Cu2+ binding modes of recombinant alpha-synuclein--insights from EPR spectroscopy

The interaction of the small (140 amino acid) protein, alpha-synuclein (alphaS), with Cu(2+) has been proposed to play a role in Parkinson's disease (PD). While some insight from truncated model complexes has been gained, the nature of the corresponding Cu(2+) binding modes in the full length protein remains comparatively less well characterized. This work examined the Cu(2+) binding of recombinant human alphaS using Electron Paramagnetic Resonance (EPR) spectroscopy. Wild type (wt) alphaS was shown to bind stoichiometric Cu(2+) via two N-terminal binding modes at physiological pH. An H50N mutation isolated one binding mode, whose g parallel, A parallel, and metal-ligand hyperfine parameters correlated well with a {NH2, N(-), beta-COO(-), H2O} mode previously identified in truncated model fragments. Electron spin-echo envelope modulation (ESEEM) studies of wt alphaS confirmed the second binding mode at pH 7.4 involved coordination of His50 and its g parallel and A parallel parameters correlated with either {NH2, N(-), beta-COO(-), N(Im)} or {N(Im), 2 N(-)} coordination observed in alphaS fragments. At pH 5.0, His50-anchored Cu(2+) binding was greatly diminished, while {NH2, N(-), beta-COO(-), H2O} binding persisted in conjunction with another two binding modes. Metal-ligand hyperfine interactions from one of these indicated a 1N3O coordination sphere, which was ascribed to a {NH2, CO} binding mode. The other was characterized by a spectrum similar to that previously observed for diethylpyrocarbonate-treated alphaS and was attributed to C-terminal binding centered on Asp121. In total, four Cu(2+) binding modes were identified within pH 5.0-7.4, providing a more comprehensive picture of the Cu(2+) binding properties of recombinant alphaS.     

Counterions influence reactivity of metal ions with cysteinyldopa model compounds

Cysteinyldopas are naturally occurring conjugates of cysteine and dopa (3,4-dihydroxy-l-phenylalanine) that are precursors to red pheomelanin pigments. Metal ions are known to influence pheomelanogenesis in vitro and may be regulatory factors in vivo. Cydo (3-[(2-amino-ethyl)sulfanyl]-4,6-di-tert-butylbenzene-1,2-diol) and CarboxyCydo (2-amino-3-(4,6-di-tert-butyl-2,3-dihydroxyphenylsulfanyl)-propionic acid) are model compounds of cysteinyldopa that retain its metal-binding functionalities but cannot polymerize due to the presence of blocking tert-butyl groups. Cydo reacts readily with zinc(II) acetate or nickel(II) acetate to form a cyclized 1,4-benzothiazine (zine) intermediate that undergoes ring contraction to form benzothiazole (zole) unless it is stabilized by coordination to a metal ion. The crystal structure of [Ni(zine)2] is reported. The acetate counteranion is required for the zinc-promoted reactivity, as neither zinc(II) sulfate nor zinc(II) chloride alone promotes the transformation. The counterion is less important for redox-active copper and iron, which both readily promote the oxidation of Cydo to zine and zole species; Cu(II) complexes of both zine and zole have been characterized by X-ray crystallography. In the case of CarboxyCydo, a 3-carboxy-1,4-benzothiazine intermediate decarboxylates to form [Cu(zine)2] under basic conditions, but in the absence of base forms a mixture of products that includes the carboxylated dimer 2,2'-bibenzothiazine (bi-zine). These products are consistent with species implicated in the pheomelanogenesis biosynthetic pathway and emphasize how metal ions, their counteranions, and reaction conditions can alter pheomelanin product distribution.     

Wet or dry multifunctional coating prepared by visible light polymerisation with fire retardant,thermal protective,and antimicrobial properties

Cellulose - Cotton, the most popular textile fibre used today, suffers from high combustibility and a propensity for microbial growth. In this study, we used oxygen tolerant, visible...     

Competitive isomerization and dimerization in co-crystals of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol and sorbic acid: a new look at stereochemical requirements for [2+2] dimerization

Competitive [2+2] photodimerization and E-->Z isomerization reactions occur in a co-crystal of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol upon irradiation with 325 nm light. At 90 K both reactions are observed, whereas at 280 K the dimerization reaction is very fast and inhibits isomerization as the nature of the chromophore is affected by the reaction. The temperature dependence of the stereospecificity of the dimerization reaction is related to the large sliding motion required to bring the reacting molecules into juxtaposition. The progress of the reactions has been monitored by photocrystallographic methods.     

A near-infrared dye for multichannel imaging

A large Stokes shift dye, composed of water-solubility and near-infrared feature, was developed for multichannel imaging applications.     

Microstructure analysis of ethylene/1-hexene co-polymers with embeddedrac-Et[Ind]2ZrCl2 metallocene catalyst

Co-polymerization of ethylene and 1-hexene usingrac-Et[Ind]₂ZrCl₂/MAO catalyst embedded in polystyrene in liquid slurry process was examined. The embedded catalyst was prepared by polymerizing a small amount of styrene. The specific activities and bulk densities of the copolymers produced by the embedded catalyst were higher than those of the homogeneous catalyst. The produced co-polymer with embedded catalyst had more random distribution of 1-hexene at the similar co-monomer content than that with homogeneous catalyst.     

Structure and total synthesis of (-)-myrionidine and (-)-schoberine, antimalarial alkaloids from Myrioneuron nutans

Two new alkaloids, (5S,9S,10R)-myrionidine (1) and (5S,9S,10R,13S)-myrionamide (2), along with the known schoberine (3), were isolated from the leaves of Myrioneuron nutans (Rubiaceae), and their structures were determined from spectral analysis, including mass spectrometry and 2D NMR. The total asymmetric syntheses of (-)-myrionidine (1), (-)-schoberine (3), their enantiomers as well as their 9-epimers derivatives were performed, allowing the determination of their absolute configuration together with that of myrionamide (2). (-)-Myrionidine (1) and its synthetic enantiomer (18) showed a significant antimalarial activity on Plasmodium falciparum.     

Rational irreducible characters and rational conjugacy classes in finite groups

We prove that a finite group has two rational-valued irreducible characters if and only if it has two rational conjugacy classes, and determine the structure of any such group. Along the way we also prove a conjecture of Gow stating that any finite group of even order has a non-trivial rational-valued irreducible character of odd degree.

     

A Pfaffian formula for the monomer–dimer model on surface graphs

We consider the monomer–dimer model on weighted graphs embedded in surfaces with boundary, with the restriction that only monomers located on the boundary are allowed. We give a Pfaffian formula for the corresponding partition function, which generalises the one obtained by Giuliani et al. (J Stat Phys 163(2):211–238, 2016) for graphs embedded in the disc. Our proof is based on an extension of a bijective method mentioned in Giuliani et al. (2016), together with the Pfaffian formula for the dimer partition function of Cimasoni–Reshetikhin (Commun Math Phys 275(1):187–208, 2007).     

Theoretical investigation of hot electron cooling process in GaAs/AlAs cylindrical quantum wire under the influence of an intense electromagnetic wave

Hot electrons cooling by phonons in GaAs/AlAs cylindrical quantum wire (CQW), under the influence of an intense electromagnetic wave (EMW), is studied theoretically. Analytic expression for the electron cooling power (CP) is derived from the quantum transport equation for phonons, using the Hamiltonian of interacting electron–optical phonon system. Both photon absorption and emission processes are considered. Numerical results show that the CP reaches maximum when the energy difference between electronic subbands equals the energy of an optical phonon plus the photon energy. Under the influence of the EMW, the negative CP is observed showing that electrons gain energy from phonon and photon instead of losing their energy. Also, the CP increases with increasing the EMW amplitude. Our results theoretically clarify the mechanism of the electron cooling process by phonons in the GaAs/AlAs CQW under the EMW, which is of significance for designing and fabricating high-speed nanoelectronic devices based on this material.