全文获取类型
收费全文 | 1371篇 |
免费 | 48篇 |
国内免费 | 4篇 |
专业分类
化学 | 879篇 |
晶体学 | 14篇 |
力学 | 51篇 |
数学 | 168篇 |
物理学 | 311篇 |
出版年
2023年 | 13篇 |
2022年 | 30篇 |
2021年 | 26篇 |
2020年 | 15篇 |
2019年 | 20篇 |
2018年 | 21篇 |
2017年 | 21篇 |
2016年 | 45篇 |
2015年 | 40篇 |
2014年 | 40篇 |
2013年 | 83篇 |
2012年 | 88篇 |
2011年 | 90篇 |
2010年 | 64篇 |
2009年 | 84篇 |
2008年 | 77篇 |
2007年 | 90篇 |
2006年 | 67篇 |
2005年 | 59篇 |
2004年 | 44篇 |
2003年 | 34篇 |
2002年 | 52篇 |
2001年 | 39篇 |
2000年 | 45篇 |
1999年 | 26篇 |
1998年 | 15篇 |
1997年 | 18篇 |
1996年 | 15篇 |
1995年 | 14篇 |
1994年 | 5篇 |
1993年 | 11篇 |
1992年 | 17篇 |
1991年 | 15篇 |
1990年 | 14篇 |
1989年 | 11篇 |
1988年 | 14篇 |
1987年 | 11篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1974年 | 3篇 |
1972年 | 1篇 |
1966年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有1423条查询结果,搜索用时 31 毫秒
31.
Gardolinski JE Ramos LP de Souza GP Wypych F 《Journal of colloid and interface science》2000,221(2):284-290
Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press. 相似文献
32.
Pedro A. Fernandes Elsa S. Henriques Vineet Pande Maria. J. Ramos Ana R. R. Maia André A. S. Almeida Bruno F. B. Silva Carla M. S. Ribeiro César F. B. Ribeiro David S. M. Ribeiro Diana A. P. Fonseca Eva M. S. Cunha Filipe R. N. C. Maia Joana A. A. Pereira João P. G. Pacheco Joaquim A. A. D. Ferreira Liliana R. C. Matos Manuel A. B. P. Pinto Maria C. S. Borges Paulo J. C. R. Magalhães Pedro F. R. D. Teixeira Pedro N. B. C. Veloso Ricarte J. F. Ferreira Sandro S. Gomes Tiago F. Barros Tiago S. J. T. Selão Virgínia M. M. C. Fernandes 《Theoretical chemistry accounts》2005,113(4):197-204
We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-12,14 -prostaglandin J2 (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs. 相似文献
33.
María Angeles Monge Enrique Gutirrez Puebla María Del Mar Ramos Gallego Carmen Pardo Jos Elguero 《Journal of heterocyclic chemistry》1992,29(2):499-502
The fluoroborate of 1H-2-methylbenzotriazolium monohydrate crystallizes in the Pbca space group [Z = 8, a = 16.734(3), b = 19.153(9), c = 6.937(1) Å], The hydrogen bond network between the three molecules, 2MeBzTr, HBF4 and H2O, corresponds to a situation intermediate between the fluoroborate of a protonated benzotriazole (BF4?.2MeBzTrH+) and a neutral benzotriazole hydrogen-bonded to fluoroboric acid (HBF4,2MeBzTr). The behaviour of the title compound in solution is also intermediate between these two extreme situations. Thus, the present compound is one of the rare examples of a proton solvated only by very weak hydrogen bond acceptors. 相似文献
34.
Excitation-energy dependence of fluorescence intensity and fluorescence lifetime has been measured for 4-dimethylaminobenzonitrile (DMABN), 4-aminobenzonitrile (ABN), 4-diisopropylaminobenzonitrile (DIABN), and 1-naphthonitrile (NN) in a supersonic free jet. In all cases, the fluorescence yield decreases rather dramatically, whereas the fluorescence lifetime decreases only moderately for S1 (pi pi*, L(b)) excess vibrational energy exceeding about 1000 cm(-1). This is confirmed by comparison of the normalized fluorescence excitation spectrum with the absorption spectrum of the compound in the vapor phase. The result indicates that the strong decrease in the relative fluorescence yield at higher energies is due mostly to a decrease in the radiative decay rate of the emitting state. Comparison of the experimental results with the TDDFT potential energy curves for excited states strongly suggests that the decrease in the radiative decay rate of the aminobenzonitriles at higher energies is due to the crossing of the pi pi* singlet state by the lower-lying pi sigma*(C[triple bond]N) singlet state of very small radiative decay rate. The threshold energy for the fluorescence "break-off" is in good agreement with the computed energy barrier for the pi pi*/pi sigma* crossing. For NN, on the other hand, the observed decrease is in fluorescence yield at higher excitation energies can best be attributed to the crossing of the pi pi* singlet state by the pi sigma* triplet state. 相似文献
35.
H. Morais C. Ramos E. Forgasc T. Cserháti N. Matos V. Almeida J. Oliveira 《Chromatographia》2002,56(1):S173-S175
Summary The extractability and stability of anthocyanins from the skins ofVitis vinifera were determined at different pH values. Anthocyanins were extracted using acetone, partitioned with chloroform and pre-purified
by solid-phase extraction (SPE). They were analysed by RP-HPLC, and the kinetic parameters of decomposition were calculated.
The total monomeric anthocyanin content was determined by spectrophotometry. Anthocianins were well separated by RP-HPLC.
The efficiency of extraction depended strongly on the pH of the extracting agent and on the character of the pigment to be
extracted. The amount of anthocyanins decreased with increasing duration of storage, more so at elevated temperatures.
Presented at Balaton Symposium '01 on High-Performance Separation Methods Siófok, Hungary, September 2–4, 2001. 相似文献
36.
37.
Bradley M Ramos J Vincent B 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1209-1215
The use of microgels for controlled uptake and release has been an area of active research for many years. In this work copolymer microgels of N-isopropylacrylamide (NIPAM) and acrylic acid (AAc), containing different concentrations of AAc and also cross-linking monomer, have been prepared and characterized. These microgels are responsive to pH and temperature. As well as monitoring the equilibrium response to changes in these variables, the rates of swelling/de-swelling of the microgel particles, on changing either the pH or the temperature, have also been investigated. It is shown that the rate of de-swelling of the microgel particles containing AAc is much faster than the rate of swelling, on changing the pH appropriately. This is explained in terms of the relative mobilities of the H(+) and Na(+) ions, in and out of the particles. It was observed that the microgels containing AAc, at pH 8, de-swelled relatively slowly on heating to 50 degrees C from 20 degrees C. This is attributed to the resistance to collapse associated with the large increase in counterion concentration inside the microgel particles. The swelling and de-swelling properties of these copolymer microgels have also been investigated in aqueous poly(ethylene oxide) (PEO) solutions, of different MW (2000-300 000). The corresponding absorbed amounts of PEO from solution onto the microgels have also been determined using a depletion method. The results, as a function of AAc content, cross-linker concentration, PEO MW, pH, and temperature, have been rationalized in terms of the ease and depth of penetration of the PEO chains into the various microgel particles and also the H-bonding associations between PEO and either the -COOH of the AAc moeities and/or the H of the amide groups (much weaker). Finally, the adsorption and desorption of the PEO molecules in to and out of the microgel particles have been shown to be extremely slow compared to normal diffusion time scales for polymer adsorption onto rigid surfaces. 相似文献
38.
The performance of reversed-phase thin-layer (RP-TLC) and reversed-phase high-performance liquid chromatography (RP-HPLC) was compared for the separation and determination of the colour pigments of chili (Capsicum frutescens) powder using a wide variety of eluent systems. No separation of pigments was achieved in RP-TLC, however, it was established that tetrahydrofuran shows an unusually high solvent strength. RP-HPLC using water-methanol-acetonitrile gradient elution separated the chili pigments in many fractions. Diode array detection (DAD) indicated that yellow pigments are eluted earlier than the red ones and chili powder contains more yellow pigments than common paprika powders. It was established that the very different absorption spectra of pigments make the use of DAD necessary. 相似文献
39.
40.
Braulio Insuasty M
Nica Ramos Jairo Quiroga Adolfo Sanchez Manuel Nogueras Norbert Hanold Herbert Meier 《Journal of heterocyclic chemistry》1994,31(1):61-64
The reaction of 4,5-diamino-1,6-dihydropyrimidin-6-ones 1 with one equivalent of the chalcones 2 leads in an acidic medium to the formation of the 2,4-diaryl-2,3,6,7-tetrahydro-1H-pyrimido[4,5-b][1,4]diazepin-6-ones 3a-m . The structure elucidation of the products is based on detailed nmr investigations including selective 13C[1H] decoupling experiments. 相似文献