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Nitroxyl spin probe in ionic micelles: A molecular dynamics study 离子胶束中硝基旋转探针的分子动力学研究
Pub Date : 2020-06-29 DOI: 10.26565/2220-637X-2020-34-02
V. Farafonov, A. Lebed
The compounds containing nitroxyl radical (NO˙) are actively used as spin probes to examine colloid systems, including lipid membranes and micelles. Their electron paramagnetic resonance spectrum provides information about the composition of the medium, in particular, the content of water there. Yet, the proper treatment of the measurement results demands understanding the microscopic characteristics of the molecular probe. In the present paper, we extend our previous studies on the microscopic state of acid-base and solvatochromic probes in surfactant micelles to the field of spin probes. We report the results of molecular dynamics simulation of a common spin probe, methyl-5-doxylstearate, in micelles of anionic (sodium n-dodecyl sulfate, SDS) and cationic (n-dodecyltrimethylammonium bromide, DTAB) surfactants. The localization of the molecule within the micelles, its shape, composition of the local environment, hydration were quantified and compared with the available relevant experimental data. No significant dissimilarity was found in the characteristics of the probe molecule in both kinds of micelles. However, the characteristics of the O˙ atom carrying the unpaired electron are pronouncedly different, namely, in DTAB micelles it is less hydrated and forms less hydrogen bonds with water. Similar situation was observed for the COO group. The main reason was found to be the interactions with cationic surfactant headgroups, which screen the O˙ atom and COO group from water. These findings allowed revisit the point of view that the surface layer of DTAB micelles as a whole is less hydrated in comparison to that of the SDS ones.
含有硝基氧自由基(NO)的化合物被积极用作旋转探针来检查胶体系统,包括脂质膜和胶束。它们的电子顺磁共振谱提供了有关介质成分的信息,特别是其中的水含量。然而,正确处理测量结果需要了解分子探针的微观特征。在本文中,我们将先前对表面活性剂胶束中酸碱和溶剂化变色探针的微观状态的研究扩展到自旋探针领域。我们报道了一种常见的自旋探针,5-羟基硬脂酸甲酯,在阴离子(正十二烷基硫酸钠,SDS)和阳离子(正十二烷基三甲基溴化铵,DTAB)表面活性剂的胶束中的分子动力学模拟结果。对分子在胶束内的定位、形状、局部环境的组成、水合作用进行了量化,并与现有的相关实验数据进行了比较。在两种胶束中,探针分子的特性没有发现显著的差异。然而,携带不成对电子的O原子的特性明显不同,即在DTAB胶束中,它的水合程度较低,与水形成的氢键较少。COO组也出现了类似的情况。主要原因被发现是与阳离子表面活性剂头基的相互作用,这些头基从水中筛选O原子和COO基团。这些发现允许重新审视这样一种观点,即与SDS胶束相比,DTAB胶束的表层作为一个整体水合程度较低。
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引用次数: 3
Atomic absorption and atomic emission with inductive connected plasma detection of Lead and Iron in strata water using new medias and standard composition samples 新介质和标准成分样品的原子吸收和原子发射电感连接等离子体检测地层水中铅和铁
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-34-05
An influence of SAS (Тriton Х-100) concentration and ultrasound treatment time on the value of analytical signal at atomic absorption and atomic emission with inductive connected plasma detection of analytes in strata water was studied. Maximal analytical signal at of Lead and Iron was reached at using nonionogenic SAS which let us to decrease surface tension of the analyzed solution and to increase absorptivity at analytes detection. It was shown that using of the modern sample preparation increase sensibility of atomic absorption detection of Lead in 1,5 times and Iron in 1,8 times. By the methods of atomic absorption and atomic emission with inductive connected plasma spectroscopy and using acetylacetonates of Lead and Iron as standard composition samples, that let us to increase sensitivity of the detection of analytes, contain of Lead and Iron in strata water was determined. By variation of the sample volume and by "injected-found out" method we have proved that systematic error is not significant. The results, obtained by two independent methods were compared according to F- and t-criteria. It was proved that dispersions are homogenous and run of the means is not sufficient and proved by random scatter. By atomic absorption method we estimated the detection limit of the analytes according to the developed methodic and show that the obtained results are lower than the same data from literature. The developed methodic, according to its metrological characteristics, is competitive at international level.
研究了SAS (Тriton Х-100)浓度和超声处理时间对感应连接等离子体探测地层水中分析物原子吸收和原子发射信号值的影响。利用非离子源性SAS达到了铅和铁的最大分析信号,降低了被分析溶液的表面张力,提高了被分析物检测的吸收率。结果表明,采用现代样品制备方法,铅的原子吸收检测灵敏度提高了1.5倍,铁的原子吸收检测灵敏度提高了1.8倍。采用原子吸收和原子发射电感连接等离子体光谱法,以乙酰丙酮酸铅和铁为标准成分样品,提高了分析物检测的灵敏度,对地层水中的铅和铁含量进行了测定。通过试样体积的变化和“注入-发现”法,证明了系统误差不显著。根据F-和t标准对两种独立方法得到的结果进行比较。用随机散点证明了离散度是齐次的,均值的运行是不充分的。用原子吸收法对分析物的检出限进行了估计,结果表明所得到的结果低于文献中相同的数据。根据所开发的计量方法的特点,在国际上具有一定的竞争力。
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引用次数: 0
Design, rheology and microstructure of food-grade emulsion-based systems for delivery of vitamin D 食品级乳基维生素D输送系统的设计、流变学和微观结构
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-35-02
The fortification of food with vitamin D has several limitations because this group of fat-soluble compounds may degrade or undergo undesirable changes during technologic processing and storage of food. The purpose of this study was to investigate emulsions for vitamin D3 delivery in commercial foods. Oil-in-water (o/w) emulsions stabilized by mixture of various proteins (whey protein isolate (WPI), skimmed milk powder (SMP) and vegan protein isolate (VPI)) as emulsifiers and carboxymethylcellulose as thickening agent were used. The shear stress and effective dynamic viscosity of the emulsions in the wide range of shear rates were experimentally determined. By approximating experimental flow curves using the power-law model, the values of the consistency coefficient and flow behavior index were obtained, which made it possible to classify the emulsions as systems with pseudoplastic flow. Within the framework of the structural approach, the rheological data were analyzed on the basis of the generalized rheological model of Casson. The contributions to the process of viscous flow calculated from the experimental data from the integral characteristics of associates of droplets and individual particles during their hydrodynamic interaction made it possible to explain the effect of changing the viscosity of emulsions from the nature of the emulsifier used. The zeta potential values determined by the dynamic light scattering method indicate the existence of a strong repulsive force as a factor for the stability of emulsions. The sign of the potential and its magnitude indicate the process of adsorption on the surface of fat droplets molecule of protein. The presence of a peak of flocculated particles in the histograms of the particle size distribution is explained by the presence of non-adsorbing polysaccharides, which are capable of the generation of aggregated emulsion structures through depletion flocculation. Regardless of the choice of the type and nature of the protein emulsifier - animal or plant origin, all studied systems were stable and can be considered for use as emulsion-based delivery systems of vitamin D. From an economic point of view, it is advisable to use dry milk as an emulsifier. The resulting emulsions can be used as a basis for the production of vitamin D3-fortified foods, in particular for dairy products.
用维生素D强化食品有一些局限性,因为这组脂溶性化合物可能在食品的工艺加工和储存过程中降解或发生不希望发生的变化。本研究的目的是研究乳剂在商业食品中的维生素D3输送。以乳清分离蛋白(WPI)、脱脂奶粉(SMP)和纯素分离蛋白(VPI)为乳化剂,羧甲基纤维素为增稠剂的混合物稳定水包油(o/w)乳剂。实验测定了乳液在较宽剪切速率范围内的剪切应力和有效动态粘度。利用幂律模型对实验流动曲线进行近似,得到了乳状液的稠度系数和流动性能指标,从而将乳状液划分为具有假塑性流动的体系。在结构方法的框架内,基于Casson广义流变模型对流变数据进行了分析。从液滴和单个颗粒在流体动力相互作用过程中的整体特性的实验数据中计算出粘性流动过程的贡献,使得从所用乳化剂的性质来解释改变乳化剂粘度的影响成为可能。动态光散射法测定的zeta电位值表明,强排斥力的存在是影响乳剂稳定性的一个因素。电势的符号及其大小反映了蛋白质分子在脂肪滴表面的吸附过程。在粒径分布的直方图中,絮凝颗粒的峰值的存在可以解释为不吸附多糖的存在,这些多糖能够通过耗尽絮凝产生聚集的乳液结构。无论选择何种类型和性质的蛋白质乳化剂-动物或植物来源,所有研究的系统都是稳定的,可以考虑用作维生素d的乳基输送系统。从经济的角度来看,建议使用干牛奶作为乳化剂。所得乳剂可作为生产维生素d3强化食品,特别是乳制品的基础。
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引用次数: 1
In memoriam: Professor V.A. Starodub (5.01.1949 – 12.11.2020) 纪念:斯塔罗杜布教授(5.01.1949 - 12.11.2020)
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-34-07
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引用次数: 0
Synthesis of 1-(methylsulfonyl)-1-propene and N,N-dimethyl-1-propene-1-sulfonamide 1-(甲基磺酰基)-1-丙烯和N,N-二甲基-1-丙烯-1-磺酰胺的合成
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-35-04
Various vinylsulfones and vinylsulfonamides have a wide range of biological activities (mainly, inhibition of different types of enzymes) and are frequently used in synthetic organic chemistry (as active dienophiles, Michael acceptors and, generally, active agents in 1,4‑addition and electrocyclization reactions). However, despite numerous synthesized substances of this type, the synthetic protocols for the obtaining of the low molecular weight representatives of these compounds – 1‑(methylsulfonyl)-1-propene and N,N‑dimethyl-1‑propene-1-sulfonamide – seem to be still little known. In the present work we report a simple, efficient and general protocol for the dehydrative synthesis of 1‑(methylsulfonyl)-1‑propene and N,N‑dimethyl-1‑propene-1‑sulfonamide starting from corresponding 1-(methylsulfonyl)-2-propanol and N,N‑dimethyl-2‑hydroxypropanesulfonamide, respectively, using MeSO2Cl/organic base system basing on the preliminary experiment of 2‑(4‑bromophenyl)-N,N‑dimethylethenesulfonamide synthesis from 2‑(4‑bromophenyl)-2‑hydroxy-N,N-dimethylethanesulfonamide. The latter in its turn has been obtained starting from N,N‑dimethylmethanesulfonamide by lithiation with n-BuLi, subsequent action of 4‑bromobenzaldehyde and further workup. The applied protocol of vinyl derivatives synthesis allows to avoid isolation of intermediate mesyl derivatives, consisting of one-pot formation of leaving group and its elimination. Accordingly to coupling constants in 1H NMR spectra, synthesized N,N‑dimethyl-1-propene-1‑sulfonamide exists as mixture of E- and Z-isomers (in the ratio 88:12), while isolated 1‑(methylsulfonyl)-1‑propene and 2-(4-bromophenyl)-N,N‑dimethylethenesulfonamide are the most stable E‑isomers. The structures of the synthesized compounds are confirmed by the methods of 1H NMR-spectroscopy and mass-spectrometry.
各种乙烯基砜和乙烯基磺酰胺具有广泛的生物活性(主要是抑制不同类型的酶),经常用于合成有机化学(作为活性亲二烯试剂,迈克尔受体,通常是1,4加成和电环化反应的活性剂)。然而,尽管有许多这种类型的合成物质,但获得这些化合物的低分子量代表-1-(甲基磺酰基)-1-丙烯和N,N -二甲基-1-丙烯-1-磺酰胺的合成方案似乎仍然知之甚少。本文在2-(4 -溴苯基)-2-羟基-N,N-二甲基-1 -丙烯磺酰胺的初步实验的基础上,提出了一种简单、高效、通用的方法,从相应的1-(甲基磺酰)-2-丙醇和N,N-二甲基-1 -丙烯磺酰胺出发,用MeSO2Cl/有机碱体系分别脱水合成1-(甲基磺酰)-1 -丙烯和N,N-二甲基-2-羟丙烯磺酰胺。从N,N -二甲基甲磺酰胺开始,经N - buli锂化,再经4 -溴苯甲醛作用,再经进一步加工,得到了后者。乙烯基衍生物合成的应用程序允许避免中间甲酰基衍生物的分离,包括离去基的一锅形成及其消除。根据1H NMR谱偶联常数,合成的N,N -二甲基-1-丙烯-1-磺酰胺是E-和z -异构体的混合物(比例为88:12),而分离的1-(甲基磺酰基)-1 -丙烯和2-(4-溴苯基)-N,N -二甲基磺酰胺是最稳定的E-异构体。合成的化合物的结构经核磁共振光谱和质谱分析证实。
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引用次数: 0
Visual binary testing of methanol contained in ethyl alcohol 乙醇中甲醇含量的目视二元检测
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-35-05
A method for control of methanol traces in rectified ethyl alcohol and alcoholic drinks based on visual binary testing using one reference sample was proposed. An indicator reaction of formaldehyde interaction (product of methanol oxidation) with chromotropic acid disodium salt was chosen for methanol screening. The conditions of indicator reaction proceeding are analogous as for the spectrophotometric technique of methanol determination: methanol was oxidized to formaldehyde with potassium permanganate in an acidic medium; the formaldehyde then reacts with chromotropic acid in the presence of hot concentrated sulfuric acid and forms a violet product (color of this product is stable for 12 hours). It was established that the absorption spectrum of the reaction product does not change on going from 96% ethanol to aqueous-ethanol solutions with a volume fraction of 40% ethanol. The maximum light absorption of the reaction product corresponded to 570 nm. All further studies were carried out in water-ethanol solutions with a volume fraction of ethanol of 40%. According to regulatory documents the normalized limiting content of methanol (clim) in ethyl alcohol of the “Lux” grade (the most common in the alcoholic industry) and alcoholic beverages is 0.01% by by volume counted upon anhydrous alcohol. The comparison sample (the solution of colored reaction product of indicator reaction) had to be less than the normilized level on the value which providing the risk of false-negative test result not more than 5%. To determination the threshold concentration of methanol in the comparison sample was applied the statistics of observation. For the aim the solution of colored product corresponding to the normalized limiting methanol concentration clim = 0.01% by volume was prepared and comparison samples with lower methanol concentrations were also prepared. The interval of unreliability was discovered with the help of observers. The frequency of detecting of the difference in the color of comparison samples and normalized sample (P(c)) changed from 0 to 1 in this interval. The value of methanol concentration 0.0072% by volume counted upon anhydrous alcohol was taken for the lower boundary of the interval and the value of methanol concentration 0.01% by volume counted upon anhydrous alcohol was chosen the upper border of the interval. This interval was divided on eight concentrations with step Dс = 0.0004% by volume. Three parallel series of solutions were prepared and 48 observations for each concentration were received. The experimental efficiency curve obtained was checked for compliance with the mathematical functions of the known distributions: normal, logistic, lognormal, exponential and Weibull distribution function using the statistical criterions c2 and Kolmogorov-Smirnov λ. The efficiency curve was described by the theoretical functions of the lognormal and Weibull distributions. Calculated at a confidence level of 0.95 estimation of the threshold
提出了一种基于视觉二值检测的精馏乙醇和酒精饮料中甲醇痕量控制方法。选择甲醇氧化产物甲醛与变色酸二钠盐相互作用的指示反应进行甲醇筛选。指示剂反应过程的条件与甲醇分光光度法测定甲醇的条件类似:在酸性介质中用高锰酸钾氧化甲醇生成甲醛;甲醛在热浓硫酸的存在下与变色酸反应,形成紫色产物(该产物的颜色在12小时内保持稳定)。结果表明,从96%乙醇到体积分数为40%乙醇的水-乙醇溶液,反应产物的吸收光谱没有变化。反应产物的最大光吸收波长为570 nm。所有进一步的研究都在乙醇体积分数为40%的水-乙醇溶液中进行。根据监管文件,“Lux”级(酒精工业中最常见的)酒精和酒精饮料中甲醇(clim)的标准限量含量按体积计算为0.01%(按无水酒精计算)。对照样品(指示剂反应的有色反应产物溶液)的值必须小于标准化水平,提供假阴性检测结果的风险不超过5%。对比较样品中甲醇的阈值浓度的测定采用了观察统计学。为此配制了归一化极限甲醇浓度(体积比)为0.01%的有色产品溶液,并配制了较低甲醇浓度的对照样品。不可靠区间是在观察者的帮助下发现的。比较样本与归一化样本颜色差异的检测频率(P(c))在此区间内由0变为1。区间的下界取无水乙醇体积计甲醇浓度为0.0072%的值,区间的上界取无水乙醇体积计甲醇浓度为0.01%的值。该区间分为8个浓度,步长dir = 0.0004%(体积)。制备了三个平行系列的溶液,每个浓度收到48个观察值。利用统计准则c2和Kolmogorov-Smirnov λ检验所得实验效率曲线是否符合已知分布的数学函数:正态分布、logistic分布、对数正态分布、指数分布和威布尔分布函数。效率曲线用对数正态分布和威布尔分布的理论函数来描述。在0.95的置信水平上计算,比较样品的阈值浓度估计为0.0073%,对应于无水酒精的体积分数。采用目视二元法测定了酒精饮料中甲醇的痕量。用气相色谱法验证了甲醇目测二元法的准确性。
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引用次数: 0
In memoriam: Associate Professor S.A. Komykhov (9.09.1971 – 22.10.2020) 纪念:科米霍夫副教授(9.09.1971 - 22.10.2020)
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-34-09
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引用次数: 0
Corrigendum to «Recent advances in theoretical investigation of titanium dioxide nanomaterials. A review» 二氧化钛纳米材料理论研究的最新进展的勘误。回顾»
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-34-06
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引用次数: 0
In memoriam: Associate Professor A.V. Kravchenko (20.12.1955 - 9.03.2020) 纪念:A.V. Kravchenko副教授(20.12.1955 - 9.03.2020)
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-34-08
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引用次数: 0
Sorption properties of polymeric beads and films containing tetraoctyl diglycolamide towards europium (III) ions 含四辛基二甘醇酰胺聚合物珠和膜对铕(III)离子的吸附性能
Pub Date : 2020-01-01 DOI: 10.26565/2220-637x-2020-35-01
The article presents results obtained during investigation of Eu(III) ion removal from aqueous solutions using triacetate cellulose films and styrene-divinylbenzene copolymer beads containing tetraoctyl diglycolamide (TODGA). A simple method for manufacturing films containing up to 50 % w/w TODGA is provided. Solution acidity effect on the removal rate of Eu(III) ions was studied. Maximum removal of Eu(III) ions was obtained in nitric acid solutions with concentrations of 1-6 mol/l. Additionally, increase in the europium removal rate is also observed at pH > 2 for beads and in the pH range of 2 to 4 for films. In the former case increase in the removal rate is explained by increase in the nitrate ion concentration in the solution and Eu(NO3)3(TODGA)3 complex formation, and in the latter case – by decrease in TODGA protonation rate with рН growth. Observed trends indicate a high similarity in surface sorption mechanisms between the materials studied. Sorption equilibrium of Eu(III) ions onto the styrene-divinylbenzene copolymer beads impregnated with TODGA is adequately fitted to Langmuir sorption isotherm. The maximum sorption capacity of this material for Eu(III) removal from solutions with nitric acid concentration of 1 mol/l is 7.4 mg/g. It has been found that the maximum removal rate of Eu(III) ions by the triacetate cellulose films is achieved for TODGA content in the films ≥ 40 % w/w. The possibility of selective europium sorption from natural water using both beads and films is shown. Although cations present in natural water do not bind to sorbents studied, there is still slight deterioration in sorption properties when moving from model solutions to natural water. Complete desorption of Eu(III) ions from the film surface is achieved by washing three times with an EDTA solution, рН = 6.8. Prepared films can be reused for Eu(III) ion removal.
本文介绍了用含四辛二醇酰胺(TODGA)的三乙酸纤维素膜和苯乙烯-二乙烯基苯共聚物珠去除水溶液中Eu(III)离子的研究结果。提供了一种制造含有高达50% w/w TODGA的薄膜的简单方法。研究了溶液酸度对Eu(III)离子去除率的影响。在浓度为1 ~ 6 mol/l的硝酸溶液中,对Eu(III)离子的去除率最大。此外,在pH为bbbb2时,珠子的铕去除率也有所增加,在pH为2至4时,薄膜的铕去除率也有所增加。前一种情况下,去除率的增加是由于溶液中硝酸盐离子浓度的增加和Eu(NO3)3(TODGA)3络合物的形成,后一种情况是由于TODGA质子化速率随着рН的增长而降低。观察到的趋势表明,所研究的材料之间的表面吸附机制高度相似。铕(III)离子在TODGA浸渍的苯乙烯-二乙烯苯共聚物珠上的吸附平衡完全符合Langmuir吸附等温线。在硝酸浓度为1 mol/l的溶液中,该材料对Eu(III)的最大吸附量为7.4 mg/g。研究发现,当膜中TODGA含量≥40% w/w时,三乙酸纤维素膜对Eu(III)离子的去除率最大。显示了利用珠和膜从天然水中选择性吸附铕的可能性。尽管天然水中存在的阳离子不与所研究的吸附剂结合,但当从模型溶液转移到天然水中时,吸附性能仍略有下降。用EDTA溶液(рН = 6.8)洗涤三次,可以使膜表面的Eu(III)离子完全脱附。制备的膜可重复用于去除Eu(III)离子。
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引用次数: 0
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Visnik Kharkivs''kogo natsional''nogo universitetu Seriia ximiia
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