Fe vibrational spectroscopy of myoglobin and cytochrome f

The Fe vibrational density of states (VDOS) has been determined for the heme proteins deoxymyoglobin, metmyoglobin, and cytochrome f in the oxidized and reduced states, using nuclear resonance vibrational spectroscopy (NRVS). For cytochrome f in particular, the NRVS spectrum is compared with multiwavelength resonance Raman spectra to identify those Raman modes with significant Fe displacement. Modes not seen by Raman due to optical selection rules appear in the NRVS spectrum. The mean Fe force constant extracted from the VDOS illustrates how Fe dynamics varies among these four monoheme proteins, and is correlated with oxidation and spin state trends seen in model heme compounds. The protein's contribution to Fe motion is dominant at low frequencies, where coupling to the backbone tightly constrains Fe displacements in cytochrome f, in contrast to enhanced heme flexibility in myoglobin.     

Cyclic homo and block copolymers through sequential double click reactions

Well‐defined linear α‐anthracene‐ω‐maleimide functionalized polystyrene (l‐Anth‐PS‐MI) and linear α‐alkyne‐ω‐maleimide functionalized poly(tert‐butyl acrylate) (l‐alkyne‐PtBA‐MI) homopolymers, and linear α‐anthracene‐ω‐maleimide functionalized PS‐b‐PtBA (l‐Anth‐PS‐b‐PtBA‐MI) and linear α‐anthracene‐ω‐maleimide functionalized PS‐b‐poly(ε‐caprolactone) (PCL) (l‐Anth‐PS‐b‐PCL‐MI) block copolymers were obtained via combination of atom transfer radical polymerization (ATRP)/ring opening polymerization (ROP) and azide‐alkyne click reaction strategy. Subsequently, these linear homo and block copolymers were efficiently clicked via Diels‐Alder reaction to give their corresponding cyclic homo and block copolymers at reflux temperature of toluene for 48 h under 7–4 × 10^?5 M conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Heterograft brush copolymers via romp and triple click reaction strategies involving CuAAC,diels–alder,and nitroxide radical coupling reactions

In this study, an equimolar mixture of oxanorbornenyl‐anthracene (ONB‐anthracene), oxanorbornenyl‐bromide (ONB‐Br), and oxanorbornenyl tosylate (ONB‐OTs) was polymerized via ring opening metathesis polymerization using the first generation Grubbs' catalyst in CH₂Cl₂ at room temperature to form poly(ONB‐anthracene‐co‐ONB‐Br‐co‐ONB‐OTs)₁₀ copolymer as a main backbone. Next, this main backbone was sequentially clicked with a furan protected maleimide‐terminated poly(methyl methacrylate), 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐terminated poly(ethylene glycol), and alkyne‐terminated poly(ε‐caprolactone) (PCL₂₀‐alkyne) via Diels–Alder, nitroxide radical coupling, and copper‐catalyzed azide‐alkyne cycloaddition, respectively, to yield a poly(ONB‐g‐PMMA‐co‐ONB‐g‐PEG‐co‐ONB‐g‐PCL)₁₀ heterograft brush copolymer © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Acrylonitrile‐containing polymers via a combination of metal‐catalyzed living radical and nitroxide‐mediated free‐radical polymerization routes

2‐Phenyl‐2‐[(2,2,6,6‐tetramethylpiperidino)oxy] ethyl 2‐bromopropanoate was successfully used as an initiator in consecutive living radical polymerization routes, such as metal‐catalyzed living radical polymerization and nitroxide‐mediated free‐radical polymerization, to produce various types of acrylonitrile‐containing polymers, such as styrene–acrylonitrile, polystyrene‐b‐styrene–acrylonitrile, polystyrene‐b‐poly(n‐butyl acrylate)‐b‐polyacrylonitrile, and polystyrene‐b‐polyacrylonitrile. The kinetic data were obtained for the metal‐catalyzed living radical polymerization of styrene–acrylonitrile. All the obtained polymers were characterized with ¹H NMR, gel permeation chromatography, and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3374–3381, 2006     

Noniron isotopes

Hyperfine Interactions - This article reports on experimental developments and first results for Mössbauer isotopes other than 57Fe. We will restrict ourselves to basic features of the...     

Sensitive voltammetric assay of etoposide using modified glassy carbon electrode with a dispersion of multi-walled carbon nanotube

A sensitive electroanalytical method for the determination of anticancer drug etoposide (ETP) using adsorptive stripping differential pulse voltammetry (AdSDPV) at a multi-walled carbon nanotube-modified glassy carbon electrode (MWCNT-modified GCE) is presented. The surface morphology of modified electrode was characterized by scanning electron microscopy. The effects of accumulation time and potential, pH, scan rate, and amount of MWCNT suspension were investigated. The calibration curve was linear in the concentration range of 2.0?×?10^?8–2.0?×?10^?6 M with the detection limit of 5.4?×?10^?9 M. The reproducibility of the peak current was found at 1.55 % (n?=?5) RSD value in pH 6.0 Britton–Robinson buffer for the MWCNT-modified GCE. The method was then successfully utilized for the determination of ETP in pharmaceutical dosage form, and a recovery of 99.55 % was obtained. The possible oxidation mechanism of ETP was also discussed. The proposed electroanalytical method using MWCNT-modified GCE is the most sensitive method for the determination of ETP with lowest limit of detection in the previously published electrochemical methods.     

Three‐arm star ring opening metathesis polymers via alkyne‐azide click reaction

The click chemistry strategy is successfully applied for the preparation of three‐arm star (A₃) ring opening metathesis polymers. A well‐defined monoazide end‐functionalized poly(N‐ethyl oxanorbornene) and a poly(N‐butyl oxanorbornene) obtained via ring opening metathesis polymerization using first generation Grubbs' catalyst are simply clicked with the trisalkyne core affording the synthesis of target star polymers. The obtained star polymers are characterized via nuclear magnetic resonance spectroscopy and gel permeation chromatography (GPC). The deconvolution analyses of GPC traces reveal that the click reaction efficiency for the star formation strongly depends on the chemical nature and the molecular weight of ROM polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2344–2351, 2009     

The Galois closure of Drinfeld modular towers

In this article we study Drinfeld modular curves X₀(pn) associated to congruence subgroups Γ₀(pn) of GL(2,Fq[T]) where p is a prime of Fq[T]. For n>r>0 we compute the extension degrees and investigate the structure of the Galois closures of the covers X₀(pn)→X₀(pr) and some of their variations. The results have some immediate implications for the Galois closures of two well-known optimal wild towers of function fields over finite fields introduced by Garcia and Stichtenoth, for which the modular interpretation was given by Elkies.     

Nanostructured core-shell Ni deposition on SiC particles by alkaline electroless coating

In this study, core-shell nanostructured nickel formation on silicon carbide (SiC) ceramic powders was achieved through the electroless deposition method using alkaline solutions. To produce a nano core-shell Ni deposition on the SiC surfaces, process parameters such as pH values, the type of reducer material, deposition temperature, stirring rate and activation procedure among others were determined. Full coverage of core-shell nickel structures on SiC surfaces was achieved with a grain size of between 100 and 300 nm, which was approximately the same deposition thickness on the SiC surfaces. The surface morphology of the coated SiC particles showed a homogenous distribution of nanostructured nickel grains characterized by scanning electron microscopy and X-ray diffraction techniques. The nanostructures of the crystalline Ni coatings were observed to be attractive for achieving both good bonding and dense structure. The thin core shell-structure of Ni on the SiC surfaces was assessed as a beneficial reinforcement for possible metal matrix composite manufacturing.