Studies on the photophysical characteristics of poly(carboxylic acid)s bound protoporphyrin IX and metal complexes of protoporphyrin IX

The copolymers of methacrylic acid with protoporphyrin IX (PPIX) and the metal complexes, zinc protoporphyrin IX and magnesium protoporphyrin IX were synthesised and characterised. Corresponding acrylic acid copolymers were also synthesised. The steady state absorption and fluorescence spectral properties of the macromolecular bound fluorophores PPIX, Zn-PPIX and Mg-PPIX were investigated. Poly(methacrylic acid) bound protoporphyrin IX, zinc protoporphyrin IX and magnesium protoporphyrin IX show an increase in the fluorescence intensity and lifetime with increase in the pH in the range 2-8 with a marked transition around pH 6.0-7.0. The fluorophore concentration in the dilute solution of the copolymers is micromolar and the fluorophore to the carboxylic acid monomer ratios in the copolymer is around 10⁻³. The molecular weight of the copolymers is 100 ± 10 kD. The fluorescence decay curves of all the fluorophore bound polymers follow biexponential decay fit independent of pH. Poly(MAA-co-PPIX) and poly(MAA-co-MgPPIX) undergo well marked pH induced structural transitions in the pH range of 6.0-7.0 whereas poly(MAA-co-ZnPPIX) undergoes pH induced structural transitions in the pH range of 4.0. In the case of polyacrylic acid copolymers the changes observed in the steady state and time resolved fluorescence studies are less marked. The distinct hydrophobic and hydrophilic environments experienced by the fluorophore bound to PMMA are attributed to the dynamics of the macromolecules in dilute aqueous solutions manifested by the α-methyl group present in the copolymer. The studies carried out using the fluorophores in the time windows from 2 ns to 12 ns indicate evolving trends in the dynamic coiling and reverse coiling of poly methacrylic acid chain.     

Spectral and thermal studies on new hydrazinium metal sulfite dihydrates

Some new hydrazinium transition metal sulfite dihydrate complexes of the formula (N₂H₅)₂M(SO₃)₂(H₂O)₂ where M=Fe, Co, Ni, Cu and Zn have been prepared and characterized by hydrazine and metal analyses, magnetic studies, electronic and infrared spectra and thermal analysis. The magnetic studies coupled with electronic spectra of iron, cobalt, nickel and copper complexes indicate their high spin octahedral nature. However the zinc complex is diamagnetic and show only the charge transfer transition. The infrared spectra shows that both the hydrazinium ions are coordinated to the metal ions, the sulfite ions are present as bidentate ligand. The simultaneous TG-DTA of these complexes were investigated in air and nitrogen atmospheres. In air, cobalt, nickel and zinc complexes give respective metal sulfate as the final residue while iron and copper complexes give the mixture of respective metal oxide and sulfate as the decomposition product. In nitrogen atmosphere respective metal sulfites are formed as the end residue.     

Synthesis and characterization of semi-interpenetrating polymer networks using biocompatible polyurethane and acrylamide monomer

Semi-interpenetrating polymer networks (semi-IPNs) of acrylamide based polyurethanes were synthesized from different NCO-terminated polyurethane prepolymers derived from polytetramethylene ether glycol (PTMEG). The resulting semi-IPNs were characterized using FTIR, DSC, and TGA measurements. Variation in the NCO/OH ratio and the molecular weight of the diol gave semi-IPNs with different types of mechanical characteristics varying from elastomer to brittle plastic properties. Differential scanning calorimetry (DSC) data revealed a difference in the glass transition temperature (T_g) of the semi-IPNs relative to the normal polyacrylamide (PAAM) network. Incorporation of polyurethane into polyacrylamide network in the form of an interpenetrating polymer networks enhanced the mechanical and thermal properties of the semi-IPNs due to higher crosslink density imparted by the hard segment content. The swelling behavior of both the semi-IPNs and the individual polyacrylamide (PAAM) network in different pH conditions were investigated to check their biocompatibility and possible usage in biomedical field. The hydrolytic stability of the semi-IPNs and the polyacrylamide (PAMM) network was studied using phosphate buffer solution. The hydrolytic stability of the semi-IPNs was found to be more compared to PAMM network. The morphology of both the semi-IPNs and the individual polyacrylamide (PAAM) network was investigated using SEM.     

HBF4·OEt2 as a mild and versatile reagent for the Ritter amidation of olefins: a facile synthesis of secondary amides

A variety of alkenes undergo smooth amidation with nitriles in the presence of HBF₄·OEt₂ at room temperature under mild conditions to afford the corresponding secondary amides in good to excellent yields. This is a highly efficient method for the preparation of α-aryl ethyl amides especially from vinyl arenes without any side reactions such as olefin polymerization. The use of readily available and easy to handle reagent HBF₄·OEt₂ makes this method simple, convenient, and practical.     

Calculation of force constants and mean amplitudes of vibration of octahedral XY6 molecules using frequencies and zeta constants

Expressions involving vibrational frequencies, Coriolis coupling constants and masses of the atoms of the molecule that are invariant under symmetrical isotopic substitutions are derived for octahedral XY₆ molecules following the method given by Jagannathan and others. These invariants are used to calculate the force constants, compliance constants and mean amplitudes of vibration of 13 molecules of XY₆-type.     

Vocal Folds Detect Ionic Perturbations on the Luminal Surface: An In Vitro Investigation

The homeostasis of fluid bathing the luminal surface of the vocal folds is important for phonation and laryngeal defense. Dehydration of the respiratory tract during mouth breathing can perturb the concentration of sodium and chloride ions in surface fluid. Exposure to dry air also increases the osmolarity of airway surface fluid. We hypothesized that viable vocal fold epithelium would detect changes in the ionic and osmotic composition of fluid on the luminal surface. Therefore, we examined bioelectric responses of vocal folds exposed to physiologically real, luminal ionic and osmotic challenges in vitro. The study used randomized factorial design with experimental and sham control groups. Fifty native ovine vocal folds were exposed to five challenges (ionic, osmotic, combined ionic-osmotic, and sham) on the luminal surface. Bioelectric measures of potential difference (PD), short-circuit current (I(SC)), and tissue resistance were assessed at prechallenge baseline, during challenge, and after removal of challenge. Ionic and combined ionic-osmotic challenges reduced PD and I(SC) (P<0.01). These reductions depended on the nature of the ionic challenge, were observed within 10 minutes, lasted for the duration of exposure, and were reversible after removal of the challenge. Conversely, sham or osmotic challenge did not alter bioelectric parameters over time (P>0.05). Viable ovine vocal fold epithelia detect ionic perturbations to the luminal surface. This sensitivity to luminal ionic challenge may be necessary to maintain the homeostasis of surface fluid.