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In this study, the impact of ultrasound irradiation on the structural characteristics and antioxidant properties of yellow tea polysaccharides with different molecular weights (Mw) were investigated. Native yellow tea polysaccharide containing YTPS-3N, YTPS-5N and YTPS-7N were prepared through precipitation with ethanol at various concentrations of 30%, 50%, and 70%, respectively, and irradiated with high intensity ultrasound (20 kHz) for 55 min to yield yellow tea polysaccharide including YTPS-3U, YTPS-5U and YTPS-7U. The molecular weight (Mw) of YTPS-3N (from 37.7 to 15.1 kDa) and YTPS-5N (from 14.6 to 5.2 kDa) sharply decreased upon ultrasound irradiation, coincidentally particle size (Zavg) was also significantly reduced for YTPS-3N (40%), YTPS-5N (48%) and YTPS-7N (54%). The high-performance liquid chromatography and Fourier transform-infrared spectroscopy analysis revealed a partial degradation of native yellow tea polysaccharide treated with ultrasound, though the monosaccharide composition was not altered. Furthermore, changes in morphology and the breakdown of native yellow tea polysaccharide upon irradiation was confirmed with the circular dichroism spectrum, atomic force and scanning electron microscopy. As a consequence, irradiation of yellow tea polysaccharide increased free radical scavenging activity with YTPS-7U exhibiting the highest levels of 2, 2-diphenyl-1-picrylhydrazyl free radical, superoxide and hydroxyl radicals scavenging activity. These results suggest that the alteration of the spatial structure of yellow tea polysaccharide can enhance its antioxidant activity which is an important property for functional foods or medicines. 相似文献
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An enantioselective carboxylative cyclization of propargylic alcohols and CO2 was realized under mild conditions,based on a kinetic resolution strategy,which enabled the synthesis of chiral cyclic carbonates and propargylic alcohols with promising yield and enantioselectivity simultaneously. 相似文献
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Thermogalvanic cells(also known as thermo-electrochemical cells) that convert waste heat energy to electricity are a new type of energy conversion device. However, the electron transfer kinetics and mass transfer of redox couples have not been thoroughly studied. Here, the ion reaction and charge transport in thermogalvanic cells are investigated by electrochemical impedance analysis. We first propose the detailed impedance model followed experimental verification on three types of electrode materials. Parameters including kinetic rate constants and ion diffusion coefficients for the electrodes are obtained by fitting the impedance data. Our study shows explicitly that impedance analysis can provide useful information on selecting suitable electrode materials for thermogalvanic cells. 相似文献
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《Acta Crystallographica. Section C, Structural Chemistry》2018,74(10):1094-1104
Structures are reported for eight Schiff bases derived from various salicylaldehydes: five are newly synthesized and re‐investigations are reported for three previously reported structures, leading, in each case, to some revision of previous conclusions. In (E)‐N‐(3,4‐dimethylisoxazol‐5‐yl)‐4‐[(2‐hydroxybenzylidene)amino]benzenesulfonamide, C18H17N3O4S, (I), and (E)‐4‐[(5‐bromo‐2‐hydroxy‐3‐methoxybenzylidene)amino]‐N‐(3,4‐dimethylisoxazol‐5‐yl)benzenesulfonamide. C19H18BrN3O5S, (II), the isoxazole rings adopt different orientations relative to the rest of the molecules, despite the additional substituents in (II) being in the aryl ring remote from the isoxazole unit. The molecules of both (E)‐4‐bromo‐2‐[(2‐hydroxyphenylimino)methyl]‐6‐methoxyphenol, C14H12BrNO3, (III), and (E)‐4‐bromo‐2‐methoxy‐6‐[(2‐methoxyphenylimino)methyl]phenol, C15H14BrNO3, (IV), are both effectively planar; while (III) adopts the phenol–imine constitution, (IV) adopts the keto–amine constitution. (E)‐2‐Methoxy‐6‐[(2‐methoxyphenylimino)methyl]phenol, C15H15NO3, (V), which was determined previously using powder X‐ray data assuming the phenol–imine constitution, has now been refined from single‐crystal X‐ray data, confirming the phenol–imine constitution. In (E)‐3‐benzoyl‐2‐[(5‐fluoro‐2‐hydroxybenzylidene)amino]‐4,5,6,7‐tetrahydrobenzo[b]thiophene, C22H18FNO2S, (VI), the fused carbocyclic ring exhibits conformational disorder; both disorder components, having populations of 0.705 (4) and 0.295 (4), adopt half‐chair conformations. The isostructural (E)‐3‐benzoyl‐2‐[(2‐hydroxybenzylidene)amino)]‐4,5,6,7‐tetrahydrobenzo[b]thiophene, C22H19NO2S, (VII), which was originally reported as having a fully ordered structure [Kaur et al. (2014). Acta Cryst. E 70 , o476–o477], has been rerefined using the original data set and found to exhibit the same type of disorder as found in (VI), with disordered populations having occupancies of 0.851 (3) and 0.149 (3). The triclinic polymorph of (E)‐[(2‐hydroxyphenylimino)methyl]phenol, C13H11NO2, (VIII), which crystallizes with Z′ = 2 in the space group P, has been described variously as occurring as the keto–amine tautomer [Maciejewska et al. (1999). J. Phys. Org. Chem. 12 , 875–880] and as the phenol–imine tautomer [Tunç et al. (2009). J. Chem. Crystallogr. 39 , 672–676]. Rerefinement of this structure using one of the original data sets shows that both of the independent molecules exist in the keto–amine form. In the structures of compounds (I), (VI), (VII) and (VIII), hydrogen bonds generate simple chains, while a chain of rings is formed in (V). Sheets are formed by hydrogen bonds in both (II) and (III), while in (IV), the sheet structure is built from aromatic π–π stacking interactions. 相似文献
8.
Kamila B. Muchowska Dominic J. Pascoe Stefan Borsley Ivan V. Smolyar Ioulia K. Mati Catherine Adam Gary S. Nichol Kenneth B. Ling Scott L. Cockroft 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14710-14716
Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions. 相似文献
9.
Anna Peterson Mari-Liis Ludvig Jevgenija Martõnova Sandra Kaabel Paul Kerner Merle Uudsemaa 《Supramolecular chemistry》2020,32(5):313-319
ABSTRACT We demonstrate that Ullman fragment-coupling can be used to synthesise an oxacalix[4]arene monocarboxylic acid, which provides easy access to its water-soluble carboxylato derivatives. Crystallographic and computational data suggest that the new carboxyl-substituted oxacalix[4]arene adopts a 1,3-alternate conformation both in the solid-state and in methanol solution. Its water-soluble tetrabutylammonium derivate can detect the herbicide paraquat at neutral pH in aqueous media (K a = 111 ± 3 M–1) and in methanol (K a = 2020 ± 70 M–1). 相似文献
10.
The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献