DIALKYL(ARYL) PHOSPHORYL DERIVATIVES OF ALKYLENE DITHIOPHOSPHATES

Dialkyl(aryl) phosphoryl derivatives of alkylene dithiophosphates of general formula (S)SP(O)(OR) ₂ : R = Pr ⁱ , Ph and G = ═CMe ₂ CMe ₂ ═, ═CH ₂ CH ₂ CHMe═, ═CH ₂ CH ₂ CH ₂ CH ₂ ═, ═CMe ₂ CH ₂ CHMe═, and ═CH ₂ CMe ₂ CH ₂ ═; have been synthesized by reacting dialkyl and diaryl phosphoryl chloride with ammonium salts of alkylene dithiophosphates in 1:1 molar ratio in refluxing benzene. The products formed are yellow-colored viscous liquids and white-colored waxy solids; they are soluble in common organic solvents and are nonvolatile, even under reduced pressure. The new compounds have been characterized by elemental analysis, molecular weight measurements and spectroscopic (IR, ¹ H NMR, and ³¹ P NMR)] data.     

Intensification of sonochemical degradation of ammonium perfluorooctanoate by persulfate oxidant

Ammonium perfluorooctanoate (APFO) is an emerging environmental pollutant attracting significant attention due to its global distribution, high persistence, and bioaccumulation properties. The decomposition of APFO in aqueous solution with a combination of persulfate oxidant and ultrasonic irradiation was investigated. The effects of operating parameters, such as ultrasonic power, persulfate concentration, APFO concentration, and initial media pH on APFO degradation were discussed. In the absence of persulfate, 35.5% of initial APFO in 46.4 μmol/L solution under ultrasound irradiation, was decomposed rapidly after 120 min with the defluorination ratio reaching 6.73%. In contrast, when 10 mmol/L persulfate was used, 51.2% of initial APFO (46.4 μmol/L) was decomposed and the defluorination ratio reached 11.15% within 120 min reaction time. Enhancement of the decomposition of APFO can be explained by acceleration of substrate decarboxylation, induced by sulfate radical anions formed from the persulfate during ultrasonic irradiation. The SO₄^−•/APFO reactions at the bubble-water interface appear to be the primary pathway for the sonochemical degradation of the perfluorinated surfactants.     

A Facile and One‐pot Synthetic Route to Functionalized Ethyl 3‐(Alkanoyl)‐2‐(alkyl imino)‐2,3‐dihydrothiazole‐4‐carboxylate Derivatives under Mild,Solventand Catalyst‐free Conditions

A new one‐pot, four‐component synthetic rout is reported for the preparation of functionalized N‐acyl‐2alkylimino‐2,3‐dihydrothiazole derivatives from the reaction between acid chlorides, ammonium thiocyanate, primary alkylamines, and ethyl bromopyruvate under mild, solvent‐ and catalyst‐free conditions at room temperature. This completely green and efficient straight forward procedure led to the desired products in good to high yields without any need to catalyst or solvent assistance and no by product was observed in all the reactions     

A Novel One‐Pot Sulfonyloxylactonization of Alkenoic Acids Mediated by Hypervalent Iodine Species Generated in situ from Ammonium Iodide

A novel and efficient one‐pot procedure was designed for the sulfonyloxylactonization of alkenoic acids by the reaction of alkenoic acids with m‐chloroperbenzoic acid and sulfonic acids in the presence of a catalytic amount of ammonium iodide in a mixture acetonitrile/2,2,2‐trifluoroethanol (4 : 1) at room temperature for 24 h, which provided the corresponding sulfonyloxy lactones in moderate‐to‐good yields.     

SiO_2/Co_3O_4核壳催化剂对AP热分解的催化性能研究

采用改良的St觟ber法制备粒径约为200 nm的单分散球形SiO2颗粒,以此为内核,分别通过液相沉淀法和尿素均匀沉淀法制备包覆形式不同的新型SiO2/Co3O4核壳式纳米催化剂。采用X-射线衍射分析(XRD)、透射电子显微镜(TEM)、红外光谱分析(IR)、拉曼光谱分析(Raman)、BET比表面积测试等手段对产物进行表征,利用差式扫描量热仪(DSC)考察SiO2/Co3O4复合物对高氯酸铵(AP)热分解反应的催化作用,探讨不同包覆形式对其催化活性的影响。结果表明,两种方法制备得到的SiO2/Co3O4复合物分别为层包覆和粒子包覆,比表面积大,具有明显的核壳结构,且粒子包覆形式的SiO2/Co3O4对AP热分解反应的催化效果最好,使AP的高温分解温度降低了110℃,放热量增加了662 J·g-1。     

The particle dimension controlling synthesis of α-MnO2 nanowires with enhanced catalytic activity on the thermal decomposition of ammonium perchlorate

Hydrothermal method synthesis of α-MnO₂ nanowires has been achieved at different temperatures in this work. X-ray diffraction and transmission electron microscopy confirmed the pure phase of the α-MnO₂ nanowires. All of the samples crystallized in a single-phase nanowires shape. The α-MnO₂ nanowires diameter increased from 11 nm to 21 nm with the increase in hydrothermal temperature from 120 °C to 200 °C. The α-MnO₂ catalytic activity on the decomposition of ammonium perchlorate (AP) was characterized through thermogravimetric analysis. The decomposition rate of AP with the addition of α-MnO₂ was size relative. The 11 nm MnO₂ nanowires exhibited the best catalytic activity, which lowered the high-temperature peak of AP by 130 °C.     

Selective and sensitive determination of lipoyllysine (protein-bound alpha-lipoic acid) in biological specimens by high-performance liquid chromatography with fluorescence detection

The direct determination of lipoyllysine (LLys) in proteins was carried out by reversed-phase high-performance liquid chromatography with fluorescence (FL) detection. The proteins containing α-lipoic acid (LA) were first hydrolyzed with several enzymes such as pronase E and subtilisin A. The disulfide bond (-S-S-) in LLys liberated from the enzyme digestion was reduced with tris(2-carboxyethyl)phosphine to the thiol form (-SH). The reduced LLys was then labeled with ammonium 4-fluoro-2,1,3-benzoxadiazole-7-sulfonate (SBD-F) at 50 °C for 1 h. The resulting fluorophore, SBD-LLys, was separated by reversed-phase chromatography and fluorometrically detected at 510 nm (excitation at 380 nm). The calibration curve obtained from the peak areas versus the injection amounts of LLys showed a good linearity. The limits of detection and quantification of LLys on the chromatogram were approximately 0.13 pmol (signal-to-noise ratio (S/N) = 3) and 0.44 pmol (S/N = 10), respectively. A good recovery (98.9-107.1%) and precision (R.S.D.: 4.49-17.2%) of LLys were also obtained using the present procedure. The proposed method was used for the determination of LLys in spinach and animal tissues. The FL derivative was completely separated without any interference by endogenous substances in the sample and sensitively detected by the fluorimetry. The assay values of LLys per 1 g wet tissues were 3.67 μg (kidney), 1.97 μg (liver), 2.09 μg (heart), 0.59 μg (brain), 0.30 μg (lung), 0.38 μg (pancreas), and 0.20 μg (spleen). The direct determination of LLys in protein using the FL labeling method is reported for the first time.     

The Oxidation of Metals with Liebig Acids

In Liebig's definition, an acid is a compound which contains one or more hydrogen atoms which may be substituted by metal atoms. Hence, reactions of Liebig acids in substance, excluding water or any other solvent, with non‐noble metals yield salts and release hydrogen. In this sense, not only the classical mineral acids such as sulfuric or nitric acid, respectively, are Liebig acids. Rather, there is a large variety of organic compounds with, for example, HO‐ or HN‐functions with acid constants that allow for substitution of the hydrogen atoms by a metal atom. Simple covalent hydrides like water and ammonia or even methane may also act as Liebig acids with conditions properly chosen. The ammonium ion, (NH₄)⁺, represents a special case as it is available in a large variety of salts and may react as an acid/oxidant or as a (base)/reductant and is also a pseudo alkali‐metal cation. The versatility of the ammonium ion is reviewed with special emphasis to its ability to function as a Liebig acid, i.e., reactions of, especially, ammonium halides with non‐noble metals.     

Preparation and characterization of diethylnicotinamidium perchlorate

The title compound is the first example of N,N′-diethylnicotinamidium, [denaH]⁺, salt which has been characterized by X-ray analysis and IR spectra. [denaH]ClO₄ was obtained from the reaction mixture prepared from N,N′-diethylnicotinamide (dena) and Fe(ClO₄)₃ in ethanol without any addition of HClO₄. The proton required for protonation of dena is produced by hydrolysis of aquairon(III) cations. In the crystal structure, cations and anions are held together by ionic interactions. The cations are linked to each other by pyridinium-carbonyl N-H⋯O=C hydrogen bonds and an infinite linear chain along axis a is formed. Dedicated to Professor Milan Melník on the occasion of his 70th birthday     

Effect of temperature on the performance of proton batteries based on chitosan–NH4NO3–EC membrane

Membranes of chitosan-based proton conductor polymer electrolyte were prepared by dissolving chitosan powder, ammonium nitrate (NH₄NO₃) salt and ethylene carbonate (EC) plasticizer in acetic acid solution. The temperature dependence of the chitosan-based membrane system was found to obey the Arrhenius relationship. The sample with the highest conductance, 18 wt.% CA + 12 wt.% NH₄NO₃ + 70 wt.% EC (CA40N70E), also possesses the lowest activation energy. From linear sweep voltammetry (LSV) results, the membrane is electrochemically stable at a potential of 1.6–1.8 V and a temperature of 298–353 K. The cells were fabricated using zinc powder (Zn) + zinc sulfate heptahydrate (ZnSO₄·7H₂O) + acetylene black (AB) + polytetrafluoroethylene (PTFE)|CA40N70E|manganese (IV) oxide (MnO₂) + AB + PTFE. The open circuit voltages of the cells are decreases as temperature increases, the same trend as that obtained by LSV. The cell performance is excellent at 333 K, with discharge capacity of 42.7 mAh, internal resistance of 16.8 Ω, maximum power density of 14.6 mW cm⁻² and a short-circuit current density of 31.0 mA cm⁻². However, at temperatures above 333 K, decomposition of the membrane degraded the electrochemical properties of the cells.