Rotation-Inversion Isomerization of Tertiary Carbamates: Potential Energy Surface Analysis of Multi-Paths Isomerization Using Boltzmann Statistics

Potential energy surface (PES) analyses at the SMD[MP2/6–311++G(d,p)] level and higher-level energies up to MP4(fc,SDTQ) are reported for the fluorinated tertiary carbamate N-ethyl-N-(2,2,2-trifluoroethyl) methyl carbamate ( VII ) and its parent system N,N-dimethyl methyl carbamate ( VI ). Emphasis is placed on the analysis of the rotational barrier about the CN carbamate bond and its interplay with the hybridization of the N-lone pair (NLP). All rotational transition state (TS) structures were found by computation of 1D relaxed rotational profiles but only 2D PES scans revealed the rotation-inversion paths in a compelling fashion. We found four unique chiral minima of VII , one pair each of E- and Z-rotamers, and we determined the eight unique rotational TS structures associated with every possible E/Z-isomerization path. It is a significant finding that all TS structures feature N-pyramidalization whereas the minima essentially contain sp²-hybridized nitrogen. We will show that the TS stabilities are affected by the synergetic interplay between NLP/CO₂ repulsion minimization, NLP→σ^*(CO) negative hyperconjugation, and two modes of intramolecular through-space electrostatic stabilization. We demonstrate how Boltzmann statistics must be applied to determine the predicted experimental rotational barrier based on the energetics of all eight rotamerization pathways. The computed barrier for VII is in complete agreement with the experimentally measured barrier of the very similar fluorinated carbamate N-Boc-N-(2,2,2-trifluoroethyl)-4-aminobutan-1-ol II . NMR properties of VII were calculated with a variety of density functional/basis set combinations and Boltzmann averaging over the E- and Z-rotamers at our best theoretical level results in good agreement with experimental chemical shifts δ(¹³C) and J(¹³C,¹⁹F) coupling constants of II (within 6 %).     

MICROEMULSION SYSTEMS WITH A NONIONIC COSURFACTANT

The conditions to obtain W/0 microemulsions using ionic surfactants and a nonionic cosurfactant, a polyoxyethylene alkyl ether, were investigated. The length of the polyoxyethylene chain was critical to obtain the typical water solubilization maximum

The variation of the W/0 microemulsion region with hydrocarbon content was different from that of the usual type of microemulsions having a medium chain length alcohol as cosurfactant. In the present systems the W/0 microemulsion region was not a direct continuation of the inverse micellar area at zero content of hydrocarbon. Addition of hydrocarbon was necessary for the formation of inverse micelles

The microemulsion regions were sensitive to the kind of hydrocarbon used; a sign of the importance of the nonionic surfactant for the stability of this kind of microemulsions.     

A book of: “Hollow Fibers. Manufacture and Applications,” Jeanette Scott,editor, Noyes Data Corporation,flew Jersey, 1981, $54.00

ABSTRACT

Silicone-in-fluorocarbon-in-water double emulsions were prepared by controlling carefully the characteristics of the emulsions composed of silicone, perfluoropoly-ethoxymethoxy difluorohydroxyethyl ether (PFPE–OH) and fluorosurfactant. In the emulsion formulation, PFPE–OH incorporated had a great influence on the droplet morphology and the stability of double emulsions. Moreover, it was observed that among the fluorocarbons, the silicone-in-fluorocarbon-in-water double emulsions could be formed effectively in the presence of a fluorosurfactant. The double emulsions prepared in this study maintained their initial emulsion stability for a long time at high temperature, meaning great usefulness in the cosmetic industry.     

Synthesis and Characterization of Polymers Derived from the Copolymerization of 1,1′-Dihydroxyethyl-2,2′-Biimidazole and the Diglycidyl Ether of Bisphenol A

Abstract

1,1′-Dihydroxyethyl-2,2′-biimidazole has been used as a copolymerizing monomer with the diglycidyl ether of bisphenol A in the preparation of biimidazole-containing epoxy polymers. Polymerization reactions were studied in bulk, with and without catalyst, and in N,N-dimethylforma-mide and anisole solvents, with and without catalyst. FT-IR and NMR spectra, molecular weight, thermal and solubility characteristics were obtained. Polymers isolated as amorphous light brown solids were found to be only sparingly soluble in THF or in highly polar nitrogen-containing solvents (DMF, NMP, pyridine). These materials exhibited molecular weights up to 37 000 for SnC1₄-catalyzed polymerization carried out in DMF. A glass-transition temperature of 391°C was observed for polymers obtained under uncatalyzed solventless conditions. The glass transition temperature was 373°C for product obtained under SnC1₄-catalyzed, solventless conditions. Thermogravimetric analysis in air of polymers obtained under varying solvent and catalyst conditions showed less than 25% weight loss below 330°C and greater than 75% weight loss above 400°C.     

Model correction for the formation of amorphous silicon by ion implantation

The critical dose at which an implanted amorphous layer in silicon is formed cannot be explained by a previous energy independent model. An energy dependent correction to this model can explain our ESR data as well as other data. The correction is most important for light ions.     

Synthesis and decay of nuclides in supernovae

Synthesis of chemical elements at conditions of nuclear statistical equilibrium is investigated for the ultramagnetized astrophysical plasma in supernovae and near to neutron stars. For iron group nuclides, the magnetic modification of nuclear structure shifts a maximum of nucleosynthesis products towards smaller mass numbers approaching titanium. Signals of ⁴⁴Ti radioactive decay in the gamma-spectra of the supernova remnant Cassiopeia A were revealed from the integral IBIS/ISGRI observational data. The gamma-ray fluxes for ⁴⁴Sc* lines with energies 67.9 and 78.4 keV are determined. The relationship between model and observational results is discussed.     

A study on the triboelectric charging of display glass during the roller transfer process–modeling and characterization

Glass substrates for displays are insulating materials capable of generating and maintaining high levels of triboelectric charges posing a risk of electrostatic discharge (ESD) damage to electronic display components. In this work, an apparatus for triboelectric charging characterization of display glass during the roller transfer process was designed and fabricated. In order to establish the reliability of the characterization, the triboelectric charge and the electrostatic potential distribution measurement system was automated. The preconditioning process of the glass and the rollers was also addressed. In order to analyze the measurements' results, a multiphysics model that considered both electrical and mechanical properties was proposed. The test parameters that were expected to affect the triboelectric charging characteristics are defined and discussed, as well as some of the characterization results such as the effects of acceleration/deceleration and maximum velocity, relative humidity and moisture on the glass and the rollers, and the conductivity of the rollers. The peak-to-peak deviation of the de-embedded triboelectric charges, due to a steady-state velocity period with different combinations of acceleration/deceleration and maximum velocities, was 14.2%. The triboelectric charges increased as the relative humidity increased from 30% to 50% with the same temperature. They also increased when the insulating rollers were replaced with dissipative rollers.     

基于ABC-SV R算法的拉曼光谱检测混合油脂肪酸含量

提出了一种基于激光拉曼光谱和人工蜂群智能优化支持向量回归机(ABC-SVR)算法的快速定量检测三组分混和油中3种脂肪酸含量的方法。该方法针对光谱数据信息与样本之间非线性、高维度的关系,建立了预测精度及建模效率均高于同类对比算法的数学模型,同时避免了气相色谱法、液相色谱法等对混合油脂肪酸含量的检测方式,根据纯种油中3种脂肪酸含量的国际标准,由油品配置体积得到脂肪酸质量,有效降低了检测成本与实验复杂程度,提高了检测工作的实用价值。首先根据一定梯度配置66组混合油检测样品,使用便携式拉曼光谱仪采集样本的拉曼光谱信息,扣除背景噪声;观察多组样本的拉曼光谱图可知,由于官能团浓度的差异,食用油的拉曼特征峰位移基本相同,特征峰的峰值明显不同,因此基于特征峰信息可以区分食用调和油的不同混合物;其次对拉曼光谱做背景扣除、光谱平滑、最大值谱线归一化三步预处理,以降低实验中不可控的外界因素及背景荧光的影响,准确提取光谱特征峰强度信息;然后根据纯种油中3种脂肪酸的国际标准含量,结合国家食品法典委员会标准CODEX STAN210-1999《指定的植物油法典标准》中规定的纯种油密度中值,由油品体积得到脂肪酸质量数;随机选取56组样本数据作为训练集,剩余10组样本数据作为预测集;以训练集光谱特征峰强度和脂肪酸质量分别作为回归模型的输入及输出值,建立SVR和PSO-SVR,ABC-SVR三种混合优化算法对比的定量分析模型,对测试集的3种脂肪酸含量分别进行预测;最后通过均方误差(MSE)、相关系数(r)及建模时间(Elapsed time)分别进行对比,建立数据表对模型精准度进行检验。实验结果表明,通过ABC-SVR定量分析模型效果最佳,3种脂肪酸含量预测值与真实值的均方差分别为0.88×10-4,16×10-4和8×10-4,均低于0.002;相关系数分别为93.43%,99.65%和99.43%,均高于93%;预测时间(Elapsed time)分别为1.26,2.42和2.14 s。因此,所提出的检测方法,具备较高的精确度、较快的建模时间,且在理论上的类似条件下可适用于其他样品检测工作,可为振动光谱学对食用油掺伪分析的进一步工作提供可行的理论依据。     

Simulation and measurement of 3D shear-driven thin liquid film flow in a duct

Three-dimensional flow behavior of thin liquid film that is shear-driven by turbulent air flow in a duct is measured and simulated. Its film thickness and width are reported as a function of air velocity, liquid flow rate, surface tension coefficient, and wall contact angle. The numerical component of this study is aimed at exploring and assessing the suitability of utilizing the FLUENT-CFD code and its existing components, i.e. Volume of Fluid model (VOF) along with selected turbulence model, for simulating the behavior of 3D shear-driven liquid film flow, through a comparison with measured results. The thickness and width of the shear-driven liquid film are measured using an interferometric technique that makes use of the phase shift between the reflections of incident light from the top and bottom surfaces of the thin liquid film. Such measurements are quite challenging due to the dynamic interfacial instabilities that develop in this flow. The results reveal that higher air flow velocity decreases the liquid film thickness but increases its width, while higher liquid flow rate increases both its thickness and width. Simulated results provide good estimates of the measured values, and reveal the need for considering a dynamic rather than a static wall contact angle in the model for improving the comparison with measured values.