On the effect of montmorillonite in the curing reaction of epoxy nanocomposites

The procedure for the fabrication of epoxy-based polymer layered silicate nanocomposites is important in respect of the nanostructure that is developed. To further our understanding of this, the influence of an organically modified clay (montmorillonite, MMT) on the curing kinetics of an epoxy resin has been studied by differential scanning calorimetry. Clay loadings of 10 and 20 mass% are used, and isothermal as well as dynamic cures have been investigated. For both cure schedules the effect of the MMT is to advance the reaction. Kinetic analysis yields values for the activation energy, but shows that the reaction cannot be described simply by the usual autocatalytic equation. The glass transition of the cured nanocomposites is lower than that for the cured neat resin, a result that is attributed to homopolymerisation taking place in addition to the epoxy–amine reaction.     

Synthesis of 3‐(substituted)‐2,4,8,15‐tetroxa‐3‐phosphadispiro[5.2.5]hexadecane‐3‐oxides

Novel 3‐(substituted)‐2,4,8,15‐tetroxa‐3‐phosphadispiro[5.2.5]hexadecane‐3‐oxides (3‐12) have been synthesized by cyclization of 1,5‐dioxaspiro[5.5]undecande‐3,3‐dimethanol (1) with various substituted aryl phosphorus dichloridates (2) in dry toluene‐THF in the presence of triethylamine at 40‐60 ^oC. Their molecular structures were determined by ir, nmr and mass spectral studies and were screened for antifungal activity against Curvularia lunata and Aspergillus niger, and antibacterial activity on Staphylococcus aureus and Escherichia coli. Most of them possess significant activity.     

Photophysical studies on binding of curcumin to bovine serum albumins

The excited-state photophysical properties of curcumin in the presence of bovine serum albumin (BSA) have been studied. The absorption and fluorescence changes in curcumin on binding to BSA have been followed at varying concentrations of either curcumin or BSA to determine the binding constant, which has been found to be approximately 10(4) to 10(5) M(-1). Stopped-flow kinetics studies suggested at least two distinct kinetic steps for the binding of curcumin to BSA. The photophysical properties of the singlet-excited state of the curcumin-BSA complex have also been studied. Whereas the absorption spectrum of curcumin is redshifted, the fluorescence spectrum of curcumin was blueshifted in the presence of BSA. The fluorescence quantum yield of curcumin on complexing with BSA was approximately 0.05. Steady-state fluorescence anisotropy studies showed a significant increase in the anisotropy value of 0.37 in BSA-bound curcumin. The fluorescence decay of the curcumin-BSA complex followed a biexponential decay with fluorescence lifetimes of 413 ps (33%) and 120 ps (67%). On the basis of these complementary results, it has been concluded that curcumin shows very high binding to BSA, probably at the hydrophobic cavities inside the protein.     

Thiocarboxylato Complexes of Biscyclopentadienyl and Bisindenyl Titanium (IV)

Reactions of biscyclopentadienyl (and bisindenyl) titanium (IV) dichlorides with sodium salts of various thiocarboxylic acids in tetrahydrofuran medium, yield the complexes of the general formula (D) ²Ti(SCOR) ² where D is cyclopentadienyl or indenyl group and R? H, CH₃, C₂H₅, C⁴H⁵ or p-C⁴H⁴CH³ group. The foul smelling complexes are monomeric in nature. The IR spectra, thermal stabilities and Some physical characteristics of these complexes have been studied.     

Evaporation of Lennard-Jones clusters

Extensive molecular dynamics simulations have been done to study the evaporation of a 13-atom Lennard-Jones cluster. The survival probability and the evaporative lifetime are calculated as a function of the cluster total energy from a classical trajectory analysis. The results are interpreted in terms of the RRK theory of unimolecular dissociation. The calculation of the binding energy of the evaporated species from the evaporation rate and the average kinetic energy release is discussed.     

Simple entry into isonucleosides: synthesis of 6-amino-9-[(3S,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-3-yl]purine

A simple and efficient method for the preparation of isonucleoside 7 is described. The preparation of 1,4-anhydroxylitol 4, a key intermediate, is described by intramolecular cyclization of (2S,3R,4R)-3,5-dibenzyloxypentan-1,2,4-triol 3 using diethyl carbonate and NaH.     

Electro-chromatography in the study of ions

Summary Change of concentration of electrolyte such as sodium chloride, potassium chloride, ammonium chloride and potassium bromide has a marked effect on the direction of migration of Cd. A very cheap set incorporating a number of Durrum'S units suitable for separation of a large number of different types of mixtures of ions has been devised.     

Self-organization of a sulfonamido-porphyrin in Langmuir monolayers and Langmuir-Blodgett films

Langmuir monolayers (LM) and Langmuir-Blodgett (LB) films of pure lipophilic meso-tetra(4-dodecylaminosulfophenyl)porphyrin (PC12) and mixed with the anionic surfactant sodium hexadecylsulfate (SHS) were studied. The molecular packing and structure of PC12 and PC12-4SHS with variable surface pressure were investigated by surface pressure-area measurements, steady-state absorption, fluorescence emission and anisotropy, as well as by fluorescence lifetime imaging microscopy (FLIM). At low surface pressure, the porphyrin molecules are organized with the rings tilted on the water surface whereas at high surface pressure the porphyrin rings achieve a more perpendicular arrangement. Using the FLIM images a gradual change of aggregates into large "islands" is observed. Different patterns are observed in the pure PC12 multilayer films (n = 3 and 5) with ordered patches superimposed which are not observed in the PC12-4SHS multilayer LB films.     

A stereotypic,transplantable liver tissue-culture system

A method of coculturing adult rat hepatic parenchymal cells (PC) and stromal cells in a three-dimensional framework of nylon filtration screens or biodegradable polymer meshes was developed in our laboratory. Rat liver stroma, which includes vascular and bile duct endothelial cells, fat-storing cells, fibroblasts, and Kupffer cells, were isolated by gradient centrifugation afterin situ liver perfusion and expanded in monolayer culture prior to seeding onto nylon screens or bioresorbable polyglycolic acid (PGA) polymers oriented into a felt-like construct. A second inoculum of freshly isolated PC was applied after the stromal cells became established. Histological analyses revealed that PC proliferation occurred until all available space for expansion within the template was exhausted. These cells retained their rounded morphology, and after 4–5 wk 7–9 “layers” of PC filled the 140-μm deep template. Dioxin-inducible cytochrome P450 activity was detected for up to 58 d in culture, and albumin, fibrinogen, transferrin, and soluble fibronectin were detected in the medium by enzyme-linked immunosorbent assay (ELISA) for 48 d in vitro. Immunohistochemical analysis of sections through the cultures confirmed the presence of these proteins as well as cytokeratin at the cellular level; the extracellular matrix stained for both collagen type III and laminin. Long-term PC proliferation and function were enhanced by the presence of stromal cells as well as by a meshwork template whose geometry allows the interaction of PC with stroma and matrix on several different planes. To permit transplantation, co-cultures of hepatic PC and stromal cells were established on PGA felt constructs instead of nylon screens. After 24 d in vitro, these constructs were grafted into sites in the mesentery, omentum, and sub-cutaneous tissues of adult Long-Evans rats. The growth of hepatocytes after 30 din situ was evident by histological analysis; grafts of co-cultures regenerated a liver-like architecture consisting of sinusoids and putative biliary structures. In addition, PC at these extrahepatic graft sites were positive for albumin, transferrin, and fibrinogen synthesis by immunohistochemistry. Graft survival was enhanced when recipients were subjected to 40% hepatectomy. Hepatic PC:stromal cell cocultures may prove useful in the restoration of liver function either by direct transplantation using PGA or similar templates, or as extracorporeal devices, using nylon screens.