Synthesis and Characterization of Nickel(II) Complex Containing 2‐(t‐Butylaminomethyl)pyrrole

Two aminopyrroles, 2‐(t‐butylaminomethyl)pyrrole ( HL1 ) and 2, 5‐di(t‐butylaminomethyl)pyrrole ( HL2 ), were synthesized and the hydrogen‐bond interactions were observed in the single‐crystal X‐ray structures of HL1 ·HCl and HL2. Bis[2‐(t‐butylaminomethyl)pyrrole]nickel( II ) [ Ni(L1) ₂] was prepared by treatment of the NiCl₂ with 2 equiv. of mono‐deprotonated HL1 in THF solvent. The solid‐state structure of Ni(L1) ₂ shows the N₄‐coordinated nickel atom, with a geometry corresponding to a square‐planar structure, in which two intramolecular C‐H···Ni interactions are present at the axial positions with contact distances of 2.77 Å. The complex displays an irreversible reduction response at ?0.66 V (vs. Fc⁺/Fc) in CH₃CN. Furthermore, ¹H, ¹³C‐HSQC NMR experiments performed at room temperature revealed that the two methylene protons of the chelating L1^?1 are chemically nonequivalent and one of them is coupled to the amino proton. The coupling constants (J_HH') observed are close to the values predicted from the vicinal Karplus correlation diagram.     

An LP-based successive overrelaxation method for linear complementarity problems

A sparsity preserving LP-based SOR method for solving classes of linear complementarity problems including the case where the given matrix is positive-semidefinite is proposed. The LP subproblems need be solved only approximately by a SOR method. Heuristic enhancement is discussed. Numerical results for a special class of problems are presented, which show that the heuristic enhancement is very effective and the resulting program can solve problems of more than 100 variables in a few seconds even on a personal computer.This research was sponsored by the Air Force Office of Scientific Research, Grant No. AFOSR-86-0124. Part of this material is based on work supported by the National Science Foundation under Grant No. MCS-82-00632.The author is grateful to Dr. R. De Leone for his helpful and constructive comments on this paper.     

phi-Values beyond the ribosomally encoded amino acids: kinetic and thermodynamic consequences of incorporating trifluoromethyl amino acids in a globular protein

The consequences of the substitution of 4,4,4-trifluorovaline for valine on the folding kinetics and thermodynamics of a globular protein are presented. Variants of the N-terminal domain of L9, a small alpha-beta protein, were prepared in which V3 or V21 was replaced by trifluorovaline. CD and NMR demonstrate that the structure is not perturbed. Both are more stable, the V3 variant by 0.8 kcal mol-1 and the V21 variant by 1.4 kcal mol-1. The increase of stability is significantly larger than that observed in coiled-coils on a per trifluoromethyl group basis. Folding is two-state, and the variants both fold faster than the wild type. The Phi-values are 0.16 and 0.11, respectively.     

Cryoreduction of methyl-coenzyme M reductase: EPR characterization of forms, MCR(ox1) and MCR (red1).

Methyl-coenzyme M reductase (MCR) catalyzes the formation of methyl-coenzyme M (CH(3)S-CH(2)CH(2)SO(3)) from methane. The active site is a nickel tetrahydrocorphinoid cofactor, factor 430, which in inactive form contains EPR-silent Ni(II). Two such forms, denoted MCR(silent) and MCR(ox1)(-)(silent), were previously structurally characterized by X-ray crystallography. We describe here the cryoreduction of both of these MCR forms by gamma-irradiation at 77 K, which yields reduced protein maintaining the structure of the oxidized starting material. Cryoreduction of MCR(silent) yields an EPR signal that strongly resembles that of MCR(red1), the active form of MCR; and stepwise annealing to 260-270 K leads to formation of MCR(red1). Cryoreduction of MCR(ox1)(-)(silent) solutions shows that our preparative method for this state yields enzyme that contains two major forms. One behaves similarly to MCR(silent), as shown by the observation that both of these forms give essentially the same redlike EPR signals upon cryoreduction, both of which give MCR(red1) upon annealing. The other form is assigned to the crystallographically characterized MCR(ox1)(-)(silent) and directly gives MCR(ox1) upon cryoreduction. X-band spectra of these cryoreduced samples, and of conventionally prepared MCR(red1) and MCR(ox1), all show resolved hyperfine splitting from four equivalent nitrogen ligands with coupling constants in agreement with those determined in previous EPR studies and from (14)N ENDOR of MCR(red1) and MCR(ox1). These experiments have confirmed that all EPR-visible forms of MCR contain Ni(I) and for the first time generated in vitro the EPR-visible, enzymatically active MCR(red1) and the activate-able "ready" MCR(ox1) from "silent" precursors. Because the solution Ni(II) species we assign as MCR(ox1)(-)(silent) gives as its primary cryoreduction product the Ni(I) state MCR(ox1), previous crystallographic data on MCR(ox1)(-)(silent) allow us to identify the exogenous axial ligand in MCR(ox1) as the thiolate from CoM; the cryoreduction experiments further allow us to propose possible axial ligands in MCR(red1). The availability of model compounds for MCR(red1) and MCR(ox1) also is discussed.     

Thermal hazard evaluation for methyl ethyl ketone peroxide mixedwith inorganic acids

Methyl ethyl ketone peroxide (MEKPO) possesses complex structures which have caused many incidents involving fires or explosions by mixing with incompatible substances, external fires, and others. In this study, reactivities or incompatibilities of MEKPO with inorganic acids (HCl, HNO₃, H₃PO₄ and H₂SO₄) were assessed by differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). Parameters obtained by the above-mentioned devices could be readily employed to discuss the runaway reaction, such as onset temperature (T ₀), heat of reaction (ΔH _d), time to maximum rate (TMR), maximum self heat rate (dT/dt)_max, adiabatic temperature rise (ΔT _ad), maximum pressure of decomposition (P _max) and so on. Mixing MEKPO with hydrochloric acid resulted in the lowest T ₀ among inorganic acids. Nitric acid not only lowered the T ₀ but also delivered the highest heat releasing rate or self heat rate (dT/dt), which was concluded to be the worst case in terms of contamination hazards during storage or transportation of MEKPO.     

Synthesis and characterization of new poly(aryl ether)s with isolated fluorophores

Four novel poly(aryl ether)s ( P1 – P4 ) consisting of alternate isolated electron‐transporting (3,3″′‐bis‐trifluoromethyl‐p‐quaterphenyl for P1 , P3 or 3,3″′‐dicyano‐p‐quaterphenyl for P2 , P4 ) and hole‐transporting fluorophores [N‐(2‐ethylhexyl)‐3,6‐bis(styryl)carbazole for P1 , P2 or 9,9‐dihexyl‐2,7‐bis(styryl)fluorene for P3 , P4 ] were synthesized and characterized. These poly(aryl ether)s can be dissolved in organic solvents and exhibited good thermal stability with 5% weight‐loss temperature above 500 °C in nitrogen atmosphere. The photoluminescent (PL) spectra of the films of these polymers showed maximum peaks at around 442–452 nm. The PL spectral results revealed that the emission of polymers was dominated by the fluorophores with longer emissive wavelength via the energy transfer from p‐quaterphenyl to 3,6‐bis(styryl)carbazole or 2,7‐bis(styryl)fluorene segments. Therefore, the p‐quaterphenyl segments function only as the electron‐transporting/hole‐blocking units in these polymers, and the other segments are the emissive centers and hole‐transporting units. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital energy levels of these polymers were measured by cyclic voltammetry. The electron‐donating nitrogen atom on carbazole resulted in the higher HOMO energy levels of P1 and P2 than those of P3 and P4 . The single‐layer light‐emitting diodes (LED) of Al/poly(aryl ether)s ( P1 – P4 )/ITO glass were fabricated. P1 , P2 , and P4 revealed blue electroluminescence, but P3 emitted yellow light as a result of the excimer emission. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2215–2224, 2002     

Magnetic fluid microstructure curved surface uniform embossing and photocuring process technology

By use of magnetism and magnetic fluid embossing technology, and in combination with the surface microstructure roughness improvement of seal‐film, this paper aimed to reach the purpose of magnetic fluid being driven under the magnetic force of an electromagnetic chuck, where the magnetic particles can be evenly scattered and stacked on the surface of the seal‐film in order to uniformly lift and convey the microstructure curved surface magnetic embossing force; thus, creating magnetic pressure in the embossing process of a microstructure curved surface. Moreover, during the process, photocuring technology is integrated with the technical features of soft lithography in order to provide more uniform curved surface embossing and photocuring process technology through the combination of fluid and magnetic force. Copyright © 2015 John Wiley & Sons, Ltd.     

Fixed Energy Universality for Generalized Wigner Matrices

We prove the Wigner‐Dyson‐Mehta conjecture at fixed energy in the bulk of the spectrum for generalized symmetric and Hermitian Wigner matrices. Previous results concerning the universality of random matrices either require an averaging in the energy parameter or they hold only for Hermitian matrices if the energy parameter is fixed. We develop a homogenization theory of the Dyson Brownian motion and show that microscopic universality follows from mesoscopic statistics.© 2016 Wiley Periodicals, Inc.