Acetyl Radical Production by the Methylglyoxal-Peroxynitrite System: A Possible Route for L-Lysine Acetylation

Methylglyoxal is an a-oxoaldehyde putatively produced in excess from triose phosphates, aminoacetone, and acetone in some disorders, particularly in diabetes. Here, we investigate the nucleophilic addition of ONOO(-), known as a potent oxidant and nucleophile, to methylglyoxal, yielding an acetyl radical intermediate and ultimately formate and acetate ions. The rate of ONOO(-) decay in the presence of methylglyoxal [k(2,app) = (1.0 +/- 0.1) x 10(3) M(-1) s(-1); k(2) approximate to 1.0 x 10(5) M(-1) s(-1)] at pH 7.2 and 25 degrees C was found to be faster than that reported with monocarbonyl substrates (k(2) < 10(3) M(-1) diacetyl (k(2) = 1.0 x 10(4) M(-1) s(-1)), or CO(2) (k(2) = 3-6 x 10(4) M(-1) s(-1)). The pH profile of the methylglyoxal peroxynitrite reaction describes an ascendant curve with an inflection around pH 7.2, which roughly coincides with the pK(a) values of both ONOOH and H(2)PO(4)(-) ion. Electron paramagnetic resonance spin trapping experiments with 2-methyl-2-nitrosopropane revealed concentration-dependent formation of an adduct that can be attributed to 2-methyl-2-nitrosopropane-CH(3)CO(center dot) (a(N) = 0.83 mT). Spin trapping with 3,5-dibromo-4-nitrosobenzene sulfonate gave a signal that could be assigned to a methyl radical adduct [a(N) = 1.41 mT; a(H) = 1.35 mT; a(H(m)) = 0.08 mT]. The 2-methyl-2-nitrosopropane-CH(3)CO(center dot) adduct could also be observed by replacement of ONOO(-) with H(2)O(2), although at much lower yields. Acetyl radicals could be also trapped by added L-lysine as indicated by the presence of W-acetyl-L-lysine in the spent reaction mixture. This raises the hypothesis that ONOO(-)/H(2)O(2) in the presence of methylglyoxal is endowed with the potential to acetylate proteins in post-translational processes.

Intralamellar structural modifications related to the proton exchanging in K(4)Nb(6)O(17) layered phase

Basic structural aspects about the layered hexaniobate of K(4)Nb(6)O(17) composition and its proton-exchanged form were investigated mainly by spectroscopic techniques. Raman spectra of hydrous K(4)Nb(6)O(17) and H(2)K(2)Nb(6)O(17)center dot H(2)O show significant modifications in the 950-800 cm(-1) region (Nb-O stretching mode of highly distorted NbO(6) octahedra). The band at 900 cm(-1) shifts to 940 cm(-1) after the replacement of K(+) ion by proton. Raman spectra of the original materials and the related deuterated samples are similar suggesting that no isotopic effect occurs. Major modifications were observed when H(2)K(2)Nb(6)O(17) was dehydrated: the relative intensity of the band at 940 cm(-1) decreases and new bands seems to be present at about 860-890 cm(-1). The H(+) ions should be shielded by the hydration sphere what preclude the interaction with the layers. Removing the water molecules, H(+) ions can establish a strong interaction with oxygen atoms, decreasing the bond order of Nb-O linkage. X-ray absorption near edge structure studies performed at Nb K-edge indicate that the niobium coordination number and oxidation state remain identical after the replacement of potassium by proton. From the refinement of the fine structure, it appears that the Nb-Nb coordination shell is divided into two main contributions of about 0.33 and 0.39 nm, and interestingly the population, i.e., the number of backscattering atoms is inversed between the two hexaniobate materials. 2009 Elsevier Ltd. All rights reserved.

Anticorrosive cerium-based coatings prepared by the sol-gel method

The development of efficient anti-corrosion and environmentally friendly coating systems are needed for the replacement of the highly toxic Cr-based conversion coatings for corrosion protection of aluminum alloys. In this study, we demonstrate that the direct application of ceramic cerium-based sol-gel coatings to AA7075-T6 substrates produces high-performance anti-corrosion layers. Electrochemical experiments and analyses of the microstructure demonstrate that the protective layers are very efficient for the passivation of the alloy surfaces operating as both passive and active barrier for corrosion protection.

Knubbved istället för vanlig ved? : slutrapport från projekt Styckeved för småskalig eldning

Chunkwood is a wood fuel with a fuel particle length between 50 and 150 mm, i.e. with a sizebetween wood chips and conventional firewood. Chunkwood can be produced and handled asrational as wood chips and can dry during storage like conventional firewood. This is known sincelong. In project Smallwood for small scale heating we have investigated if chunkwood can be usedin a small scale as a fuel for heating detached houses in conventional firewood boilers as well asautomatically fed to a boiler in a similar way as wood chips. We have also compared completesystems for small scale production, distribution and heating with chunkwood, wood chips andconventional firewood.Storage of chunkwood produced for testing small scale boilers confirmed that chunkwood can dryduring storage at least as good as conventional firewood. Tests in different boilers for detachedhomes showed that chunkwood can be used in conventional firewood boilers as well as in automaticallyfed wood chips boilers. Chunkwood can be delivered to the customer to the same or lowercost as wood chips and firewood, but need much less handling by the customer than conventionalfirewood. However, if chunkwood is used in a conventional firewood boiler, it needs some handlingby shovel and wheelbarrow. Technical development of handling from the storage to the boiler isneeded. In a somewhat larger scale, e.g. a boiler for apartment blocks or a small district heatingsystem, chunkwood should be very interesting as a replacement of fuel pellets or fuel briquettes. Itwould be interesting with some projects, which in this scale demonstrates the whole system fromthe forest to heat.

Taming Complexity in Australian Income Tax

Taxpayers and tax authorities recognise that complex Australian income tax law is in need of simplification - during the past decade there have been two ineffective attempts at simplification of the tax law - first by redrafting the law in plain English without addressing structural issues - second by the proposed wholesale replacement of the legislation with a new foundation, incorporating most of the causes of the complexity in the current law - with tax law growing in size and complexity, new paths to simplification must be considered.

Crown ethers : applications in inorganic synthesis

The ability of macroheterocyclic compounds to complex with ionic species has led to the synthesis and investigation of many multidentate macroheterocyclic species. The most stable complexes are formed between macrocyclic polyetheral ligands (crown ethers) with alkali or alkaline earth metal iona. There is an excellent correlation of the stability of these complexes with the size of the cation and the site of the cavity in the macrocyclic ligand. Additional factors, such as the basicity of the ligand and the solvating ability of the solvent, also play important roles in the stabilization of the complex. The stability of such complexes has been advantageously used to increase anionic reactivity and has been successfully applied to several organic fluorinations, oxidations, and similar reactions. The use of macrocyclic ligands in inorganic syntheses of otherwise difficult to obtain fluoro compounds has not been reported. O-carborane and m-carborane, C2BlOHl2, are icosahedral cage systems derived from Bl2H122- by replacement of BH with the isoelectronic CH group. These stable molecules exhibit electron-deficient bonding which can best be explained by delocalization of electrons. This delocalization gives rise to stability similar to that found in aromatic hydrocarbons. Crown ether activated potassium fluoride has been successfully employed in the conversion of alkyl, acyl and aryl halides to their respective fluorides. Analogously halide substituted carboranes were prepared, but their fluoro-derivatives were not obtained. The application of crown ethers in the synthesis of transition metal complexes is relatively unexplored. The usual synthesis of fluoro-derivative transition metal complexes involves highly reactive and toxic fluorinating agents such as antimony trifluoride, antimony penta fluoride. bromine trifluoride and hydrogen fluoride, An attempted preparation of the hexafluoroosmate (IV) ion via a crown activated, or naked fluoride~was unsuccessful. Potassium hexafluoroosmate (IV), K208F6. was eventually prepared using bromine trifluoride as a fluorinating and oxidizing agent .

Squeeze pin implementation in a high pressure die casting

This paper discusses the implementation of hydraulically operated squeeze pins to reduce porosity formation in cast aluminium bearing caps. Two complete sets are cast in an eight-cavity die with a 2000t cold chamber high pressure die casting machine. The initial die configuration used a sliding core assembly with stationary pins to core a through hole in a thick section of the front cam caps. This configuration resulted in high post machining scrap rates, primarily due to porosity associated with solidification shrinkage. Replacement of the sliding core assembly with a squeeze pin unit substantially reduced shrinkage porosity in the critical region, with consequent reductions in the scrap rate. The squeeze pins are actuated 1.5s after the piston reaches the high shot changeover position, but can be successfully engaged between I and 3.5 seconds after high shot changeover. Density measurements and visual inspection confirmed the substantial improvement in porosity levels in the critical region of the castings.

Are employees entitled to more?

George Lopez, chair of CPA Australia's insolvency and reconstruction committee reported in Australian CPA (November 2001) on the replacement of the Commonwealth Government Employee Entitlements Support Scheme (EESS) with a new scheme, the General Employee Entitlements Redundancy Scheme (GEERS). Both schemes provide a safety net by which government pays employees their service entitlements and then takes the employees' place in claims against the insolvent employer organisation. Such schemes are fundamentally inequitable as ultimately they require taxpayers and shareholders to foot the bill for the mistakes, excesses, misdemeanours or incompetence of employers. Similar arrangements have been proposed in the past. For instance, the Australian Law Reform Commission's Harmer Report (1988) contained a recommendation that a wage earner (fidelity-type) protection fund be established. In the state of Victoria, local government legislation already exists to ensure that long service leave entitlements are funded.

Reduction in sugar-sweetened beverages is not associated with more water or diet drinks

Objective The Dutch Obesity Intervention in Teenagers (DOiT) is a school-based randomised controlled trial that was effective in decreasing the consumption of sugar-sweetened beverages among adolescents. The present study examined, using mediation analysis, whether this decrease in consumption of sugar-sweetened beverages could be explained by an increase in the consumption of water or diet drinks.

Design Participants completed a questionnaire about their beverage consumption at baseline and at 8 months (immediately post-intervention), 12- and 20-month follow-ups. A series of multi-level linear regression analyses were performed to examine water and diet drink consumption as potential mediators of the intervention effect on the consumption of sugar-sweetened beverages.

Setting Eighteen Dutch secondary schools.

Subjects A total of 747 adolescents (mean age: 12·7 years).

Results In addition to the DoiT intervention effect of a reduction in the consumption of sugar-sweetened beverages at 8 months (−284 ml/d; 95 % CI −420, −148) and 12 months (−260 ml/d; 95 % CI −360, −160), there was also a significant reduction in diet drinks at 8 months (−52 ml/d; 95 % CI −89, −16). There was no significant difference in water consumption at any follow-up. The decrease in sugar-sweetened beverage consumption could not be explained by an increase in water or diet drink consumption at any time point.

Conclusions Interventions aimed at reducing sugar-sweetened beverage consumption may be effective without changing consumption of other beverages. Reducing sugar-sweetened beverages was, however, a main message of the DOiT intervention. It is possible that a concomitant promotion of water may have resulted in a greater increase in water intake and replacement of sugar-sweetened beverages with water.

Biomimetic porous titanium scaffolds for orthopaedic and dental applications

The development of artificial organs and implants for replacement of injured and diseased hard tissues such as bones, teeth and joints is highly desired in orthopedic surgery. Orthopedic prostheses have shown an enormous success in restoring the function and offering high quality of life to millions of individuals each year. Therefore, it is pertinent for an engineer to set out new approaches to restore the normal function of impaired hard tissues.

Over the last few decades, a large number of metals and applied materials have been developed with significant improvement in various properties in a wide range of medical applications. However, the traditional metallic bone implants are dense and often suffer from the problems of adverse reaction, biomechanical mismatch and lack of adequate space for new bone tissue to grow into the implant. Scientific advancements have been made to fabricate porous scaffolds that mimic the architecture and mechanical properties of natural bone. The porous structure provides necessary framework for the bone cells to grow into the pores and integrate with host tissue, known as osteointegration. The appropriate mechanical properties, in particular, the low elastic modulus mimicking that of bone may minimize or eliminate the stress-shielding problem. Another important approach is to develop biocompatible and corrosion resistant metallic materials to diminish or avoid adverse body reaction. Although numerous types of materials can be involved in this fast developing field, some of them are more widely used in medical applications. Amongst them, titanium and some of its alloys provide many advantages such as excellent biocompatibility, high strength-to-weight ratio, lower elastic modulus, and superior corrosion resistance, required for dental and orthopedic implants. Alloying elements, i.e. Zr, Nb, Ta, Sn, Mo and Si, would lead to superior improvement in properties of titanium for biomedical applications.

New processes have recently been developed to synthesize biomimetic porous titanium scaffolds for bone replacement through powder metallurgy. In particular, the space holder sintering method is capable of adjusting the pore shape, the porosity, and the pore size distribution, notably within the range of 200 to 500 m as required for osteoconductive applications. The present chapter provides a review on the characteristics of porous metal scaffolds used as bone replacement as well as fabrication processes of porous titanium (Ti) scaffolds through a space holder sintering method. Finally, surface modification of the resultant porous Ti scaffolds through a biomimetic chemical technique is reviewed, in order to ensure that the surfaces of the scaffolds fulfill the requirements for biomedical applications.

Proline residues within spacer peptide p1 are important for human immunodeficiency virus type 1 infectivity, protein processing, and genomic RNA dimer stability

The full-length human immunodeficiency virus type 1 (HIV-1) mRNA encodes two precursor polyproteins, Gag and GagProPol. An infrequent ribosomal frameshifting event allows these proteins to be synthesized from the same mRNA in a predetermined ratio of 20 Gag proteins for each GagProPol. The RNA frameshift signal consists of a slippery sequence and a hairpin stem-loop whose thermodynamic stability has been shown in in vitro translation systems to be critical to frameshifting efficiency. In this study we examined the frameshift region of HIV-1, investigating the effects of altering stem-loop stability in the context of the complete viral genome and assessing the role of the Gag spacer peptide p1 and the GagProPol transframe (TF) protein that are encoded in this region. By creating a series of frameshift region mutants that systematically altered the stability of the frameshift stem-loop and the protein sequences of the p1 spacer peptide and TF protein, we have demonstrated the importance of stem-loop thermodynamic stability in frameshifting efficiency and viral infectivity. Multiple changes to the amino acid sequence of p1 resulted in altered protein processing, reduced genomic RNA dimer stability, and abolished viral infectivity. The role of the two highly conserved proline residues in p1 (position 7 and 13) was also investigated. Replacement of the two proline residues by leucines resulted in mutants with altered protein processing and reduced genomic RNA dimer stability that were also noninfectious. The unique ability of proline to confer conformational constraints on a peptide suggests that the correct folding of p1 may be important for viral function.

In vivo chromatic aberration in eyes implanted with intraocular lenses

Purpose. To measure in vivo and objectively the monochromatic aberrations at different wavelengths, and the chromatic difference of focus between green and infrared wavelengths in eyes implanted with two models of intraocular lenses (IOL).


Methods. Eighteen eyes participated in this study: nine implanted with Tecnis ZB99 1-Piece acrylic IOL and nine implanted with AcrySof SN60WF IOL. A custom-developed laser ray tracing (LRT) aberrometer was used to measure the optical aberrations, at 532 nm and 785 nm wavelengths. The monochromatic wave aberrations were described using a fifth-order Zernike polynomial expansion. The chromatic difference of focus was estimated as the difference between the equivalent spherical errors corresponding to each wavelength.


Results. Wave aberration measurements were highly reproducible. Except for the defocus term, no significant differences in high order aberrations (HOA) were found between wavelengths. The average chromatic difference of focus was 0.46 ± 0.15 diopters (D) in the Tecnis group, and 0.75 ± 0.12 D in the AcrySof group, and the difference was statistically significant (P < 0.05). Chromatic difference of focus in the AcrySof group was not statistically significantly different from the Longitudinal chromatic aberration (LCA) previously reported in a phakic population (0.78 ± 0.16 D). The impact of LCA on retinal image quality (measured in terms of Strehl ratio) was drastically reduced when considering HOA and astigmatism in comparison with a diffraction-limited eye, yielding the differences in retinal image quality between Tecnis and AcrySof IOLs not significant.


Conclusions. LRT aberrometry at different wavelengths is a reproducible technique to evaluate the chromatic difference of focus objectively in eyes implanted with IOLs. Replacement of the crystalline lens by the IOL did not increase chromatic difference of focus above that of phakic eyes in any of the groups. The AcrySof group showed chromatic difference of focus values very similar to physiological values in young eyes.

Does urbanization have the potential to create an ecological trap for powerful owls (Ninox strenua)?

Landscape transformation associated with urbanization is one of the most damaging and pervasive impacts humans have on natural ecosystems. The response of species to increasing urbanization has become a major focus of research globally. Powerful owls ( Ninox strenua) are a top-order predator the have been shown to reside in urban environments, but increasing urbanization has also been demonstrated to significantly reduce available habitat. In this paper we use species distribution models established for key food and nesting resources of powerful owls across an urban-forest gradient to constrain habitat predictions from a previously developed powerful owl species distribution model. This multi-criteria decision analysis (MCDA) approach allowed us to investigate the impacts of urbanization on potential powerful owl habitat when challenged with food and nesting requirements. As powerful owls only use tree cavities for nesting we propose that the cue for settlement in an area is associated with the presence of habitat and food and as such breeding requirements may be disconnected from settlement requirements.Our results demonstrate that incorporation of a general prey resource (at least one group of arboreal marsupials) as a cue for settlement does not reduce the amount of available habitat for powerful owls substantially. Further constraining the model with a tree cavity resource, however, leads to a substantial reduction in powerful owl habitat in the urban and urban fringe environments. If a diverse prey resource (two or more groups of arboreal marsupials) is used as the cue for settlement, this sees a substantial reduction in available habitat in urban environments. Incorporation of tree cavities into this model does not reduce the available habitat for powerful owls substantially.We propose that powerful owls do not need a diverse prey base for survival, and that breeding resources are unlikely to be a cue for settlement. As such, we argue in this paper that increasing urbanization has the potential to create an ecological trap for powerful owls as there is a significant difference between habitat capable of supporting powerful owls, and habitat in which owls can breed.Management of powerful owls in urban environments will be difficult, but this research highlights the potential for the use of nest boxes to enhance the breeding activities in increasingly urbanized environments. Replacement of this critical resource may be able to reverse any potential ecological trap that is occurring. © 2014 Elsevier Ltd.

Contribuição ao estudo das hepatectomias parciais com oclusão do fluxo sanguíneo aferente

O tratamento cirúrgico dos tumores hepáticos tem sido um grande desafio na história evolutiva da cirurgia. No passado, as altas taxas de morbidade e mortalidade limitavam sua aplicação como opção terapêutica. O refinamento da técnica de ressecção hepática está associado a menores índices de mortalidade e morbidade peri-operatória e, embora, a mortalidade tenha sido reduzida a menos de 10% nos serviços especializados, a morbidade ainda é bastante significativa, sendo que a hemorragia grave e a embolia aérea permanecem como complicações graves das hepatectomias. O controle da perda sanguínea é o objetivo primordial durante este tipo de cirurgia. As técnicas descritas, com a finalidade de conter a hemorragia transoperatória, são aquelas associadas à redução do fluxo sanguíneo ao fígado, seja através da oclusão vascular aferente ou manobra de Pringle por clampeamento do pedículo hepático, seja por exclusão vascular total do órgão. Hepatectomias parciais podem ser realizadas com pequeno sangramento e, mesmo quando associadas a períodos prolongados de isquemia tecidual, não foram identificadas lesões parenquimatosas ou falência hepática persistente. A redução na necessidade de reposição de sangue, no período peri-operatório, está associada a menor morbidade e à diminuição significativa na incidência de sepse abdominal. O objetivo deste estudo foi o de avaliar uma série de hepatectomias parciais com oclusão do fluxo sanguíneo aferente, em pacientes portadores de patologias benignas e neoplasias malignas. Foram analisadas 60 hepatectomias em 59 pacientes com oclusão do fluxo sanguíneo aferente quanto a possíveis fatores de risco para morbidade e mortalidade, bem como a relação entre o tempo de isquemia hepática e a variação das transaminases, tempo de protrombina e bilirrubinas, e destes, com a evolução pós-operatória. A prevalência de complicações pós-operatórias foi de 43,3% e a mortalidade de 6,7%. O fator de risco significativo para mortalidade foi tempo cirúrgico mais prolongado, quando comparado com os pacientes que não foram a óbito. Para a morbidade pós-operatória, foram identificados como fatores de risco a idade acima de 60 anos, cirurgia por neoplasia maligna, parênquima hepático anormal, ou seja, presença de cirrose, esteatose ou colestase, perda sanguínea necessitando reposição de mais de uma unidade de sangue e outros procedimentos cirúrgicos concomitantes. Na análise multivariada por regressão logística, estes fatores de risco foram reduzidos, apenas, para presença de cirrose, esteatose ou colestase. O tempo de isquemia não apresentou relação com a morbi-mortalidade pós-operatória. A variação das transaminases foram mais acentuadas nos casos com maior tempo de isquemia, porém, retornaram aos níveis pré-operatórios em, aproximadamente, uma semana. Não houve variação de tempo de protrombina e bilirrubinas quanto ao tempo de isquemia. A variação de AST e ALT não foram diferentes entre os pacientes com e sem morbidade pós-operatória.

Liquidez e fluxo de caixa: um estudo teórico sobre alguns elementos que atuam no processo de formação do caixa e na determinação do nível de liquidez de empresas privadas não financeiras

O trabalho procura mapear e interpretar o processo de formação de caixa decompondo e analisando as atividades que contribuem para liberar ou retirar recursos do fluxo de caixa. Procura também avançar no problema da determinação do nível ótimo de liquidez que deve ser mantido pelas empresas.