Safety and structural analysis of polymers produced in manufacturing process of alpha-lipoic acid

Alpha-Lipoic acid has recently been permitted for use in foodstuffs and is contained in tablets and capsules. Although alpha-lipoic acid is synthesized from adipic acid, the safety of polymers produced during the purification and drying processes has been an issue of concern. Hence, we examined the safety profiles of thermally denatured polymer (LAP-A) and ethanol-denatured polymer (LAP-B) produced in the manufacturing process of alpha-lipoic acid. Furthermore, we conducted structural analysis of these polymers by 1H-NMR and FAB-MS spectroscopy. In a consecutive ingestion test, male and female mice ingested diet containing 0.1 and 0.2% LAP-A and -B for 4 weeks. Blood uric acid, potassium and lactate dehydrogenase (LDH) tended to increase without dose-dependency. Relative liver weights were also increased. However, male dogs that were orally administered LAP-B (500 mg/kg) once did not show any abnormalities in blood parameters or general condition. These findings indicate that alpha-lipoic acid polymers are not acutely toxic; however, chronic ingestion of these polymers may affect liver and kidney functions.     

Dietary intake of dioxins in Japan in 2016 with time trends since 1998

Total diet samples collected from seven regions throughout Japan in 2016 were analysed for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls (DL-PCBs), known collectively as dioxins. This led to estimates of the latest dietary intake of these contaminants for the general Japanese population (≥1 year old). The average daily intake of dioxins for a person weighing 50 kg, calculated at non-detected congener concentrations assumed to be equal to zero, was estimated to be 0.54 pg TEQ (toxic equivalents) kg^?1 body weight (bw) day^?1. This value is well below the tolerable daily intake of 4 pg TEQ kg^?1 bw day^?1 for dioxins in Japan. The average intake was highest from fish and shellfish, followed by meat and eggs. The TEQ contribution of the fish and shellfish group to the total dietary TEQs was significant (89%). The DL-PCBs accounted for about 67% of the dioxin intake. The latest dioxin intake level was compared with previous estimates from total diet study results obtained annually since 1998 to determine the time trends in the dietary intake of dioxins in Japan. Overall, the average dioxin intake appeared to be decreasing gradually during the period of study. The previous average intakes of dioxins ranged from 0.58 to 1.9 pg TEQ kg^?1 bw day^?1. The latest average intake was the lowest since 1998 and was about one-third of the average intake in 1998. This decreasing trend in the dietary intake of dioxins was mainly influenced by the decreased dioxin intakes from two food groups, fish and shellfish, and meat and eggs.     

Self-equilibrium configurations of composite strands

We consider the problem of determining the equilibrium of composite strands consisting of a single core yarn surrounded by n-helical side yarns with pre-twists in the absence of any external load: the self-equilibrium configuration (SEC). We formulate the self-equilibrium problem on the basis of the Kirchhoff rod model in which the contact between yarns in three-dimensional space is taken into account in order to include large helical angles and geometrical constraints. We numerically determine the SECs and elucidate the effect of the following factors on them: the pre-twist of each yarn, the ratio of Young’s modulus of the core yarn to that of the side yarn, and the number of side yarns. The present results allow us to characterize the initial unloaded state of composite strands.     

Relationships between base-catalyzed hydrolysis rates or glutathione reactivity for acrylates and methacrylates and their NMR spectra or heat of formation

The NMR chemical shift, i.e., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs) between the base-catalyzed hydrolysis rate constants (k1) or the rate constant with glutathione (GSH) (log k(GSH)) for acrylates and methacrylates and the (13)C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δC(α) and δC(β)) or heat of formation (Hf) calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between k1 and δC(β), but not δC(α), was obtained for methacrylates (r(2) = 0.93), but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r(2) = 0.89). By contrast, log k(GSH) for acrylates and methacrylates was linearly related to their δC(β) (r(2) = 0.99), but not to Hf. These findings indicate that the (13)C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.     

Damage of yeast cells induced by pulsed light irradiation

DNA damage, such as formation of single strand breaks and pyrimidine dimers was induced in yeast cells after irradiation by pulsed light, which were essentially the same as observed with continuous ultraviolet (UV) light. The UV-induced DNA damage is slightly higher than seen with pulsed light. However, increased concentration of eluted protein and structural change in the irradiated yeast cells were observed only in the case of pulsed light. A difference in the inactivation effect between pulsed light and UV light was found and this suggested cell membrane damage induced by pulsed light irradiation. It is proposed that pulsed light can be used as an effective sterilizing method for the yeast Saccharomyces cerevisiae.     

Efficient electrochemical decomposition of perfluorocarboxylic acids by the use of a boron-doped diamond electrode

The electrochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) was achieved by the use of a boron-doped diamond (BDD) electrode. The PFOA decomposition follows pseudo-first-order kinetics, with an observed rate constant (k₁) of 2.4 × 10^− 2 dm³ h^− 1. Under the present reaction conditions, k₁ increased with increasing current density and saturated at values over 0.60 mA cm^− 2. Therefore, the rate-limiting step for the electrochemical decomposition of PFOA was the direct electrochemical oxidation at lower current densities. In the proposed decomposition pathway, direct electrochemical oxidation cleaves the C-C bond between the C₇F₁₅ and COOH in PFOA and generates a C₇F₁₅ radical and CO₂. The C₇F₁₅ radical forms the thermally unstable alcohol C₇F₁₅OH, which undergoes F⁻ elimination to form C₆F₁₃COF. This acid fluoride undergoes hydrolysis to yield another F⁻ and the perfluorocarboxylic acid with one less CF₂ unit, C₆F₁₃COOH. By repeating these processes, finally, PFOA was able to be totally mineralized to CO₂ and F⁻. Moreover, whereas the BDD surface was easily fluorinated by the electrochemical reaction with the PFOA solution, medium pressure ultraviolet (MPUV) lamp irradiation in water was able to easily remove fluorine from the fluorinated BDD surface.     

Fabrication and characterization of poly‐γ‐glutamic acid nanofiber

Poly‐γ‐glutamic acid (γ‐PGA) is a natural polymer that is widely recognized as a component in the viscous filaments of fermented soybean (natto). γ‐PGA is known for its superior biodegradability, biocompatibility and water retention characteristics. Crosslinked γ‐PGA is commonly used as a hydrogel, but it is not used in the fiber form because it is soluble in water. In this study, we demonstrate the use of γ‐PGA‐Na for production of water insoluble γ‐PGA nanofibers by electrospinning. This result was accomplished using an aqueous solvent containing 10 wt % of an oxazoline component polymer as the crosslinking agent and by heat treatment. The crosslinking reaction was evaluated by solid‐state NMR. The nanofiber webs showed a high level of moisture absorption capability while retaining their fibrous shape. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Colored Fluorescent Silk Made by Transgenic Silkworms

Silk is a protein fiber used to weave fabrics and as a biomaterial in medical applications. Recently, genetically modified silks have been produced from transgenic silkworms. In the present study, transgenic silkworms for the mass production of three colors of fluorescent silks, (green, red, and orange) are generated using a vector originating from the fibroin H chain gene and a classical breeding method. The suitability of the recombinant silks for making fabrics is investigated by harvesting large amounts of the cocoons, obtained from rearing over 20 thousand silkworms. The application of low temperature and a weakly alkaline solution for cooking and reeling enables the production of silk fiber without loss of color. The maximum strain tolerated and Young's modulus of the fluorescent silks are similar to those of ordinary silk, although the maximum stress value of the recombinant silk is slightly lower than that of the control. Fabrics with fluorescent color are demonstrated using the recombinant silk, with the color persisting for over two years. The results indicate that large amounts of genetically modified silk can be made by transgenic silkworms, and the silk is applicable as functional silk fiber for making fabrics and for use in medical applications.     

Plasma CVD of (BaSr)TiO3 Dielectrics for Gigabit DRAM Capacitors

Electron cyclotron resonance (ECR) plasma chemical vapor deposition (CVD) of (BaSr)TiO₃ dielectrics is reviewed. The oxygen plasma lowered the crystallization temperature and carbon contamination. (BaSr)TiO₃ CVD process was developed under conditions of relatively low deposition rate of 1.1 nm/min and a relatively low deposition temperature of 550°C. Utilizing this process, we developed a gigabit dynamic random access memory (DRAM) capacitor technology involving the preparation of a thin (BaSr)TiO₃ capacitor dielectric over a RuO₂/Ru storage node contacting a TiN/TiSi _X /poly-Si plug. The ECR plasma CVD enabled uniform deposition of gigabit-DRAM-quality (BaSr)TiO₃ films on the electrode sidewalls. The storage node contact improved in endurance against oxidation, by fabricating the buried-in TiN/TiSi _X plug (TiN-capped plug) under the RuO₂/Ru storage node. (BaSr)TiO₃ films with a small equivalent SiO₂ thickness of 0.38 nm and a leakage current density of 8.5×10^–7 A/cm² at an applied voltage of 1.0 V, were obtained without any further annealing process. An equivalent SiO₂ thickness of 0.40 nm on the RuO₂ sidewall was also achieved. It is concluded that this technology has reached the requirements for gigabit DRAM capacitors.     

Starch Gelation Process Observed by FT-IR/ATR Spectrometry with Multivariate Data Analysis

For directly observing changes related to the gelation process of starch, IR spectra of starch in water while heating were obtained using FT-IR/ATR spectrometry. Relationships between gelation and spectral changes were examined using factor analysis, evolving factor analysis (EFA) and three-way principal component analysis (PCA). Absorption at 3300 and 1610 cm^-1 decreased with temperature but absorption at 1000 cm^-1 increased. The factor score plot patterns of amylose, amylopectin and rice starches were similar but those of potato and corn starches were unique. EFA indicated variances relating to changes caused in starch and water as different factors. Loadings of the starch component 2 in three-way PCA correlated with starch granule sizes.