Computational examination of the electrophilic reaction on oxidative polymerization of phenyltrimethylsilane with sulfur chloride

Phenyltrimethylsilane possesses a higher HOMO energy (–9.34 eV) than nonsubstituted benzene (>0.41 eV). The π electron of the phenyltrimethylsilane localizes on the benzene ring at the ipso position rather than at the para position. Two center energies calculated by the MNDO-PM3 method indicate that the C? Si bond is facilitated to cleave in comparison with the C? H (para position) one of the benzene ring. Phenyltrimethylsilane and phenyl bis(trimethylsilane) were polymerized with sulfur chloride through the cationic oxidative polymerization. The product is isolated as oligo(p-phenylene sulfide), with a melting point of 150–190°C. An electrophile attacks the carbon atom linked to the Si atom in phenyltrimethylsilane. The new synthetic route of PPS can be established on the basis of the computational calculation.     

Synthesis and transformations of metallocycles. 9. Regioselective and stereoselective synthesis of al-substitutedtrans-3,4-dialkylaluminocyclopentanes catalyzed by (η5-C5H5)2ZrCl2

A new stereoselective method is developed for the synthesis of 1-chloro-, 1-alkoxy-, and 1-N,N-dialkylaminoalumino-cyclopentanes from -olefins, metallic magnesium, and aluminum halides (AlCl₃, RO-AlCl₂, R₂N-AlCl₂) in the presence of catalytic amounts of Cp₂ZrCl₂ (Cp=⁵-C₅H₅). The products from hydrolysis and deuterolysis of the Al-substituted 3,4-dialkylaluminocyclopentanes (ACP) have the threo configuration.For Communication 8, see [1].Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 450054 Ufa. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1393–1397, June, 1992.     

Thermal decomposition of ammonium fluoroferrates (NH4)xFeF2x (2≤x≤3)

Different ammonium fluoroferrates (NH₄)_xFeF_2x (2≤x≤3) have been investigated. The thermal decomposition of the compounds obtained can be interpreted by their identical crystal structures (cryolite type). The decomposition products of all ammonium fluoroferrates formed in initial stage are isostructural of NH₄FeF₄. The decomposition is accompanied by the partial reduction of Fe(III) to Fe(II) by ammonium isolated. The end product of the thermal decomposition is FeF₂ and FeF₃ mixture.     

二芳基汞的合成

将氯化重氮苯的溶液加入氯化汞、维生素C、丙酮和少量氯化铜的混合物中,得到80％的氯化苯汞;如在反应混合物中补加维生素C、氯化铜和浓氨水,则得到二苯汞。用同样的方法制备了其他的二芳基汞,并讨论了反应可能的机理。     

Thermal degradation behavior of radiation synthesized polydiallyldimethylammonium chloride

Thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC) studies were carried out on gamma radiation synthesized polydiallyldimethylammonium chloride (PDADMAC). The polymer was found to undergo thermal degradation in two stages. The first stage showed a weight loss of 33% and the second stage showed a weight loss of 67%. The DSC thermogram shows two endothermic peaks corresponding to the two stages in the TG thermogram and the experimental enthalpy change associated with the first and second stages were 650 J g⁻¹ and 129.5 J g⁻¹, respectively. The nth-order kinetic parameters (order of the reaction, activation energy and the pre-exponential factor) were determined from a single dynamic DSC or thermogravimetric (TG) thermogram by the method of least square. Theoretical TG/differential thermogravimetric (DTG) and DSC thermograms derived from the calculated kinetic parameters were in good agreement with the experimental ones at the heating rate employed. However, the kinetic parameters determined using TG and DSC were different. This leads to the conclusion that the degradation mechanism could be complicated and may consists of a number of parallel or consecutive reactions. The glass transition temperature (T_g) of the polymer was found to be around 150 °C depending on the test method employed.     

A novel synthesis of organic diselenapolysulfides

A family of organic polychalcogenides with a common structure of RSeS_xSeR (with x=1, 2, 3 and R=CH₃, Ph, PhCH₂, O₂NC₆H₄CH₂) as well as cyclic 5,5-dimethyl-1,2-dithia-3,7-diselenacycloheptane were synthesized in good yield and high purity from the reaction of Ph₃CS_xCl with corresponding diselenides in chloroform at room temperature. Mechanistic aspects of the insertion involving the formation of an intermediate (RSeS_xCPh₃) are discussed.     

Low-Cost Potentiometric Sensor for Chloride Measurement in Continuous Industrial Process Control

Recently, the new updates in legislation about drinking water control and human health have increased the demand for novel electrochemical low-cost sensors, such as potentiometric ones. Nowadays, the determination of chloride ion in aqueous solutions has attracted great attention in several fields, from industrial processes to drinking water control. Indeed, chloride plays a crucial role in corrosion, also influencing the final taste of beverages, especially coffee. The main goal is to obtain devices suitable for continuous and real-time analysis. For these reasons, we investigated the possibility to develop an easy, low-cost potentiometric chloride sensor, able to perform analysis in aqueous mediums for long immersion time and reducing the need of periodic calibration. We realized a chloride ion selective electrode made of Ag/AgCl sintered pellet and we tested its response in model solutions compatible with drinking water. The sensor was able to produce a stable, reproducible, and accurate quantification of chloride in 900 s, without the need for a preliminary calibration test. This opens the route to potential applications of this sensor in continuous, in situ, and real time measurement of chloride ions in industrial processes, with a reduced need for periodic maintenance.     

Low-Molecular Pyrazine-Based DNA Binders: Physicochemical and Antimicrobial Properties

Pyrazine and its derivatives are a large group of compounds that exhibit broad biological activity, the changes of which can be easily detected by a substituent effect or a change in the functional group. The present studies combined theoretical research with the density functional theory (DFT) approach (B3LYP/6-311+G**) and experimental (potentiometric and spectrophotometric) analysis for a thorough understanding of the structure of chlorohydrazinopyrazine, its physicochemical and cytotoxic properties, and the site and nature of interaction with DNA. The obtained results indicated that 2-chloro-3-hydrazinopyrazine (2Cl3HP) displayed the highest affinity to DNA. Cytotoxicity studies revealed that the compound did not exhibit toxicity toward human dermal keratinocytes, which supported the potential application of 2Cl3HP in clinical use. The study also attempted to establish the possible equilibria occurring in the aqueous solution and, using both theoretical and experimental methods, clearly showed the hydrophilic nature of the compound. The experimental and theoretical results of the study confirmed the quality of the compound, as well as the appropriateness of the selected set of methods for similar research.     

Evaluation of Water Ammonium Ion Test Kit and Its Feasibility for the Analysis of Protein in Food

The traditional method for the determination of protein in food needs the operations of digestion, distillation, absorption, and titration; therefore, it is complicated and time-consuming and requires professional personnel. Is there a more convenient and faster detection method that can directly determine the ammonium ions in protein digestion solution to obtain the protein content of food and avoid the distillation–absorption–titration process? The feasibility of water ammonium ion test kits for food protein rapid detection was discussed here. After digestion, the protein in food transforms into ammonium ions in the digestion solution. Because of the variety of food, there are many different inorganic ions left in the food digestion solution, and at the same time, digestion agents are added in the digestion process and become potential interference factors in ammonium determination. Therefore, the detection accuracy of ammonium test kits needs to be evaluated first, including their anti-interference ability. The standard curve of ammonium was established by the test kit. When the ammonium concentration was 0.00–2.50 mg/L, the absorbance at 620 nm was linearly related to the ammonium concentration, the determination coefficient R² was 0.9995, and the detection limit of this method was 0.01 mg/L. The influences of temperature, pH value, and reaction time on the test kit method were discussed. The precision was 0.90–3.33%; the repeatability was 1.71–4.86%; and the recovery rate of tap water, river water, and sea water was controlled within 90–103%. The anti-interference ability of the evaluated test kit was better than that of the national standard detection method. The test kit, combined with sample pretreatment and protein conversion formula, was used to detect protein in different types of food (milk powder, rice flour, wheat flour, soy, banana, milk, fish food, chicken food, and dog food). The results showed that there were no significant differences (ρ > 0.05) between the national method and the test kit method. The ammonium ion test kit method shortened the determination time and had higher sensitivity, showing its potential for the rapid determination of food protein.     

一种超高耐久混凝土——梯度结构混凝土

分析超高耐久混凝土的研究现状,提出了一种高耐久、低成本的超高耐久混凝土--梯度结构混凝土(Gradient Structural Concrete,简称GSC),采用电量法和氯离子扩散系数法来评价梯度结构混凝土的抗氯离子渗透性能,最后进行梯度结构混凝土的寿命预测与成本分析.结果表明,高性能混凝土(High Performance Concrete,简称HPC)、无细观界面过渡区水泥基复合材料(Meso-interfacial transition zone-free cement-based materials,简称 MIF)和梯度结构混凝土MIF-HPC的6 h导电量和氯离子扩散系数的排列顺序均为:HPC>MIF-HPC>MIF,其抗氯离子渗透性能排列顺序为:MIF>MIF-HPC>HPC.梯度结构混凝土的成本会有所增加,但由于其氯离子渗透性能大幅降低,其使用寿命得到大幅延长,使得其年损耗费用大幅下降.