Carboxylic acid to amide hydrogen bonding. 10-Oxo-semirubins

Using their amide (and pyrrole) groups, dipyrrinones act as hydrogen bonding receptors for carboxylic acids, as found in a large number of 10-oxo-semirubins (1-6). The latter can be synthesized readily by Friedel-Crafts coupling of 9-H dipyrrinones with half-ester acid chlorides or diacid dichlorides of α,ω-dicarboxylic acids, ranging from C₂ to C₁₀. With ω-oxo-alkanoic acid chains of C₅ or ≥C₅, intramolecular hydrogen bonding is observed. With acid chains <C₅ hydrogen bonding is not observed. Uncharacteristically (for dipyrrinones), 10-oxo-dipyrrinone acids (1-6) and their corresponding esters (1e-6e) remain monomeric in hydrogen bond promoting solvents.     

Process intensification using cavitation: optimization of oxidation conditions for synthesis of sulfone

Cavitation can be effectively used for intensification of chemical reactions due to the production of free radicals and conditions of high temperatures and pressures locally. In the present work, use of cavitation for the intensification of the synthesis of sulfone has been explored. The oxidation of thioether or sulfide to synthesize corresponding sulfone with 30% H₂O₂ as an oxidant was studied under acoustic cavitation and the results have been compared with the conventional approach based on the use of mechanical agitation. The aim has been also to optimize the different operating conditions viz. molar ratio of reactants to the oxidizing agent, type of the catalyst as well as its concentration, type of the solvent and the reactant concentration, so as to maximize the degree of intensification. It was observed that under the optimized conditions of sonication, the yield of sulfone was about five to six times higher as compared to the conventional approach of using mechanical agitation only.     

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在自行设计与建造的液态锂铅合金鼓泡器实验系统上,开展了气-液接触法提取液态锂铅合金中的氢。实验结果表明,氦气比氩气更适合作填料塔的载带气;塔温越高,塔出口端氢含量越大;载气流速对出口端氢含量的影响呈锯齿状,无明显规律。实验结果虽然与文献数据有差别,但可以认为采用气-液接触法提取液态锂铅中的氢同位素是可行的,提取效率是随液态锂铅在填料塔中滞留的时间增长而增大的。     

H_4PMo_(11)VO_(40)催化氧化2-甲基萘制备甲萘醌

以磷钼钒杂多酸H4PMo11V1O40为催化剂、乙酸为溶剂,用双氧水氧化2-甲基萘制备2-甲基萘醌.实验表明:H4PMo11V1O40具有一定的催化活性.通过正交试验和单因素试验考察了催化剂用量、乙酸用量、双氧水用量、反应时间、反应温度等对收率的影响,获得较佳的合成条件:杂多酸∶2-MN(质量比)=7%,乙酸∶2-MN(质量比)=10.5∶1,双氧水∶2-甲基萘(摩尔比)=4.2∶1,较适宜的温度为40~50℃,反应时间为30 min.     

Microhydration of Alanine in Gas Phase Studied by Quantum Chemical Method and ABEEMσπ/MM Fluctuating Charge Model

A fluctuating charge interaction potential function for alanine-water was constructed in the spirit of newly developed ABEEMσπ/MM(atom-bond electronegativity equalization method at the σπ level fused into molecular mechanics). The properties of gaseous neutral alanine-(H₂O)_n(n=1-7) clusters were systematically investigated by quantum mechanics(QM) and the constructed ABEEMσπ/MM potential, such as conformations, hydrogen bonds (H-bonds), interaction energies, charge distributions, and so on. The results of ABEEMσπ/MM model are in fair agreement with those of QM and available experimental data. For isolated alanine, compared with those of experimental structure, the average absolute deviations(AAD) of bond length and bond angle are 0.002 nm and 1.4°, respectively. For alanine-water clusters, the AAD of interaction energies and H-bond lengths are only 3.77 kJ/mol and 0.012 nm, respectively, compared to the results of MP2/aug-cc-pVDZ//MP2/6-311+G^** method. The ABEEMσπ charges fluctuate with the changing conformation of the system, and can accurately and reasonably reflect the interpolarization between water and alanine. The presented alanine-water potential function may provide a basis for further simulations on related aqueous solutions of biomolecules.     

Theoretical Insights into Intermolecular Hydrogen-Bonding Strengthening in Fluorenone-Methanol Complexes Induced by Electronic Excitation and Bulk Solvent Effect (cited: 1)

This work presents a theoretical insight into the variation of the site-specific intermolecular hydrogen-bonding (HB), formed between C=O group of fluorenone (FN) and O?H groups of methanol (MeOL) molecules, induced by both the electronic excitation and the bulk solvent effect. Through the calculation of molecular ground- and excited-state properties, we not only demonstrate the characters of HB strengthening induced by electronic excitation and the bulk solvent effect but also reveal the underlying physical mechanism which leads to the HB variation. The strengthening of the intermolecular HB in electronically excited states and in liquid solution is characterized by the reduced HB bond-lengths and the red-shift IR spectra accompanied by the increasing intensities of IR absorption corresponding to the characteristic vibrational modes of the O-H and C=O stretching. The HB strengthening in the excited electronic states and in solution mainly arises from the charge redistribution of the FN molecule induced by the electronic excitation and bulk solvent instead of the intermolecular charge transfer. The charge redistribution of the solute molecule increases the partial dipole moment of FN molecule and the FN-MeOL intermolecular interaction, which subsequently leads to the HB strengthening. With the bulk solvent effect getting involved, the theoretical IR spectra of HBed FN-MeOL complexes agree much better with the experiments than those of gas-phase FN-MeOL dimer. All the calculations are carried out based on our developed analytical approaches for the first and second energy derivatives of excited electronic state within the time-dependent density functional theory.     

Solvent Effect on Characteristic Vibration of IR Spectrum of 4,4'-Dibromodiphenyl Ether

The optimal geometry, IR spectrum and vibration assignment of 4,4＇-dibromodiphenyl ether（BDE-15） in gas phase were calculated via the density functional theory（DFT） at the level of B3LYP/6-3 l＋G（d）. Based on the vi- bration assignment, the calculation of vibration frequencies and intensities of 5 main vibration types of BDE-15 in 25 kinds of solvents was carried out by means of a self-consistent reaction field（SCRF） theoretical model at the level of B3LYP/6-31＋G（d） to analyze the solvent effect on the vibration of IR spectrum of BDE-15. To study the solvent ef- fect further, C--O asymmetric stretching vibration fluctuating, which is relatively acute in both vibration frequency and intensity, was selected as the characteristic vibration to establish different linear solvation energy relation（LSER） models for solvent categoring. Solvent parameters（a, /3, ~r＊）, acceptable number（AN） and quantitative structure- activity relationship（QSAR） models were established via chemical quantum parameters of solvent moleculer, which were first been introduced to investigate different solvent-solute interaction mechanisms in alcoholic and non-alcoholic solvents on molecular level. At last, a single solvent molecule was embedded in the framework of po- larizable continuum model（PCM） to validate the effect of hydrogen bonding on solvent-solute interaction in alcohol solvents. The obtained results show that 5 main vibration types of BDE-15 in different solvents have small variation range in frequency and intensity and all the vibration frequencies in solvents are lower than those in gas phase, de- creasing along with the increasing of the dielectric Constant（e） of solvents exponentially. In contrast, all the vibration intensities in solvents are greater than those in gas phase and present positive exponential trend. Twenty-five solvents were divided into two categories（non-alcoholic solvents and alcoholic solvents） by LSER. The CmO asymmetric stretching vibration was mainly reg     

Rapid Evaluation of Individual Hydrogen Bonding Energies in Linear Water Chains

A model is proposed to rapidly evaluate the individual hydrogen bonding energies in linear water chains. We regarded the two O--H bonds of a water molecule as two dipoles. The magnitude of the O--H bond dipole mo- ment can be varied due to the other water molecules＇ presence. An analytic potential energy function, which explicitly contains the permanent dipole-dipole interactions, the polarization interactions, the van der Waals interactions and the covalent interactions, was therefore established. The individual hydrogen bonding energies in a series of linear water chains were evaluated via the analytic potential energy function and compared with those obtained from the CP-corrected MP2/aug-cc-pVTZ calculations. The results show that the analytic potential energy function not only can produce the individual hydrogen bonding energies as accurately as the CP-corrected MP2/aug-cc-pVTZ method, but is very efficient as well, demonstrating the model proposed is reasonable and useful. Based on the individual hy- drogen bonding energies obtained, the hydrogen bonding cooperativity in the linear water chains was explored and the natures of the hydrogen bonding in these water chains were discussed.     

Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H₂/kg dry biomass. The product gas was a mixed gas containing 72%H₂, 26%CO₂, 1.9%CO, and a trace amount of CH₄. It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H₂ yield (about 20%-50%). The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H₂O. In addition, the CuZn-Al₂O₃ catalyst in the water-gas shift bed could also increase the absolute H₂ yield via shifting CO to CO₂.     

Ab initio Study on Ionization Energies of 3-Amino-1-propanol

Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311++G** level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated that two most stable conformers display the in-tramolecular OH…N hydrogen bonds. The vertical ionization energies of these conformers calculated with ab initio electron propagator theory in the P3/aug-cc-pVTZ approximation are in agreement with experimental data from photoelectron spectroscopy. Natural bond orbital analyses were used to explain the differences of IEs of the highest occupied molec-ular ortibal of conformers. Combined with statistical mechanics principles, conformational distributions at various temperatures are obtained and the temperature dependence of pho-toelectron spectra is interpreted.