Polymers,composites, and characterization of conducting polyfuran and poly(2‐bromoaniline)

Polyfuran (PFu), poly(2‐bromoaniline) (P2BrAn), and poly(2‐bromoaniline)/polyfuran (P2BrAn/PFu) composites were synthesized by coupling using various solvents and oxidants. 2‐Bromoaniline (2BrAn) was polymerized using FeCl₃ and (NH₄)₂S₂O₈ in aqueous HCl medium. PFu was synthesized using FeCl₃ and SbCl₃ in anhydrous media (CHCl₃, CH₃CN). Furan was polymerized using both salts in CHCl₃ medium, whereas it could be polymerized using only FeCl₃ in CH₃CN medium. The new electrically conducting composites were prepared by chemical oxidative polymerization using polyfuran synthesized with SbCl₃ and poly(2‐bromoaniline). The polymers and composites were characterized using conductivity, magnetic susceptibility, infrared spectra (FTIR), UV‐Vis spectra, thermal analysis (TGA), and scanning electron microscopy (SEM) measurements. It was found that PFu(SbCl₃) has the lowest thermal stability. Thus, the thermal stability of PFu was increased by preparing composites. The chemical structures of P2BrAns and composites have been found from UV‐Vis results to contain quinone‐imine units along the polymer chain. Magnetic susceptibility measurements indicated that the polymers and composites were diamagnetic or paramagnetic. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2048–2057, 2005     

Duplex processing for increased adhesion of sputter deposited Ti1-xAlxN coatings on a Fe–25%Co–15%Mo tool material

Recently, carbide-free alloying systems with yield strength R_p0.1 of up to 4000 MPa and outstanding thermal stability are available, which offer the possibility to elevate coating deposition temperatures up to 600 °C. The present work demonstrates that the limited Ti_1−xAl_xN coating adhesion on a Fe–25%Co–15%Mo grade caused by the absence of carbides in the substrates can be significantly improved from HF 4 to HF 2 in the Rockwell adhesion test by plasma-assisted nitriding during sputter etching. X-ray photoelectron spectroscopy measurements reveal that the nitrogen diffusion zone is confined to the first few nanometre of the substrate surface, while mainly Mo–N and partly Fe–N bondings are formed. X-ray diffraction exhibits the formation of cubic Mo₂N in the nitrided layer. The coatings show a single-phase face-centered cubic Ti_1-xAl_xN structure tending to a preferred (110) growth orientation with increasing nitriding time. Tribological tests performed at room temperature and 650 °C indicate superior wear performance of duplex Ti_1-xAl_xN coated Fe–25%Co–15%Mo.     

Preconcentration and matrix elimination for the determination of Pb(II), Cd(II), Ni(II), and Co(II)by 8‐hydroxyquinoline anchored poly(styrene‐divinylbenzene) microbeads

Poly(styrene-divinylbenzene), PS-DVB, microbeads were modified with 8-hydroxyquinoline (8-HQ) following nitration, reduction of  NO₂ to NH₂, and conversion of NH₂ to diazonium salt. Characterization of pristine,  NO₂,  NH₂,  NN⁺Cl⁻, and 8-QH functional groups modified microbeads was made by Fourier transform-infrared spectrometry (FTIR) and porosimetry. Total reflectron-X-ray florescence spectrometer (TXRF) was used to test the affinity of the 8-HQ modified microbeads to toxic metal ions. 8-HQ-modified microbeads were used to examine the adsorption capacity, recovery, preconcentration, and the matrix elimination efficiency for Pb(II), Cd(II), Ni(II), and Co(II) ions as a function of changing pH, initial metal-ion concentrations, and also equilibrium adsorption time of the studied metal ions. Preconcentration factors for the studied toxic metal ions were found to be more than 500-fold and recovery between 93.8% and 100.6%. Ultratrace toxic metal-ion concentrations in sea water were determined easily by using modified microbeads. Reference sea-water sample was used for the validation of the method, and it was found that recovery, preconcentration, and the matrix elimination were performed perfectly. For the desorption of the toxic metal ions, 3M of HNO₃ was used and desorption ratio shown to be more than 96%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Refining Genotypes and Phenotypes in KCNA2-Related Neurological Disorders

Pathogenic variants in KCNA2, encoding for the voltage-gated potassium channel K_v1.2, have been identified as the cause for an evolving spectrum of neurological disorders. Affected individuals show early-onset developmental and epileptic encephalopathy, intellectual disability, and movement disorders resulting from cerebellar dysfunction. In addition, individuals with a milder course of epilepsy, complicated hereditary spastic paraplegia, and episodic ataxia have been reported. By analyzing phenotypic, functional, and genetic data from published reports and novel cases, we refine and further delineate phenotypic as well as functional subgroups of KCNA2-associated disorders. Carriers of variants, leading to complex and mixed channel dysfunction that are associated with a gain- and loss-of-potassium conductance, more often show early developmental abnormalities and an earlier onset of epilepsy compared to individuals with variants resulting in loss- or gain-of-function. We describe seven additional individuals harboring three known and the novel KCNA2 variants p.(Pro407Ala) and p.(Tyr417Cys). The location of variants reported here highlights the importance of the proline(405)–valine(406)–proline(407) (PVP) motif in transmembrane domain S6 as a mutational hotspot. A novel case of self-limited infantile seizures suggests a continuous clinical spectrum of KCNA2-related disorders. Our study provides further insights into the clinical spectrum, genotype–phenotype correlation, variability, and predicted functional impact of KCNA2 variants.     

Energy Metabolites as Biomarkers in Ischemic and Dilated Cardiomyopathy

With more than 25 million people affected, heart failure (HF) is a global threat. As energy production pathways are known to play a pivotal role in HF, we sought here to identify key metabolic changes in ischemic- and non-ischemic HF by using a multi-OMICS approach. Serum metabolites and mRNAseq and epigenetic DNA methylation profiles were analyzed from blood and left ventricular heart biopsy specimens of the same individuals. In total we collected serum from n = 82 patients with Dilated Cardiomyopathy (DCM) and n = 51 controls in the screening stage. We identified several metabolites involved in glycolysis and citric acid cycle to be elevated up to 5.7-fold in DCM (p = 1.7 × 10⁻⁶). Interestingly, cardiac mRNA and epigenetic changes of genes encoding rate-limiting enzymes of these pathways could also be found and validated in our second stage of metabolite assessment in n = 52 DCM, n = 39 ischemic HF and n = 57 controls. In conclusion, we identified a new set of metabolomic biomarkers for HF. We were able to identify underlying biological cascades that potentially represent suitable intervention targets.     

(BaTiO3)1-x + (Co0.5Ni0.5Nb0.06Fe1.94O4)x nanocomposites: Structure,morphology, magnetic and dielectric properties

Two phase-based nanocomposites consisting of dielectric barium titanate (BaTiO₃ or BTO) and magnetic spinel ferrite Co_0.5Ni_0.5Nb_0.06Fe_1.94O₄ (CNNFO) have been synthesized through solid state route. Series of (BaTiO₃)_1-x + (Co_0.5Ni_0.5Nb_0.06Fe_1.94O₄)_x nanocomposites with x content of 0.00, 0.25, 0.50, 0.75, and 1.00 were considered. The structure has been examined via X-rays diffraction (XRD) and indicated the occurrence of both perovskite BTO and spinel CNNFO phases in various nanocomposites. A phase transition from tetragonal BTO structure to cubic structure occurs with inclusion of CNNFO phase. The average crystallites size of BTO phase decreases, whereas that for the CNNFO phase increases with increasing x in various nanocomposites. The morphological observations revealed that the porosity is highly reduced, and the connectivity between grains is enhanced with increasing x content. The optical properties have been investigated by UV−vis diffuse reflectance spectroscopy. The deduced band gap energy (E_g) value is found to reduce with increasing the content of spinel ferrite phase. The magnetic as well as the dielectric properties were also investigated. The analysis showed that CNNFO ferrite phase greatly affects the magnetic properties and dielectric response of BTO material. The obtained findings can be useful to enhance the performances of magneto-dielectric composite-based systems.     

Self-sufficient Cytochrome P450s and their potential applications in biotechnology

Cytochrome P450s(CYPs) are ubiquitously found in all kingdoms of life, playing important role in various biosynthetic pathways as well as degradative pathways; accordingly find applications in a vast variety of areas from organic synthesis and drug metabolite production to modification of biomaterials and bioremediation.Significantly, CYPs catalyze chemically challenging C—H and C—C activation reactions using a reactive high-valent iron-oxo intermediate generated upon dioxygen activation at their heme center,while the other oxygen atom is reduced to the level of water by electrons provided through a reductase partner protein.Self-sufficient CYPs, encoding their heme domain and reductase protein in a single polypeptide, facilitate increased catalytic efficiency and render a less complicated system to work with.The self-sufficient CYP enzyme from CYP102A family(CYP102A1, BM3) is among the earliest and most-investigated model enzymes for mechanistic and structural studies as well as for biotechnological applications.An increasing number of self-sufficient CYPs from the same CYP102 family and from other families have also been reported in last decade.In this review, we introduce chemistry and biology of CYPs, followed by an overview of the characteristics of self-sufficient CYPs and representative reactions.Enzyme engineering efforts leading to novel self-sufficient CYP variants that can catalyze synthetically useful natural and non-natural(nature-mimicking) reactions are highlighted.Lastly, the strategy and efforts that aim to circumvent the challenges for improved thermostability, regio-and enantioselectivity,and total turnover number; associated with practical use of self-sufficient CYPs are reviewed.     

Entropy generation in the flow system generated in between two parallel plates due to bivertical motion of the top plate

Thermodynamic irreversibility in the flow system provides information on the energy and power losses in the system. Minimization of entropy generation in the flow system enables for the parametric optimization of the system operation. In the present study, parallel plates, in between, filled with the fluid are considered. The fluid motion resulted from the bi-vertical compression of the top plate of the parallel plates is examined. The entropy generation rate in the flow system is formulated after considering the constant movement of the top plate, constant applied load, and the combination of the constant velocity and applied load to the top plate. The optimum operating conditions related to the fluid motion in between the parallel plates is determined through the entropy analysis. It is found that the combination of the constant velocity and the constant applied load resulted in the low entropy generation rate.     

Variation of part thickness and compaction pressure in vacuum infusion process

In vacuum infusion (VI), it is difficult to manufacture a composite part with small dimensional tolerances, since the thickness of the part changes during resin injection. This change of thickness is due to the effect of varying compaction pressure on the upper mold part, a vacuum bag. In this study, random fabric layers with an embedded core distribution medium is used. The thickness of the composite part and resin pressure are monitored using multiple dial gages and pressure transducers; the results are compared with the model developed by Correia et al. [Correia NC, Robitaille F, Long AC, Rudd CD, Simacek P, Advani SG. Analysis of the vacuum infusion molding process: I. Analytical formulation. Composites Part A: Applied Science and Manufacturing 26, 2005. p. 1645–1656]. To use this model, two material characteristics databases are constructed based on the process parameters: (i) the thickness of a dry/wet fabric preform at different compaction pressures, and (ii) the permeability of the preform at different thicknesses. The dry-compacted preform under vacuum is further compacted due to fiber settling in wet form after resin reaches there; the part thickens afterwards as the resin pressure increases locally. The realistic model solution can be achieved only if the compaction characterization experiments are performed in such a way that the fabric is dry during loading, and wet during unloading, as in the actual resin infusion process. The model results can be used to design the process parameters such as vacuum pressure and locations of injection and ventilation tubes so that the dimensional tolerances can be kept small.