The photolysis of poly(p-hydroxystyrene)

The photochemistry of poly(p-hydroxystyrene) (PPHS) has been investigated, thin films being exposed to 254 nm radiation under high vacuum at 298K. H₂ is the principal volatile product, but small amounts of H₂O are also formed. The polymer becomes rapidly coloured, but unlike other styrene polymers, which remain yellow, PPHS undergoes a progressive colour change from yellow through orange to brown. Infrared spectral data indicate the depletion of OH group concentration, and a concomitant formation of carbonyl, possibly quinonoid species. Crosslinking is rapid and no chain scission was detected. It is likely that the polymeric phenoxy radicals formed by photolysis or by subsequent H-abstraction contribute to the formation of both quinonoid species and crosslinks. The mechanism of the photolysis is discussed.     

Kinetic study of triphenylphosphine addition to para‐benzoquinone

Kinetics of the addition reaction of triphenylphosphine to para‐benzoquinone in 1,2‐dichloroethane as solvent was studied. Initial rate method was used to determine the order of the reaction with respect to the reactants. Pseudo‐first‐order method was also used to calculate the rate constant. This reaction was monitored by UV‐vis spectrophotometry at 520 nm by variable time method. On the basis of the obtained results, the Arrhenius equation of this reaction was obtained: The activation parameters, E_a, ΔH^#, ΔG^#, and ΔS^# at 300 K were 5.701, 6.294, 19.958 kcal mol^?1 and ?45.853 cal mol^?1 K^?1, respectively. This reaction is first and second order with respect to triphenylphosphine and para‐benzoquinone, respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:472–479, 2004     

Heterogenized peroxopolyoxotungstate catalyst on the surface of clicked magnetite‐graphene oxide nanocomposite: Magnetically recoverable epoxidation catalyst

A new heterogeneous catalyst for the epoxidation of olefins was prepared by immobilization of peroxophosphotungstate anions on the surface of clicked magnetite‐graphene oxide as magnetically recoverable support. To prepare the heterogeneous catalyst, the clicked magnetite‐graphene oxide support was prepared by thiolene click reaction of thiol functionalized graphene oxide with vinyl modified magnetite nanoparticles. The tailored support was then modified with aminopropyl groups followed by electrostatic interaction with peroxophosphotungstate anions to achieve the desired heterogeneous catalyst. Characterization of the catalyst was performed by various physicochemical methods which confirmed the successful immobilization of peroxopolyoxotungstate species on the surface of clicked magnetite‐graphene oxide. Catalytic activity of the catalyst revealed its high catalytic activity and selectivity in the epoxidation of various olefins in the presence of H₂O₂ as green oxidant. This heterogeneous catalyst can be magnetically reused several times without significant loss of activity and selectivity.     

Click functionalization of magnetite nanoparticles: A new magnetically recoverable catalyst for the selective epoxidation of olefins

A new magnetically recoverable heterogeneous molybdenum catalyst was developed by means of a click chemistry approach. First, silica‐coated magnetite nanoparticles were functionalized using a bidentate ligand via thiol–ene click reaction of mercaptopropyl‐modified magnetite nanoparticles with acrylic acid. Then, a molybdenum complex was covalently supported on the surface of the clicked silica‐coated magnetite nanoparticles. The prepared catalyst was characterized using Fourier transform infrared and inductively coupled plasma optical emission spectroscopies, X‐ray diffraction, vibrating sample magnetometry and transmission electron microscopy. The catalytic performance of the prepared heterogeneous catalyst was investigated in the epoxidation of olefins with tert‐butyl hydroperoxide as oxidant. This catalyst could be reused for five runs without significant loss of activity and selectivity.     

Cup-shaped E,E-stilbenophane: synthesis,crystal structure and supramolecular chemistry

A new E,E-stilbenophane was synthesised and characterised. The crystal structure of this cyclophane shows that this molecule has a cup-shaped structure, which hosts a phenyl ring of neighbouring molecule as guest in its cavity with a π–π distance of about 3.7 Å. Moreover, the NMR spectra and theoretical analysis (gauge-independent atomic orbitals (GIAO) and quantum theory of atoms in molecules (QTAIM)) suggest that the silver recognition by E,E-stilbenophane host molecules is based on cation–π interactions in which the π-electrons of the double bonds play a major role.     

Time-dependent discrete road network design with both tactical and strategic decisions

This paper aims to model and investigate the discrete urban road network design problem, using a multi-objective time-dependent decision-making approach. Given a base network made up with two-way links, candidate link expansion projects, and candidate link construction projects, the problem determines the optimal combination of one-way and two-way links, the optimal selection of capacity expansion projects, and the optimal lane allocations on two-way links over a dual time scale. The problem considers both the total travel time and the total CO emissions as the two objective function measures. The problem is modelled using a time-dependent approach that considers a planning horizon of multiple years and both morning and evening peaks. Under this approach, the model allows determining the sequence of link construction, the expansion projects over a predetermined planning horizon, the configuration of street orientations, and the lane allocations for morning and evening peaks in each year of the planning horizon. This model is formulated as a mixed-integer programming problem with mathematical equilibrium constraints. In this regard, two multi-objective metaheuristics, including a modified non-dominated sorting genetic algorithm (NSGA-II) and a multi-objective B-cell algorithm, are proposed to solve the above-mentioned problem. Computational results for various test networks are also presented in this paper.     

Anomalous scaling in surface roughness evaluation of electrodeposited nanocrystalline Pt thin films

Atomic force microscopy (AFM) is used to measure the surface roughness of crystalline Pt thin films as a function of film thickness and growth rate. Our films were electrodeposited on Au/Cr/glass substrates, under galvanostatic control (constant current density), from a single electrolyte containing Pt⁴⁺ ions. Crystalline structure of the films was confirmed by X-ray diffraction (XRD) technique. The effect of growth rate (deposition current density) and film thickness (deposition time) on the kinetic roughening of the films were studied using AFM and roughness calculation. The data is consistent with a rather complex behaviour known as “anomalous scaling” where both local and large scale roughnesses show power law dependence on the film thickness.     

ArF laser surface modification of polyethersulfone film: Effect of laser fluence in improving surface biocompatibility

ArF laser treatment of polyethersulfone (PES) films was performed to improve biocompatibility of surfaces. For this purpose, the threshold fluence for laser ablation of PES was obtained from experimental measurements and then samples were irradiated at 2 separate ranges of fluences, i.e. below and above the ablation threshold. In order to investigate the physico-chemical changes, the modified surfaces were characterized by attenuated total reflectance (ATR) infrared spectroscopy and contact-angle measurements. The biocompatibility of the treated samples in comparison to those untreated was examined in vitro using a platelet adhesion test. The number of adhered platelets was obtained using the lactate dehydrogenase (LDH) method. For surfaces irradiated below the ablation threshold, a high reduction in the number of the adhered platelets was observed; while this number increased in samples treated at the fluence above the ablation threshold. The change in platelet adhesion was attributed to the change in chemistry and roughness of the irradiated surfaces.     

MRI of thermally denatured blood: methemoglobin formation and relaxation effects

Focal regions of T₁-shortening have been observed in magnetic resonance imaging (MRI)-monitored thermal ablations of perfused tissues. The aims of this study were two-fold: to find evidence for heat-induced conversion of hemoglobin (Hb) to methemoglobin (mHb), and to investigate the effects of heat treatment of in-vitro blood components upon their MR relaxation times. Spectrophotometric studies were performed to confirm the heat-induced formation of methemoglobin. Preparations of whole and fractionated blood, previously submitted to elevated temperatures of 40°C to 80°C, were imaged and the relaxation times were calculated. Optical absorption spectra of samples containing free Hb, heated to 60°C, showed increased light absorption at 630 nm, evident of mHb presence. Short T₁ values in whole blood (1.13 s) and packed red blood cell (0.65 s) compartments, heated at 60°C, compared to their baseline values (1.62 s and 0.83 s, respectively), were attributed to mHb formation. In relation to MRI-guided thermal interventions, these results suggest a possible explanation for observation of hyperintense regions on T₁-weighted images.