Some Physico-Chemical Studies of Organo-Metallic Compounds

The physico-chemical properties such as molecular weight, conductivity, and absorption spectra have been determined with a miscellany of organometallic compounds in connection with studies on their dissociation, and their constitution. Also, their reactions toward oxygen, nitrous oxioe, hydrogen (catalytic with platinum) have been investigated for the same purpose as well as to test electronic structures proposed for the constitution of nitrous oxide and organometallic compounds

Self-consistent field predictions for quenched spherical biocompatible triblock copolymer micelles

We have used the Scheutjens-Fleer self-consistent field (SF-SCF) method to predict the self-assembly of triblock copolymers with a solvophilic middle block and sufficiently long solvophobic outer blocks. We model copolymers consisting of polyethylene oxide (PEO) as solvophilic block and poly(lactic-co-glycolic) acid (PLGA) or poly({\ko}-caprolactone) (PCL) as solvophobic block. These copolymers form structurally quenched spherical micelles provided the solvophilic block is long enough. Predictions are calibrated on experimental data for micelles composed of PCL-PEO-PCL and PLGA-PEO-PLGA triblock copolymers prepared via the nanoprecipitation method. We establish effective interaction parameters that enable us to predict various micelle properties such as the hydrodynamic size, the aggregation number and the loading capacity of the micelles for hydrophobic species that are consistent with experimental finding.Comment: accepted for publication in Soft Matte

Band inversion driven by electronic correlations at the (111) LaAlO3_3/SrTiO3_3 interface

Quantum confinement at complex oxide interfaces establishes an intricate hierarchy of the strongly correlated $d$-orbitals which is widely recognized as a source of emergent physics. The most prominent example is the (001) LaAlO$_3$/SrTiO$_3$(LAO/STO) interface, which features a dome-shaped phase diagram of superconducting critical temperature and spin-orbit coupling (SOC) as a function of electrostatic doping, arising from a selective occupancy of $t_{2g}$ orbitals of different character. Here we study (111)-oriented LAO/STO interfaces - where the three $t_{2g}$ orbitals contribute equally to the sub-band states caused by confinement - and investigate the impact of this unique feature on electronic transport. We show that transport occurs through two sets of electron-like sub-bands, and the carrier density of one of the sets shows a non-monotonic dependence on the sample conductance. Using tight-binding modeling, we demonstrate that this behavior stems from a band inversion driven by on-site Coulomb interactions. The balanced contribution of all $t_{2g}$ orbitals to electronic transport is shown to result in strong SOC with reduced electrostatic modulation.Comment: 5 pages, 4 figures, (+ supplemental material

Formation and structure of ionomer complexes from grafted polyelectrolytes

We discuss the structure and formation of Ionomer Complexes formed upon mixing a grafted block copolymer (poly(acrylic acid)-b-poly(acrylate methoxy poly(ethylene oxide)), PAA21-b-PAPEO14) with a linear polyelectrolyte (poly(N-methyl 2-vinyl pyridinium iodide), P2MVPI), called grafted block ionomer complexes (GBICs), and a chemically identical grafted copolymer (poly(acrylic acid)-co-poly(acrylate methoxy poly(ethylene oxide)), PAA28-co-PAPEO22) with a linear polyelectrolyte, called grafted ionomer complexes (GICs). Light scattering measurements show that GBICs are much bigger (~70–100 nm) and GICs are much smaller or comparable in size (6–22 nm) to regular complex coacervate core micelles (C3Ms). The mechanism of GICs formation is different from the formation of regular C3Ms and GBICs, and their size depends on the length of the homopolyelectrolyte. The sizes of GBICs and GICs slightly decrease with temperature increasing from 20 to 65 °C. This effect is stronger for GBICs than for GICs, is reversible for GICs and GBIC-PAPEO14/P2MVPI228, and shows some hysteresis for GBIC-PAPEO14/P2MVPI43. Self-consistent field (SCF) calculations for assembly of a grafted block copolymer (having clearly separated charged and grafted blocks) with an oppositely charged linear polyelectrolyte of length comparable to the charged copolymer block predict formation of relatively small spherical micelles (~6 nm), with a composition close to complete charge neutralization. The formation of micellar assemblies is suppressed if charged and grafted monomers are evenly distributed along the backbone, i.e., in case of a grafted copolymer. The very large difference between the sizes found experimentally for GBICs and the sizes predicted from SCF calculations supports the view that there is some secondary association mechanism. A possible mechanism is discussed

Methionine sulfoxide reductase B from Corynebacterium diphtheriae catalyzes sulfoxide reduction via an intramolecular disulfide cascade

Corynebacterium diphtheriae is a human pathogen that causes diphtheria. In response to immune system–induced oxidative stress, C. diphtheriae expresses antioxidant enzymes, among which are methionine sulfoxide reductase (Msr) enzymes, which are critical for bacterial survival in the face of oxidative stress. Although some aspects of the catalytic mechanism of the Msr enzymes have been reported, several details still await full elucidation. Here, we solved the solution structure of C. diphtheriae MsrB (Cd-MsrB) and unraveled its catalytic and oxidation-protection mechanisms. Cd-MsrB catalyzes methionine sulfoxide reduction involving three redox-active cysteines. Using NMR heteronuclear single-quantum coherence (HSQC) spectra, kinetics, biochemical assays, and MS analyses, we show that the conserved nucleophilic residue Cys122 is S-sulfenylated after substrate reduction, which is then resolved by a conserved cysteine, Cys66, or by the non-conserved residue Cys127. We noted that the overall structural changes during the disulfide cascade expose the Cys122–Cys66 disulfide to recycling through thioredoxin (Trx). In the presence of hydrogen peroxide, Cd-MsrB formed reversible intra- and intermolecular disulfides without losing its Cys-coordinated Zn2+, and only the non-conserved Cys127 reacted with the low-molecular-weight (LMW) thiol mycothiol, protecting it from overoxidation. In summary, our structure–function analyses reveal critical details of the Cd-MsrB catalytic mechanism, including a major structural rearrangement that primes the Cys122–Cys66 disulfide for Trx reduction and a reversible protection against excessive oxidation of the catalytic cysteines in Cd-MsrB through intra- and intermolecular disulfide formation and S-mycothiolation

Calculation of the Phase Behavior of Lipids

The self-assembly of monoacyl lipids in solution is studied employing a model in which the lipid's hydrocarbon tail is described within the Rotational Isomeric State framework and is attached to a simple hydrophilic head. Mean-field theory is employed, and the necessary partition function of a single lipid is obtained via a partial enumeration over a large sample of molecular conformations. The influence of the lipid architecture on the transition between the lamellar and inverted-hexagonal phases is calculated, and qualitative agreement with experiment is found.Comment: to appear in Phys.Rev.

Validation of a patient-specific hemodynamic computational model for surgical planning of vascular access in hemodialysis patients

Vascular access dysfunction is one of the main causes of morbidity and hospitalization in hemodialysis patients. This major clinical problem points out the need for prediction of hemodynamic changes induced by vascular access surgery. Here we reviewed the potential of a patient-specific computational vascular network model that includes vessel wall remodeling to predict blood flow change within 6 weeks after surgery for different arteriovenous fistula configurations. For model validation, we performed a multicenter, prospective clinical study to collect longitudinal data on arm vasculature before and after surgery. Sixty-three patients with newly created arteriovenous fistula were included in the validation data set and divided into four groups based on fistula configuration. Predicted brachial artery blood flow volumes 40 days after surgery had a significantly high correlation with measured values. Deviation of predicted from measured brachial artery blood flow averaged 3% with a root mean squared error of 19.5%, showing that the computational tool reliably predicted patient-specific blood flow increase resulting from vascular access surgery and subsequent vascular adaptation. This innovative approach may help the surgeon to plan the most appropriate fistula configuration to optimize access blood flow for hemodialysis, potentially reducing the incidence of vascular access dysfunctions and the need of patient hospitalization

Self-consistent field theory for the interactions between keratin intermediate filaments

Background: Keratins are important structural proteins found in skin, hair and nails. Keratin Intermediate Filaments are major components of corneocytes, nonviable horny cells of the Stratum Corneum, the outermost layer of skin. It is considered that interactions between unstructured domains of Keratin Intermediate Filaments are the key factor in maintaining the elasticity of the skin. Results: We have developed a model for the interactions between keratin intermediate filaments based on self-consistent field theory. The intermediate filaments are represented by charged surfaces, and the disordered terminal domains of the keratins are represented by charged heteropolymers grafted to these surfaces. We estimate the system is close to a charge compensation point where the heteropolymer grafting density is matched to the surface charge density. Using a protein model with amino acid resolution for the terminal domains, we find that the terminal chains can mediate a weak attraction between the keratin surfaces. The origin of the attraction is a combination of bridging and electrostatics. The attraction disappears when the system moves away from the charge compensation point, or when excess small ions and/or NMF-representing free amino acids are added. Conclusions: These results are in concordance with experimental observations, and support the idea that the interaction between keratin filaments, and ultimately in part the elastic properties of the keratin-containing tissue, is controlled by a combination of the physico-chemical properties of the disordered terminal domains and the composition of the medium in the inter-filament region. Keywords: Stratum corneum, Skin keratins, Intermediate filaments, Unstructured terminal domains, Bridging attractio