Kapok/cotton fabric–polypropylene composites

Kapok/cotton fabric has been used as reinforcement for conventional polypropylene and maleic anhydride grafted polypropylene resins. Treating the reinforcement with acetic anhydride and sodium hydroxide has modified the fabric (fibres). Thermal and mechanical properties of the composites were investigated. Results show that fibre modification gives a significant improvement to the thermal properties of the plant fibres, whereas tests on the mechanical properties of the composites showed poor tensile strength. Mercerisation and weathering were found to impart toughness to the materials, with acetylation showing slightly less rigidity compared to other treatments on either the fibre or composites. The modified polypropylene improved the tensile modulus and had the least toughness of the kapok/cotton reinforced composites. MAiPP reinforced with the plant fibres gave better flexural strength and the same flexural modulus at lower fibre content compared with glass fibre reinforced MAiPP.     

Photoreduction of Ru(bpy)(3)2+ by amines in aqueous solution. Kinetics characterization of a long-lived nonemitting excited state

The photochemistry of Ru(bpy)(3)+2 in the presence of amines was investigated in water by laser flash photolysis. N,N'-Dimethylaniline and p-phenylenediamine quench the luminescent metal to ligand charge transfer (MLCT) excited state of the complex by an electron transfer reaction that produces the semireduced form Ru(bpy)3+ in relatively high yields. On the other hand, triethylamine (TEA) and aniline do not quench the MLCT. Nevertheless, when laser flash irradiation at 532 nm is carried out in the presence of these amines, the formation of Ru(bpy)3+ is clearly detected by its transient absorption at 510 nm. These results are interpreted by an electron transfer reaction with the participation of a nonemitting excited state of the complex, formed independently of the MLCT from the Franck-Condon or the relaxed singlet excited state. The rate constants for the quenching of this state by TEA and aniline and the quantum yields for Ru(bpy)(3)+ were determined. The new state is formed in a very fast process and has a lifetime of ca 4 micros in water.     

Tin-mediated synthesis of lyso-phospholipids

1-O-Acyl-sn-glycero-3-phosphocholine and 1-O-acyl-sn-glycero-3-phosphoric acid have been prepared selectively and with high yields from the corresponding diols, glycerophosphoryl choline and glycerol-3-phosphate. Starting from the diols, the activated tin ketals were prepared in 2-propanol by reaction with dialkyltin oxide. The intermediates were acylated in the same solvent with long-chain fatty acid chlorides, giving the corresponding 1-acyl-lyso-phospholipids in high yield and with complete regioselectivity. The catalytic nature of the tin-mediated acylation and the relevance of the solvent are discussed.     

Effect of micellar systems on the equilibrium of chemical reactions: Acidity and binding constants of polymethylphenols in sodium dodecyl sulphate

The variations of the acidity constants in the presence of sodium dodecyl sulphate (SDS) are used to estimate the binding constants of a series of methyl-substituted phenols with the SDS micelles. The contribution of each methyl group to the transfer free energy from water to micelles is about —520 cal mol^-1, irrespective of the position in the benzene ring.     

The excited-state interaction of resazurin and resorufin with amines in aqueous solutions. Photophysics and photochemical reactions

The photophysics and photochemical behavior of the phenoxazin-3-one dyes, resazurin and resorufin, have been studied in aqueous solutions. The irradiation of resazurin in the presence of amines leads to deoxygenation of the N-oxide group, giving resorufin. This photoreaction is highly dependent on the amine structure and is efficient only in the presence of tertiary aliphatic amines. The absorption and fluorescence properties of these dyes are dependent on pH. At pH above 7.5 both dyes are in their anionic form. For resorufin this form is highly fluorescent (phiF = 0.75). At lower pH the fluorescence is strongly reduced. The N-oxide dye presents a very weak fluorescence quantum yield (0.11), which also is reduced at low pH. Flash photolysis experiments allowed characterization of the triplet state and the transients formed after irradiation of these dyes in the absence and presence of amines. The triplet quantum yields are 0.08 for resazurin and 0.04 for resorufin. The photodeoxygenation of N-oxide in the presence of amines occurs from the triplet state.     

Long chain heterocyclic dyes. Part Two. Surface active dyes

A series of heterocyclic cyanine dyes were prepared. Unsymmetrical dyes showed self-micellizing properties due to the presence of two positive charges and of a long alkyl chain. Symmetrical dyes, containing three positive charges and not containing the hydrophobic chain, did not give rise to micelles. The physical properties of the dyes and their spectra were briefly discussed. Cationic (HTAB) and anionic (SDS) surfactants gave strong interactions with surface active dyes, leading to deaggregation and solvation phenomena.     

Salt-induced Charge Separation in Photoinduced Electron Transfer Reactions. The Effect of Ion Size*

The effect of added salts on the efficiency for photoinduced charge separation in two typical electron acceptor (A)/electron donor (D) systems was studied by the technique of laser flash photolysis. We investigate the exciplex-forming pyrene/p-dicyanobenzene (Py/DCB) and pyrene/N,N-dimethylaniline (Py/DMA) systems in ethyl acetate. The salts selected for this study are tetrabutylammonium chloride, tetrahexylammonium chloride, lithium perchlorate, sodium perchlorate, tetrabutylammonium perchlorate, sodium tetraphenylborate and tetrabutylammonium tetraphenyl-borate. In most cases, the salts quench the emission of the exciplexes with rate constants near the diffusional rate limit in ethyl acetate. An apparent red shift of the fluorescence maximum of the exciplexes with increasing salt concentration is also generally observed. Laser flash photolysis experiments showed that in the absence of the salts both A/D systems yield exclusively the triplet excited state of the polyaromatic. However, in the presence of many of the electrolytes studied, induced free radical ion formation is observed. The experimental efficiencies for induced charge separation (n) depend on the A/D system and on the nature of the salt. The measured n values vary between 0 and 0.5. The most striking variation corresponds to the lithium and sodium perchlorates. These salts are almost totally inefficient in quenching the Py/DCB exciplex, while they quench and induce charge separation from the Py/DMA exciplex with a high yield. The effect of the different salts on both exciplexes may be rationalized by using the concept of the soft/hard character of the interacting ions.