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

Profit-oriented disassembly-line balancing

As product and material recovery has gained importance, disassembly volumes have increased, justifying construction of disassembly lines similar to assembly lines. Recent research on disassembly lines has focused on complete disassembly. Unlike assembly, the current industry practice involves partial disassembly with profit-maximization or cost-minimization objectives. Another difference between assembly and disassembly is that disassembly involves additional precedence relations among tasks due to processing alternatives or physical restrictions. In this study, we define and solve the profit-oriented partial disassembly-line balancing problem. We first characterize different types of precedence relations in disassembly and propose a new representation scheme that encompasses all these types. We then develop the first mixed integer programming formulation for the partial disassembly-line balancing problem, which simultaneously determines (1) the parts whose demand is to be fulfilled to generate revenue, (2) the tasks that will release the selected parts under task and station costs, (3) the number of stations that will be opened, (4) the cycle time, and (5) the balance of the disassembly line, i.e. the feasible assignment of selected tasks to stations such that various types of precedence relations are satisfied. We propose a lower and upper-bounding scheme based on linear programming relaxation of the formulation. Computational results show that our approach provides near optimal solutions for small problems and is capable of solving larger problems with up to 320 disassembly tasks in reasonable time

Bowl Shaped Cavitands Dimerize and Complex Certain Organic Guests in Organic Solvents which Themselves are Poor Guests

The syntheses and binding properties of rigidly bowl-shaped polycyclic cavitands (1—4) are reported. Attached to the four aryl rim positions of the bowls are four benzenes substituted in their para positions with four CC^Me, Br, OH or NO2 groups, which deepen the bowls. Attached to the base of the bowls are four pentyl feet, which increase the solubilities of these hosts in organic solvents. Of the four hosts, only the one containing the CO2Me groups dimerized both in the crystalline state and in solution in ten deute- rated solvents which themselves are poor guests. In three other deuterated solvents, no dimerization was observed. A crystal structure of the dimer showed that one p-MeC^CCs^ group of each monomer occupied the cavity of its complexing partner in a reciprocating double host-guest arrangement. Such a structure is compatible with the ^H-NMR spectra of the dimer in solution. The dimer was also detected in its FAB-MS. The tetrabromocavitand at low concentrations in CD2CI2 complexed MeCC^C^Me, MeCC^Me, PhCC^Me and MeCOC^CC^Me. Tetranitrocavitand 4 also complexed MeC02CH2Me in CD2CI2 as solvent

Benefit finding in renal transplantation and its association with psychological and clinical correlates:A prospective study

OBJECTIVES: The identification of positive psychological changes, including benefit finding (BF), in chronic illness has gained substantial interest. However, less is known about BF in the context of a positive medical intervention. End-stage renal disease (ESRD) can be regarded as a burdensome condition, but transplantation is expected to restore physical and psychological functioning to a large extent after a period of illness. The aim of this study was to examine (1) changes in BF from pre- to 12 months post-transplantation, (2) the concurrent association of disease-related characteristics and optimism to BF, and (3) the potential causal relations between BF and distress. METHODS: In this longitudinal study, 319 patients completed questionnaires before, 3 months, 6 months, and/or 12 months post-transplantation. Multilevel models were used for the analyses. Measures included the Illness Cognitions Questionnaire to measure BF, the Life Orientation Test to measure optimism, and the General Health Questionnaire to measure distress. RESULTS: Benefit finding increased from pre- to post-transplantation. Fewer symptoms and comorbidities, and more optimism, were related to more BF over all time-points. The direction of the relation between BF and distress changed over time. Before transplantation, distress predicted an increase in BF, whereas post-transplantation, distress predicted a decrease in BF. The causal relation between BF and distress post-transplantation appeared to be reciprocal. CONCLUSIONS: A positive medical intervention such as renal transplantation might facilitate the development of BF. This study indicates the need for longitudinal research on the relation between BF and psychological health in the face of positive events. Statement of contribution What is already known on this subject? Benefit finding refers to the identification of positive psychological changes following a negative life event. Individuals can experience benefit finding following chronic illness. The positive event of kidney transplantation is associated with improvements in patients' physical and psychological functioning. What does this study add? Benefit finding increases from pre- to post-kidney transplantation. Fewer symptoms and comorbidities, and higher optimism are related to more benefit finding. Before transplantation, distress predicts an increase in benefit finding. After transplantation, there appears to be a reciprocal relation between distress and benefit finding such that distress predicts a decrease in benefit finding and benefit finding predicts a decrease in distress

Engineered Ovalbumin Nanoparticles for Cancer Immunotherapy

Ovalbumin (OVA) is a protein antigen that is widely used for eliciting cellular and humoral immune responses in cancer immunotherapy. As an alternative to solute OVA, engineering approach is developed herein towards protein nanoparticles (pNPs) based on reactive electrospraying. The resulting pNPs are comprised of polymerized OVA, where individual OVA molecules are chemically linked via poly(ethylene glycol) (PEG) units. Controlling the PEG/OVA ratio allows for fine‐tuning of critical physical properties, such as particle size, elasticity, and, at the molecular level, mesh size. As the PEG/OVA ratio decreased, OVA pNPs are more effectively processed by dendritic cells, resulting in higher OT‐I CD8+ cells proliferation in vitro. Moreover, pNPs with lower PEG/OVA ratios elicit enhanced lymphatic drainage in vivo and increased uptake by lymph node macrophages, dendritic cells, and B cells, while 500 nm OVA pNPs show poor draining lymph nodes delivery. In addition, pNPs with lower PEG/OVA ratios result in higher anti‐OVA antibody titers in vivo, suggesting improved humoral immune responses. Importantly, OVA pNPs result in significantly increased median survival relative to solute OVA antigen in a mouse model of B16F10‐OVA melanoma. This work demonstrates that precisely engineered OVA pNPs can improve the overall anti‐tumor response compared to solute antigen.As an alternative to solute antigens for cancer immunotherapy, protein nanoparticles (pNPs) comprised of polymerized antigen linked by poly(ethylene glycol) units are developed based on reactive electrospraying. This engineering approach allows fine tuning the physico‐chemical properties of pNPs such as particle size, elasticity, and mesh size. These properties are related to pNPs enhanced antigen‐specific immune responses and improved anti‐tumor efficacy.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/163384/3/adtp202000100-sup-0001-SuppMat.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/163384/2/adtp202000100.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/163384/1/adtp202000100_am.pd

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

Perceptions of oral health adequacy and access in Michigan nursing facilities

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/72951/1/j.1741-2358.2007.00202.x.pd

Self-Construal and Concerns Elicited by Imagined and Real Health Problems 1

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/74826/1/j.1559-1816.2007.00283.x.pd

Rise Time and Recovery of GaAs Photoconductive Semiconductor Switches

Fast rise time applications have encouraged us to look at the rise time dependences of lock-on switching. Our tests have shown rise time and delay effects which decrease dramatically with increasing electric field across the switch and/or optical energy used in activating lock-on. Interest in high repetition rate photoconductive semiconductor switches (PCSS), which require very little trigger energy (our 1.5-cm long switches have been triggered with as little as 20 {mu}J), has also led us to investigate recovery from lock-on. Several circuits have been used to induce fast recovery, the fastest being 30 ns. The most reliable circuit produced a 4-pulse burst of +/{minus} 10-kV pulses at 7 MHz with 100-{mu}J trigger energy per pulse. 11 refs., 10 figs

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