Analysis of regioisomers of triacylglycerols of northern currant seed oil by tandem mass spectrometry

Currant oils have special health properties due to their moderate contents of α‐linolenic, γ‐linolenic and stearidonic acids. The distribution of fatty acids (FA) in the triacylglycerols (TAG) may affect the beneficial effects. Seed oils of wild northern red currant (NRC) (Ribes spicatum L.) from Northern Finland and of wild alpine currant (AC) (R. alpinum L.) from the South‐West coast of Finland were investigated. The purified TAG were analysed by tandem mass spectrometry by applying the ammonia negative ion chemical ionisation – collision‐induced dissociation method. Molecular weight fractions rich in C18:3 FA and C18:4 FA were investigated. Of the total oil, the molecular weight species 54:7 (ACN:DB), 54:8 and 54:9 were more abundant in NRC than in AC, being 21.0%, 15.8%, 7.4% and 16.2%, 11.2%, 4.8%, respectively (p <0.05). The species 52:6 was more abundant in AC (3.1%) than in NRC (2.6%) (p <0.05). The preferential order of FA to be in the sn‐2 position in both berries was typically C18:1 > C18:2 > C18:4 > C18:3. No difference was observed between relative locations of C16:0 FA and C18:3 FA in either of the oils. Within the TAG consisting of FA combinations C18:3/C18:3/C18:1 (54:7), C18:1 was more preferentially in the sn‐2 position (p <0.05) in AC (93.2%) than in NRC (74.6%), and in the case of C18:3, the preference was vice versa. Within the molecular weight species 54:9, FA combination C18:4/C18:3/C18:2, linoleic acid preferentially occupied the secondary position (p <0.005) in both berries, and the proportion of the TAG regioisomer pair sn‐C18:3‐C18:4‐C18:2 + sn‐C18:2‐C18:4‐C18:3 was more abundant (30.2%) in NRC than in AC (15.3%). Within the TAG species 52:6, proportions of all the existing combinations, C16:0/C18:3/C18:3, C16:0/C18:4/C18:2 and C16:1/C18:3/C18:2, varied between the two berry species (p <0.005).     

CONTENTS OF CYTOCHROMES IN YEAST

The contents of cytochromes in yeast were determined quantitatively from the absorption spectra, using a solid cell paste of intact yeast. During the industrial production of baker's yeast, the contents of the cytochromes, particularly of cytochrome aa₃ at successive stages, increased gradually with increasing aeration. In semi-aerobically grown baker's yeast, the contents of cytochromes aa₃, b and c were 0·9, 2·9 and 2·9 × 10^?5 moles/litre of fresh yeast (total amount 6·7 × 10^?5 moles/litre), while in vigorously aerated commercial baker's yeast the respective values were 2·3, 4·8 and 5·2 × 10^?5 moles/litre (total amount 12·3 × 10^?5 moles/litre). In brewer's yeasts separated after the brewing process, the contents of cytochromes were markedly lower than in baker's yeast grown with limited aeration, whereas in top-fermenting yeast the total cytochrome content, aa₃ + b + c, was in some samples markedly higher, 7·1 × 10^?5 moles/litre, than in bottom-fermenting brewer's yeast, 2·4 × 10^?5 moles/litre. When brewer's bottom yeast was grown on a laboratory scale under increasing aeration, a maximum appeared in the cytochrome contents when aeration was moderate, and increased aeration inhibited the formation of cytochromes. The cytochrome contents in brewer's bottom yeast may exceed the amounts found in commercial baker's yeast. In addition to aeration, the type of metabolism influences the amounts of cytochromes in yeast.     

Synthesis and rheological properties of an associative star polymer in aqueous solutions

Rheological properties of aqueous solutions and hydrogels formed by an amphiphilic star block copolymer, poly(acrylic acid)-block-polystyrene (PAA₅₄-b-PS₆)₄, were investigated as a function of the polymer concentration (C_p), temperature, and added salt concentration. The water-soluble polymer synthesised by atom transfer radical polymerization (ATRP) was found to form hydrogels at room temperature at polymer concentrations, C_p, over 22 g/L due to the interpolymer hydrophobic association of the PS blocks. Increasing C_p leads to stronger elastic networks at room temperature that show a gel-to-solution transition with increasing temperature. Increase of ionic strength decreases the moduli compared with the pure hydrogel but did not affect the gel-sol transition temperature significantly. Small-angle X-ray experiments showed two distinct scattering correlation peaks for samples above the gelling C_p, which indicates the aggregates formed due to hydrophobic association. Upon heating the intensity of the scattering correlation peaks was found to decrease indicating the loss of the network structure due to thermal motion.     

Development of an automated fracture assessment system for nuclear structures

A program system for fracture assessment of nuclear power plant structures has been developed. The system consists of an easy-to-use program for engineering analysis and an automated finite element (FE) program system for more accurate analysis with solid three-dimensional (3D) models. The VTTSIF (SIF stress intensity factor) program for engineering fracture assessment applies either the weight function method or superposition method in calculating the stress intensity factor, and the fatigue crack growth analysis is based on the Paris equation. The structural geometry cases of the VTTSIF program are organized in an extendable subroutine database. The generation of a 3D FE model of a cracked structure is automated by the ACR program (automatic finite element model generation for part through cracks). The FE analyses are created with generally accepted commercial programs, and the virtual crack extension method (VCE) is used for fracture parameter evaluation by the VTTVIRT postprocessor program (program for J-integral evaluation using virtual crack extension method). The several test cases have demonstrated that the accuracy of the present system is satisfactory for practical applications.     

FREE NUCLEOTIDES IN RESTING AND METABOLIZING BAKER'S YEAST*

The free nucleotides of semi-aerobically and aerobically cultured baker's yeast in different industrial stages have been investigated under different conditions: during growth and at rest, and during respiration and fermentation of different substrates. The amounts of protein and nucleic acids diminish progressively during industrial propagation, while the amount of free nucleotides falls only during the last stage of propagation. In yeasts cultured under different conditions of aeration and nutrient addition, the nucleotide spectra were rather similar, but the proportions of the free nucleotides change considerably when the yeast passes from the resting state to growth or metabolism. On transfer from respiration to fermentation the nucleotide spectrum remained practically unchanged. However, a small addition of ethanol to a respiring yeast suspension caused clear alterations in the spectrum, the most obvious being the reduced amount of nucleotides with energy-rich phosphate bonds.     

Comparison between infrared and Raman spectroscopic analysis of maturing rabbit cortical bone

The molecular composition of the organic and inorganic matrices of bone undergoes alterations during maturation. The aim of this study was to compare Fourier transform infrared (FT-IR) and near-infrared (NIR) Raman microspectroscopy techniques for characterization of the composition of growing and developing bone from young to skeletally mature rabbits. Moreover, the specificity and differences of the techniques for determining bone composition were clarified. The humeri of female New Zealand White rabbits, with age range from young to skeletally mature animals (four age groups, n = 7 per group), were studied. Spectral peak areas, intensities, and ratios related to organic and inorganic matrices of bone were analyzed and compared between the age groups and between FT-IR and Raman microspectroscopic techniques. Specifically, the degree of mineralization, type-B carbonate substitution, crystallinity of hydroxyapatite (HA), mineral content, and collagen maturity were examined. Significant changes during maturation were observed in various compositional parameters with one or both techniques. Overall, the compositional parameters calculated from the Raman spectra correlated with analogous parameters calculated from the IR spectra. Collagen cross-linking (XLR), as determined through peak fitting and directly from the IR spectra, were highly correlated. The mineral/matrix ratio in the Raman spectra was evaluated with multiple different peaks representing the organic matrix. The results showed high correlation with each other. After comparison with the bone mineral density (BMD) values from micro-computed tomography (micro-CT) imaging measurements and crystal size from XRD measurements, it is suggested that Raman microspectroscopy is more sensitive than FT-IR microspectroscopy for the inorganic matrix of the bone. In the literature, similar spectroscopic parameters obtained with FT-IR and NIR Raman microspectroscopic techniques are often compared. According to the present results, however, caution is required when performing this kind of comparison.     

Crack initiation and arrest in a pressurized thermal shock test for a model pressure vessel made of VVER-440 reactor pressure vessel steel

A joint pressure vessel integrity research programme involving three partners is being carried out during 1990–1995. The partners are the Central Research Institute of Structural Materials “Prometey” from Russia, IVO International Ltd (IVO) from Finland, and the Technical Research Centre of Finland (VTT). The main objective of the research programme is to increase the reliability of the VVER-440 reactor pressure vessel safety analysis. This is achieved by providing material property data for the VVER-440 pressure vessel steel, and by producing experimental understanding of the crack behaviour in pressurized thermal shock loading for the validation of different fracture assessment methods. The programme is divided into four parts: pressure vessel tests, material characterization, computational fracture analyses, and evaluation of the analysis methods. The testing programme comprises tests on two model pressure vessels with artificial axial outer surface flaws. The first model vessel had circumferential weld seam at the mid-length of the vessel. A special embrittling heat treatment is applied to the vessels before tests to simulate the fracture toughness at the end-of-life condition of a real reactor pressure vessel. The sixth test on the first model led to crack initiation followed by arrest. After the testing phase, material characterization was performed. Comparison of calculated and experimental data generally led to a good correlation, although the work is being continued to resolve the discrepancies between the measured initiation and arrest properties of the material.     

A workbench for distributed production management systems

An end-user oriented workbench approach in the design of distributed production management systems (DPMS) is presented. We shall also deal with models and design of DPMS. Changes anticipated in design processes, roles and professionality required are discussed. In fact, complete structural rearrangements in the design of production management systems (PMS) are expected towards the end of this decade. The ideas presented are based on an on-going research project at Helsinki University of Technology (the so-called HUTDPMS project).