FTIR characterization of heterocycles lumazine and violapterin in solution: effects of solvent on anionic forms

Fourier transform infrared (FTIR) spectra have been obtained from solution samples of the heterocycles uracil, lumazine, and violapterin and reveal interpretable carbonyl stretching frequencies. Spectra of conjugate bases of lumazine and violapterin demonstrate decreases in these carbonyl stretching frequencies upon ionization. Based on isotopic shifts from amide deuterated analogs, semiempirical QCFF/PI calculations were used to assign the vibrational frequencies in the region 1100-1800 cm-1 observed from samples in dimethylsulfoxide (DMSO) and aqueous solutions to specific normal modes. The observed deuterium shifts and the calculations suggest that, in some cases, N-H bending motions are coupled to the C=O stretching motions of the pyrimidine ring. These data suggest that for lumazine anions a change in solvent can significantly change the mixing of the N-H bending and C=O stretching vibrational motions. This implies that vibrational analysis for lumazine species in relatively noninteracting media like nonpolar solvents, mulls or pellets cannot necessarily be transferred to the system when it is dissolved in a polar, hydrogen-bonding solvent such as water. Although other explanations can be offered, our vibrational analysis suggests that the changes in normal mode composition of the predominantly C=O stretching vibrations of lumazine anion on going from dimethylsulfoxide to water solution are consistent with a change in the predominant tautomer of the heterocycle. This change appears to correspond to a shifting of the location of the remaining acidic proton to a different ring nitrogen atom. This interpretation is of interest in view of recent ab initio calculations which suggest that proton shifts may occur during the hydroxylation of lumazine as mediated by the enzyme xanthine oxidase.     

Preparation and characterisation of α-methylstyrene–butadiene latexes for paper coating applications

The purpose of this work is to demonstrate how α-methylstyrene (AMS) can replace styrene in preparing styrene–butadiene (SB) type latexes and to compare the properties of the paper coating of the prepared α-methylstyrene–butadiene emulsion with the commercial styrene–butadiene latex reference sample. A lot of work is nowadays being conducted on different biorefinery concepts replacing fossil oil with biomass based raw materials due to the expected rise of the fossil oil cost. Aromatics can in principle be produced from renewable raw materials, such as lignin, sugars and terpenes for example. The potential methods include thermochemical conversions, catalytic fast pyrolysis, metabolic engineering, catalytic aromatisation and dehydrogenation among others. Terpenes, such as α-limonene and pinene, are possible sources of aromatics, and they can indeed be catalytically converted to p-cymene. Industrial hydrodealkylation and disproportionation processes developed by major petrochemical companies can further convert p-cymene to BTX aromatics or simultaneously dehydrogenate the alkyl chain of p-cymene to styrenic monomers such as α-methylstyrene. Based on the measured paper properties for uncalendered and calendered coated samples, AMS proved to be adequate to replace the oil based styrene in commercial reference SB latexes. Even though the emulsion polymerisation for the α-methylstyrene–butadiene latex was not optimised, almost all tested properties were at least equally good as in the commercial reference sample. α-Methylstyrene containing coating colours had slightly higher viscosity than the other coating colours. Coating colours containing α-methylstyrene seems to have an improved water retention compared to the commercial reference styrene–butadiene latex coating colour and the laboratory prepared styrene–butadiene coating colour. The paper coated with the commercial reference latex containing coating colour was less porous than the other coated papers. Despite of that, both dry and wet surface strength were at least equally good as in the case of the commercial reference latex. The results are promising when thinking of the future development of the bio-based latexes.     

Cellulose/acrylic acid copolymer blends for films and coating applications

Enzymatically treated cellulose was dissolved in a NaOH/ZnO solvent system and mixed together with poly(ethylene‐co‐acrylic acid) (PE‐co‐AA) or poly(acrylamide‐co‐acrylic acid) (PAA‐co‐AA) polymers, in order to improve the properties of dissolved cellulose and to prepare homogeneous cellulose‐based blends for films and coatings. The solution stage properties of the blends were evaluated by rheological methods and the precipitated dry blends were characterized by dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy. Paperboard coating tests done at laboratory scale showed dissolved cellulose/acrylic acid copolymer‐based blends function well as coating materials. All of the tested blends showed a good resistance against grease in the coating trials, having grease resistance from 60 to 69 days despite a very thin (～2 µm) coating layer. In addition, cellulose/PE‐co‐AA coating showed improved water vapor and oxygen barrier properties when compared with neat dissolved cellulose‐coated paperboard. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40286.     

Modulation of the inhibitory substrate properties of oligodendrocytes by platelet-derived growth factor

Although growth cones typically collapse after encountering O1/galactocerebroside (GalC)-positive oligodendrocytes, the majority of growth cones traversed oligodendrocytes, which were raised for 8-10 d in medium containing 10 ng/ml platelet-derived growth factor (PDGF). Oligodendrocytes raised 8-10 d in control medium caused growth cone collapse as they normally do, but failed to elicit this response after being transferred to PDGF-containing medium for an additional 8-10 d. The opposite was observed when PDGF-treated oligodendrocytes were brought to control medium. Growth cones collapsed when contacting these cells. Oligodendrocytes also lost their collapse-inducing activity when raised in medium conditioned by astrocytes, known to produce PDGF. Antibody IN-1 is directed against against neurite growth inhibitors (NI), proteins of 35 and 250 kDa on the surface of O1/GalC-positive oligodendrocytes, which are known to elicit growth cone collapse. IN-1 immunoreactivity was markedly reduced in PDGF-treated oligodendrocytes. However, both PDGF-treated and control oligodendrocytes exhibited myelin-associated glycoprotein, proteolipid protein, and myelin basic protein immunoreactivity. This suggests that PDGF-treatment affects NI expression but does not interfere with the expression of advanced myelin marker proteins. Because NI cause growth cone collapse, the loss of collapse-inducing activity by PDGF-treated oligodendrocytes suggests that PDGF regulates, directly or indirectly, the expression of these proteins.     

The effect of temperature and culture history on the attachment of Metallosphaera hakonensis to mineral sulfides with application to heap bioleaching

Temperatures in excess of 60 °C are required for efficient bioleaching of chalcopyrite. Within heaps, colonisation of the mineral with thermophilic archaea is important in reaching and maintaining these high temperatures. The effect of temperature and culture history on the attachment of Metallosphaera hakonensis, an extreme thermophilic acidophile identified as a key player in heap bioleaching, to sulfide concentrates and low-grade ore was investigated in shake flasks and packed beds. Attachment studies were conducted at 25 °C, 45 °C and 65 °C. The results show a clear relationship between increasing temperature and attachment efficiency for both suspended and packed bed systems. Attachment at 25 °C was low. Increasing the temperature to 45 °C improved attachment efficiency by between 50% and 100% while a further increase to 65 °C improved attachment by an additional 20-50%. Cells cultured on elemental sulfur as energy source prior to contacting showed 1.3 times greater affinity for the mineral concentrate than those cultured on sulphide mineral concentrates or ferrous sulphate. In contrast to previous studies using mesophilic organisms the selective attachment of Metallosphaera to sulfide minerals, relative to gangue, was less pronounced. Attachment efficiency was lower in the packed bed system which more closely mimicked flow through a heap. The cell surface properties surface charge and hydrophobicity as well as metabolic activity were investigated to provide insight into the observed phenomena. The data suggest that retention of thermophiles within the heap could be enhanced by a secondary inoculation following elevation of the temperature above 40 °C by the mesophilic pioneer species.     

Selective disruption by protein kinases of G-protein-mediated Ca2+ channel modulation

1. We studied the effects of phorbol-12-myristate, 13-acetate (PMA) on G-protein-mediated inhibition of Ca2+ channels by several neurotransmitters in rat superior cervical ganglion (SCG) sympathetic neurons, with the use of the whole cell patch clamp. PMA attenuated membrane-delimited inhibition of calcium currents (ICa) by norepinephrine (NE) and somatostatin by more than half, but did not attenuate inhibition by M1 muscarinic receptors, which use a diffusible cytoplasmic messenger. Inhibition of ICa by NE through pertussis-toxin-sensitive and -insensitive G proteins was equally attenuated by PMA. PMA enhanced ICa in about half the neurons (enhancement of 10 +/- 1%, mean +/- SE) and strongly reduced the holding current in 44 of 61 cells. 2. The M-type K+ current (IM) was not suppressed by PMA, and PMA did not attenuate inhibition of IM by muscarinic agonists, which is also via a diffusible cytoplasmic messenger. 3. Attenuation of NE and somatostatin inhibition by PMA was blocked by 1 microM staurosporine, a broad-spectrum protein kinase inhibitor. Tests with three inhibitors selective for distinct isoforms of protein kinase C (PKC) gave mixed results. PMA's actions were unaffected by 1 microM calphostin C, blocked by 500 nM bisindolylmaleimide, and unaffected by the pseudosubstrate inhibitor PKC19-36. 4. Thus we find that two membrane-delimited signaling pathways that inhibit ion channels in rat SCG neurons are strongly attenuated by PMA, but signaling pathway(s) that use a diffusible cytoplasmic messenger are not. We speculate that a nonstandard PKC isoform, perhaps PKC mu, mediates PMA actions.     

Studies on the current 137Cs body burden of children in Belarus--can the dose be further reduced?

After the Chernobyl reactor accident wide areas of Belarus were contaminated with radioactive fallout. The verification and documentation of the long-term development of radiation doses is still going on. A population group of special concern are the children living in contaminated regions. The annual dose limit of 1 mSv is still exceeded in some cases, essentially due to high body burdens of (137)Cs as indicated by screening measurements with portable incorporation monitors. In this situation the evaluation of possible dose reduction measures in addition to the control of food contamination is being investigated. Special attention is given to the therapeutic application of a pectin preparation (Vitapect), for which a dose-lowering effect is presumed by Belarusian scientists. In a placebo-controlled double-blind study, several groups of contaminated children received a pectin compound named Vitapect for a two-week period during their stay in a sanatorium. For comparison the same number of control groups were given a placebo preparation. The (137)Cs body burden of the children was measured at the beginning and the end. The mean relative reduction of the specific activity within the Vitapect groups was found to be approximately 33%, whereas the specific activity of the children who received a placebo decreased only by approximately 14%, due to clean food supply. It is known that pectins chemically bind cations like caesium in the gastrointestinal tract and thereby increase faecal excretion. Theoretical calculations based on this assumption and considering metabolism processes are qualitatively consistent with the experimentally found retention of radiocaesium in the human body after pectin treatment.     

The Iridium‐Catalyzed Synthesis of Symmetrically and Unsymmetrically Alkylated Diamines under Mild Reaction Conditions

An iridium catalyst – stabilized by an anionic P,N ligand – was used for the symmetrical and unsymmetrical monoalkylation of para‐, meta‐, and ortho‐benzenediamines. Benzyl and aliphatic alcohols were used as alkylating reagents. 28 derivatives were synthesized. 14 of them are new compounds. Furthermore, the alkylation of the pharmacological important diamine Dapson^® (dapsone) is described. 14 dapsone derivatives were synthesized among them 9 new compounds.     

A novel control method for dispersed converters providing dynamic frequency response

Active power converters are flexible and highly dynamic. Many power converters, as battery charging devices, use only a small part of their technical capabilities. This paper develops a new control method that combines the primary converter function with grid frequency control. Doing this, the frequency stability can be influenced positively, using the power converters control potential, without penetrating its primary functions under normal power system conditions. In case of severe frequency deviations, priority is given to this grid support functionality, which can significantly improve the security of supply. If the converter’s control algorithm does not take frequency stability aspects into consideration, the impact of thousands of these devices on the grid frequency stability will be negative. Electric and hybrid cars with battery storage and plug-in capabilities are used as an example for power conversion units. The impact of many cars, with the referred control method, on the UCTE (Union for the Co-ordination of Transmission of Electricity) grid frequency can be observed by simulations. Even a small percentage of electric cars can significantly influence the grid frequency after a power plant disconnection fault. No communication between network operator and converter is necessary for the basic grid supporting functions. Dispersed frequency support as suggested by the developed control method could be adopted as a requirement to future grid codes.     

Age standardized incidence rates of oral cancer in South Africa, 1988-1991

While numbers of papers on oral cancer in South Africa have been published, there have been very few studies on standardized morbidity rates. This paper has developed data collected by the National Cancer Registry from the entire country for the four year period 1988-1991 to present frequency, age standardized incidence rates (ASIRs) and life-time risk (LR) for histologically-diagnosed intra-oral cancers in female and male Asian, black, coloured and white South Africans. During this period 5396 cases of oral cancer were diagnosed in a total number of 157,307 cancer cases (3.4 per cent) excluding squamous cell carcinoma (SCC) and basal cell carcinoma (BSC) of the skin. Intra-oral cancer in all South African females and males accounted, respectively, for 1.8 per cent and 5.0 per cent of all cancers. There was a male preponderance in black, coloured and white groups but females were affected more frequently than men among Asians. The incidence in Asian women (6.66) was higher than those of the women in any of the other population groups, whereas the lowest incidence was found in black women (1.75). The incidence rate in coloured men was particularly high (13.13) whereas the incidence in white males (8.06) was not substantially lower than among black males (9.05). Differences between the eight groups were not significant (X2 = 6.24, df = 3, p > 0.1). The Cumulative Life Time Risk (LR) of developing intra-oral cancer for males and females in the four population groups ranged from 1:65 in coloured males to 1:455 for black females. Gender differences in LR in both black and coloured groups, signals substantial differences in exposure to known carcinogens for this disease. It is disturbing to note that the incidence in the period 1988-1991 was higher in Indian women that it was in 1964-1966, and that educative preventive measures have failed. Similarly, the incidence of intra-oral cancer in coloured men of 13.13 is substantially higher than the figure of 8.8 reported in 1979. If this is an accurately reflected trend, then a major educative programme needs to be pursued in this direction if the relative risk of one in 65 is to be reduced.