Ruthenium-catalyzed methoxycarbonylation of styrene

Methoxycarbonylation of styrene in the presence of homogeneous Ru catalysts is reported for the first time. Available Ru₃(CO)₁₂ together with halide source such as [bmim]Br, NaBr or LiCl represents active and easy to handle methoxycarbonylation catalyst. The key advantage of the new catalytic systems over traditional Pd catalysts is their high activity at CO pressure as low as 5 bar.     

Optimization of heterogeneous Catalyst-assisted fatty acid methyl esters biodiesel production from Soybean oil with different Machine learning methods

There is a growing attention to the bio and renewable energies due to fast depletion of fossil fuels as well as the global warming problem. Here, we developed a modeling and simulation method by means of artificial intelligence (AI) for prediction of the bioenergy production from vegetable bean oil. AI methods are well known for prediction of complex and nonlinear process. Three distinct Adaptive Boosted models including Huber regression, LASSO, and Support Vector Regression (SVR) as well as artificial neural network (ANN) were applied in this study to predict actual yield of Fatty acid methyl esters (FAME) production. All boosted utilizing the Adaptive boosting algorithm. The important influencing parameters on the biodiesel production such as the catalyst loading (CAO/Ag, wt%) and methanol to oil (Soybean oil) molar ratio were selected as the input variables of models while the yield of FAME production was selected as output. Model hyper-parameters were tuned to maintain generality while improving prediction accuracy. The models were evaluated using three distinct metrics Mean Absolute Error (MAE), Root Mean Square Error (RMSE), and R². Error rates of 8.16780E-01, 4.43895E-01, 2.06692E + 00, and 3.92713 E-01 were obtained with the MAE metric for boosted Huber, SVR, LASSO and ANN models. On the other hand, the RMSE error of these models were about 1.092E-02, 1.015E-02, 2.669E-02, and 1.01174E-02, respectively. Finally, the R-square score were calculated for boosted Huber, boosted SVR, and boosted LASSO as 0.976, 0.990, 0.872, and 0.99702, respectively. Therefore, it can be concluded that although the boosted SVR and ANN models were better models for prediction of process efficiency in terms of error, but all algorithms had high accuracy. The optimum yield of 83.77% and 81.60% for biodiesel production were observed at optimum operating values from boosted SVR and ANN models, respectively.     

Sonochemical approach for synthesis of zinc oxide-poly methyl methacrylate hybrid nanoparticles and its application in corrosion inhibition

Hybrid nanoparticles (HNPs) with zinc oxide and polymethyl metha acrylate (inorganic/ polymer) were synthesized through the exploitation of ultrasound approach. The synthesized HNPs were further characterized employing transmission electron microscopy and x-ray diffraction. ZnO-PMMA based HNPs exhibit excellent protection properties to mild steel from corrosion when gets exposed to acidic condition. Electrochemical impendence spectroscopy (EIS) analysis was accomplished to evaluate the corrosion inhibition performance of MS panel coated with 2 wt% or 4 wt% of HNPs and its comparison with bare panel and that of loaded with only standard epoxy coating., Tafel plot and Nyquist plot analysis depicted that the corrosion current density (I_corr) decreases from 16.7 A/m² for bare material to 0.103 A/m² for 4% coating of HNPs. Applied potential (E_corr) values shifted from negative to positive side. These results were further supported by qualitative analysis. The images taken over a period of time indicated the increase in lifetime of MS panel from 2 to 3 days for bare panel to 10 days for HNPs coated panel, showing that ZnO-PMMA HNPs have potential application in metal protection from corrosion by forming a passive layer.     

Extraction of methyl xanthines and their UHPLC–DAD determination in consumable beverages used in Eastern province of Saudi Arabia

Coffee and tea are the most widely consumed beverages worldwide. However, the consumer may be unaware of the exact amount of methyl xanthine (MX, i.e. caffeine [C], theobromine [TB] and theophylline [TH]) consumed, as most of the products do not list the proper amounts. This may lead to serious risks including cardiovascular, kidney and stimulant effects. The aim of the study was to determine the MX amount in ready-to-use beverages (coffee and tea) collected from various outlets in the city of Al-Khobar, Saudi Arabia. Forty different samples of espresso, black coffee and red tea were collected. A fast, reliable and efficient UHPLC–DAD method was developed and validated for MX determination. Total lipids were extracted and fractionated in order to determine glycolipids, phospholipids and neutral lipids. The r² value for the method was 0.980–0.988 in a linearity range of 0.5–200 ppm. The range for MX (C [0.02–2.39 mg/ml], TB [0.00–0.10 mg/ml] and TH [0.00–0.004 mg/ml]) and total lipids was 1–5 g. The amount of glycolipids (3.1 g) was higher among the lipid fractions followed by phospholipids (1.8 g) and neutral lipids (0.25 g). In general, espresso beverages (20–30 ml) contained high amounts of MX whereas black coffee beverages contained high amount of lipids. Most of the beverages expressed C, TB, TH, lipids or their fractions; however, the product with high amounts of MX and lipids at the same time was espresso (brands Chemistry and Wogard). Although the MX and lipid levels in these beverages well below the allowed limits, care must still be taken, especially when using the beverages with high serving volumes (200–250 ml) or coffee prepared via the filter method i.e. black coffee, using a high temperature for a longer time.     

埋层界面和空气表面和频光谱信号贡献的调控

本文研究表明通过膜厚控制和表面等离激元增强方法可有效区分隐藏界面和空气表面的和频振动光谱信号. 以氟化钙基底支撑的PMMA薄膜为模型，观察到隐藏界面和空气表面对和频信号贡献的变化. 通过监控羰基和甲基伸缩振动基团，发现薄PMMA膜的和频信号来自PMMA/空气表面的化学基团-CH₂、-CH₃、-OCH₃和C=O，而厚PMMA膜的和频信号则来自基底/PMMA埋层界面的-OCH₃和C=O基团. 随制膜浓度增大，埋层界面C=O基团的取向角从65°下降到43°，且浓度大于或等于0.5 wt%时，取向角等于45°±2°. 相比之下，空气表面C=O的取向角落在21°∽38°之间. 在金纳米棒存在条件下，表面等离激元可以极大地增强和频信号，尤其是来自埋层界面信号.     

HFIP-Functionalized Co3O4 Micro-Nano-Octahedra/rGO as a Double-Layer Sensing Material for Chemical Warfare Agents

Semiconductor metal oxides (SMO)-based gas-sensing materials suffer from insufficient detection of a specific target gas. Reliable selectivity, high sensitivity, and rapid response–recovery times under various working conditions are the main requirements for optimal gas sensors. Chemical warfare agents (CWA) such as sarin are fatal inhibitors of acetylcholinesterase in the nerve system. So, sensing materials with high sensitivity and selectivity toward CWA are urgently needed. Herein, micro-nano octahedral Co₃O₄ functionalized with hexafluoroisopropanol (HFIP) were deposited on a layer of reduced graphene oxide (rGO) as a double-layer sensing materials. The Co₃O₄ micro-nano octahedra were synthesized by direct growth from electrospun fiber templates calcined in ambient air. The double-layer rGO/Co₃O₄-HFIP sensing materials presented high selectivity toward DMMP (sarin agent simulant, dimethyl methyl phosphonate) versus rGO/Co₃O₄ and Co₃O₄ sensors after the exposure to various gases owing to hydrogen bonding between the DMMP molecules and Co₃O₄-HFIP. The rGO/Co₃O₄-HFIP sensors showed high stability with a response signal around 11.8 toward 0.5 ppm DMMP at 125 °C, and more than 75 % of the initial response was maintained under a saturated humid environment (85 % relative humidity). These results prove that these double-layer inorganic–organic composite sensing materials are excellent candidates to serve as optimal gas-sensing materials.     

g-C3N4催化石墨化碳质材料的制备及光催化性能研究

通常采用以氢氧化物作为造孔剂,过渡金属硝酸盐或氯化物作为石墨化催化剂的传统两步法策略制备多孔石墨化碳材料。然而制备过程中多涉及有毒和腐蚀性试剂,且多步骤的过程耗时较长。本文以双氰胺为原料通过热缩聚反应得到g-C₃N₄,采用高铁酸钾为催化剂一步法实现g-C₃N₄的同步碳化-石墨化,并研究其光催化性能。与传统的两步法相比,该方法耗时少、效率高、无污染。与初始的g-C₃N₄材料相比,石墨化g-C₃N₄衍生碳质材料不仅显著改善了可见光的吸收,而且大大增强了光催化活性。研究了不同石墨化温度对g-C₃N₄衍生碳质材料在可见光下降解甲基橙溶液的影响。700 ℃下制备的衍生碳质材料的降解率为12.4 mg/g。光电化学测试结果表明,多孔g-C₃N₄衍生碳质材料的光生载流子密度、电荷分离和光电流(提高了5.4倍)均得到显著提高。因此,该简便、灵活方法为提高g-C₃N₄衍生碳质材料的吸附和光催化性能提供了一种有前景的、高效的途径。     

TEMPO-mediated radical polymerization in the synthesis of poly(methyl methacrylate) macromonomer

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Regular/abnormal variation in the strength and nature of the halogen bond between H2Te and the dihalogens: Prominent effect of methyl substituents

The halogen-bonded complexes between H₂Te/Me₂Te and the dihalogen molecules XY (XY = F₂, Cl₂, Br₂, I₂, ClF, ClBr, BrF, BrCl, BrI, IF, ICl, IBr) have been studied to investigate the dependence of its strength and nature on the halogen donor X and its adjoining atom Y, as well as the methyl groups in the electron donor. The interaction energy varies between −1.7 and − 43.5 kcal/mol, indicating that the Te atom in H₂Te/Me₂Te has a strong affinity for the dihalogen molecules. For the H₂Te-XY complex, the halogen bond is stronger for the heavier halogen donor X atom and the strong electron-withdrawing group Y. However, for Me₂Te-XY, the halogen bond is stronger for the lighter halogen donor X atom. The H₂Te/Me₂Te-F₂ complex has the largest interaction energy, although the σ-hole on F₂ is the smallest in magnitude. In most of the complexes, the electrostatic and polarization contributions to the binding strength are similar in magnitude. However, for H₂Te/Me₂Te-F₂, the polarization contribution is much larger than the electrostatic contribution, with a significant contribution from charge transfer.     

In Situ Incorporation of Praziquantel in Polymer Microparticles through Suspension Polymerization for Treatment of Schistosomiasis

Schistosomiasis is one of the major public health problems worldwide. Even though this is a common illness among preschool children in poor countries, treatment is carried out mainly through the administration of praziquantel tablets, which has some disadvantages, such as the strong bitter taste. As an alternative to overcome this problem, the development of new encapsulated praziquantel formulations is demanded. For this reason, suspension polymerizations are carried out for the in situ encapsulation of praziquantel into polymer microparticles, using methyl methacrylate (MMA) and cationic compounds (diethylaminoethyl methacrylate, DEAEMA, and dimethylaminoethyl methacrylate, DMAEMA) as comonomers. This technique allows for the preparation of polymer microparticles with high encapsulation efficiencies (>90%) with characteristic sizes ranging from 0.5 to 1500 µm. Drug release profiles show that praziquantel is released from poly(methyl methacrylate) microparticles slowly due to the existence of strong diffusional resistance. On the other hand, the addition of cationic comonomers renders polymer particles sensitive to pH variations, allowing for faster release of praziquantel in acidic environments, as found in the stomach.