Formic acid catalyzed keto-enol tautomerizations for C2 and C3 enols: Implications in atmospheric and combustion chemistry

Enols are important species in atmospheric and combustion chemistry. However, their implications in these environments are not well established due to a lack of accurate rate constants and mechanisms to determine their fate. In this work, we investigate the formic acid catalyzed keto-enol tautomerizations converting vinyl alcohol, propen-2-ol and 1-propenol into acetaldehyde, acetone and propanal, respectively. High-level ab initio and multistructural torsional variational transition state theory calculations are performed with small-curvature tunneling corrections to obtain rate constants in the temperature range 200 K-3000 K. Tunneling is shown to be pronounced as a consequence of very narrow adiabatic potential energy curves, and indicates a need to revisit previous calculations. We show the implications of the studied reactions on the fate of enols under combustion relevant conditions by detailed kinetic modeling simulations. The yield of vinyl alcohol predicted by our calculated rate constants may be useful to lessen the underestimation of organic acids concentrations in current atmospheric models.     

Mechanism and rate constants of the CH2 + CH2CO reactions in triplet and singlet states: A theoretical study

Ab initio and density functional CCSD(T)-F12/cc-pVQZ-f12//B2PLYPD3/6-311G** calculations have been performed to unravel the reaction mechanism of triplet and singlet methylene CH₂ with ketene CH₂CO. The computed potential energy diagrams and molecular properties have been then utilized in Rice–Ramsperger–Kassel–Marcus-Master Equation (RRKM-ME) calculations of the reaction rate constants and product branching ratios combined with the use of nonadiabatic transition state theory for spin-forbidden triplet-singlet isomerization. The results indicate that the most important channels of the reaction of ketene with triplet methylene lead to the formation of the HCCO + CH₃ and C₂H₄ + CO products, where the former channel is preferable at higher temperatures from 1000 K and above. In the C₂H₄ + CO product pair, the ethylene molecule can be formed either adiabatically in the triplet electronic state or via triplet-singlet intersystem crossing in the singlet electronic state occurring in the vicinity of the CH₂COCH₂ intermediate or along the pathway of CO elimination from the initial CH₂CH₂CO complex. The predominant products of the reaction of ketene with singlet methylene have been shown to be C₂H₄ + CO. The formation of these products mostly proceeds via a well-skipping mechanism but at high pressures may to some extent involve collisional stabilization of the CH₃CHCO and cyclic CH₂COCH₂ intermediates followed by their thermal unimolecular decomposition. The calculated rate constants at different pressures from 0.01 to 100 atm have been fitted by the modified Arrhenius expressions in the temperature range of 300–3000 K, which are proposed for kinetic modeling of ketene reactions in combustion. © 2018 Wiley Periodicals, Inc.     

Preparation,Characterization and ex vivo Intestinal Permeability Studies of Ibuprofen Solid Dispersion

The aim of the present study was to improve the solubility and dissolution rate of ibuprofen and to evaluate, ex vivo, the intestinal permeation. Solid dispersions (SD) were prepared with Kollicoat IR^® by solvent evaporation technique in different drug:carrier ratios. The permeation intestinal of ibuprofen was evaluated by inverted intestinal sac method. The SD was characterized by solubility equilibrium, FT-IR, DSC, PXRD, SEM, and dissolution rate. The solubility, dissolution rate, and permeability were significantly greater for SD 1:2. The PXRD, SEM and DSC indicated a partial change in the crystalline state of ibuprofen. The solubility equilibrium of SD (1:2) was approximately 15 times greater than the solubility of ibuprofen. Dissolution rate enhancement was attributed to the decreased crystallinity of the ibuprofen, and increase of wettability and decrease of particle size. In conclusion, dissolution rate and intestinal permeability of ibuprofen were enhanced by the use of Kollicoat IR^® carrier in the SD formulation.     

生物电化学系统降解多环芳烃萘及微生物群落研究

采用单室空气阴极微生物燃料电池(MFC)反应器构型, 以不同浓度萘为基底物质, 考察MFC的产电性能、 萘降解率、 化学需氧量(COD)和总有机碳含量(TOC)降解率及MFC阴阳极微生物活性和多样性. 结果表明, 循环伏安曲线受不同浓度萘的影响变化较为明显, 随着萘浓度的增大, 最大功率密度呈下降趋势, 且萘对MFC的阴极电极电势影响较大; 当萘的浓度为15 mg/L时, MFC最大功率密度可达(645.841±28.08) mW/m ²; 对萘的降解率高达100%, 且MFC对COD和TOC的降解率随着萘浓度的提高而增大, 但是增大的速率逐渐减小. 对MFC阳极微生物膜进行高通量测序发现, Geobacter是优势菌属, 相对丰度达81%, 阴极主要以Aquamicrobium为主.     

油浆高温快速裂解过程的气固相产物研究

采用高频炉快速热解装置研究油浆的高温快速热解特性,考察了热解温度、氮气流量对气固相产物的组成和产率的影响。温度是影响气相产物产率的关键因素,气相产物主要为甲烷、氢气和乙烯,升高温度可提高甲烷和氢气的产率,而乙烯产率受高温下二次反应的影响在800℃到达最大值后逐渐降低,乙烷、丙烯产率较小且受二次反应的影响在700℃到达最大值后逐渐降低,温度高于800℃时会有少量乙炔生成且升温可提高乙炔产率。增加氮气流量可降低甲烷、氢气分压,缩短乙烯、丙烯等在高温区的停留时间,从而增加气相产物的产率。积炭产率随热解温度升高迅速增加,氮气流量的增加能够削弱二次反应从而降低积炭产率。     

Research on Ice Crystal Growth Inside the Vitrified Vs55 with Magnetic Nanoparticles During Devitrification by Cryomicroscopy

The effect of magnetic nanoparticles(mNPs) on the devitrification crystallization of typical vitrification solution Vs55 was systematically explored by differential scanning calorimetry(DSC) and cryomicroscope system. The results show tliat,(i) the mNPs coated by both carboxylic acid(CA) and polyethylene glycol(PEG) had little effect on the glass transition temperature(rg) of Vs55, but had significant effect on the devitrification transition temperature(7a) and devitrification enthalpy(Hrd),(ii) in the range of the devitrification area(-85- 0℃), the MNPs coated by CA can significantly accelerate the devitrification of Vs55 as the isothermal temperatures and the cooling rates increased, and the ice growth rate was 0.37 p.m/s at the isothermal temperature of-85 ℃, and was about 2.19 gm/s at -75℃. Also, the ice growth rates rose from 1.72 pm/s to 3.54 pm/s when the cooling rates were increased from 2 ℃/min to 100 ℃/min(at the isothennal temperature of -75℃),(iii) magnetic nanoparticles coated by both PEG and CA could promote the devitrification of Vs55, for instance, without any crystal growth inside Vs55 at the isothermal temperature of-80℃, but 1.04 and 2.31 gm/s for adding magnetic nanoparticles coated by CA and PEG, respectively. Compared with the samples coated by CA, PEG promoted the devitrification of Vs55 in a much more positive way, and the ice growth rates were 0.62 and 6.25 μm/s at the isothermal temperatures of -85 and -75 ℃, respectively. Tliese results indicate that the surface coating of MNPs could significantly affect tlie recrystallization of Vs55, and further work should be conducted in the future research.     

A high-speed image sensing technique with adjustable frame rate based on an ordinary CCD

In the sinusoidal phase modulating interferometer technique, the high-speed CCD is necessary to detect the interference signals. The reason of ordinary CCD's low frame rate was analyzed, and a novel high-speed image sensing technique with adjustable frame rate based on an ordinary CCD was proposed. And the principle of the image sensor was analyzed. When the maximum frequency and channel bandwidth were constant, a custom high-speed sensor was designed by using the ordinary CCD under the control of the special driving circuit. The frame rate of the ordinary CCD has been enhanced by controlling the number of pixels of every frame; therefore, the ordinary of CCD can be used as the high frame rate image sensor with small amount of pixels. The multi-output high-speed image sensor has the deficiencies of low accuracy, and high cost, while the high-speed image senor with small number of pixels by using this technique can overcome theses faults. The light intensity varying with time was measured by using the image sensor. The frame rate was up to 1600 frame per second (f/s), and the size of every frame and the frame rate were adjustable. The correlation coefficient between the measurement result and the standard values were higher than 0.98026, and the relative error was lower than 0.53%. The experimental results show that this sensor is fit to the measurements of sinusoidal phase modulating interferometer technique.     

Optimizing 10 Gbps optical communication system with duty cycle selection of return to zero pulse

We have investigated the return-to-zero (RZ) pulse duty cycle for single-channel Standard Single mode fiber (SSMF), Non Zero Dispersion shifted fibers (normal NZDSF and anomalous NZDSF fiber) for 10 Gbps optical fiber communication system. We give a comprehensive look on the behavior of variable duty cycle optical RZ pulse indicating that lowest bit error rate for duty cycle 0.8 among the duty cycle values 0.2, 0.4, 0.6 and 0.8 investigated for the case of SSMF. The single repeaterless mode fiber length is increased from existing 55 km at duty cycle 0.2 to fiber length 85 km by keeping duty cycle at 0.8. The result is also emphasized through the 10 dB Q value improvement and corresponding improvement in average eye opening diagram. The normal NZDSF show similar improvement but at greater fiber length, it offers BER 10⁻⁹ at length 110 km with duty cycle 0.2. NZDSF operating length can further be increased to length 160 km by keeping duty cycle 0.8. The corresponding 8 dB Q value improvement and Average eye opening improvement also supports the result through its graphical variation. Thirdly Anomalous NZDSF for same optical communication system showed that 0.2 duty cycle value give operational length of 130 km which could be extended to 160 km if 0.8 duty cycle is kept. The corresponding 8 dB Q value improvement, average eye-opening improvement endorsed the fact in the graphs.     

基于滑速比的气水两相流气相流量计算方法研究

目前对气水两相流的分相流量的研究中,多是针对两相流总流量和液相分相流量进行,对气相分相流量的研究很少.本文利用文丘里管和含气率传感器对空气水两相流气相流量计算方法进行了研究,在均相流模型基础上考虑了滑速比因素造成的影响,探讨了两相流气相流量计算方法.结果表明,该方法相对于传统的均相流模型在计算精度上得到了显著提高.     

全息光盘存储器的数据存取与像素匹配

全息光盘存储(HDS)技术作为一种非常具有潜力的新型信息存储技术, 是下一代光盘发展的目标。在全息光盘存储系统中, 为了实现数据精确快速地写入和读出, 降低误码率, 需要在整个高分辨率页面上实现空间光调制器(SLM)与光电阵列耦合器(CCD)之间1∶1像素匹配。在体全息存储理论和光学设计理论基础上, 研究实现SLM和CCD像素1∶1匹配的方法, 提出了实现像素匹配的要求和条件, 并且按照此要求完成该全息光盘存储器的光学系统。实验中, 分别使用随机数据掩膜版和SLM实现了对CCD的512×512精确像素匹配, 在光学系统中引入存储介质条件下, 图像质量良好, 掩膜版和SLM原始误码率分别为2.5×10-4和1.5×10-4。