Synthesis of 6-(perfluoroalkyl)salicylates by [3+3] cyclization of 1,3-bis(silyl enol ethers) with 3-ethoxy-1-(perfluoroalkyl)prop-2-en-1-ones

6-(Perfluoroalkyl)salicylates were prepared by [3+3] cyclization of 1,3-bis(silyl enol ethers) with 3-ethoxy-1-(perfluoroalkyl)prop-2-en-1-ones.     

Analysis of organic acids in wines by Fourier-transform infrared spectroscopy

Fourier-transform infrared (FTIR) spectroscopy has been a major point of development in many wine laboratories in recent years. It enables almost instant analysis of several properties of wine, usually with very good precision and accurate results. Nevertheless, validation procedures should not be forgotten and should be fully performed. Recovery experiments were performed by spiking wine samples with different amounts of organic acids (tartaric, malic, lactic, acetic and citric—the most prominent in wines). After FTIR analysis of the total acidity and of each organic acid concentration, recoveries were calculated. For total acidity recovery results were, in general, good and very close to 100% (64–111%). On the other hand, for individual organic acid concentrations, the recovery results were lower than 100% (11–73%) for all spiking additions. These results could be explained by spectroscopic interferences between the organic acids. Because they have similar infrared spectra, it is not easy to distinguish between them and, therefore, to achieve accurate calibration. When total acidity, with a different infrared spectrum from the other abundant compounds in the wine, was taken as a single property the recovery results were acceptable.     

Organic acid solutions in the chromatography of inorganic ions VIII. Cation-exchange of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media

Summary The cation-exchange behaviour of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the ammonium form. Separation of Fe(III)/Cu(II), Fe(III)/Cu(II)/Zn(II), Fe(III)/Co(II)/Mn(II), Cu(II)/Ni(II)/Mn(II), Fe(III)/Cu(II)/Co(II)/Mn(II), Fe(III)/Cu(II)/Ni(II)/Cd(II), Yb(III)/Eu(III), Sc(III)/Y(III),Sc(III)/Yb(III)/Dy(III) and Nb(V)/Yb(III)/Ho(III) has been achieved, among others.This work was supported by C.N.R. of Italy.     

Determination of ten organic acids by low pressure liquid chromatography

Summary Organic acids, such as lactic, malic and citric acids, are involved in primary metabolism of all living organisms. Their presence in food products contributes to the flavour and their equilibrium with inorganic cations defines to a large extent the acidity of the food preparations. A resin cation-exchanger device, normally used for separating amino-acids, can be adapted for characterizing 10 organic acids: formic, propionic, fumaric, succinic, lactic, malic tartaric, citric, and oxalic. Two monitoring systems were used, one of them based on specific iron III salt coloration with hydroxy-acids.     

ξ-potential and surface dye-ability of poly(vinyl alcohol) fiber with different degree of formalization in a cationic dye solution

Summary The surface dyeability of the poly(vinyl alcohol) fiber with different degree of formalization was studied by measuring -potential of the fiber in alkaline aqueous solutions (pH 10) of a cationic dye Methylene Blue. With the increase in the dye concentration, the sign of the -potential of the fiber changed from negative to positive and thereafter the positive value approximated to saturated value, and the amount of dye adsorbed (expressed in mol/cm²-fiber) increased also. These results may possibly be attributed to the formation of the electrostatic bond between the fiber and the dye. The linear relations were found between and logC _d and its slope did not change with rise of temperature. The free energy of dyeing G (negative) calculated from the slope of the -logC _id curve, etc. increased with increasing the degree of formalization of the fiber. This fact corresponds to the increase in the surface dye adsorption with increasing the degree of formalization. With increasing the degree of formalization, the heat of dyeing H (negative) increased and the entropy of dyeing S (positive) decreased. The positive value of S for each fiber, suggests the formation of hydrophobic bond as a driving force to the dyeing of Methylene blue on the fiber surface in addition to the electrostatic bond.This paper is Part XXVII in a series on Studies on -potentials and Surface Dyeability of Natural and Synthetic Fibers in Dye Solution. Part XXVI: T. Suzawa andK. Kawakami, Nippon Kagaku Kaishi1975, No. 7,1134.     

Robust interface on ENR-50/TiO2 nanohybrid material based sol-gel technique: Insights into synthesis,characterization and applications in optical

In this work, the sol–gel technique was used to prepare a new organic–inorganic hybrid from Epoxidized Natural Rubber (ENR-50) and Titanium dioxide (TiO₂) by blending different content of titania precursors (10, 30, and 50 wt%) with an ENR-50 matrix. A wide range of analyses was conducted to understand the nature of this hybrid and also to evaluate its potential uses in applications required high refractive index such as micro optical and optoelectronic devices. Results indicated that the ring-opening reaction of epoxide groups in ENR-50 increased with the increase of titania content in the hybrid resulting a strong bonding between titania and ENR-50 through TiOC bond, which was observed in FTIR spectrum at 1027–1028 cm⁻¹. It is also observed a slight decrease in the intensity of the amorphous peak along with a new crystalline peak appeared at 2θ = 23 and 27° due to the crystalline nature of titania. The hybrids showed three thermal degradation steps in the range of temperature 76 to 769 °C due to the existence of the Ti moieties with the mixture of polymer chains, which in turn shifted the T_g at 24.3, 26.9 and 28.1 °C for the hybrid at 10, 30, and 50 wt% TiO₂ compared to the T_g of ENR-50 at −18.4 °C respectively. The morphology of the ENR-50 showed clear changes during of the synthesis of ENR-50/TiO₂ hybrids, these changes were proven by SEM, TEM, and AFM analyses. Uv–Vis results showed that the higher wavelength peak at 293 nm has shifted to 296, 298 and 300 nm for the hybrid at 10, 30, and 50 wt% TiO₂ respectively due to the strong interaction between titania precursors and ENR-50 matrix. Furthermore, the hybrids showed good optical transparency in the visible light range.     

Quantitative studies on furfural and organic acid formation during hydrothermal,acidic and alkaline degradation ofD-xylose

Summary Chromatographic analysis of the degradation ofD-xylose either in plain water or aqueous sulfuric acid at temperatures ranging from 180 – 220°C gave up to 50 mol% of furfural. Activation energies did not differ significantly between reactions in plain water (E _a =119.4 kJ/mol), 0.001M H₂SO₄ (E _a =120.6 kJ/mol), 0.01M H₂SO₄ (E _a =130.8 kJ/mol), and 0.1M H₂SO₄ (E _a =120.7 kJ/mol). However, under alkaline conditions the activation energy was only 63.7 kJ/mol, indicating a different reaction mechanism. Isotachophoretic analyses revealed the formation of pyruvic, formic, glycolic, lactic, and acetic acid. While the relative yields of these acids ranged from 0.8 to 7% under hydrothermal and acidic conditions, 10 – 23% were obtained in alkaline degradation.

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Quantitative Studien zur Bildung von Furfural und organischen Säuren während des hydrothermalen, sauren und alkalischen Abbaues vonD-Xylose

Zusammenfassung Die chromatographische Analyse des Abbaues vonD-Xylose in reinem Wasser und Schwefelsäure bei Temperaturen von 180 – 220°C ergab die Bildung von bis zu 50 mol% Furfural. In bezug auf die Aktivierungsenergie zeigten sich keine signifikanten Unterschiede zwischen dem Abbau vonD-Xylose in reinem Wasser (E _a =119.4 kJ/mol), 0.001M H₂SO₄ (E _a =120.6 kJ/mol), 0.01M H₂SO₄ (E _a =130.8 kJ/mol), and 0.1M H₂SO₄ (E _a =120.7 kJ/mol). Unter alkalischen Bedingungen hingegen betrug die Aktivierungsenergie nur 63.7 kJ/mol. Dies weist auf einen unterschiedlichen Reaktionsmechanismus hin. Ferner konnte mittels Isotachophorese die Bildung von Brenztraubensäure, Ameisensäure, Glycolsäure, Milchsäure und Essigsäure nachgewiesen werden. Während sich die relativen Ausbeuten in Wasser und Schwefelsäure zwischen 0.8 und 7% bewegten, betrugen sie unter alkalischen Bedingungen 10 bis 23%.

     

Solvatochromism in Binary Solvent Mixtures by Means of a Penta‐tert‐butyl Pyridinium N‐Phenolate Betaine Dye

The solvatochromic behavior of a penta‐tert‐butyl prydinium N‐phenolate betaine dye was studied using UV‐visible spectrophotometry in several binary mixture solvents. The solvent polarity parameter, E_T (1) (kcal. mol^?1) was calculated from the position of the longest‐wavelength intramolecular charge transfer absorption band of this penta‐tert‐butyl betaine dye. For binary solvent mixtures, all plots of E_T (1) versus the mole fraction of a more polar component are nonlinear owing to preferential solvation of the probe by one component of the binary solvent mixture. In the computation of E_T (1) it was assumed that the two solvents mixed interact to form a common structure with an E_T (1) value not always intermediate between those of the two solvents mixed. The results obtained are explained by the strong synergism observed for some of the binary mixtures with strong hydrogen bond donors (HBD) solvents such as alcohols.     

累托石/聚丙烯插层纳米复合材料的制备与性能

采用熔融共混法制备了有机改性累托石 (OREC)粘土 均聚聚丙烯 (PP)纳米复合材料 ,以X 射线衍射分析 (XRD)及透射电子显微镜分析 (TEM)观察了复合材料的相貌结构 ,研究了复合材料的力学性能及热性能 .结果表明 ,OREC在添加份数较少时可与均聚聚丙烯熔融插层形成插层型聚丙烯纳米复合材料 ,该复合材料与纯PP相比 ,具有较高的拉伸强度、断裂伸长率及冲击强度 .在有机粘土添加 2 %时 ,复合材料的拉伸强度、断裂伸长率、冲击强度最高 ,与纯PP相比 ,2 %添加量的聚丙烯纳米复合材料拉伸强度提高 6 5 7% ,断裂伸长率提高 2 89 3% ,冲击强度提高 14 1% ,10 %失重率时对应的热分解温度提高 50K .