Facile fabrication of AgCl@polypyrrole-chitosan core-shell nanoparticles and polymeric hollow nanospheres

A one-step sequential method for preparing AgCl@polypyrrole-chitosan core-shell nanoparticles and subsequently the formation of polypyrrole-chitosan hollow nanospheres is reported. The formation of the core and the shell is performed in one reaction medium almost simultaneously. Transmission electron microscopy (TEM) images show the presence of core-shell nanoparticles and hollow nanospheres. Ultraviolet-visible (UV-vis) studies reveal that AgCl was formed first followed by polypyrrole. X-ray diffration (XRD) and UV-vis studies show that AgCl was present in the core-shell nanoparticles and could be removed completely from the core.     

Efficient synthesis of cellulose furoates in 1-<Emphasis Type="Italic">N</Emphasis>-butyl-3-methylimidazolium chloride

The ionic liquid 1-N-butyl-3-methylimidazolium chloride ([C₄mim]⁺Cl⁻) was investigated as reaction media for the homogeneous acylation of cellulose with 2-furoyl chloride in the presence of pyridine. The preparation of cellulose furoate depending on the reaction conditions, the cellulose type and the pyridine content was studied. Cellulose furoates with a degree of substitution in the range from 0.46 to 3.0 were accessible, i.e., under mild conditions, with a low excess of reagent and in a short reaction time. The products were characterized by elemental analysis, perpropionylation, ¹H- and ¹³C NMR spectroscopy and FTIR spectroscopy. Thomas Heinze is the member of the European Polysaccharide Network of Excellence (EPNOE), www.epnoe.eu     

Synthesis of poly(<Emphasis Type="Italic">N</Emphasis>-methylolacrylamide)/polymethylacrylamide hybrids via frontal free-radical polymerization

In this study, poly(N-methylolacrylamide)/polymethylacrylamide (PNMA/PMAA) hybrids were produced successfully by frontal free-radical polymerization at ambient pressure. In a typical run, the appropriate amounts of reactants (N-methylolacrylamide, NMA; methylacrylamide, MAA) and initiator (ammonium persulfate) were dissolved in dimethyl sulfoxide at ambient temperature. Frontal polymerization (FP) was initiated by heating the wall of the tube with a soldering iron, and the resultant hot fronts were allowed to self-propagate throughout the reaction vessel. Once initiated, no further energy was required for polymerization to occur. The dependences of the front velocity and front temperature on the initiator concentration, reactant dilution, and NMA/MAA components were thoroughly investigated. The front temperatures were between 69 and 116 °C, depending on the persulfate concentration. We have also investigated the FP of PNMA/PMAA hybrids with N-methyl-2-pyrrolidone as solvent. Results show that FP can be exploited as a means for the preparation of PNMA/PMAA hybrids with the potential advantage of higher throughput compared to the traditional mode.     

Supramolecular isomerism in the hydrogen-bonded network of (5<Emphasis Type="Italic">R</Emphasis>,10<Emphasis Type="Italic">R</Emphasis>)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-<Emphasis Type="Italic">cde</Emphasis>]chromene monohydrate

A new compound (5R, 10R)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-cde]chromene monohydrate was obtained from 3,4-dihydroxybenzaldehyde in aerobic basic aqueous ethanol solution in the presence of manganese chloride and triethylamine and crystallized in orthorhombic P2₁2₁2₁ space group (denoted as 1). When 1 was recrystallized from aqueous methanol, it was transformed to another crystal (2) with the same composition but in P2₁/n space group. The drastic difference in the extensive hydrogen bond network makes 1 a 3D and 2 a 2D infinite supramolecular structure, respectively.     

Solvent and thiourea adsorption/intercalation effects on the solid-state electrochemistry of α-phase nickel hydroxide nanoparticles

Nanoparticles of α-phase nickel hydroxide were synthesized by a single-step hydrothermal method using urea as the hydrolytic agent. Precipitated powders were of pure turbostratic α-phase as confirmed by x-ray diffraction profile. The ageing of α-Ni(OH)₂ in 1.0 M alkali solutions is investigated for pure non-intercalated α-Ni(OH)₂ and thiourea intercalated/absorbed α-phase nanomaterials. The α-Ni(OH)₂ powder immobilized on the surface of graphite electrodes shows a gradual α→β phase transformation with continuous voltammetric cycling, and the concentration gradient of water that exists in the layered-double-hydroxide-like interlayers of α-phase and the solution was shown to play a crucial role on the high electrochemical activity of this phase nickel hydroxide. To understand the role of water in the ageing process, concomitant entries of non-aqueous solvents like ethanol and acetonitrile along with thiourea were effected. Cyclic voltammetric measurements of thiourea-treated α-Ni(OH)₂ samples revealed that hydroxyl ion influx during the anodic oxidation depends on the counter flux of solvent molecules, and if the intercalated the solvent is acetonitrile, then the electrochemical activity of α-Ni(OH)₂ reduced drastically; Q _a/Q _c>1 for water as solvent in the interlayers α-Ni(OH)₂ and Q _a/Q _c<1 for ethanol and acetonitrile as solvents. The α-phase gets stabilized in the presence of thiourea with water and ethanol as co-intercalates. Transmission electron microscope images of α-Ni(OH)₂ and thiourea-treated samples show a change in particle size and morphology. Elemental CHNS analysis confirms the presence of sulphur in the thiourea intercalated samples.     

An investigation of nonadiabatic interactions in Cl(2Pj) + D2 via crossed-molecular-beam scattering

We have determined limits on the cross section for both electronically nonadiabatic excitation and quenching in the Cl((2)P(j)) + D(2) system. Our experiment incorporates crossed-molecular-beam scattering with state-selective Cl((2)P(12,32)) detection and velocity-mapped ion imaging. By colliding atomic chlorine with D(2), we address the propensity for collisions that result in a change of the spin-orbit level of atomic chlorine either through electronically nonadiabatic spin-orbit excitation Cl((2)P(32)) + D(2)-->Cl(*)((2)P(12)) + D(2) or through electronically nonadiabatic spin-orbit quenching Cl(*)((2)P(12)) + D(2)-->Cl((2)P(32)) + D(2). In the first part of this report, we estimate an upper limit for the electronically nonadiabatic spin-orbit excitation cross section at a collision energy of 5.3 kcal/mol, which lies above the energy of the reaction barrier (4.9 kcal/mol). Our analysis and simulation of the experimental data determine an upper limit for the excitation cross section as sigma(NA)< or =0.012 A(2). In the second part of this paper we investigate the propensity for electronically nonadiabatic spin-orbit quenching of Cl(*) following a collision with D(2) or He. We perform these experiments at collision energies above and below the energy of the reaction barrier. By comparing the amount of scattered Cl(*) in our images to the amount of Cl(*) lost from the atomic beam we obtain the maximum cross section for electronically nonadiabatic quenching as sigma(NA)< or =15(-15) (+44) A(2) for a collision energy of 7.6 kcal/mol. Our experiments show the probability for electronically nonadiabatic quenching in Cl(*) + D(2) to be indistinguishable to that for the kinematically identical system of Cl(*) + He.     

Synthesis,characterization and third-order nonlinear optical properties of ruthenium(II) complexes containing 2-(4-nitrophenyl)imidazo[4,5-f] [1,10]phenanthroline

Two novel Ru^II complexes [Ru(phen)₂(PNOPH)]²⁺ and [Ru(dmp)₂ (PNOPH)]²⁺ (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, PNOPH = 2-(4-nitrophenyl)imidazo-[4,5-f][1,10]phenanthroline) and their deprotoned complexes were synthesized and characterized by ES–MS, ¹H - n.m.r, u.v.–vis. and electrochemistry. The crystal structure of the deprotonated complex [Ru(dmp)₂ (PNOP)][ClO₄] · CH₃CN was determined by means of X-ray single crystal diffraction. Nonlinear optical properties of the Ru^II complexes were investigated by Z-scan techniques in DMF solution, and all of them exhibited both NLO absorption and self-defocusing effect. The corresponding effective NLO susceptibilities |³ | of the complexes are 2.39 × 10^-12–5.80 × 10^-12 esu.     

Context-dependent behavior of the enterocin iterative polyketide synthase; a new model for ketoreduction

Heterologous expression and mutagenesis of the enterocin type II polyketide synthase (PKS) system suggest for the first time that the association of an extended set of proteins and substrates is needed for the effective production of the enterocin-wailupemycin polyketides. In the absence of its endogenous ketoreductase (KR) EncD in either the enterocin producer "Streptomyces maritimus" or the engineered host S. lividans K4-114, the enterocin minimal PKS is unable to produce benzoate-primed polyketides, even when complemented with the homologous actinorhodin KR ActIII or with EncD active site mutants. These data suggest that the enterocin PKS requires EncD to serve a catalytic and not just a structural role in the functional PKS enzyme complex. This strongly implies that EncD reduces the polyketide chain during elongation rather than after its complete assembly, as suggested for most type II PKSs.     

Parametric Integer Programming Analysis: A Contraction Approach

An algorithm is presented for solving families of integer linear programming problems in which the problems are "related" by having identical objective coefficients and constraint matrix coefficients. The righthand-side constants have the form b + θd where b and d are conformable vectors and θ varies from zero to one.The approach consists primarily of solving the most relaxed problem (θ = 1) using cutting planes and then contracting the region of feasible integer solutions in such a manner that the current optimal integer solution is eliminated.The algorithm was applied to 1800 integer linear programming problems with reasonable success. Integer programming problems which have proved to be unsolvable using cutting planes have been solved by expanding the region of feasible integer solutions (θ = 1) and then contracting to the original region.     

The Use of Versatile Distribution Families in Some Stochastic Inventory Calculations

Previous works on stochastic inventory problems have often assumed that an item's lead time demand follows a "convenient" distribution such as the normal, the γ or the Weibull. First, this paper argues that these convenient distributions may be overly restrictive and unrealistic, and points out the versatility and realism of using four-parameter distributions of the Pearson's and the Schmeiser-Deutsch's systems. Second, using these four-parameter distributions, this paper presents practical `manual" methods for computing the stock-out probability, reorder level and expected lost sales of an inventory item and for solving the lot-size reorder-point model. Some of these methods are actually simpler than the ones developed previously for the more restrictive distributions.