Group additivity calculation of the standard molal thermodynamic properties of aqueous amino acids, polypeptides and unfolded proteins as a function of temperature, pressure and ionization state

International audienceThermodynamic calculation of the chemical speciation of proteins and the limits of protein metastability affords a quantitative understanding of the biogeochemical constraints on the distribution of proteins within and among different organisms and chemical environments. These calculations depend on accurate determination of the ionization states and standard molal Gibbs free energies of proteins as a function of temperature and pressure, which are not generally available. Hence, to aid predictions of the standard molal thermodynamic properties of ionized proteins as a function of temperature and pressure, calculated values are given below of the standard molal thermodynamic properties at 25°C and 1 bar and the revised Helgeson-Kirkham-Flowers equations of state parameters of the structural groups comprising amino acids, polypeptides and unfolded proteins. Group additivity and correlation algorithms were used to calculate contributions by ionized and neutral sidechain and backbone groups to the standard molal Gibbs free energy (? G°), enthalpy (? H°), entropy (S°), isobaric heat capacity (C°P), volume (V°) and isothermal compressibility (?°T) of multiple reference model compounds. Experimental values of C°P, V° and ?°T at high temperature were taken from the recent literature, which ensures an internally consistent revision of the thermodynamic properties and equations of state parameters of the sidechain and backbone groups of proteins, as well as organic groups. As a result, ? G°, ? H°, S° C°P, V° and ?°T of unfolded proteins in any ionization state can be calculated up to T~-300°C and P~-5000 bars. In addition, the ionization states of unfolded proteins as a function of not only pH, but also temperature and pressure can be calculated by taking account of the degree of ionization of the sidechain and backbone groups present in the sequence. Calculations of this kind represent a first step in the prediction of chemical affinities of many biogeochemical reactions, as well as of the relative stabilities of proteins as a function of temperature, pressure, composition and intra- and extracellular chemical potentials of O2 and H2, NH3, H2PO4 and CO2

Deformabilidad en hormigones con agregados reciclados

Diversos trabajos han demostrado la factibilidad de elaborar hormigones con agregados reciclados, sin embargo sobre algunos aspectos poco explorados aún existen informaciones contrapuestas. Entre ellos se destacan el comportamiento diferido del hormigón (contracción y fluencia) y la capacidad de deformación en tracción (extensibilidad). Estas propiedades afectan directamente el grado de fisuración que puede tener una estructura de hormigón, lo que adquiere una significativa relevancia en la práctica, al considerar su vida en servicio. En este trabajo se presenta un estudio de la deformabilidad de hormigones que contienen 50 o 100 % de agregado grueso obtenido a partir de la trituración de losas de pavimento. Los resultados se comparan con los de otros dos hormigones elaborados con idénticas proporciones de materiales componentes variando el tipo de agregado grueso, piedra partida granítica o piedra partida cuarcítica. Se evaluaron la resistencia a tracción, la extensibilidad en flexión bajo cargas rápidas, y la fluencia en compresión. Bajo cargas de corta duración se encontró una deformabilidad creciente en el hormigón con mayor contenido de agregados reciclados, tanto en flexotracción como en compresión; también se midieron mayores valores de contracción libre y de fluencia. A partir de los resultados surge que es posible estimar la deformabilidad del hormigón con agregados reciclados siguiendo criterios similares a los aplicados en hormigones con agregados naturales; las diferencias de deformabilidad se pueden justificar considerando la menor rigidez del agregado reciclado.Different works have demonstrated the feasibility of elaborating concrete with recycled aggregates, nevertheless there is still opposite information about some aspects that have not been widely studied. The differed behaviour (shrinkage and creep) and the deformation capacity in tension (extensibility) of concrete are among them. These properties have a direct effect over the degree of cracking that can have a concrete structure so, considering its service life, they acquire a significant relevance in practice. This paper presents a study on the deformability of concretes that contain 50 or 100 % of coarse aggregate obtained from crushed pavement slabs. The results are compared with those obtained on other two concretes prepared with the same mixture proportions varying only the type of coarse aggregate, granitic crushed stone or quartzitic crushed stone. The tensile strength, extensibility in flexure under rapid rate of loading and creep in compression were evaluated. It was found that under short term loads the deformability of concrete increases with the content of recycled aggregates, both in flexure and in compression, grater values of free shrinkage and creep were also measured. From the obtained results it appears that the deformability of concrete with recycled aggregates can be estimated following the same criteria applied to concrete with natural aggregate, the differences in deformability can be justified considering the lower stiffness of the recycled aggregate

Sulfur-mediated electron shuttling during bacterial iron reduction

Microbial reduction of ferric iron [Fe(III)] is an important biogeochemical process in anoxic aquifers. Depending on groundwater pH, dissimilatory metal-reducing bacteria can also respire alternative electron acceptors to survive, including elemental sulfur (S0). To understand the interplay of Fe/S cycling under alkaline conditions, we combined thermodynamic geochemical modeling with bioreactor experiments using Shewanella oneidensis MR-1. Under these conditions, S. oneidensis can enzymatically reduce S0 but not goethite (α-FeOOH). The HS– produced subsequently reduces goethite abiotically. Because of the prevalence of alkaline conditions in many aquifers, Fe(III) reduction may thus proceed via S0-mediated electron-shuttling pathways

Molecular-scale substrate anisotropy and crowding drive long-range nematic order of cell monolayers

The ability of cells to reorganize in response to external stimuli is important in areas ranging from morphogenesis to tissue engineering. Elongated cells can co-align due to steric effects, forming states with local order. We show that molecular-scale substrate anisotropy can direct cell organization, resulting in the emergence of nematic order on tissue scales. To quantitatively examine the disorder-order transition, we developed a high-throughput imaging platform to analyze velocity and orientational correlations for several thousand cells over days. The establishment of global, seemingly long-ranged order is facilitated by enhanced cell division along the substrate's nematic axis, and associated extensile stresses that restructure the cells' actomyosin networks. Our work, which connects to a class of systems known as active dry nematics, provides a new understanding of the dynamics of cellular remodeling and organization in weakly interacting cell collectives. This enables data-driven discovery of cell-cell interactions and points to strategies for tissue engineering.Comment: 29 pages, 7 figure

Calculation of the relative metastabilities of proteins using the CHNOSZ software package

<p>Abstract</p> <p>Background</p> <p>Proteins of various compositions are required by organisms inhabiting different environments. The energetic demands for protein formation are a function of the compositions of proteins as well as geochemical variables including temperature, pressure, oxygen fugacity and pH. The purpose of this study was to explore the dependence of metastable equilibrium states of protein systems on changes in the geochemical variables.</p> <p>Results</p> <p>A software package called CHNOSZ implementing the revised Helgeson-Kirkham-Flowers (HKF) equations of state and group additivity for ionized unfolded aqueous proteins was developed. The program can be used to calculate standard molal Gibbs energies and other thermodynamic properties of reactions and to make chemical speciation and predominance diagrams that represent the metastable equilibrium distributions of proteins. The approach takes account of the chemical affinities of reactions in open systems characterized by the chemical potentials of basis species. The thermodynamic database included with the package permits application of the software to mineral and other inorganic systems as well as systems of proteins or other biomolecules.</p> <p>Conclusion</p> <p>Metastable equilibrium activity diagrams were generated for model cell-surface proteins from archaea and bacteria adapted to growth in environments that differ in temperature and chemical conditions. The predicted metastable equilibrium distributions of the proteins can be compared with the optimal growth temperatures of the organisms and with geochemical variables. The results suggest that a thermodynamic assessment of protein metastability may be useful for integrating bio- and geochemical observations.</p

A compact, short-pulse laser for near-field, range-gated imaging

This paper describes a compact laser, which produces high power, wide-angle emission for a near-field, range-gated, imaging system. The optical pulses are produced by a 100 element laser diode array (LDA) which is pulsed with a GaAs, photoconductive semiconductor switch (PCSS). The LDA generates 100 ps long, gain-switched, optical pulses at 904 nm when it is driven with 3 ns, 400 A, electrical pulses from a high gain PCSS. Gain switching is facilitated with this many lasers by using a low impedance circuit to drive an array of lasers, which are connected electrically in series. The total optical energy produced per pulse is 10 microjoules corresponding to a total peak power of 100 kW. The entire laser system, including prime power (a nine volt battery), pulse charging, PCSS, and LDA, is the size of a small, hand-held flashlight. System lifetime, which is presently limited by the high gain PCSS, is an active area of research and development. Present limitations and potential improvements will be discussed. The complete range-gated imaging system is based on complementary technologies: high speed optical gating with intensified charge coupled devices (ICCD) developed at Los Alamos National Laboratory (LANL) and high gain, PCSS-driven LDAs developed at Sandia National Laboratories (SNL). The system is designed for use in highly scattering media such as turbid water or extremely dense fog or smoke. The short optical pulses from the laser and high speed gating of the ICCD are synchronized to eliminate the back-scattered light from outside the depth of the field of view (FOV) which may be as short as a few centimeters. A high speed photodiode can be used to trigger the intensifier gate and set the range-gated FOV precisely on the target. The ICCD and other aspects of the imaging system are discussed in a separate paper

Pre-notification letter type and response rate to a postal survey among women who have recently given birth

Background: Surveys are commonly used in health research to assess patient satisfaction with hospital care. Achieving an adequate response rate, in the face of declining trends over time, threatens the quality and reliability of survey results. This paper reports on a postal satisfaction survey conducted with women who had recently given birth, and explores the effect of two strategies on response rates. Methods: A sample of 2048 Australian women who had recently given birth were invited to participate in a postal survey about their recent experiences with maternity care. The study design included two different strategies intended to increase response rates: a randomised controlled trial testing two types of pre-notification letter (with or without the option of opting out of the survey), and a request for consent to link survey data with existing routinely collected health data (omitting the latter data items from the survey reduced survey length and participant burden). Results: The survey had an overall response rate of 46%. Women receiving the pre-notification letter with the option of opting out of the survey were more likely to actively decline to participate than women receiving the letter without this option, although the overall numbers of women were small (27 versus 12). Letter type was not significantly associated with the return of a completed survey. Among women who completed the survey, 97% gave consent to link their survey data with existing health data. Conclusions: Seeking consent for record linkage was highly acceptable to women who completed the survey, and represents an important strategy to add to the arsenal for designing and implementing effective surveys. In addition to aspects of survey design, future research should explore how to more effectively influence personal constructs that contribute to the decision to participate in surveys.NHMR

Spinal involvement in mucopolysaccharidosis IVA (Morquio-Brailsford or Morquio A syndrome): presentation, diagnosis and management.

Mucopolysaccharidosis IVA (MPS IVA), also known as Morquio-Brailsford or Morquio A syndrome, is a lysosomal storage disorder caused by a deficiency of the enzyme N-acetyl-galactosamine-6-sulphate sulphatase (GALNS). MPS IVA is multisystemic but manifests primarily as a progressive skeletal dysplasia. Spinal involvement is a major cause of morbidity and mortality in MPS IVA. Early diagnosis and timely treatment of problems involving the spine are critical in preventing or arresting neurological deterioration and loss of function. This review details the spinal manifestations of MPS IVA and describes the tools used to diagnose and monitor spinal involvement. The relative utility of radiography, computed tomography (CT) and magnetic resonance imaging (MRI) for the evaluation of cervical spine instability, stenosis, and cord compression is discussed. Surgical interventions, anaesthetic considerations, and the use of neurophysiological monitoring during procedures performed under general anaesthesia are reviewed. Recommendations for regular radiological imaging and neurologic assessments are presented, and the need for a more standardized approach for evaluating and managing spinal involvement in MPS IVA is addressed