Determination of positional distribution of butyryl groups in milkfat triacylglycerols,triacylglycerol mixtures,and isolated positional isomers of triacylglycerols by gas chromatography and1H nuclear magnetic resonance spectroscopy

Positional isomers (1-butyryl-2X-3Y-rac-glycerol and 2-butyryl-1X-3Y-rac-glycerol;X,Y=long-chain acyls) of saturated triacylglycerols (TAG) with 34 and 40 acyl carbons were shown to separate in two chromatographic peaks on immobilized phenyl(65%) methylsilicone column by gas-liquid chromatography, and on reversed-phase ODS-1 column by high-performance liquid chromatography. The analysis of 500-MHz¹H nuclear magnetic resonance (NMR) spectra showed distinct differences between 2-butyryl-1X-3Y-rac-glycerol and 1-butyryl-2X-3Y-rac-glycerol isomers in the resonance signals of methylene and methine protons of glycerol backbone, and carbon-2 methylene of acyl groups, and methyl protons of butyryl group. The¹H NMR spectra of three interesterified mixtures of three monoacid TAG containing saturated butyrate and caproate TAG and unsaturated butyrate TAG showed that triplets of methyl protons of butyryl groups atsn-1(3)- andsn-2-positions in saturated and unsaturated TAG had similar chemical shifts and that the chemical shift of caproyl methyl protons was different from those of butyryl methyl protons. The positional distribution of butyryl groups in isolated positional isomers of butyrate TAG, interesterified TAG mixtures, and natural and interesterified butteroil can be determined by integration of these signals.     

Supplementation with evening primrose oil in atopic dermatitis: Effect on fatty acids in neutrophils and epidermis

We investigated the effect of oral supplementation with evening primrose oil, containing 72% linoleic acid (18∶2n−6) and 10% γ-linolenic acid (18∶3n−6), on the epidermal and neutrophil phospholipid fatty acid composition in 15 patients with atopic dermatitis (AD). Three different dose levels, 4, 8 and 12 capsules per day containing 0.5 g oil, were given to three groups of patients. The only n−6 fatty acid showing a significant (p<0.05) dose-related increase was dihomo-γ-linolenic acid (20∶3n−6) in neutrophil phospholipids. The highest dose increased dihomo-γ-linolenic acid by 45% in neutrophil phospholipids, by 46% in lesion-free epidermal phosphatidylcholine, and by 15% in lesion-free epidermal phosphatidylethanolamine. In both lesional and lesion-free epidermis, supplementation resulted in a rise in the ratio between n−6 and monounsaturated fatty acids, reaching significance (p<0.05) in lesional epidermis. This study shows that moderate and favorable fatty acid changes can be obtained in the epidermis of AD patients, when given 6 g per day of oil rich in n−6 fatty acids. The abnormal lipid and fatty acid pattern of the atopic epidermis may be involved in the pathogenesis of the disease, and should therefore be the target for future therapeutic approaches with fatty acid supplements.     

Ribosome display of mammalian receptor domains

Many mammalian receptor domains, among them a large number of potential therapeutic target proteins, are highly aggregation-prone upon heterologous expression in bacteria. This severely limits functional studies of such receptor domains and also their engineering towards improved properties. One of these proteins is the Nogoreceptor, which plays a central role in mediating the inhibition of axon growth and functional recovery after injury of the adult mammalian central nervous system. We show here that the ligand binding domain of the Nogoreceptor folds to an active conformation in ternary ribosomal complexes, as formed in ribosome display. In these complexes the receptor is still connected, via a C-terminal tether, to the peptidyl tRNA in the ribosome and the mRNA also stays connected. The ribosome prevents aggregation of the protein, which aggregates as soon as the release from the ribosome is triggered. In contrast, no active receptor was observed in phage display, where aggregation appears to prevent incorporation of the protein into the phage coat. This strategy sets the stage for rapidly studying defined mutations of such aggregation-prone receptors in vitro and to improve their properties by in vitro evolution using the ribosome display technology.     

A new method for measuring the transfer of oxygen in liquids. MeasurementS of oxygen transfer from bubbles in water and in water + 1-butanol

At the base of a column of liquid 20 cm in diameter and well over 1 m in height, oxygen bubbles of constant volume were formed and released with a frequency of approximately one bubble per second. Measurements were carried out on bubbles with volumes ranging from 0·2 to 2 cm³. The mass transfer per bubble was determined by measuring the increase in oxygen concentration of the liquid phase with an oxygen electrode and counting the number of bubbles. The results were reproducible within 3 per cent, and it is probable that still better results are attainable with this method.The measurements were initially performed in distilled water to test the apparatus. Later, water—butanol mixtures were employed in order to determine the influence of butanol on the mass transfer. The results of the latter experiments have been checked with a theory published previously [23, 24]. Theory and results appear to be in satisfactory agreement.     

An enterprise architecture framework for multi-attribute information systems analysis

Enterprise architecture is a model-based IT and business management discipline. Enterprise architecture analysis concerns using enterprise architecture models for analysis of selected properties to provide decision support. This paper presents a framework based on the ArchiMate metamodel for the assessment of four properties, viz., application usage, system availability, service response time and data accuracy. The framework integrates four existing metamodels into one and implements these in a tool for enterprise architecture analysis. The paper presents the overall metamodel and four viewpoints, one for each property. The underlying theory and formalization of the four viewpoints is presented. In addition to the tool implementation, a running example as well as guidelines for usage makes the viewpoints easily applicable.     

Oligomerization of phenyl glycidyl ether in the presence of ZnCl2

Summary In the presence of ZnCl₂ phenyl glycidyl ether reacts to different products owing to the ring-opening reaction of the oxirane and the cleavage of the ether bond. Using HPLC and offline mass spectrometry most of the reaction products could be identified.A reaction scheme and the supposed reaction mechanism were described involving the formation of chlorine — containing oligomers and low molecular weight by — products resulting from the cleavage of the ether bond of the monomer. Conclusions were drawn for original polyfunctional epoxy resin systems.     

Furfural Oxidation with Hydrogen Peroxide Over ZSM-5 Based Micro-Mesoporous Aluminosilicates

Micro-mesoporous aluminosilicates based on ZSM-5 zeolite, obtained by a dual template method, as well as in the presence of a dual-functional template (i.e. a Gemini-type surfactant), were tested in the oxidation of furfural with hydrogen peroxide. Even substantial changes in acidity and porosity of the catalysts result in minor variations of selectivity towards the desired products. Application of the synthesized zeolite-based materials in the oxidation of furfural with hydrogen peroxide leads to formation of 2(5H)-furanone (yield up to 28.5%) and succinic acid (up to 19.5%) as the main C4 reaction products. The kinetic model developed previously to treat the results for oxidation of furfural over sulfated zirconia was able to describe the data also for micro-mesoporous aluminosilicates.

Graphical Abstract

     

Analysis of triacylglycerols by silver-ion high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

Triacylglycerols of the seed oils rich in α- and/or γ-linolenic acid moieties were separated by silver-ion high-performance liquid chromatography (HPLC) followed by on-line atmospheric pressure chemical ionization-mass spectrometric (APCI-MS) detection. Mass spectra of most triacylglycerols exhibited abundant [M + H]⁺ and [M − RCO₂]⁺ ions, which defined the molecular weight and the molecular association of fatty acyl residues of a triacylglycerol, respectively. Silver ions formed weaker complexes with triacylglycerols containing γ-linolenic acid than with those containing α-linolenic acid, i.e., the elution order of molecules wasXYT _γ>XYT _α’,XT _γ T _α>XT _α T _α>, andT _γ T _γ T _γ>T _γ T _γ T _α>T _γ T _α T _α>T _α T _α T _α, whereT _α=α-linolenic acid,T _γ=γ-linolenic acid, andX, Y=fatty acids different from linolenic acid. Furthermore, silver-ion HPLC resulted in partial separation within equally unsaturated triacylglycerols according to differences in the combined number of acyl carbons. Regioisomeric forms of triacylglycerols were not determined from the seed oil samples, although differences were measured with reference compounds in the relative abundances of [M − RCO₂]⁺ ions formed by a loss of a fatty acyl residue from thesn-2 position and thesn-1/3 positions. Silverion HPLC/APCI-MS provided valuable information for structure elucidation of seed oil triacylglycerols: 43 molecular species were identified from cloudberry seed oil, 39 from evening primrose oil, 79 from borage oil, 44 from alpine currant, and 56 from black currant seed oils. The quantitation requires to be studied further, especially in those cases where several molecular weight species of triacylglycerols eluted in a single chromatographic peak.     

Zero-sound attenuation in rotating and stationary3He-A and3He-B

We report on measurements of zero-sound attenuation in rotating and stationary³He-A and³He-B, in magnetic fields up to 350 mT. Strong and highly nonlinear rotation speed dependencies of sound amplitudes have been observed in both phases. The data gives information on vortex types and core sizes, although the analysis is not straightforward. The anomalous attenuation in³He-B at 200 mT near the AB transition, both in the stationary and in the rotating state, is interpreted to arise from the distortion of the energy gap of the B phase. Excess attenuation during the AB phase change was observed. Evidence for soft vortex cores in³He-B is presented. In addition, a critical velocity in the vortex free state, related to a textural transition, and the vortex creation times have been measured in³He-B. Furthermore, a metastable structure, possibly a new vortex state, has been observed in³He-B by rotating the sample through the A B transition.     

Extended bisection method for parameter identification of the transient heat conduction equation for thermo-elastic deformations during drilling

A new interdisciplinary approach is discribed to identifying unknown parameters using an extended version of the known interval bisection method. This developed method is based on the use of finite elements for calibrating the simulation calculation. The resulting thermo-elastic deformations which occur in drilling processes with impaired cooling lubrication are to be used as correction values for tool positioning in the NC control. Based on the strong impact on workpiece temperature of machining, a simulation approach is presented for calculating the temperature fields and their thermo-elastic consequences. In addition, methods are presented to correct these effects. This paper particularly deals with the temperature fields of drilling operations. Special attention is paid to the technique employed for iterative numerical determination of the unknown heat flux η _w and heat transfer coefficient \(\bar {\gamma }\) values. Finally, the data obtained from experiments are compared with those achieved by numerical simulation in order to verify the efficiency of simulation and determination of parameters.