全文获取类型
收费全文 | 353篇 |
免费 | 20篇 |
国内免费 | 12篇 |
专业分类
化学 | 359篇 |
晶体学 | 1篇 |
物理学 | 25篇 |
出版年
2024年 | 1篇 |
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 12篇 |
2016年 | 13篇 |
2015年 | 14篇 |
2014年 | 24篇 |
2013年 | 37篇 |
2012年 | 21篇 |
2011年 | 32篇 |
2010年 | 20篇 |
2009年 | 26篇 |
2008年 | 35篇 |
2007年 | 31篇 |
2006年 | 18篇 |
2005年 | 16篇 |
2004年 | 18篇 |
2003年 | 13篇 |
2002年 | 13篇 |
2001年 | 3篇 |
2000年 | 6篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1995年 | 1篇 |
1992年 | 3篇 |
1991年 | 2篇 |
排序方式: 共有385条查询结果,搜索用时 171 毫秒
21.
22.
《Journal of Polymer Science.Polymer Physics》2018,56(8):652-663
In this work, poly(3‐hexylthiophene) (P3HT) films prepared using the matrix‐assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE‐deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side‐chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin‐cast films, though the MAPLE‐deposited films are more disordered. In‐plane carrier mobilities in the MAPLE‐deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE‐deposited simples are consistently lower than those in the solvent‐cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 652–662 相似文献
23.
Margarida S. Miranda Luís Pinto da Silva Joaquim C. G. Esteves da Silva 《Journal of Physical Organic Chemistry》2014,27(1):47-56
2‐Ethylhexyl 4‐methoxycinnamate (EHMC) is a very commonly used UVB filter that is known to isomerize from the (E) to the (Z) isomer in the presence of light. In this study, we have performed high level quantum chemical calculations using density functional theory (DFT) with the B3LYP density functional and extended basis sets to study the gas‐phase molecular structure of EHMC and its energetic stability. Calculations were also performed for related smaller molecules cinnamic acid and 4‐methoxycinnamic acid. Charge delocalization has been analyzed using natural charges and Wiberg bond indexes within the natural bond orbital analysis and using nucleus independent chemical shifts. Density functional theory calculations reveal that the (E) isomer of EHMC is more stable than the (Z) by about 20 kJ mol?1 in both the gas and aqueous phases. The enthalpy of formation in the gas phase of (E)‐EHMC was derived from an isodesmic bond separation reaction. Long‐range corrected DFT calculations in implicit water were made in order to understand the excited state properties of the (E) and (Z) isomers of EHMC. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
24.
Shin-ichi Kondo Kimihiro Endo Jun Iioka Keisuke Sato Yuka Matsuta 《Tetrahedron letters》2017,58(43):4115-4118
We have successfully prepared 5-(2-phenylethynyl)isophathalilc acid as a signaling unit and the corresponding derivatives for an anion receptor 2 and a barbiturate receptor 4. Receptor 2 showed characteristic UV–vis changes and dramatic fluorescence quenching upon the addition of anions and receptor 4 showed UV–vis and an OFF-ON fluorescence changes upon the addition of dibutylbarbituric acid based on the diphenylethyne moiety. 相似文献
25.
26.
Grażyna Bartkowiak Elżbieta Wyrzykiewicz Grzegorz Schroeder Anna Walkowiak Anna Szponar Ilona Pawlak 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1429-1436
Eighteen new 2,4-di-ortho- (meta- and para-) bromo-(chloro- and nitro-)benzylthio-5-bromouracils (and 6-methyluracils) have been prepared. The structures of these compounds were confirmed by spectral (IR, UV/vis, 1H NMR) and elemental analyses. Estimation of pharmacotherapeutic potential has been made for synthesized compounds on the basis of prediction of activity spectra for substances (PASS). 相似文献
27.
Ella Kazakova Julia Morozova Diana Mironova Victor Syakaev Liya Muslinkina Alexander Konovalov 《Supramolecular chemistry》2013,25(12):831-841
Here, we report on the study of cationic amidoammonium calix[4]resorcinarenes 1–5 of various lipophilicity capable of binding acid–base indicator methyl orange (MO). We identified the contributions of macrocycle aggregation and conformational mobility in the binding of MO. The effective pKa values of bound MO systematically decrease as the size and the packing density of the aggregates increase with an increase in calixresorcinarene lipophilicity. Consideration of a series of macrocycles clearly shows that large aggregates form most stable complexes, binding guests not on individual level but as aggregates. It was found that the most stable MO complex with 5 is formed due to electrostatic binding with ammonium groups of the macrocycle and incapsulation of MO in a hydrophobic layer of the aggregates. We have shown that competitive binding of MO and cationic surfactants by aggregates of 5 is suitable for visual/spectrophotometric detection of colourless anionic substrates. 相似文献
28.
Interactions of cucurbit[7]uril (Q[7] host) with guest adenine (g1), adenosine (g2) and 2′,3′-o-isopropylideneadenosine (g3) were studied in details by 1H NMR, UV absorption spectroscopy, fluorescence spectroscopy and high performance liquid chromatography (HPLC) methods. We found that the suitable pH range for interaction was between 1 and 7, and the optimal pH range was between 2 and 4. The 1H NMR analysis indicated that Q[7] selectively interacted with the adenine moiety of the guests g1 and g2, while Q[7] selectively interacted with the D-ribose sugar ring moiety of the guest g3. Moreover, 1H NMR spectra showed that the exchange between the bound guest and the free guest was fast on the NMR time scale for the Q[7]-g1 and Q[7]-g2 systems. However, an obvious equilibrium between the bound host/guest and the unbound host/guest were observed in the Q[7]-g3 complex. Several methods were used to determine quantitatively the stability of the three host–guest inclusion complexes formed between Q[7] and the guests. The formation constants by UV and fluorescence were 1.90 × 105 L mol? 1 and 1.34 × 105 L mol? 1 for Q[7]-g1, 9.41 × 104 L mol? 1 and 4.24 × 104 L mol? 1 for Q[7]-g2, 4.50 × 104 L mol? 1 and 3.62 × 104 L mol? 1 for Q[7]-g3, respectively. HPLC method was also introduced to explore the interactions between Q[7] and the adenine and its derivatives. The formation constants of the host–guest inclusion complexes, as determined by HPLC, were 6.76 × 104 L mol? 1 for Q[7]-g1, 1.80 × 104 L mol? 1 for Q[7]-g2, 3.01 × 104 L mol? 1 for Q[7]-g3 respectively. Our study suggested that Q[7] could be a suitable host for the delivery of bioactive molecules, such as the adenine and its derivatives. 相似文献
29.
2-Arylazo-5,5,10,10,15,15,20,20-octamethylcalix[4]pyrroles (azo-OMCPs) have been synthesised by the reaction of calix[4]pyrrole with aryldiazonium chloride in 15–45% yields. The solution-state binding studies of the synthesised hosts were investigated by absorption spectroscopy and 1H NMR in DMSO and CDCl3, respectively. These receptors, appended with electron-donating and electron-withdrawing groups, displayed enhanced affinity and selectivity for fluoride anion. Well-defined colour change in the visible region of the spectrum was observed upon addition of fluoride ion in DMSO solution of azo-OMCPs. Detailed NMR studies in CDCl3 revealed that azo-OMCPs with nitro and chloro groups have higher binding affinity for fluoride ion. 相似文献
30.
The synthesis of simple, chromogenic pyridine-2,6-dicarboxylic acid amides, derivatives of isomeric nitroanilines and aminonitrophenols, and their ion binding properties are described. The ligands' response to ionic species was examined by naked eye and was studied with the use of UV–vis spectroscopy in DMSO and its mixture with water. The effect of the localisation and the type of the substituents in aromatic rings were discussed. 1H NMR experiments were carried out to probe the mechanism of anion recognition, i.e. complexation via hydrogen bond formation versus ligand deprotonation. A selective response of N,N′-bis(2-hydroxy-4-nitrophenyl)pyridine-2,6-dicarboxamide (L5) towards dihydrogen phosphate was found in both DMSO and DMSO–water (95:5) solvent mixture. The structure of N,N′-bis(2-hydroxy-5-nitrophenyl)pyridine-2,6-dicarboxamide (L4) was confirmed by X-ray crystallography. 相似文献