Amphiphilic membranes crosslinked and reinforced by POSS

This article concerns the synthesis and characterization of novel tricomponent amphiphilic membranes consisting of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments cocrosslinked and reinforced by octasilane polyhedral oligomeric silsesquioxane (octasilane‐POSS) cages. Rapid and efficient network synthesis was effected by cocrosslinking diallyl‐telechelic PEG (A‐PEG‐A) and divinyl‐telechelic PDMS (V‐PDMS‐V) with pentamethylpentacyclosiloxane (D₅H), using Karstedt's catalyst in conjunction with Et₃N cocatalyst and water. Films were prepared by pouring charges in molds and crosslinking by heating at 60 °C for several hours. The films were characterized by sol fractions and equilibrium swelling both in hexane and water, extent of crosslinking, contact angle hysteresis, oxygen permeability, thermogravimetric analysis, and mechanical properties. The crosslinking of octasilane‐POSS achieved by the same catalyst system was studied in separate experiments. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4337–4352, 2004     

Synthesis and burst strength of water‐swollen immunoisolatory tubules

A series of amphiphilic hydrogel tubules have been prepared by copolymerizing/crosslinking hydrophilic poly(dimethylacrylamide) segments with hydrophobic di‐, tri‐, and octamethacrylate‐telechelic polyisobutylene crosslinkers, and their elastic modulus and burst strength in the water‐swollen state were investigated. Because the burst characteristics of hydrogels have not yet been quantitatively investigated, equipment was designed and built to generate fundamental insight into the burst properties of thin‐walled (200–250 μm) narrow lumen (2–3 mm i.d.) water‐swollen tubules. The theory developed to describe quantitatively the inflation behavior of thin‐walled rubber tubules was adapted to treat our experimental observations. Changes in the burst strength, elastic modulus, and expansion during the inflation of hydrogel tubules were interpreted in terms of the molecular weight of the hydrophilic segments between crosslinking sites (M_{c,hydrophilic}), which in turn was calculated according to the rubber elasticity theory. According to these investigations, the burst strength of our water‐swollen amphiphilic tubules is in the 0.2–0.5 MPa range, which is sufficient for implantation and immunoisolatory applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2075–2084, 2002     

Influence of nano-AL2O3-catalyst sizes on hydrogen formation at the water radiolysis under ionizing radiation

The aim of this study was to investigate the regularities of molecular hydrogen formation from water dispersing Al₂O₃ nanoparticles irradiated with gamma ray. It was established that formed molecular hydrogen’s yield changed depending on the size of the catalyst, so that yield of molecular hydrogen formed on the surface with small size is 1.4–1.6 times greater than the one with big size. Equal distribution of nanocatalyst in water medium and much more adsorption of water molecule on the catalyst surface result in more efficient radiolysis process.     

Numerical-analytic implementation of the higher-order canonical Van Vleck perturbation theory for the interpretation of medium-sized molecule vibrational spectra

Anharmonic vibrational states of semirigid polyatomic molecules are often studied using the second-order vibrational perturbation theory (VPT2). For efficient higher-order analysis, an approach based on the canonical Van Vleck perturbation theory (CVPT), the Watson Hamiltonian and operators of creation and annihilation of vibrational quanta is employed. This method allows analysis of the convergence of perturbation theory and solves a number of theoretical problems of VPT2, e.g., yields anharmonic constants y(ijk), z(ijkl), and allows the reliable evaluation of vibrational IR and Raman anharmonic intensities in the presence of resonances. Darling-Dennison and higher-order resonance coupling coefficients can be reliably evaluated as well. The method is illustrated on classic molecules: water and formaldehyde. A number of theoretical conclusions results, including the necessity of using sextic force field in the fourth order (CVPT4) and the nearly vanishing CVPT4 contributions for bending and wagging modes. The coefficients of perturbative Dunham-type Hamiltonians in high-orders of CVPT are found to conform to the rules of equality at different orders as earlier proven analytically for diatomic molecules. The method can serve as a good substitution of the more traditional VPT2.     

Calculation of anharmonic intensities in vibrational spectra of raman scattering and full interpretation of the vibrational spectrum of <Emphasis Type="Italic">trans</Emphasis>-1,3-butadiene

The anharmonic model of vibrations of polyatomic molecule makes it possible, using the secondorder perturbation theory, to interpret vibrational spectra in detail with resonances taken into account and to calculate the band intensities in spectra for fundamental frequencies, overtones, and combination frequencies. For molecules possessing a center of symmetry (to which trans-1,3-butadiene belongs), many vibration modes have zero intensities of absorption in IR spectra due to the mutual exclusion rule. For meaningful analysis of vibrations of such molecules, measurement of Raman scattering (RS) spectra is necessary, as is developing a theoretical model for calculating the anharmonic intensity. Perturbation theory (PT) in the form of contact transformations (CTs) has proven applicable for calculating the anharmonic intensities in RS spectra. The FORTRAN software program ANCO has been developed, which allows the calculation of vibration frequencies and IR-RS intensities of fundamental vibrations, overtones, and combination frequencies on the basis of second-order PT in form of CTs using the polynomial representation of potential energy, dipole moment and polarizability surfaces. The obtained frequencies and modes of anharmonic vibrations are provided, as well as interpretation of the experimental spectrum of the trans-1,3-butadiene molecule. A procedure for calculating the scale factors of the anharmonic force field is proposed. We also show that within the anharmonic vibration model, these factors are close to unity.     

The Existence and Behavior of Global Solutions to a Mixed Problem with Acoustic Transmission Conditions for Nonlinear Hyperbolic Equations with Nonlinear Dissipation

A mixed problem with acoustic transmission conditions for nonlinear hyperbolic equations with nonlinear dissipation is considered. The existence, uniqueness, and exponential decay of global solutions to this problem with focusing nonlinear sources are proved Additionally, the existence of global solutions and the solution blow-up in a finite time are proved for the case of defocusing nonlinear sources.     

Existence of Solutions of Nonlinear Strongly Dissipative Wave Equations with Acoustic Transmission Conditions

Computational Mathematics and Mathematical Physics - The mixed problem for nonlinear strongly dissipative wave equations with acoustic transmission conditions is considered. An existence and...     

Conversion of Straight-Run Naphtha to C5−C6 Alkanes on Co(Ni)/HZSM–5/SO 4 2- —ZrO2 Composite Catalysts

Russian Journal of Applied Chemistry - The conversion of straight-run naphtha on composite catalytic systems containing HZSM-5 zeolite modified with 0.4 wt % Co or Ni and 15% SZ (10% SO 4 2-...