Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

Synthesis of Small‐Sized,Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating

In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g^?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging.     

Experimental Investigations on the Thermal Diffusion Characteristics and Photoluminescence in Multiphase Micro Fluids Containing ZnO Micro Tubes and Fluorescein Dye

Optics and Spectroscopy - Scattering of light by disordered structures is normally detrimental to their applicability in many optoelectronic devices. However, some micro and nanostructures are...     

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

A Recursive Algorithm for Order Cycle-time that Minimizes Logistics Cost

A firm's logistics cost, including shipping and inventory-carrying, is a substantial percentage of its sales. Nevertheless, typical inventory-control methods ignore or insufficiently represent the shipping cost. This paper describes a recursive algorithm that determines the reorder cycle-time that minimizes total logistics cost. It allows for a realistic accounting of shipping cost, which is modelled here as a function of shipping distance and weight. The algorithm uses a relaxation procedure to identify a suitable initial approximation to the optimal order cycle-time and then, through a series of recursive steps, moves to the optimal result. We demonstrate the algorithm with a single item, with a group of items that share a common order cycle, and with multi-items when item demands are random variables. Experience with this algorithm indicates that it converges to the optimal result in a very few steps.     

Polyhedral <Emphasis Type="Italic">K</Emphasis><Subscript><Emphasis Type="Italic">2</Emphasis></Subscript>

 Using elementary graded automorphisms of polytopal algebras (essentially the coordinate rings of projective toric varieties) polyhedral versions of the group of elementary matrices and the Steinberg and Milnor groups are defined. They coincide with the usual K-theoretic groups in the special case when the polytope is a unit simplex and can be thought of as compact/polytopal substitutes for the tame automorphism groups of polynomial algebras. Relative to the classical case, many new aspects have to be taken into account. We describe these groups explicitly when the underlying polytope is 2-dimensional. Already this low-dimensional case provides interesting classes of groups. Received: 13 December 2001 / Revised version: 24 June 2002 The second author was supported by the Deutsche Forschungsgemeinschaft, INTAS grant 99-00817 and TMR grant ERB FMRX CT-97-0107 Mathematics Subject Classification (2000): 14L27, 14M25, 19C09, 52B20     

Synthesis of molecular imprinted organic-inorganic hybrid polymer binding caffeine

Random copolymers of poly{(methacrylamide)-co-(vinyl trimethoxysilane)} and poly{(methacrylic acid)-co-(vinyl trimethoxysilane)} were synthesized via a free radical polymerization reaction. Acid catalyzed sol-gel process of tetraethylorthosilicate (TEOS) with aforementioned polymers in the presence of methyl xanthine class of alkaloid like caffeine resulted in the formation of highly transparent monoliths. Solvent extraction of the template leaves behind the recognition sites intact with high selectivity towards the print molecule. The ionic and non-specific adsorptions, which are considered to be the main disadvantages of the molecularly imprinted polymers (MIP), are prevented to a considerable extent by the end capping of surface silanol groups. The template binding efficiencies of MIP were determined by HPLC analysis.     

A high‐resolution scheme for low Mach number flows

A method for computing low Mach number flows using high‐resolution interpolation and difference formulas, within the framework of the Marker and Cell (MAC) scheme, is presented. This increases the range of wavenumbers that are properly resolved on a given grid so that a sufficiently accurate solution can be obtained without extensive grid refinement. Results using this scheme are presented for three problems. The first is the two‐dimensional Taylor–Green flow which has a closed form solution. The second is the evolution of perturbations to constant‐density, plane channel flow for which linear stability solutions are known. The third is the oscillatory instability of a variable density plane jet. In this case, unless the sharp density gradients are resolved, the calculations would breakdown. Under‐resolved calculations gave solutions containing vortices which grew in place rather than being convected out. With the present scheme, regular oscillations of this instability were obtained and vortices were convected out regularly. Stable computations were possible over a wider range of sensitive parameters such as density ratio and co‐flow velocity ratio. Copyright © 2004 John Wiley Sons, Ltd.     

Separation and Determination of Chloroplast Pigments from Spinach by Thin-Layer Chromatography: a Student Laboratory Experiment

JPC – Journal of Planar Chromatography – Modern TLC -