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81.
Qianqian Zhai Zhihua Lu Jing Wang Weina Wang Yudong Ma Caili Yue 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):803-811
AbstractA method of Fourier transform near-infrared (FT-NIR) spectroscopy combined with partial least squares (PLS) model was successfully applied to investigate the hydrolysis kinetics of four kinds of silane coupling agents (phenyltriethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltriethoxysilane) in an acid-catalyzed EtOH system. The fast scanning speed and high sensitivity of the FT-NIR spectroscopy, and the powerful data processing ability of the PLS, enabled the method to quantitatively and accurately catch the fast changing H2O concentration during the hydrolysis processes without delay, realizing the study of the fast-paced hydrolysis reactions of the silane coupling agents. The results showed that electrophilic substitution occurred in the hydrolysis reactions, which followed second-order reactions and greatly depend on the catalyst concentration and reaction temperature. The hydrolysis rate constants, activation energy, and Arrhenius Frequency factors were gained. In conclusion, the FT-NIR PLS model is a powerful tool for hydrolysis kinetics researching of the silane coupling agents. 相似文献
82.
Quantitative structure-activity relationships (QSARs) based on the octanol/water partition coefficient were employed to predict acute toxicities of 36 substituted aromatic compounds and their mixtures. In this study, the model developed by Verhaar et al. was modified and used to calculate octanol/water partition coefficients of chemical mixtures. To validate the model, acute toxicities of these chemicals were measured to Vibrio fischeri in terms of EC50. The results indicated that the obtained QSAR models could be used to predict toxicities of samples consisting of these substituted aromatic compounds, individually or in combinations. The obtained equations were proved to be robust enough by using the leave-one-out test method. By classifying these chemicals into two groups, polar and non-polar, the toxicities of chemical mixtures within each group can be predicted accurately from their calculated partition coefficients. 相似文献
83.
FT‐IR spectroscopic and thermodynamic measurements were designed to explore the effect of a macromolecular crowder, dextran, on the temperature and pressure‐dependent phase diagram of the protein Ribonuclease A (RNase A), and we compare the experimental data with approximate theoretical predictions based on configuration entropy. Exploring the crowding effect on the pressure‐induced unfolding of proteins provides insight in protein stability and folding under cell‐like dense conditions, since pressure is a fundamental thermodynamic variable linked to molecular volume. Moreover, these studies are of relevance for understanding protein stability in deep‐sea organisms, which have to cope with pressures in the kbar range. We found that not only temperature‐induced equilibrium unfolding of RNase A, but also unfolding induced by pressure is markedly prohibited in the crowded dextran solutions, suggesting that crowded environments such as those found intracellularly, will also oppress high‐pressure protein unfolding. The FT‐IR spectroscopic measurements revealed a marked increase in unfolding pressure of 2 kbar in the presence of 30 wt % dextran. Whereas the structural changes upon thermal unfolding of the protein are not significantly influenced in the presence of the crowding agent, through stabilization by dextran the pressure‐unfolded state of the protein retains more ordered secondary structure elements, which seems to be a manifestation of the entropic destabilization of the unfolded state by crowding. 相似文献
84.
Qing Lv Qing Zhang Wentao Li Haiyu Li Pi Li Qiang Ma Xianshuang Meng Meiling Qi Hua Bai 《Journal of separation science》2013,36(21-22):3534-3549
This paper presents a method for the simultaneous determination of 48 fragrance allergens in four types of toys (plastic toys, play clays, plush toys, and paper toys) based on GC with ion trap MS/MS. Compared with single‐stage MS, MS/MS is superior in terms of the qualification and quantification of a large range of compounds in complicated matrices. Procedures for extraction and purification were optimized for each toy type. The method proved to be linear over a wide range of concentrations for all analytes with correlation coefficients between 0.9768 and 0.9999. Validation parameters, namely, LODs and LOQs, ranged from 0.005–5.0 and from 0.02–20 mg/kg, respectively. Average recoveries of target compounds (spiked at three concentration levels) were in the range of 79.5–109.1%. Intraday and interday repeatabilities of the proposed method varied from 0.7–10.5% and from 3.1–13.4%, respectively. The proposed method was used to monitor fragrance allergens in commercial toy products. Our findings indicate that this method is an accurate and effective technique for analyzing fragrance allergens in materials composed of complex components. 相似文献
85.
Jiangmei Li Haiyun Zhai Zuanguang Chen Qing Zhou Zhenping Liu Zihao Su 《Journal of separation science》2013,36(21-22):3608-3614
A novel method combining molecular imprinting and SPE was developed in a capillary column for the determination of auramine O in shrimp. The capillary monolithic column was prepared by UV‐initiated in situ polymerization, using auramine O as template and methacrylic acid and ethylene dimethacrylate as functional monomer and cross‐linker, respectively. The properties of the prepared capillary monolithic column were investigated under the optimized conditions coupled with HPLC, and then the morphologies of the inner polymers were characterized by SEM. The calibration curve was expressed as A = 103C + 19.8 (r = 0.9992) with a linear range of 0.25–25.0 μg/mL, and the recoveries of auramine O at different concentrations in shrimp ranged from 90.5 to 92.4% with RSDs ranging from 2.1 to 4.4%. The capacities of the molecularly imprinted polymer and nonimprinted polymer columns were 0.722 and 0.147 μg/mg, respectively, and the LOD (S/N = 3) of auramine O in shrimp was 17.85 μg/kg. Under the selected conditions, the enrichment factors obtained were higher than 70‐fold. The results indicate that the prepared molecularly imprinted capillary monolithic column was reliable and applicable to the analysis of auramine O in shrimp. 相似文献
86.
Due to the synthetic flexibility and special enantioselectivity, chiral ionic liquids (CILs) have heightened interest and an increasing number of CILs has been designed and utilized. In this work, CIL named l-1-butyl-3-(2-propionic-1-ether) imidazolium bromide ([BAlaIM]Br) derived from natural amino acids was synthesized, with chiral center at cation moiety. Chiral stationary phases for gas chromatography were then prepared by mixing the CIL with polymeric ionic liquid ([PSOMIM][NTf2], homemade) at different ratios (4:1, 2:1, and 1:1). The column efficiency was measured to be about 3,200 plates m?1 (8 m × 0.25 mm i.d.) when the content of [BAlaIM]Br was 50 % (mass percent) in the mixed stationary phase. All columns were coated via the static coating method using 0.30 % (w/v) of stationary phases dissolved in methanol. The results showed that the CIL contributed to the selectivity of stationary phase toward positional isomers dichlorobenzenes, methylnaphthalenes and pinenes, etc. Meanwhile, [BAlaIM]Br showed better selectivity for enantiomers such as carvones, citronellals, limonenes and camphors. The interactions between chiral selector and enantiomers were also discussed. 相似文献
87.
In the present research, a type of imprinted hydrogels, in which 5-fluorouracil is complexed non-covalently to the monomers and cross-linked into the hydrogel matrix, is synthesized in order to evaluate the possibility of their applications in sustaining the release of 5-fluorouracil due to the drug’s heightened interactions with the imprinted binding sites. Because of the hydrophility, hydrogels can absorb large amounts of water. As a result, drug release mechanisms are different from hydrophobic polymers. Mathematical model has been established to predict the drug release from the hydrogel matrix as a function of time. The drug release mechanism when immersed in release medium is discussed based on mathematical analysis. Swelling studies are performed and the capability of the hydrogels to reload 5-fluorouracil in aqueous solutions is evaluated. In vitro release studies after reloading are conducted. Mathematical analysis suggest that drug release kinetics from the hydrogels fit Fickian mechanism, further evaluation of the fitness for different hydrogel types reveal that the conformation of binding sites can play a very important role in deciding the kind of drug release mechanism. Experiments reveal that all hydrogels show swelling property. The imprinted hydrogels bind much more 5-fluorouracil than non-imprinted ones, and they sustain 5-fluorouracil release better than non-imprinted hydrogels. This research indicates that the imprinted hydrogels would be a potential promising device for drug delivery. 相似文献
88.
α,β-Unsaturated aldimines were specifically oxidized to amides with Oxone in the presence of AlCl3 as a Lewis acid in CH2Cl2. No migration of aryl group occurred in the rearrangement reaction. 相似文献
89.
A practical method for the preparation of cycloalkenyl boronic acid pinacol esters is described. These important synthetic intermediates are typically made using more expensive methods like transition metal-catalyzed borylation of alkenyl halides or triflates. In this work, they are obtained from the simple corresponding cycloalkanones, which are subjected to Shapiro reaction conditions followed by trapping with a borate ester. The requisite products are obtained in very good to excellent yields, and the reactions can be scaled up to multigram amounts. By providing a simple alternative to common methods that make use of expensive transition-metal catalysts and formation of sensitive intermediates, this convenient method will be useful for the synthesis of ring-containing partners for Suzuki–Miyaura cross-coupling and other reactions employing boronic esters as substrates. 相似文献
90.
Ranran Du Bingbing Suo Huixian Han Yibo Lei Gaohong Zhai 《International journal of quantum chemistry》2013,113(22):2464-2470
Potential energy curves of 22 electronic states of RhN have been calculated by the complete active space second‐order perturbation theory method. The X1Σ0+ is assigned as the ground state, and the first excited state a3Π0+ is 978 cm?1 higher. The 1Δ(I) and B1Σ+ states are located at 9521 and 13,046 cm?1 above the ground state, respectively. The B1Σ+ state should be the excited state located 12,300 cm?1 above the ground state in the experimental study. Moreover, two excited states, C1Π and b3Σ+, are found 14,963 and 15,082 cm?1 above the X1Σ+ state, respectively. The transition C1Π1–X1Σ0+ may contribute to the experimentally observed bands headed at 15,071 cm?1. There are two excited states, D1Δ and E1Σ+, situate at 20,715 and 23,145 cm?1 above the X1Σ+ state. The visible bands near 20,000 cm?1 could be generated by the electronic transitions D1Δ2–a3Π1 and E1Σ+0–X1Σ+0 because of the spin–orbit coupling effect. © 2013 Wiley Periodicals, Inc. 相似文献