Role of solvent in the compatibility of a vinylchloride–vinylacetate–maleic acid terpolymer and nitrocellulose blends

The compatibility of cast films of a vinylchloride–vinylacetate–maleic acid terpolymer (VMCH) and nitrocellulose (NC) blends is influenced by solvents. Transparent films of VMCH/NC blends are obtained when cast from solvents such as tetrahydrofuran or cyclohexanone, whereas hazy films are obtained when cast from solvents such as acetone or ethylacetate. Visible spectroscopy and phase morphology were used to analyse the compatibility–incompatibility of the blend. Differential scanning calorimetry (DSC) studies demonstrate that the transparent film is compatible, but the hazy film is incompatible. Fourier transform infra-red (FTIR) studies establish that a greater interaction is observed between the polymer pair in case of the compatible blend than in the case of the incompatible blend. A solvent dependency of blend compatibility is reflected in this study. The conformational state of the polymers in solution, which is responsible for the compatibility phenomena, may depend on the donor number and/or Taft-β value of the solvent. The greater the donor number and/or the Taft-β value, the higher may be the level of interaction between the solvent and the polymer molecules, which in turn may give a compatible blend after removal of the solvent.     

Mechanism of ruthenium tetroxide-catalysed oxidation of aldoses by alkalineN-bromoacetamide

The kinetics of oxidation of three aldoses (glucose, mannose and galactose) byN-bromoacetamide (NBA) in the presence of an alkaline solution of RuO₄ as catalyst and Hg(OAc)₂ as co-catalyst and as a scavenger for bromide have been investigated. The main products of the oxidation are the corresponding aldonic acids. The reaction is zero order with respect to aldose and OH⁻. First order dependence of the reaction on both NBA and RuO₄ at low concentrations shifts to zero order at higher concentrations. Addition of acetamide decreases the reaction rate, while addition of Hg(OAc)₂ has the opposite effect. No significant effect of ionic strength was observed. OBr⁻ is postulated as the reactive oxidising species and a mechanism involving co-catalysis by RuO₄ and Hg^II is proposed. TMC 2588     

Multipole plasmon resonances of submicron silver particles

Single crystal, silver particles of 215 +/- 10 nm size were synthesized in solution using the hydrogen reduction method and were characterized by UV-visible extinction spectroscopy and electron microscopy. The extinction spectra reveal the presence of higher order multipoles of the plasmon resonance, such as quadrupole, octupole, and hexadecapole, in addition to the dipole. The formation of higher order multipoles was continuously monitored during the particles growth. Mie extinction calculations were performed and are in good agreement with the measured extinction spectra. The frequency shift of all plasmon modes was measured as a function of the refractive index of the surrounding dielectric medium.     

Versatile self-complexing compounds based on covalently linked donor-acceptor cyclophanes

A range of covalently linked donor-acceptor compounds which contain 1) a hydroquinone (HQ) unit, 2) a 1,5-dioxynaphthalene (DNP) ring system, or 3) a tetrathiafulvalene (TTF) unit as the pi-donor, and 4) cyclobis(paraquat-p-phenylene) (CBPQT(4+)) as the pi-accepting tetracationic cyclophane were prepared and shown to operate as simple molecular machines. The pi-donating arms can be included inside the cyclophane in an intramolecular fashion by virtue of stabilizing noncovalent bonding interactions. What amounts to self-complexing/decomplexing equilibria were shown to be highly temperature dependent when the pi-donating arm contains either an HQ or DNP moiety. The thermodynamic parameters associated with the equilibria have been unraveled by using variable-temperature (1)H NMR spectroscopy. The negative DeltaH degrees and DeltaS degrees values account for the fact that the "uncomplexed" conformation becomes the dominant species, since the entropy gain associated with the decomplexation process overcomes the enthalpy loss resulting from the breaking of the donor-acceptor interactions. The arm's in-and-out movements with respect to the linked cyclophanes can be arrested by installing a bulky substituent at the end of the arm. In the case of compounds carrying a DNP ring system in their side arm, two diastereoisomeric, self-complexing conformations are observed below 272 K in hexadeuterioacetone. By contrast, control over the TTF-containing arm's movement is more or less ineffective through the thermally sensitive equilibrium although it can be realized by chemical and electrochemical ways as a result of TTF's excellent redox properties. Such self-complexing compounds could find applications as thermo- and electroswitches. In addition, the thermochromism associated with the arm's movement could lead to some of the compounds finding uses as imaging and sensing materials.     

Structures and properties of self-assembled monolayers of bistable [2]rotaxanes on Au (111) surfaces from molecular dynamics simulations validated with experiment

Bistable [2]rotaxanes display controllable switching properties in solution, on surfaces, and in devices. These phenomena are based on the electrochemically and electrically driven mechanical shuttling motion of the ring-shaped component, cyclobis(paraquat-p-phenylene) (CBPQT(4+)) (denoted as the ring), between a tetrathiafulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) ring system located along a dumbbell component. When the ring is encircling the TTF unit, this co-conformation of the rotaxane is the most stable and thus designated the ground-state co-conformer (GSCC), whereas the other co-conformation with the ring surrounding the DNP ring system is less favored and so designated the metastable-state co-conformer (MSCC). We report here the structure and properties of self-assembled monolayers (SAMs) of a bistable [2]rotaxane on Au (111) surfaces as a function of surface coverage based on atomistic molecular dynamics (MD) studies with a force field optimized from DFT calculations and we report several experiments that validate the predictions. On the basis of both the total energy per rotaxane and the calculated stress that is parallel to the surface, we find that the optimal packing density of the SAM corresponds to a surface coverage of 115 A(2)/molecule (one molecule per 4 x 4 grid of surface Au atoms) for both the GSCC and MSCC, and that the former is more stable than the latter by 14 kcal/mol at the optimum packing density. We find that the SAM retains hexagonal packing, except for the case at twice the optimum packing density (65 A(2)/molecule, the 3 x 3 grid). For the GSCC and MSCC, investigated at the optimum coverage, the tilt of the ring with respect to the normal is theta = 39 degrees and 61 degrees, respectively, while the tilt angle of the entire rotaxane is psi = 41 degrees and 46 degrees , respectively. Although the tilt angle of the ring decreases with decreasing surface coverage, the tilt angle of the rotaxane has a maximum at 144 A(2)/molecule (the 4 x 5 grid/molecule) of 50 degrees and 51 degrees for the GSCC and MSCC, respectively. The hexafluorophosphate counterions (PF(6)(-)) stay localized around the ring during the 2 ns MD simulation. On the basis of the calculated density profile, we find that the thickness of the SAM is 40.5 A at the optimum coverage for the GSCC and 40.0 A for MSCC, and that the thicknesses become less with decreasing surface coverage. The calculated surface tension at the optimal packing density is 45 and 65 dyn/cm for the GSCC and MSCC, respectively. This difference suggests that the water contact angle for the GSCC is larger than for the MSCC, a prediction that is verified by experiments on Langmuir-Blodgett monolayers of amphiphilic [2]rotaxanes.     

Polymerization of methyl methacrylate using isatoic anhydride–bromine donor–acceptor complex as the photoinitiator

Isatoic anhydride (IA) alone did not initiate photopolymerization of methyl metacrylate (MMA) at 40°C when exposed to visible light for about 180 min. But IA, when used in combination with bromine (Br₂) as the initiator, initiated the photopolymerization of MMA readily under the same conditions. This behavior was explained by the formation of a donor-acceptor type of complex between IA and Br₂ in the presence of MMA. The polymerization was found to proceed via a free radical mechanism and the radical generation process was considered to follow an initial complexation reaction between the initiator components and monomer. The complex initiator showed nonideal kinetics for the present system (initiator exponent < 0.5) and was analyzed. The monomer exponents varied from 0.83 to 1.15 normally depending on the nature of solvent used. Initiator-dependent chain termination was significant as well as the bimolecular mode of chain termination. © 1993 John Wiley & Sons, Inc.     

The effect of reduction on rhenium(I) complexes with binaphthyridine and biquinoline ligands: a spectroscopic and computational study

A number of rhenium complexes with binaphthyridine and biquinoline ligands have been synthesized and studied. These are [Re(L)(CO)3Cl] where L = 3,3'-dimethylene-2,2'-bi-1,8-naphthyridine (dbn), 2,2'-bi-1,8-naphthyridine (bn), 3,3'-dimethylene-2,2'-biquinoline (dbq), and 3,3'-dimethyl-2,2'-biquinoline (diq). This series represents ligands in which the electronic properties and steric preferences are tuned. These complexes are modeled using density functional theory (DFT). An analysis of the resonance Raman spectra for these complexes, in concert with the vibrational assignments, reveals that the accepting molecular orbital (MO) in the metal-to-ligand charge transfer (MLCT) transition is the LUMO and causes bonding changes at the inter-ring section of the ligand. The electronic absorption spectroelectrochemistry for the reduced complexes of [Re(dbn)(CO)3Cl], [Re(dbq)(CO)3Cl], and [Re(diq)(CO)3Cl] suggest that the singly occupied MO is delocalized over the entire ligand structure despite the nonplanar nature of the diq ligand in [Re(diq)(CO)3Cl]. The IR spectroelectrochemistry for [Re(dbn)(CO)3Cl], [Re(dbq)(CO)3Cl], and [Re(bn)(CO)3Cl] reveal that reduction lowers the CO ligand vibrational frequencies to a similar extent in all three complexes. The substitution of naphthyridine for quinoline has little effect on the nature of the singly occupied MO. These data are supported by DFT calculations on the reduced complexes, which reveal that the ligands are flattened out by reduction: This may explain the similarity in the properties of the reduced complexes.     

Boundedness and asymptotic behavior of solutions for a diffusive epidemic model

The aim of this paper is to study the existence and the asymptotic behavior of solutions for some reaction–diffusion equations arising in epidemic biology phenomena. We will show that for a rather broad class of nonlinearities, the solutions are global and uniformly bounded, and under suitable assumptions on the parameters of the system, these solutions converge as time goes to infinity to a disease‐free equilibrium point. Copyright © 2016 John Wiley & Sons, Ltd.