Synthesis and structural characterization of double metal cyanides of iron and zinc: catalyst precursors for the copolymerization of carbon dioxide and epoxides

Several synthetic approaches for the preparation of double metal cyanide (DMC) derivatives of iron(II) and zinc(II) are described. These include (1) metathesis reactions of ZnCl(2) or ZnI(2) with KCpFe(CN)(2)CO in aqueous solution, (2) reactions of KCpFe(CN)(2)CO and its phosphine-substituted analogues with Zn(CH(3)CN)(4)(BF(4))(2) and subsequent displacement of acetonitrile at the zinc centers by the addition of a neutral (phosphine) or anionic (phenoxide) ligand, and (3) reactions of the protonated HCpFe(CN)(2)(phosphine) complexes with Zn(N(SiMe(3))(2))(2), followed by the addition of phenols. All structures are based on a diamond-shaped planar arrangement of the Fe(2)(CN)(4)Zn(2) core with various appended ligands at the metal sites. Although attempts to replace the iodide ligands in [CpFe(mu-CN)(2)PPh(3)ZnI(THF)](2) with acetate using silver acetate failed, two novel cationic mixed-metal cyanide salts based on the [CpFe(PPh(3))(mu-CN)(2)Zn(NC(5)H(5))](2)(2+) framework were isolated from pyridine solution and their structures were defined by X-ray crystallography. The anionic ligand bound to zinc in these derivatives, which serve as an anionic polymerization initiator, was shown to be central to the catalytic copolymerization reaction of CO(2)/epoxide to provide polycarbonates and cyclic carbonates. The structurally stabilized phosphine-strapped complexes [CpFe(mu-CN)(2)Zn(X)THF](2)(mu-dppp), where X = I or phenolate, were shown to be thermally stable under the conditions (80 degrees C) of the copolymerization reaction by in situ infrared spectroscopy. Both of these derivatives were proposed to serve as mimics for the heterogeneous DMC catalysts in the patent literature, with the derivative where the initiator is a phenolate being more active for the production of polycarbonates.     

The combination of benzo[a]pyrene and ultraviolet A causes an in vivo time-related accumulation of DNA damage in mouse skin

Polycyclic aromatic hydrocarbons, including benzo[a]pyrene (BaP), are ubiquitous environmental carcinogens. BaP is metabolized in vivo to reactive intermediates that become covalently bound to DNA and form BaP-DNA adducts, an initial event in carcinogenesis. Ultraviolet A (UVA) synergizes with BaP to significantly enhance genetic damage and accelerate carcinogenic processes. This study was initiated to investigate in vivo cellular changes related to carcinogenesis induced by repeated exposures to BaP plus UVA. Simulated chronic exposure to an environmental carcinogen and sunlight was conducted through biweekly topical application of BaP followed 2 h later by UVA exposure over a 10 week period. BaP diol epoxide (BPDE)-DNA adducts were measured in vivo by immunohistochemistry using an anti-BPDE-DNA monoclonal antibody. Oxidative DNA damage was measured by the detection of 8-hydroxy-2'-deoxyguanosine (8-OHdG) formation using high-performance liquid chromatography. Alterations in the cell cycle that were relevant to carcinogenesis were revealed by changes in p53, as identified in vivo using a polyclonal anti-p53 antibody. We found that cells containing BPDE-DNA adducts and nuclear p53 expression significantly increased between 2 and 10 weeks of BaP-UVA treatment, whereas neither BPDE-DNA adducts nor significant changes in p53 were observed in untreated skin. Using regression analysis, oxidative 8-OHdG damage also showed a parallel increase over 2-10 weeks (r = 0.80). These results indicate that genetic damage caused by exposures to BaP plus UVA accumulates with time and increases the potential for inductive events leading to carcinogenesis and tumor formation.     

Method for achievement of a multigigawatt peak power by compressing microwave pulses of a relativistic backward-wave oscillator in a helical waveguide

We show theoretically that the use of a circular oversized waveguide with a helically corrugated internal surface as a dispersive medium ensures efficient compression of frequency-modulated microwave pulses up to peak powers of about 10 GW. According to the calculations, a pulse with the required frequency modulation can be obtained in a relativistic backward-wave oscillator operated in the 3-cm wavelength range and producing an output power of hundreds of megawatts. In a demonstration experiment, a 80-ns pulse of kilowatt power with frequency modulation in a 5% band was compressed to a 1.5-ns pulse with a 25-fold power amplification. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 50, No. 1, pp. 40–53, January 2007.     

The Rayleigh-like collapse of a conical bubble

Key to the dynamics of the type of bubble collapse which is associated with such phenomena as sonoluminescence and the emission of strong rebound pressures into the liquid is the role of the liquid inertia. Following the initial formulation of the collapse of an empty spherical cavity, such collapses have been termed "Rayleigh-like." Today this type of cavitation is termed "inertial," reflecting the dominant role of the liquid inertia in the early stages of the collapse. While the inertia in models of spherical bubble collapses depends primarily on the liquid, experimental control of the liquid inertia has not readily been achievable without changing the liquid density and, consequently, changing other liquid properties. In this paper, novel experimental apparatus is described whereby the inertia at the early stages of the collapse of a conical bubble can easily be controlled. The collapse is capable of producing luminescence. The similarity between the collapses of spherical and conical bubbles is investigated analytically, and compared with experimental measurements of the gas pressures generated by the collapse, the bubble wall speeds, and the collapse times.     

Optimal Inventory Rule for a Linear Trend in Demand with a Constant Replenishment Period

The classical deterministic inventory model is considered for the case of constant time between each replenishment and linear trend in demand. The optimum policy is derived and shown to apply to both positive and negative trends. This policy is used in two examples considered in earlier papers on linear trend. It is shown to give only slightly higher costs than the optimal policy with varying replenishment periods, and is compared with a recent heuristic for that case.     

Interpretation of EUV emissions observed by Mills et al.

A porous anodic alumina sample with ordered channels was studied in order to characterise its efficiency as a positron-positronium converter at cryogenic temperatures. The effects of gas adsorption were found to be vacuum dependent and considerable up to 200 nm depth inside the sample. At higher depths it was possible to identify a temperature dependent positronium formation mechanism and the related activation energy was determined to be in an interval from 8.7 to 16 meV. Because of this mechanism the Ps yield decreases to a few percent with decreasing temperature and it can be considered unsuitable for an efficient cryogenic positronium production.     

First principle and ReaxFF molecular dynamics investigations of formaldehyde dissociation on Fe(100) surface

Detailed formaldehyde adsorption and dissociation reactions on Fe(100) surface were studied using first principle calculations and molecular dynamics (MD) simulations, and results were compared with available experimental data. The study includes formaldehyde, formyl radical (HCO), and CO adsorption and dissociation energy calculations on the surface, adsorbate vibrational frequency calculations, density of states analysis of clean and adsorbed surfaces, complete potential energy diagram construction from formaldehyde to atomic carbon (C), hydrogen (H), and oxygen (O), simulation of formaldehyde adsorption and dissociation reaction on the surface using reactive force field, ReaxFF MD, and reaction rate calculations of adsorbates using transition state theory (TST). Formaldehyde and HCO were adsorbed most strongly at the hollow (fourfold) site. Adsorption energies ranged from ?22.9 to ?33.9 kcal/mol for formaldehyde, and from ?44.3 to ?66.3 kcal/mol for HCO, depending on adsorption sites and molecular direction. The dissociation energies were investigated for the dissociation paths: formaldehyde → HCO + H, HCO → H + CO, and CO → C + O, and the calculated energies were 11.0, 4.1, and 26.3 kcal/mol, respectively. ReaxFF MD simulation results were compared with experimental surface analysis using high resolution electron energy loss spectrometry (HREELS) and TST based reaction rates. ReaxFF simulation showed less reactivity than HREELS observation at 310 and 523 K. ReaxFF simulation showed more reactivity than the TST based rate for formaldehyde dissociation and less reactivity than TST based rate for HCO dissociation at 523 K. TST‐based rates are consistent with HREELS observation. © 2013 Wiley Periodicals, Inc.     

On the algorithmic complexity of coloring simple hypergraphs and steiner triple systems

In this paper we establish that decidingt-colorability for a simplek-graph whent≧3,k≧3 is NP-complete. Next, we establish that if there is a polynomial time algorithm for finding the chromatic number of a Steiner Triple system then there exists a polynomial time “approximation” algorithm for the chromatic number of simple 3-graphs. Finally, we show that the existence of such an approximation algorithm would imply that P=NP. Dedicated to Paul Erdős on his seventieth birthday