Living anionic surface initiated polymerization (LASIP) of isoprene from silica nano- and glass particles

Living anionic surface initiated polymerization (LASIP) of isoprene from initiator modified silica nano- and glass particles is conducted. In order to prepare polyisoprene-silica composites, the surfaces of the particles are modified with three coupling agents, each bearing a diphenyl ethylene (DPE) moiety with different alkyl-spacer lengths, thus separating the DPE moiety in different distance from the particles’ surfaces. Surface initiated polymerization reactions from modified particle surfaces are performed by using n-BuLi to activate the DPE units and benzene as solvent via LASIP. Grafted polyisoprene-silica composites are analyzed via TGA, resulting in grafting densities of the produced inorganic-polymer composites in the range from 0.10 to 0.24 chains/nm². Analysis via GPC reveals polydispersity values ranging from 1.1 to 1.7. The final microstructure of the grafted polyisoprene is investigated via NMR, revealing 15% 1,2, 35% cis-1,4 and 50% trans-1,4, irrespective of the spacer length of the DPE bearing coupling agent.     

ANP application for evaluating Turkish mobile communication operators

The proposed decision model, based on Analytic Network Process (ANP), has been developed in order to determine the dynamics of the Global System for Mobile Communications (GSM) market. In accordance with the sequence of ANP, first of all, the problem was structured and modeled. At the next step, a quantitative analysis was conducted with the customers in order to assess the importance of the related factors and forecast the market shares of the Turkish mobile communication operators. The forecasted market share values were compared with actual ones for the validation of the decision model. The assessed importance of the factors in a valid model would be a potential competitive advantage for the mobile operators.     

On the stability and properties of the polyacrylate/Na-MMT nanocomposite obtained by seeded emulsion polymerization

For high performance waterborne coatings usually polymer latexes with low emulsifier content are more preferred. Although polymer/clay nanocomposites offer improved properties, it is difficult to produce clay based nanocomposite latexes containing low emulsifier due to the stabilization problems especially caused by organoclays. Present study deals with the preparation of a tBA/BA/MAA ternary copolymer/clay nanocomposite containing 3 wt.% sodium montmorillonite (Na⁺-MMT) via seeded emulsion polymerization. Experimentally it was observed that even the usage of hydrophilic clay caused stabilization problem and a certain amount of emulsifier (>1 wt.%) was necessary to obtain stable latexes. In addition, the usage of a low molecular weight water soluble polymer as steric barrier was found to increase the stability of system. Obtained nanocomposite latex showed fine particle size diameter (127 nm) and very narrow size distribution (PDI = 0.06). The WAXD and TEM investigations indicated that a mostly exfoliated nanocomposite was obtained. Thermal analyses (DSC, DMTA and TGA) showed that there was no change at T_g of the copolymer while very high improvement was obtained for elastic modulus and a slight increase in thermal stability. According to the rheological measurements, the nanocomposite latex showed a higher low shear viscosity, a stronger shear thinning behavior and an improved physical stability in comparison to the reference latex.     

Selective syntheses of vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs); building blocks for π-conjugated systems

Selective syntheses of 3,4-vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs), having Ph, 4-CH₃OC₆H₄, 4-BrC₆H₄, 4-NO₂C₆H₄ and 4-(CH₃)₂NC₆H₄ groups, were achieved through the reaction of 1,8-diketone with phosphorus decasulfide (P₄S₁₀). The reaction could be shifted between VDTT and DTT by adding base (sodium bicarbonate) or acid (para-toluenesulfonic acid), respectively, to the reaction mixture. While the VDTTs were obtained in moderate yields, an important achievement has been made with the syntheses of the DTTs, obtaining them in higher yields compared with the previous report. Polymers of the VDTTs, which are the analogues of ethylenedioxythiophene, EDOT, were prepared using FeCl₃. Unfortunately, all attempts for their electropolymerization failed. Spin density calculations revealed that none of the VDTTs had a significant positive spin density at the ‘α’ carbon atoms of the thiophene ring. Considering their solubility and functional groups, which could be further derivatized, they are useful building blocks for the preparation of new organic materials.     

Solubilizing effect of the p-phosphonate calix[n]arenes towards poorly soluble drug molecules such as nifedipine, niclosamide and furosemide

This article reports the solubilization of the practically water insoluble drug molecules such as nifedipine, niclosamide and furosemide by guest:host inclusion complexation with p-phosphonates calix[n]arenes as drug soluble agent. This complexation studies were carried out by using the phase solubility technique. From the obtained results, it was observed that the solubility of drug molecules was significantly increased in the presence of calix[n]arene host molecules. The increase in solubility of drugs by the calix[n]arene was most probably due to inclusion complexation between drug molecules and cavities of the calixarene skeleton similar to drug:cyclodextrin complexes.     

An adaptive large neighborhood search algorithm for a selective and periodic inventory routing problem

We study a selective and periodic inventory routing problem (SPIRP) and develop an Adaptive Large Neighborhood Search (ALNS) algorithm for its solution. The problem concerns a biodiesel production facility collecting used vegetable oil from sources, such as restaurants, catering companies and hotels that produce waste vegetable oil in considerable amounts. The facility reuses the collected waste oil as raw material to produce biodiesel. It has to meet certain raw material requirements either from daily collection, or from its inventory, or by purchasing virgin oil. SPIRP involves decisions about which of the present source nodes to include in the collection program, and which periodic (weekly) routing schedule to repeat over an infinite planning horizon. The objective is to minimize the total collection, inventory and purchasing costs while meeting the raw material requirements and operational constraints. A single-commodity flow-based mixed integer linear programming (MILP) model was proposed for this problem in an earlier study. The model was solved with 25 source nodes on a 7-day cyclic planning horizon. In order to tackle larger instances, we develop an ALNS algorithm that is based on a rich neighborhood structure with 11 distinct moves tailored to this problem. We demonstrate the performance of the ALNS, and compare it with the MILP model on test instances containing up to 100 source nodes.     

A reformulation for the stochastic lot sizing problem with service-level constraints

We study the stochastic lot-sizing problem with service level constraints and propose an efficient mixed integer reformulation thereof. We use the formulation of the problem present in the literature as a benchmark, and prove that the reformulation has a stronger linear relaxation. Also, we numerically illustrate that it yields a superior computational performance. The results of our numerical study reveals that the reformulation can optimally solve problem instances with planning horizons over 200 periods in less than a minute.     

Preparation of a series of Ru(II) complexes with N-heterocyclic carbene ligands for the catalytic transfer hydrogenation of aromatic ketones

The reaction of [RuCl(2)(p-cymene](2) with Ag-N-heterocyclic carbene (NHC) complexes yields a series of [(p-cymene)Ru(NHC)] complexes (2a-f). All synthesised compounds were characterized by elemental analysis, NMR spectroscopy and the molecular structure of 2a was determined by X-ray crystallography. All complexes have been tested as catalysts for the transfer hydrogenation of aromatic ketones, showing excellent activity in this reaction.