全文获取类型
收费全文 | 27449篇 |
免费 | 517篇 |
国内免费 | 113篇 |
专业分类
化学 | 15520篇 |
晶体学 | 188篇 |
力学 | 818篇 |
综合类 | 9篇 |
数学 | 3789篇 |
物理学 | 7755篇 |
出版年
2023年 | 129篇 |
2022年 | 365篇 |
2021年 | 452篇 |
2020年 | 403篇 |
2019年 | 364篇 |
2018年 | 448篇 |
2017年 | 400篇 |
2016年 | 694篇 |
2015年 | 600篇 |
2014年 | 675篇 |
2013年 | 1108篇 |
2012年 | 1394篇 |
2011年 | 1584篇 |
2010年 | 905篇 |
2009年 | 860篇 |
2008年 | 1349篇 |
2007年 | 1295篇 |
2006年 | 1168篇 |
2005年 | 1594篇 |
2004年 | 1617篇 |
2003年 | 1144篇 |
2002年 | 795篇 |
2001年 | 656篇 |
2000年 | 598篇 |
1999年 | 393篇 |
1998年 | 326篇 |
1997年 | 325篇 |
1996年 | 383篇 |
1995年 | 347篇 |
1994年 | 344篇 |
1993年 | 355篇 |
1992年 | 352篇 |
1991年 | 284篇 |
1990年 | 230篇 |
1989年 | 216篇 |
1988年 | 204篇 |
1987年 | 183篇 |
1986年 | 184篇 |
1985年 | 245篇 |
1984年 | 229篇 |
1983年 | 199篇 |
1982年 | 216篇 |
1981年 | 201篇 |
1980年 | 187篇 |
1979年 | 160篇 |
1978年 | 183篇 |
1977年 | 150篇 |
1976年 | 145篇 |
1974年 | 141篇 |
1973年 | 128篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
901.
Vanessa Gisele Pasqualotto Severino Cristiane de Melo CazalMoacir Rossi Forim Maria Fátima das Graças Fernandes da SilvaEdson Rodrigues-Filho João Batista FernandesPaulo Cezar Vieira 《Journal of chromatography. A》2009,1216(19):4275-4281
High-speed counter-current chromatography (HSCCC) with a two-phase solvent system (hexane–ethanol–acetonitrile–water 10:8:1:1, v/v) was applied to examine the leaves of Hortia oreadica, which afforded the known limonoid guyanin (1), the alkaloids rutaecarpin (2) and dictamnine (6), the dihydrocinnamic acid derivatives methyl 5,7-dimethoxy-2,2-dimethyl-2H-1-benzopyran-6-propanoate (3), 5,8-dimethoxy-2,2-dimethyl-2H-1-benzopyran-6-propanoic acid (4), together with the new E-3,4-dimethoxy-α(3-hydroxy-4-carbomethoxyphenyl)cinnamic acid (5). The recovery of compounds 1–6 was determined by comparison with LC-atmospheric pressure chemical ionization MS/MS data: 66.2%, 93.1%, 102.5%, 101.2%, 99.0% and 84.9%, respectively. Compound 3 showed IC50 of 23.6 μM against Plasmodium falciparum and 15.6 μM against Trypanosoma brucei rhodesienses and was not toxic to KB cells (IC50 > 100 μM). 相似文献
902.
Lauro M. de Souza Thales R. CiprianiCarolina F. Sant’Ana Marcello IacominiPhilip A.J. Gorin Guilherme L. Sassaki 《Journal of chromatography. A》2009,1216(1):99-105
Two-dimensional liquid chromatography–electrospray ionization mass spectrometry was employed to analyze flavonol glycosides present in leaves of Maytenus ilicifolia, frequently used in traditional Brazilian medicine. Since they contain many flavonol glycosides, including isomers, one-dimensional liquid chromatography did not give complete separation and identification, yielding overlapping of compounds with different molecular weights. Thus, employing size exclusion chromatography in the first and reversed phase in the second dimension, a great number of flavonol glycosides could be identified and its relative abundances determined. The majority of glycosides contained kaempferol or quercetin as aglycones, and glycosides with previously unreported structures were also present and characterized. 相似文献
903.
904.
[reaction: see text] On the basis of KIE experiments, the ring opening of cis-bicyclo[4.2.0.]oct-7-ene has been suggested as an anti-Woodward-Hoffmann reaction candidate. We hereby report the results of a high-level computational study of the alternate reaction pathways which proves that the energy profiles show a clear preference for the conrotatory (W-H allowed) ring opening followed by double-bond isomerization. Computed KIE values for the aforementioned mechanism are in good agreement with the experimental values. 相似文献
905.
Valente AJ Burrows HD Pereira RF Ribeiro AC Costa Pereira JL Lobo VM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(13):5625-5629
The effect of EuCl3 on the aggregation processes of sodium dodecyl sulfate was investigated. Electrical conductivity data, combined with Eu(III) luminescence measurements, suggest that the formation of micelles involving EuCl3 and SDS occurs at low SDS concentration; the formation of these mixed aggregates was also monitored by light scattering, which indicates that the addition of EuCl3 to SDS concentration at values below the critical micelle concentration of the pure surfactant results in a much higher light scattering than that found just with SDS micelles. It was also found that the Eu(III)/DS- complexes are formed with a binding ratio which varies between 20 and 4, depending on the initial concentration of Eu(III). As the concentration increases, turbidity occurs initially, but solutions become clear subsequently. In contrast to the behavior of SDS in the presence of aluminum(III), no flocculation was observed. From the analysis of electrical conductivity data and comparison with other systems, it is suggested that growth of aggregates happens, probably with formation of nonspherical systems. At the highest concentrations these may involve just Eu(III) and DS- ions. The effect of temperature on the SDS micellization process was studied. The calculated free energy of SDS micellization is not dependent on the initial EuCl3 but is dependent on the final balance between the presence of counterions in solution (ionic strength) and the temperature. 相似文献
906.
de Sousa M de Castro B Abad S Miranda MA Pischel U 《Chemical communications (Cambridge, England)》2006,(19):2051-2053
A simple set of five components was used to design molecular logic gates based on phthalimide-sensitised Tb(III) luminescence, including the first report of an enabled NOR (EnNOR) gate. 相似文献
907.
Pinto ML Pires J Carvalho AP de Carvalho MB 《The journal of physical chemistry. B》2006,110(1):250-257
Adsorption isotherms of toluene and ethyl benzene, at 25 degrees C and 40 degrees C, were determined in two microporous activated carbons and one zeolite. Significant differences were found in the adsorption behavior, at low pressures, between the two vapors on the same adsorbent material. The quantities of adsorbed ethyl benzene at 25 degrees C, in the low-pressure region, were lower than what was observed at 40 degrees C in all the studied adsorbents, contrary to what was found for toluene. This fact was not related to kinetic effects at the two temperatures nor to vapor swelling of the adsorbents structure. Also, there was no molecular sieving since at high pressures the toluene and ethyl benzene occupied the same adsorption space. The differences found in the ethyl benzene adsorption at the two temperatures pose difficulties in the analysis of the adsorption data and, therefore, in the prediction of results. This is discussed in the analysis of the results with the application of the Dubinin-Astakhov equation and in the estimation of the isosteric heats of adsorption. The adsorption potentials of two possible ethyl benzene conformations were estimated for the adsorption in the pores of activated carbon from the Horvath and Kawazoe model, and the values compared with those found experimentally. The results were interpreted in terms of the ethyl benzene conformation effects when the molecule is confined in pores that are about the same size of one of the conformations. 相似文献
908.
Antunes A de Rossi W Zezell DM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,64(5):1142-XXXIV
Laser irradiation on hard tissue has produced a resistant surface that is likely to prevent caries. In this study, human enamel and dentine were exposed to nanosecond pulsed Nd:YAG laser with energy densities of 20-40 J/cm(2) and pulse width of 6 ns inducing chemical changes in these tissues. Infrared analysis of human dental enamel and dentine was performed using the KBr method (2mg sample/300 mg KBr). A correlation between non-lased and lased spectra was performed that gives an indication of the changes in organic and inorganic compounds after laser-tissue interaction. Spectra of teeth simultaneously show the inorganic and organic parts of the tissue. The principal bands: amide bands A, I, II, and III from the collagen-matrix, phosphate from the mineral content, and carbonate bands were identified. The normalized area of peak versus peak position was determined. Changes of the bands attributed to the collagen matrix were verified after Nd:YAG irradiation. The present results suggest a chemical modification of organic and mineral compounds by laser. The spectral results indicated an alteration in the absorption bands relative to, essentially, organic compounds. 相似文献
909.
Aline B. de P. Abrantes Gustavo C. Dias Nadja C. Souza‐Pinto Mauricio S. Baptista 《Photochemistry and photobiology》2019,95(1):355-363
The p53 protein exerts fundamental roles in cell responses to a variety of stress stimuli. It has clear roles in controlling cell cycle, triggering apoptosis, activating autophagy and modulating DNA damage response. Little is known about the role of p53 in autophagy‐associated cell death, which can be induced by photoactivation of photosensitizers within cells. The photosensitizer 1,9‐dimethyl methylene blue (DMMB) within nanomolar concentration regimes has specific intracellular targets (mitochondria and lysosomes), photoinducing a typical scenario of cell death with autophagy. Importantly, in consequence of its subcellular localization, photoactive DMMB induces selective damage to mitochondrial DNA, saving nuclear DNA. By challenging cells having different p53 protein levels, we investigated whether p53 modulates DMMB/light‐induced phototoxicity and cell cycle dynamics. Cells lacking p53 activity were slightly more resistant to photoactivated DMMB, which was correlated with a smaller sub‐G1 population, indicative of a lower level of apoptosis. DMMB photosensitization seems to induce mostly autophagy‐associated cell death and S‐phase cell cycle arrest with replication stress. Remarkably, these responses were independent on the p53 status, indicating that p53 is not involved in either process. Despite describing some p53‐related responses in cells challenged by photosensitization, our results also provide novel information on the consequences of DMMB phototoxicity. 相似文献
910.
Taís Vanessa Gabbay Alves Eraldo José Madureira Tavares Fauze Ahmad Aouada Charles Alberto Brito Negrão Marcos Enê Chaves Oliveira Anivaldo Pereira Duarte Júnior Carlos Emmerson Ferreira da Costa José Otávio Carréra Silva Júnior Roseane Maria Ribeiro Costa 《Journal of Thermal Analysis and Calorimetry》2011,106(3):717-724
This paper reports the thermal characterization of polyacrylamide-co-methylcellulose hydrogels and the constituent monomers (acrylamide and methylcellulose). Polymeric materials can be used
to produce hydrogels, which can be natural, synthetic, or a mixture. The hydrogels described here were obtained by free radical
polymerization, in the presence of N,N′-methylene-bis-acrylamide as a cross-linker agent. Four acrylamide concentrations were used for the synthesis of hydrogels:
3.6, 7.2, 14.7, and 21.7% (w/v). The materials so obtained were analyzed by TG, DTG, DSC, and FT-IR. The TG curves of acrylamide
and methylcellulose showed three mass loss events. In DSC curves, the acrylamide exhibited one melting peak at 84.5 °C, and
methylcellulose indicated one exothermic event. Nevertheless, acrylamide was considered more stable than methylcellulose.
The TG curves of the hydrogels exhibited three mass loss events, and on the DSC curves, three endothermic events were observed.
It was verified that the different acrylamide proportions influenced the thermic behavior of hydrogels, and that the authors
considered the 7.2% hydrogel a promising drug carrier system. The absorption bands were well defined, confirming the presence
of the functional groups in the samples. 相似文献