Protein engineering of alcohol dehydrogenases; effects of amino acid changes at positions 93 and 48 of yeast ADH1

By protein engineering we have investigated changes to two aminoacid residues (Trp93 and Ser48) in the substrate pocket of yeastalcohol dehydrogenase 1. Upon changing Thr48 to serine we producedan enzyme which has markedly greater activity towards aliphaticalcohols with chain length up to 8, together with a generalincrease in catalytic activity (V/K). Changes at position 93were less pronounced, with the Phe enzyme being more activethan the parent towards the range of alcohols but with the alanineenzyme showing very little difference from the wild-type. Enzymeswith the double changes at 48 and 93 showed increased activitytowards alcohols with 3–8 carbons but the increases werenot additive over the single changes. The enzymes with changesat the two positions would metabolize both stereoisomers of2-octanol whereas the parent ADH would attack only one of them.None of the engineered enzymes would attack cyclohexanol oraromatic alcohols. The results are in general agreement withthe prediction that reducing the size of amino acids in thesubstrate pocket would enhance the ability to oxidize alcoholslarger than ethanol.     

Image Analysis and Computer Simulation of Nanoparticle Clustering in Combustion Systems

The current work presents a new method to model and characterize the formation and growth of nanoparticles clusters which includes the three dimensional geometric properties of the clusters, such as aspect ratios, main chain length, radius of gyration, fractal dimension and fractal prefactor. In the model, semi-stochastic mathematics is used to represent varying levels of Coulomb and van der Waals forces during clustering of monodisperse particles. Parametric studies of the relative particle interactions are conducted to evaluate the effects on cluster geometry. Radius of gyration and main chain length were identified as the geometric properties with the greatest sensitivity to changes in the interparticle forces. To demonstrate the analytical capability of the approach, clusters of combustion-generated tin dioxide (SnO₂) nanoparticles were imaged and evaluated to identify the dominant forces controlling cluster morphology. The results show the geometry of the SnO₂ clusters is a result of strong Coulomb interactions.     

Formation of BaCrO4 NanoCrystallites within Thermally Evaporated Sodium Bis-2-Ethylhexyl-Sulfosuccinate and Stearic Acid Thin Films

This paper describes the growth of barium chromate (BaCrO₄) nanocrystallites within thermally evaporated thin films of stearic acid (StA) and sodium bis-2-ethylhexyl-sulfosuccinate by a process of Ba²⁺ ion entrapment followed by in situ reaction with CrO₄²⁻ ions. Dense spherical assemblies of BaCrO₄ nanocrystallites of very uniform size (∼50 nm) were obtained within the two different host matrices. The spherical assemblies were composed of smaller (ca. 5–10 nm size) BaCrO₄ crystals indicating that efficient size control over crystal size may be exercised by the matrix. Contact angle measurements of the BaCrO₄–StA and BaCrO₄–sodium bis-2-ethylhexyl-sulfosuccinate films indicated that they were hydrophobic, thus pointing to the possible role of hydrophobic interaction between the StA and sodium bis-2-ethylhexyl-sulfosuccinate monolayer-covered BaCrO₄ crystals in the assembly process.     

Optically stimulated luminescence (OSL) and laser excited photo luminescence of electron beam treated (EBT) diamonds: Radiation sensitization and potential for tissue equivalent dosimetry

We report the first optically stimulated luminescence (OSL; blue light stimulated luminescence (BLSL) and infrared light stimulated luminescence (IRSL)) results on colored diamonds and present experimental evidence that electron beam treatment (EBT) increases the radiation sensitivity of diamonds to a level that makes them suitable for low level radiation dosimetry. A suite of seven samples was examined. These comprise a white, three brown and three yellow diamond pieces. The FT-IR spectra of these diamonds revealed the nature and concentration of nitrogen impurity. The white diamond was kept as a control. The brown and yellow (with varied saturation) diamonds were irradiated by a 1.7 MeV electron beam. These turned blue/dark green; three of them were then heated in vacuum in the temperature range of 850-900 °C for two hours. Heating turned the irradiated diamonds to lemon yellow, pink, and purple colors. The irradiated and unheated blue samples were designated as 2C and 2D.The control sample, an un-irradiated white type Ia diamond, did not yield any significant IRSL/BLSL with doses up to 100 Gy. The BLSL/IRSL sensitivity of irradiated and heat treated diamonds was very poor, and depended on the heat cycle and hence were not pursued. Sample 2C exhibited significant BLSL and negligible IRSL sensitivity. Sample 2D gave an intense orange red emission under IR excitation as also responded to BLSL. The dose response of the BLSL signal in 2C suggested a minimum detectable dose of ~ 0.1 Gy and its use as a tissue equivalent dosimeter.Based on supporting experiments such as laser excited photoluminescence, we suggest that the BLSL process in 2C is primarily driven by carbon vacancies, which release a mobile hole when excited by GR2 band in the blue region. BLSL intensity exhibited a maximum around 285 °C. Given that TL glow peak also occurs near this temperature and that the nitrogen-interstitial carbon (N-Ci) complex also forms at this temperature (as reported in the literature), and it appears that the e-h recombination at sites with N-Ci complex could be involved in BLSL production. Laser excited photoluminescence (PL) at wavelengths 325, 514 and 785 nm and absorption spectra in UV-Visible range gave insights into the contrasting BLSL/IRSL responses of 2C and 2D. These differences were due to differences in nitrogen impurity complexes and the concentration of carbon vacancies produced by EBT in 2C and 2D. In 2D, the presence of Ni as NE8 center (four nitrogens coordinated to Ni) giving 800 nm emission on 785 nm excitation, appeared to suppress BLSL and sensitize IRSL in the orange window.     

Electrostatic assembly of nanoparticles and biomacromolecules

The controlled assembly of nanoparticles in thin film form on solid supports, both as monolayers and as superlattice structures, is a problem of considerable topical interest. Among the many interactions used to program the assembly of nanoparticles, electrostatic forces are particularly interesting for many reasons. This Account deals with assembling surface-modified nanoparticles in thin film form using electrostatic interactions at the air-water interface and in thermally evaporated lipid films. The generality of the electrostatic assembly protocol is demonstrated in the immobilization of DNA and proteins in lipid films.     

Synthesis and water absorbency of crosslinked superabsorbent polymers

A series of novel copolymer superabsorbents based on monomer acrylamide (AM), potassium methacrylate (KMA), and 2‐hydroxyethyl methacrylate (HEMA) were prepared by copolymerization using ammonium persulfate (APS) as an initiator and N,N‐methylenebisacrylamide (MBA) as a crosslinking agent. The synthetic variables (the monomer concentration, crosslinker concentration, and initiator concentration) were also studied. The experimental results of superabsorbent polymers (SAPs) show a better absorbency in both water and NaCl solutions. The copolymers were characterized by IR spectroscopy. The water retention in the soil was enhanced using the above superabsorbents. The use of SAPs for the growth of groundnut plants was also investigated. SAPs can be considered for water‐managing materials for agriculture and horticulture purposes in desert and drought‐prone areas. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1795–1801, 2002     

Molecular and thermal studies of carbon fiber precursor polymers with low thermal‐oxidative stabilization characteristics

In this investigation, terpolymers, copolymers, and homopolymer of acrylonitrile with dimethylaminopropyl acrylamide (DMAPA), itaconic acid (IA) viz., poly(acrylonitrile‐ran‐3‐dimethylaminopropyl acrylamide‐ran‐itaconic acid) [P(AN‐DMAPP‐IA)], poly(acrylonitrile‐co‐3, dimethylaminopropyl acrylamide) [P(AN‐DMAPP)] were synthesized with varying amounts of comonomers using solution polymerization process. The chemical structure, composition, bonding network were determined employing infrared, 1H and, 13‐carbon nuclear magnetic resonance spectroscopic techniques. Molecular characteristics of as‐synthesized polymers such as different kinds of average molecular weights, molecular weight distribution were estimated applying solution viscometry and size exclusion chromatography. The influence of comonomers (DMPAA, IA) on the thermal stabilization characteristics of acrylonitrile terpolymers in comparison with copolymers and homopolymers of acrylonitrile were studied using differential scanning calorimetry (DSC), hyphenated thermal techniques (thermal gravimetry coupled with differential thermal analyzer).The DSC curves of P(AN‐DMAPP‐IA) exhibit a distinct broader bimodal peaks with thermal exotherm initiating at as low as 165 °C, and followed by two peaks with temperature difference of 42 °C, releasing the evolved heat at a release rate of 0.7–0.11 J g^?1s^?1over 10 min as compared to 1.2, 7.5 J g^?1s^?1 in 4.5, 2 min as observed in P(AN‐DMAPP), polyacrylonitrile, respectively. The thermal stability of P(AN‐DMAPP‐IA) and P(AN‐DMAPP), as evidenced by TGA‐DTA was found to be higher than PAN homopolymers. Specific heat capacity measurements confirmed the DSC results. Bulk densities of P(AN‐DMAPP‐IA) were in the range 0.31–0.35 g/cc. These results confirm the low‐temperature stabilization characteristics and suitability of P(AN‐DMAPP‐IA) as low cost carbon fiber precursor polymers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46381.     

Studies on Micellar Behavior of PEO‐PBO or PEO‐PBO‐PEO Copolymers,or Surface Active Amphiphilic Ionic Liquids in Aqueous Media and Exploration of the Micellar Solutions for Solubilization of Dexamethasone and its Delayed Release

The aggregation behavior of a di‐ and tri‐block copolymers of type PEO‐PBO, PEO‐PBO‐PEO, surface‐active ionic liquid (SAIL) of type 4‐dodecyl‐4‐methylmorpholinium chloride [C₁₂mmor][Cl], and 1‐dodecyl‐1‐methylpyrrolidinium chloride [C₁₂mpyrr][Cl]) in water as well as in 10 mM of a poorly water soluble dexamethasone (dex) aqueous solution was studied by determining the critical micelle concentrations using drug solubilization, surface tension, and isothermal titration calorimetry (ITC) methods. ITC measurements were also made on solutions prepared by mixing the micellar aqueous solutions of copolymers and simple aqueous solutions of SAIL across the mole fractions at three different temperatures (298.15, 308.15, and 318.15 K). The thermodynamic parameters, namely Gibbs free energy (ΔG_m), enthalpy (ΔH_m), and entropy (ΔS_m), of micellization were calculated, and it was observed that the negative ΔG_m and positive ΔS_m for the mixture solutions increase with the increase in mole fraction of SAIL. Otherwise, the micellization is reported to be a spontaneous and highly entropy‐driven process. The dex‐solubilized micellar solutions were mixed with agar to obtain standing gels. The gel samples were dry‐cast into thin films, and the release of dex from films by simple dilution was monitored by UV measurements. The drug release data was fitted to several mechanistic models, and it was inferred that the release mechanism for dex from thin films is non‐Fickian for mixtures and Fickian in copolymer or SAIL micellar aqueous solutions. The transport of dex is diffusion‐controlled with diffusivities of 5.8–12 × 10^?11 m² s^?1 for copolymer micelles, 5–11 × 10^?11 m² s^?1 for micelles of SAIL, and 3–14 × 10^?11 m² s^?1 for the mixed micelles of copolymer and SAIL in aqueous media.     

Edge doping of graphene sheets

We present a direct comparison between two fundamental methods of chemically doping the 2-dimensional graphene sheet: (1) passivation of dangling σ-bonds resulting from a vacancy defect and (2) charge transfer from adsorption on the pristine basal plane. Using electron beam lithography and the negative tone resist hydrogen silsesquioxane, we are able to observe the doping contribution from the passivation of such defects that naturally reside along the edge of graphene sheets, and directly compare them to the doping limitations of basal plane adsorption methods. We demonstrate that the passivation of the edge is over three orders of magnitude more efficient for chemical doping than adsorption, in terms of conducting carriers donated per available C-atom. Moreover, as large-area graphene sheets are tailored into nanoscale devices, and the portion of C-atoms that occupy the edge increases, we demonstrate that edge decoration becomes a more pronounced method of chemical doping, exhibiting a scaling law that will induce vast carrier densities and dominance over adsorption techniques in the nanoscale.     

Preparation of activated graphene and effect of activation parameters on electrochemical capacitance

Activation parameters such as temperature and the amount of potassium hydroxide (KOH) were varied during the synthesis of activated microwave-exfoliated graphite oxide (a-MEGO) and the effects of these parameters on the specific surface area of a-MEGO and electrochemical capacitance of a-MEGO electrodes were investigated. At 800 °C and a KOH/MEGO mass ratio of 6.5, a maximum specific surface area of 3100 m²/g was obtained and a high specific capacitance of 172 F/g (at 1 A/g constant current and 3.5 V maximal voltage) was measured in a two-electrode cell with a-MEGO electrodes in an organic electrolyte.