Water–ice phase transition probed by Raman spectroscopy

Raman spectroscopy was used to study the liquid–solid water phase transition. Special attention was devoted to the OH stretching band of the Raman spectrum, which shows monotonous changes in the temperature range between 10 and − 15 °C. The interpretation of this spectral change, as well as a careful analysis of its integrated scattered intensity, led to a spectral marker that allows the determination of the water phase (liquid or solid), and the efficient identification of the liquid–solid phase transition itself. Copyright © 2011 John Wiley & Sons, Ltd.     

Gold nanoparticles on a thiol-functionalized silica network for ascorbic acid electrochemical detection in presence of dopamine and uric acid

A simple preparation methodology able to stabilize gold nanoparticles and to obtain an electrode which detects ascorbic acid, uric acid, and dopamine by different techniques is presented. A 3-mercaptopropyl-functionalized silica network was synthesized using the sol–gel method. Gold nanoparticles (nAu) were immobilized on the material at synthesis by adding a sol of these previously prepared particles to the reaction mixture. The electrochemical behavior of the SiO₂/MPTS/Au carbon paste electrode was studied using cyclic voltammetry in the presence of a hexacyanoferrate probe molecule. The presence of nAu in the functionalized silica network changes the electrochemical characteristics of the material, favoring the electron transfer process of this complex ion. The SiO₂/MPTS/Au electrode was proven to be an efficient tool in the simultaneous determination of ascorbic acid (H₂AA), dopamine (DA), and uric acid (UA) using square wave voltammetry techniques. With the nAu on the electrode, an increase in the peak current related to the redox process of the H₂AA, DA, and UA was observed. The separations of the anodic peak potentials between DA/H₂AA and UA/H₂AA were 310 and 442?mV, respectively. The results obtained show that the SiO₂/MPTS/Au electrode can be used in the simultaneous determination of H₂AA, DA, and UA.     

A convenient route to dinuclear chloro-bridged platinum(II) derivatives via nitrile complexes

The syntheses of the complexes [PtCl(2)(NCR)L] [R = Me, Et; L = PPh(3); R = Et, L = Py, CO] and [PtCl{(κ(2)-P,C)P(OC(6)H(4))(OPh)(2)}(NCEt)] are described starting from the easily available [PtCl(2)(NCR)(2)]. The stability of the products under different experimental conditions is discussed as well as their use as precursors to dinuclear complexes [Pt(μ-Cl)ClL](2). The crystal and molecular structures of cis-[PtCl(2)(NCEt)(PPh(3))], [SP-4-2]-[PtCl{(κ(2)-P,C)P(OC(6)H(4))(OPh)(2)}(NCEt)] and trans-[Pt(μ-Cl){(κ(2)-P,C)P(OC(6)H(4))(OPh)(2)}](2) are reported.     

Preparation and characterization of chloroaluminum phthalocyanine-loaded solid lipid nanoparticles by thermal analysis and powder X-ray diffraction techniques

Solid lipid nanoparticles (SLN) without drug and SLN loaded with chloroaluminum phthalocyanine (AlClPc) were prepared by solvent diffusion method in aqueous system and characterized by thermal analyses and X-ray diffraction (XRD) in this study. Determination of particle size, zeta potential (ZP), and encapsulation efficiency were also evaluated. SLN containing AlClPc of nanometer size with high encapsulation efficiency and ZP were obtained. The results indicated that the size of SLN loaded with AlClPc is larger than that of the inert particle, but ZP is not changed significantly with incorporation of the drug. In differential scanning calorimetry (DSC) curves, it was observed that the melting point of stearic acid (SA) isolated and in SLN occurred at 55 and 64 °C, respectively, suggesting the presence of different polymorphs. DSC also shows that the crystallinity state of SLN was much less than that of SA isolated. The incorporation of drug in SLN may have been favored by this lower crystallinity degree of the samples. XRD techniques corroborated with the thermal analytic techniques, suggesting the polymorphic modifications of stearic acid.     

Bootstrap Algorithms for Risk Models with Auxiliary Variable and Complex Samples

Resampling methods are often invoked in risk modelling when the stability of estimators of model parameters has to be assessed. The accuracy of variance estimates is crucial since the operational risk management affects strategies, decisions and policies. However, auxiliary variables and the complexity of the sampling design are seldom taken into proper account in variance estimation. In this paper bootstrap algorithms for finite population sampling are proposed in presence of an auxiliary variable and of complex samples. Results from a simulation study exploring the empirical performance of some bootstrap algorithms are presented.      

Assembly maps and realization of splitting obstructions

In 1987 Kharshiladze introduced the concept of type for an element in a Wall group, and proved that the elements of first and second type cannot be realized by normal maps of closed manifolds. This approach is sufficiently easy for computing the assembly maps and sometimes very effective. Here we give a geometrical interpretation of this approach by using the Browder–Quinn surgery obstruction groups for filtered manifolds. To understand the obtained relations we give algebraic definitions of the element types which are based on the algebraic surgery theory of Ranicki. Our approach describes a level of indeterminate for the algebraic passing to surgery on a codimension k submanifold of a given Browder–Livesay filtration. Then we study the realization of splitting obstructions by simple homotopy equivalences of closed manifolds, and compute the assembly maps for some classes of groups.     

A sufficient condition for the liveness of weighted event graphs

Weighted event graphs (in short WEG) are widely used to model industrial problems and embedded systems. In an optimization context, fast algorithms checking the liveness of a marked WEG must be developed. The purpose of this paper is to develop a sufficient condition of liveness of a WEG. We first show that any unitary WEG can be transformed into a graph in which the values of the arcs adjacent to any transition depend on the transition. Then, a simple sufficient condition of liveness can be expressed on this new graph and polynomially computed. This condition is shown to be necessary for a circuit with two transitions.     

Toughness of epoxies modified by preformed acrylic rubber particles

A bisphenol-A diglycidyl ether resin, cured with isophorone-diamine at 60°C, was modified by means of preformed core-shell acrylic rubber particles. Blends with rubber contents up to 30 phr by wt were tested. The fracture toughness depended linearly on the amount of rubber and significant improvement was found. No deterioration of temperature resistance was also observed. The viscosity of resin/modifier mixtures was controlled by means of antifoaming agents. A comparison with liquid acrylonitrile-butadiene copolymers showed that core-shell particles are efficacious tougheners. The effect of a bimodal particle size distribution was considered. In the size range investigated (0.2+5μm) no synergic effect was observed.     

Multi-Layer Pipes for Hydrocarbons Conveyance

The replacement of metals with plastics in piping systems is a well established practice in a vast range of public and industrial applications. However, difficulties still exist, mainly related to the limited chemical resistance of the polymers commonly used in pipe manufacturing to some conveyed fluids. This prevents using plastic pipes in important applications such as the transport of liquid hydrocarbons, particularly in oil fields. The use of chemically resistant polymers, such as fluorinated polyolefins, is precluded by high cost and poor mechanical properties. Co-extrusion of multi-layer pipes carrying an internal chemically resistant liner can be a viable alternative capable to extend the use of plastic pipes to refining and chemical industries. An experimental PE/PA multi-layer pipe has been developed whose resistance to diffusion and mechanical properties have been tested. Tests in real oil fields confirm the good performance of the new pipes.     

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory-based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH₂OO, CH₃CHOO, (CH₃)₂COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene-derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH₂OO and (CH₃)₂COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever-growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing ¹ππ* state, and how this varies with CI, with conformer and with excitation wavelength. The later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo-induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non-adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI.