Catalytic activity of Pt and Pd in gaseous reactions of H2 and CH4 oxidation at low pressures

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Optimisation of the ultrasound-assisted extraction of betalains and polyphenols from Amaranthus hypochondriacus var. Nutrisol

The present study optimised the ultrasound-assisted extraction (UAE) of bioactive compounds from Amaranthus hypochondriacus var. Nutrisol. Influence of temperature (25.86–54.14 °C) and ultrasonic power densities (UPD) (76.01–273.99 mW/mL) on total betalains (BT), betacyanins (BC), betaxanthins (BX), total polyphenols (TP), antioxidant activity (AA), colour parameters (L*, a*, and b*), amaranthine (A), and isoamaranthine (IA) were evaluated using response surface methodology. Moreover, betalain extraction kinetics and mass transfer coefficients (K_La) were determined for each experimental condition. BT, BC, BX, TP, AA, b*, K_La, and A were significantly affected (p < 0.05) by temperature extraction and UPD, whereas L*, a*, and IA were only affected (p < 0.05) by temperature. All response models were significantly validated with regression coefficients (R²) ranging from 87.46 to 99.29%. BT, A, IA, and K_La in UAE were 1.38, 1.65, 1.50, and 29.93 times higher than determined using conventional extraction, respectively. Optimal UAE conditions were obtained at 41.80 °C and 188.84 mW/mL using the desired function methodology. Under these conditions, the experimental values for BC, BX, BT, TP, AA, L*, a*, b*, K_La, A, and IA were closely related to the predicted values, indicating the suitability of the developed quadratic models. This study proposes a simple and efficient UAE method to obtain betalains and polyphenols with high antioxidant activity, which can be used in several applications within the food industry.     

Bi4Ge3O12:Er3+晶体中的高阶混合效应对EPR g因子的影响

通过对角化364×364完全能量矩阵的理论方法,对掺杂在Bi₄Ge₃O₁₂晶体中的Er³⁺的Stark能级和EPR参数进行了研究,同时,定量分析了高阶晶体场混合效应和J-J混合效应对EPR g因子的影响。研究结果表明:对Er³⁺来说,最主要的J-J混合效应来源于多重态谱项²K_15/2,其对EPR g因子的贡献约占2.5%,而最主要的高阶晶体场混合效应来源于第一激发多重态⁴I_13/2和基态多重态⁴I_15/2之间的晶体场混合,其对各向异性g因子中g_⊥的贡献大致是g_//的两倍(即g_⊥约占 0.21%,g_//约占0.092%),其他更高阶的晶体场混合和J-J混合效应可以忽略不计。因此,对于Er³⁺掺杂的络合物系统来说,只考虑基态多重态⁴I_15/2对EPR g因子的贡献应该是一个很好的近似。     

UPLC-Q/TOF-MS coupled with multivariate analysis for comparative analysis of metabolomic in Dendrobium nobile from different growth altitudes

Dendrobium nobile alkaloids (DNLA) and glycosides are the main active components extracted from Dendrobium nobile Lindl. (D. nobile) used for thousands of years in China. The pharmacological effects of the above chemical components are significantly different. D. nobile is mainly grown at an altitude ranging from 230 to 800 m in Chishui City, Northwest Guizhou Province. However, it is unclear whether the metabolite in D. nobile is influenced by the planting altitude. Hence, to reveal the different metabolite in D. nobile cultivated at the altitude of 336 m, 528 m, and 692 m, ultra-high performance liquid chromatography with Q/TOF-MS couple with multivariate analysis were developed. Using the orthogonal partial least squares-discriminant analysis, 19 different metabolites were discovered and then tentatively assigned their structures as alkaloids and glycosides by comparing mass spectrometry data with in-house database and literature. Moreover, the result of semiquantitative analysis showed the content of dendrobine that was belonged to alkaloids significantly increased at the altitude of 692 m, whereas the content of glycosides demonstrated an accumulation trend at the altitude of 528 m. The results could provide valuable information for the optimal clinical drug therapeutics and provide a reference for quality control.     

Liquid interfacial nanoarchitectonics: Molecular machines,organic semiconductors,nanocarbons, stem cells,and others

The concept of nanoarchitectonics has been proposed as an extensional development of nanotechnology through fusions with material science and the other fields. In nanoarchitectonics, nano-units of atoms, molecules, and nanomaterials are architected into construction of functional material systems. In order to assemble intended structures or hierarchical structures from nano-units, it is more useful to confine nano-units at the interface. In addition, nanoarchitectonics is expected to output functions by harmonizing many units in dynamic environments. However, the liquid interfaces still have lots of unexplored matters in nanoscale because supports by advanced apparatus and techniques in nanotechnology are not always available. Specifically, this review paper summarizes examples of research on molecular manipulation, molecular arrangement and assembly, materials synthesis, and life manipulation at the liquid interface. These examples demonstrate that the liquid interface enables the control of dynamic functions of various size regions, from molecular-level phenomena such as the control of molecular machines to techniques of living creature size such as the control of stem cell differentiation. Liquid interfaces are very useful environments for controlling dynamic functions for a wide range of targets and would have tremendous potential in terms of functional exploration. The great potential of nanoarchitectonics at the liquid interface and the challenges to be solved in the future are also discussed.     

β-Silylacrylate as a Multipurpose Reagent in Organic Synthesis

Acrylates are well known electrophilic alkenes having multitude of applications in organic synthesis. They are very good acceptors in Michael addition reactions and are good enophile/dienophile/dipolarophile partners in cycloaddition reactions. Replacing the β-alkyl/aryl groups in acrylates by a silicon group would be interesting. In addition to the conventional reactions displayed by acrylates, β-silylacrylates (β-SAs) can show reactivity specifically related to the silicon group. Many conventional organic reactions such as hydrodimerization, organocatalytic asymmetric Michael additions, inter- and intra-molecular Diels–Alder reactions, and asymmetric 1,3-dipolar cycloadditions have been used to generate the complex chemical entities from β-SAs. Some of the reaction outcomes were vastly influenced by the silicon substituent. This review describes the practical synthesis β-SAs and their use as starting point in complex molecule generation including total synthesis of some natural products/bioactive molecules.     

Fe-Doped CoS2 Nanoarrays: Efficient Electrocatalytic Nitrate Reduction to Ammonia under Ambient Conditions

The electrocatalytic nitrate reduction reaction (NO₃⁻RR) enables the reduction of nitrate to ammonium ions under ambient conditions. It was considered as an alternative reaction for the production of ammonia (NH₃) in recent years. In this paper, we report that the Fe doping CoS₂ nanoarrays can effectively catalyze the formation of NH₃ from nitrate (NO₃⁻) under ambient conditions. This is mainly due to the increase of the NO₃⁻ reaction active site by Fe doping and the porous nanostructure of the catalyst, which greatly improves the catalytic activity. Specifically, at −0.9 V vs. RHE, the NH₃ yield rate (R_NH3) of Fe−CoS₂/CC is 17.8×10⁻² mmol h⁻¹ cm⁻² with Faraday Efficiency (FE) of 88.93 %. Besides, such catalyst shows good durability and catalytic stability, which provides the possibility for the future application of electrocatalytic NH₃ production.     

Thiacalixarene Appended Azo-based Supramolecular Systems: Self-assembly and Photo Tuning Reversible Liquid Crystalline Properties

Four new azo-based supramolecular materials containing thiacalixarene core substituted by variable alkoxy groups ( TFA₁ – TFA₄ ) have been designed and synthesized for the mesomorphic and photoswitching properties. The liquid crystalline behavior were accomplished by using DSC, POM, and XRD studies. All azo-based thiacalixarene based materials with short and higher chain length display columnar hexagonal mesophase with broad temperature range. The thermal behavior of all the materials was investigated by DSC and TGA study. The structural and conformational study of the lower rim functionalized materials was confirmed by using different techniques. These thiacalixarene moulded liquid crystalline compounds shows columnar self-assembly type behavior and higher thermal stability. The introduction of bi-substituted azo-ester network towards the lower rim of thiacalixarene core has impact on the electron delocalization and liquid crystalline properties. The photoswitching properties suggested cis and trans azo-isomerization under radiation of UV light and higher thermal back relaxation time. The mesogenic behaviour of compound TFA₂ and TFA₄ were demolished by the influence of cis and trans isomerization. The structure-property correlation is studied to understand the variation in mesogenic properties with the substitution of variable alkoxy side chain.     

Separation and purification of quinolyridine alkaloids from seeds of Thermopsis lanceolata R. Br. by conventional and pH-zone-refining counter-current chromatography

In this work, the preparative separation of quinolyridine alkaloids from seeds of T. lanceolata by conventional and pH-zone-refining counter-current chromatography. Traditional counter-current chromatography separation was performed by a flow-rate changing strategy with a solvent system of ethyl acetate-n-butanol-water (1:9:10, v/v) and 200 mg sample loading. Meanwhile, the pH-zone-refining mode was adopted for separating 2.0 g crude alkaloid extracts with the chloroform-methanol-water (4:3:3, v/v) solvent system using the stationary and mobile phases of 40 mM hydrochloric acid and 10 mM triethylamine. Finally, six compounds, including N-formylcytisine (two conformers) ( 1 ), N-acetycytisine (two conformers) ( 2 ), (-)-cytisine ( 3 ), 13-β-hydroxylthermopsine ( 4 ), N-methylcytisine ( 5 ), and thermopsine ( 6 ) were successfully obtained in the two counter-current chromatography modes with the purities over 96.5%. Moreover, we adopted nuclear magnetic resonance and mass spectrometry for structural characterization. Based on the obtained findings, the pH-zone-refining mode was the efficient method to separate quinolyridine alkaloids relative to the traditional mode.     

Kinetics and products of ozonation of C.I. Reactive Red 195 in a semi-batch reactor

Textile wastewater shows great threats to the environment if not well pretreated before discharge. A promising technique, ozonation, was applied to remove the color in dye solutions containing C.I. Reactive Red 195 (RR195) in a semi-batch reactor. The decolorization of RR195 by the ozone process followed pseudo-first-order kinetics. Several factors which influenced the efficiency of decolorization were studied and the reaction rate constant (k) obtained with different operational parameters was compared. Our results showed that RR195 was more easily degraded in acidic than in alkaline conditions. The dyeing auxiliaries (sodium carbonate and sodium chloride) that acted as radical scavengers could enhance the decolorization process, and the ozonation time for total color removal lengthened if the initial dye concentration was higher. The analysis of the ozonation products was performed by liquid chromatography-tandem mass spectrometer and a possible degradation pathway was predicted according to the ozonation products and structure of RR195. Our results indicated that ozonation was effective in the color removal of dyes, but further treatment might be necessary since the ozonation products are high toxic.