tubes of known length and internal diameter. Once produced, the mixture of the carrier gas and acetone, the reference material, is sent through a chromatographic flame ionisation detector. Its signal reaches a constant level after a time corresponding to the stabilization time of the generator. The technique described is simple and gives repeatable results. 相似文献
38.
M.Victoria Mart?&#x;nez-D?&#x;azSagrario Esperanza Andrés de la EscosuraMarinella Catellani Sami YunusSilvia Luzzati Tomás Torres 《Tetrahedron letters》2003,44(46):8475-8478
Two new donor-acceptor copolymers comprising a polythiophene backbone, and bearing phthalocyanine chromophores on the side chains have been prepared. Preliminary photophysical characterization of these materials by FTIR photoinduced absorption indicates that electron transfer from the polythiophene to the phthalocyanine units takes place. 相似文献
39.
Martinez Alvarez R Herrera Fernandez A Chioua M Ramiro Perez P Villalba Vilchez N Guzman Torres F 《Rapid communications in mass spectrometry : RCM》1999,13(24):2480-2488
Several 5,6-dialkyl-2,4-diarylpyrimidines were prepared and their electron ionization (EI) mass spectra reported. The benzylic cleavage takes place easily together with an important McLafferty rearrangement. The involvement of the nitrogen atom appears to be important in the fragmentation of 5-methyl-substituted pyrimidines. In contrast, the 6-methyl-substituted pyrimidines undergo benzylic cleavage without hydrogen transfer. Thus, the difference in the mass spectrometric behaviour allows the identification of these isomeric compounds which, in contrast, exhibit only small differences in their NMR spectra. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
40.
Low temperature infrared spectra of light induced metastable states MS1 and MS2 of the nitroprusside anion in Na(2)[Fe(CN)(5)NO].2H(2)O, isotopically normal and substituted with (15)NO and N(18)O, are presented and discussed. As a consequence of the relatively high population of the MS2 state achieved by further irradiation with 1064 nm light of samples previously irradiated with 488.0 nm light, new bands were seen for the first time, and others, previously reported, were confirmed. The comparison of the spectral data obtained for the FeNO moiety of the isotopically normal as well as of the (15)NO and N(18)O substituted anion with the results of quantum chemical (DFT) calculations support the assignment of the bands which appear after successive irradiations to MS1, the linear Fe(eta(1)-ON) linkage isomer, and to MS2, the side-bound Fe(eta(2)-NO) isomer. 相似文献