Physico-chemical aspects of polyethylene processing in an open mixer. Part 21: Improved product yields on true bimolecular hydroperoxide decomposition

The product yields from the reaction between two hydroperoxide groups have been re-calculated. This is a consequence of the fact that β-scission of secondary alkoxy radicals cannot be neglected in the high temperature range of the polyethylene processing experiments (170-200 °C). It must be taken into account in addition to disproportionation/combination and hydrogen abstraction by alkoxy radicals. The increased complexity caused by the additional reaction results mainly from the larger number of caged radical pairs involved in the reactions and also in the calculations. Among other products it becomes possible to calculate the yields of aldehyde and vinyl groups that would not result from hydroperoxide decomposition in the absence of β-scission. The yields of the main oxidation products such as alcohols, ketones and trans-vinylene groups are reduced to some extent in comparison with the values calculated if β-scission is neglected. The vinyl group yield corresponds to slightly more than 10% of the yield of trans-vinylene groups in the temperature range of the experiments. The aldehyde yield is significantly larger than the vinyl group yield and is important in the whole temperature range examined. Main-chain scissions are important at the temperatures of the experiments. They become more important than the sum of the different combination reactions from a temperature of 200 °C on.     

Synthesis and properties of allenic natural products and pharmaceuticals

Nowadays, about 150 natural products comprising an allenic or cumulenic structure are known. The chemistry of these compounds has turned out to be a very attractive and prolific area of interest: advances in the isolation and characterization of new allenic natural products have led to the establishment of efficient synthetic procedures which in many cases also open up an access to enantiomerically pure target molecules. Inspired by the intriguing biological activities of many allenic natural products, allene moieties are now systematically introduced in pharmacologically active classes of compounds (steroids, prostaglandins, amino acids, nucleosides). The functionalized allenes thus obtained often exhibit impressive activities as mechanism-based enzyme inhibitors, cytotoxic, or antiviral agents. A prerequisite for further developments in this field is the efficient stereoselective synthesis of allene derivatives.     

Synthesis of phthalide derivatives using nickel-catalyzed cyclization of o-haloesters with aldehydes

The reaction of o-bromobenzoate (1 b) with benzaldehyde (2 a) in the presence of [NiBr(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) and zinc powder in THF (24 hours, reflux temperature), afforded 3-phenyl-3H-isobenzofuran-1-one (3 a) in an 86 % yield. Similarly, o-iodobenzoate reacts with 2 a to give 3 a, but in a lower yield (50 %). A series of substituted aromatic and aliphatic aldehydes (2 b, 4-MeC(6)H(4)CHO; 2 c, 4-MeOC(6)H(4)CHO; 2 d, 3-MeOC(6)H(4)CHO; 2 e, 2-MeOC(6)H(4)CHO; 2 f, 4-CNC(6)H(4)CHO; 2 g, 4-(Me)(3)CC(6)H(4)CHO; 2 h, 4-C(6)H(5)C(6)H(4)CHO; 2 i, 4-ClC(6)H(4)CHO; 2 j, 4-CF(3)C(6)H(4)CHO; 2 k, CH(3)(CH(2))(5)CHO; 2 l, CH(3)(CH(2))(2)CHO) also underwent cyclization with o-bromobenzoate (1 b) producing the corresponding phthalide derivatives in moderate to excellent yields and with high chemoselectivity. Like 1 b, methyl 2-bromo-4,5-dimethoxybenzoate (1 c) reacts with tolualdehyde (2 b) to give the corresponding substituted phthalide 3 m in a 71 % yield. The methodology can be further applied to the synthesis of six-membered lactones. The reaction of methyl 2-(2-bromophenyl)acetate (1 d) with benzaldehyde under similar reaction conditions afforded six-membered lactone 3 o in a 68 % yield. A possible catalytic mechanism for this cyclization is also proposed.     

Supercritical fluid chromatography of petroleum products using flameless sulfur chemiluminescence detection

Supercritical fluid chromatography using flameless sulfur chemiluminescence detection has been investigated for the analysis of sulfur compounds in petroleum products. The chromatography and detection system was easy to implement and exhibited good precision, linearity, selectivity, and sensitivity. A minimum detectable limit of 0.3 pg sulfur/s was obtained, and response to sulfur in different sulfur species was nearly equimolar.     

The significance of complex polysaccharides in personal care formulations

Complex polysaccharides have numerous pharmacological activities, such as antioxidant, antibacterial, antiviral, immunomodulating, anticoagulant and anticancer effects. In personal care products, these biopolymers are used as thickener and stabilizing agents or as moisturizing ingredients that could be beneficial to the skin. Various polysaccharides, such as glycosaminoglycans (GAGs), hyaluronic acid (HA), carrageenan, fucose, fucoidan, chitin, chitosan, etc., have applications in cosmeceutical industries. GAGs and HA incorporated in moisturizing creams strengthen the skin barrier by forming a protective layer which prevents transdermal water loss. Therefore, these polysaccharides have been formulated into potential cosmeceuticals and biopharmaceuticals.     

INTROMISSION OF WATER-REPELLENT AND HYDROSCOPIC PROPERTIES SIMULTANEOUSLY TO PP BY PLASMA DISCHARGE METHOD

Plasma-induced surface graft copolymerization of acrylic acid on polypropylene non-woven fabric (PP-g-AA) and polypropylene membrane were reported. The extents of grafting were controlled by the plasma and polymerization condition. Hexadecyltrimethyl ammonium bromide was then coupled with the carboxyl group of PP-g-AA to obtain a polyion complex (PIC). At last, CF4 plasma was used to give PICs hydrophobic property. The moisture regain and water-repellency of the processed PICs was investigated. The surfaces were characterized using ATR FT-IR and XPS. The result indicates that the products have very high ability to adsorb moisture, even better than cotton fiber. At the same time, the products show excellent hydrophobic property, which can‘t be wetted by those reagents whose surface tensions were higher than 327mN/m.     

Donator-Acceptor Komplex Chromatographie Tetrachlorphthalimidopropylsilica,eine neue,chemisch gebundene Phase,geeignet zur Trennung von Kohleverflüssigungsprodukten und anderen technischen aromatischen Gemischen mit der Hochleistungsflüssigkeitschromatographie

Summary The preparation of a new tetrachlorophthalimidophase for HPLC is described. The capacity ratios (k) of about forty aromatics and twenty nitrogen-containing aromatics were determined. Most of the compounds used were alkylated. It was shown that the aromatics were eluted according to the number of rings, only slightly influenced by the substituents. A similar elution order was not observed with the heteroaromatics. The performance of the stationary phase is demonstrated, performing separations of coal liquids and other aromatic mixtures.

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Donator-Acceptor Komplex Chromatographie Tetrachlorphthalimidopropylsilica, eine neue, chemisch gebundene Phase, geeignet zur Trennung von Kohleverflüssigungsprodukten und anderen technischen aromatischen Gemischen mit der Hochleistungsflüssigkeitschromatographie

Zusammenfassung Es wird die Synthese einer neuen Tetrachlorphthalimid-Phase für die HPLC beschrieben. Anhand von Elutionsversuchen mit über vierzig Aromaten und zwanzig N-Heteroaromaten, die größtenteils alkyliert waren, konnte gezeigt werden, daß kondensierte Aromaten unabhängig vom Alkylierungsgrad streng nach der Zahl der aromatischen Ringe eluiert werden, was für die Heterocyclen nicht zutrifft. Die Kapazitätsverhältnisse (k) der untersuchten Verbindungen werden angegeben. Die Leistungsfähigkeit der Phase wird an der chromatographischen Trennung von Kohleverflüssigungsprodukten und anderen komplexen, aromatischen Gemischen demonstriert.

     

In situ neutron powder diffraction investigation of the hydration of tricalcium aluminate in the presence of gypsum

The hydration of a 1:3 molar ratio of tricalcium aluminate, Ca₃Al₂O₆, to gypsum, CaSO₄·2D₂O, was investigated at temperatures of 25, 50, and 80 °C using time-of-flight powder neutron diffraction combined with multiphase Rietveld structural refinement. It was shown that ettringite, Ca₆[Al(OD)₆]₂(SO₄)₃·∼26D₂O, was the first and only hydration product of the system, in contrast to a prior investigation which suggested the occurrence of a precursor phase prior to the formation of ettringite. Kinetics data showed that the hydration reaction is very sensitive to temperature: hydration at 25 °C was characterized by a single kinetic regime while hydration at higher temperatures consisted of two distinct kinetic regimes. The presence of two kinetic regimes was attributed to a change in either the dimensionality of the growth process or a change in the rate controlling mechanism in the hydration reaction.     

Identification of irradiated foods by monitoring radiolytically produced hydrocarbons

Many countries allow the treatment of foods with low doses of ionizing radiation to reduce microbial and insect infestations, inhibit maturation, and extend shelf life. Therefore, a reliable method is needed to identify irradiated foods and to determine their compliance with respect to allowable absorbed radiation dose. Several approaches for the identification of irradiated foods have been developed such as measurement of radiolytic products, chemiluminescence, and thermoluminescence, and the use of electron spin resonance spectroscopy to measure free radicals trapped in bone. A method for the determination of radiolytically produced hydrocarbons was developed in our laboratory to evaluate the utility of monitoring these compounds as indicators of food irradiation. The method involves the extraction of the radiolytic hydrocarbons from foods and their quantitation by gas chromatography. Concentrations of the radiolytically produced hydrocarbons increased linearly with radiation doses ranging from 0 to 6 kGy. The limit of detection appears to be approximately 1 kGy. The method was found to be useful for the identification of gamma-irradiated foods such as shrimp, frog legs, pork, beef, and poultry. Results of the method evaluation studies of these food matrices as well as factors affecting hydrocarbon production and determination will be presented.     

Flammability studies of 3-methyl pyridine/water system

In industrial processes, information on the safety property of chemicals is essentially crucial for safe handling during unit operations. Ensuring the safe use of combustible or flammable substances in processes is unlikely without detailed investigations of their flammability characteristics and related hazards. We studied 3-methyl pyridine (3-picoline), e.g., flammability limits (LFL/UFL), maximum explosion pressure (P _max), maximum explosion pressure rise (dP/dt)_max, minimum oxygen concentration (MOC), vapor deflagration index (K _g), and characterized the influence of inert steam (H₂O) on critical parameters for 3-picoline/water mixtures at 270°C, 1 atm, various oxygen concentrations, and vapor mixing ratios (100/0, 30/70, 10/90 and 5/95 vol.%) with a 20-L-Apparatus in simulated conditions, respectively. The results showed that the flammability characteristics of 3-picoline_(aq) all increased with the oxygen concentration. However, as the composition of inert steam increased, the flammability parameters and the degree of fire and explosion hazards were significantly reduced, instead. This study elucidated the flammability properties of 3-picoline mixed with inert steam. The conclusions could be applied to proactively prevent the relevant processes from incurring fire and explosion accidents.