Benefits of working capital sharing in supply chains

Supply chain finance and working capital management are important avenues to reduce supply chain costs. Small suppliers may not have sufficient working capital to finance their operations and efficiently supply their customers. We develop a model that captures the fundamental aspects of financial and operational planning in a two-stage supply chain, with both strong and weak members. A strong member can negotiate for more favorable financing rates, more advantageous payment terms, and shorter lead times than a weaker member. We investigate two working capital allocation scenarios. In the dedicated working capital allocation scenario, the members of the supply chain each have their own working capital. In the joint working capital allocation scenario, the members of the supply chain have a joint pool of working capital. Our results demonstrate significant benefits when the members of the supply chain share the working capital. We also show that extending payment delays to a supplier upstream results in higher overall supply chain costs.     

Selective Production of Phenol on Bifunctional,Hierarchical ZSM-5 Zeolites

Mono- and bimetallic Ni-, Ru- and Pt-modified hierarchical ZSM-5 materials were prepared by impregnation technique and characterized by X-ray diffraction (XRD), N₂ physisorption, temperature-programmed reduction (TPR–TGA), ATR–FTIR and solid state NMR spectroscopy. Formation of finely dispersed nickel, ruthenium and platinum species was observed on the bimetallic catalysts. It was found that the peculiarity of the used zeolite structure and the modification procedure determine the type of formed metal oxides and their dispersion and reducibility. The samples’ acidity was studied via FTIR spectroscopy of adsorbed pyridine. The changes in the zeolite structure were studied via solid-state NMR spectroscopy. The catalysts were investigated in a gas-phase hydrodeoxygenation, transalkylation and dealkylation reaction of model lignin derivative molecules for phenol production.     

Synthesis of Poly(α‐alkyl β,L‐aspartate)s by Transesterification

A new procedure for the preparation of poly(α‐alkyl β,L ‐aspartate)s based on the transesterification of polyα‐benzyl β,L ‐aspartate) with alcohols in the presence of titanium tetrabutoxide is described. The reaction proceeded to almost total conversion without substantial racemization or imidation. Thermal properties of the resulting polymers were comparable to those of their homologues obtained by anionic ring‐opening polymerization of β‐lactams and their thermal stability is even higher.     

Diacetylene-containing polymers IV. Novel diacetylene-containing polyamides and copolyamides

New monomers, bis(3-ethynyl)dianilides, were synthesized from 3-ethynylaniline and different diacid dichlorides and were polymerized by oxidative polycoupling to give soluble high molecular weight film forming diacetylene-containing polyamides. UV-induced and thermal cross-linking of the polymer were studied. A correlation was found between the chain flexibility and the absoprtion peaks of visible spectra of cross-linked polymer films. Third order nonlinear optical susceptibility (χ⁽³⁾) of the polymer films was in the range of 10⁻¹⁰-10⁻⁹ esu.     

Metal-metallothioneins like proteins investigation by heteroatom-tagged proteomics in two different snails as possible sentinel organisms of metal contamination in freshwater ecosystems

Metal speciation analysis in MLPs was carried out in two snails, Marisa cornuarietis and Pomacea bridgesi, in order to investigate them as possible sentinel organisms of heavy metal contamination. To carry out this study snails born in a non-contaminated environment were divided into two groups: a control group and a contaminated one with cadmium administered for 40 days. Subsequently, we investigated the speciation of the induced MLPs in exposed animals in relation to controls. In order to obtain the MLP fraction, cytosols from both snail species where subjected to size-exclusion fractionation, monitoring on-line the metal signal (Cd, Cu and Zn) by ICP-MS while protein elution was followed by on-line UV detection. MLP fraction was then separated by anion-exchange (AE)-FPLC using optimal chromatographic conditions for the separation of the different MLP isoforms in both snail species. Specific detection of separated metalloforms was carried out again by the hyphenation of the AE chromatographic system with ICP-MS. The determination of the amount of metal bound to MLPs was carried out by post-column isotope dilution analysis ICP-MS, finding that the snail M. cornuarietis accumulated higher concentrations of cadmium than P. bridgesi. Thus this first snail could therefore be a better candidate sentinel organism of pollution in natural waters. Identification and characterization of the isoforms separated in M. cornuarietis was carried out for the entire or intact isoforms by MALDI-TOF and then conventional triptic digestion was also carried out to identify the nature of the formed peptides. The presence identification of a MLP isoform of relatively low molecular weight in M. cornuarietis is reported.     

Synthesis and reactivity of new functionalized Pd(II) cyclometallated complexes with boronic esters

Treatment of the functionalized Schiff base ligands with boronic esters 1a, 1b, 1c and 1d with palladium (II) acetate in toluene gave the polynuclear cyclometallated complexes 2a, 2b, 2c and 2d, respectively, as air-stable solids, with the ligand as a terdentate [C,N,O] moiety after deprotonation of the -OH group. Reaction of 1j with palladium (II) acetate in toluene gave the dinuclear cyclometallated complex 5j. Reaction of the cyclometallated complexes with triphenylphosphine gave the mononuclear species 3a, 3b, 3c, 3d and 6j with cleavage of the polynuclear structure. Treatment of 2c with the diphosphine Ph₂PC₅H₄FeC₅H₄PPh₂ (dppf) in 1:2 molar ratio gave the dinuclear cyclometallated complex 4c as an air-stable solid.Deprotection of the boronic ester can be easily achieved; thus, by stirring the cyclometallated complex 3a in a mixture of acetone/water, 3e is obtained in good yield. Reaction of the tetrameric complex 2a with cis-1,2-cyclopentanediol in chloroform gave complex 2c after a transesterification reaction. Under similar conditions complexes 3a and 3d behaved similarly: with cis-1,2-cyclopentanediol, pinacol or diethanolamine complexes 3c, 3b, 3g and 3f, were obtained. The pinacol derivatives 3b and 3g experiment the Petasis reaction with glyoxylic acid and morpholine in dichloromethane to give complexes 3h, and 3i, respectively.     

Functionalized single graphene sheets derived from splitting graphite oxide

A process is described to produce single sheets of functionalized graphene through thermal exfoliation of graphite oxide. The process yields a wrinkled sheet structure resulting from reaction sites involved in oxidation and reduction processes. The topological features of single sheets, as measured by atomic force microscopy, closely match predictions of first-principles atomistic modeling. Although graphite oxide is an insulator, functionalized graphene produced by this method is electrically conducting.     

Epoxy/poly(benzyl methacrylate) blends: miscibility, phase separation on curing and morphology

Diglycidyl ether of bisfenol-A (DGEBA)/polybenzyl methacrylate (PBzMA) blends cured with 4,4’-diaminodiphenylmethane (DDM) were studied. Miscibility, phase separation, cure kinetics and morphology were investigated through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Non-reactive DGEBA/PBzMA blends are miscible over the whole composition range. The addition of PBzMA to the reactive (DGEBA+DDM) mixture slows down the curing rate, although the reaction mechanism remains autocatalytic. On curing, initially miscible (DGEBA+DDM)/PBzMA blends phase separate, arising two glass transition temperatures that correspond to a PBzMA-rich phase and to epoxy network. Cured epoxy/PBzMA blends present different morphologies as a function of the PBzMA content.     

Structural studies of spiroarsoranes derived from 2-aminophenols

This paper describes the structural studies of 2-phenyl-9,9′-dimethyl-2,2′-spirobis(1,3,2-λ⁵-benzoxazarsoline) 5, 2-phenyl-8,8′-dimethyl-2,2′-spirobis(1,3,2-λ⁵-benzoxazarsoline) 6 by ¹H,¹³C,¹⁵N NMR in [²H₆]DMSO and CDCl₃. The solid state studies were made by X-ray experiments. Infrared spectroscopy was obtained in CDCl₃ and the vibrational signals were assigned using DFT calculations. The nature of the As–N, As–C and As–O bonds in these compounds was established by NBO studies.