Solid-state Thermal Polymerization of Sodium Acrylate

Initiation and propagation processes in thermally initiated solid-state polymerization of sodiumvacrylate have been studied. The kinetics of initiation, followed with the electron spin resonancev technique, leads to an activation energy E of 28.8 kcal/mol, which is attributed to the formation of dimeric radicals. The activation energy of 16 f 1 kcaVmol obtained for the solid-state polymerization of sodium acrylate by chemical analysis and differential scanning calorimetry has been attributed to the propagation process.

The ethyl, 1- and 2-propyl, and other simple alky carbanions do not exist

A combination of experimental data and theoretical calculations has been used to estimate the electron affinities of simple primary, secondary, and tertiary alkyl radicals and the proton affinities of the corresponding anions. With the exception of cyclopropyl, such carbanionsâ are indicated to be unstable towards loss of an electron and are not expected to exist as long-lived species in the gas phase.

Generation of H2O2 in biomembranes

Knowledge of the generation of H202 in cellular oxidations has existed for many years. It has been assumed that H202 is tOxiC tO cells and the presence of catalase is indicative of a detoxication mechanism. Other radicals of oxygen were recently recognized to be more potent destructive agents of biological material than H202. Also catalase and other peroxidases utilize H202 in some cellular oxidation processes leading to several important metabolites. Thus, the generation of H202 in cellular processes seems to be purposeful and H202 can not be dismissed as a mere undesirable byproduct. Biological formation of H202 is not limited to the previously known flavoproteins and some copper enzymes, but other redox systems, particularly heme and non-heme iron proteins, are now found to undergo auto-oxidation yielding H202. The capacity for generation of H202 is now found to be widespread in a variety of organisms and in the organdies of the cells. The reduction of oxygen to H20 by mitochondrial cytochrome oxidase being the predominant oxygen-utilizing reaction had over-shadowed the importance of the quantitatively minor pathways. Under aerobic conditions generation of H202 by a Variety of biomembranes has now been found to be a physiological event interlinked with phenomena such as phagocytosis, transport processes and thermogenesis in some as yet unidentified way. The underlying mechanisms of these processes seem to involve generation and utilization of H202 in mitochondria, microsomes, peroxisomes or plasma membranes. This review gives an account of the potential of biomembranes to generate H202 and its implication in the cellular processes.

Photo-induced double-strand DNA and site-specific protein cleavage activity of L-histidine (mu-oxo)diiron(III) complexes of heterocyclic bases

Three oxo-bridged diiron(III) complexes of L-histidine and heterocyclic bases [Fe-2(mu-O)(L-his)(2)(B)(2)](ClO4)(2) (1-3), where B is 2,2'-bipyridine (bpy),1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), were prepared and characterized. The bpy complex 1 was structurally characterized by X-ray crystallography. The molecular structure showed a {Fe-2(mu-O)} core in which iron(III) in a FeN4O2 coordination is bound to tridentate monoanionic L-histidine and bidentate bpy ligands. The Fe center dot center dot center dot Fe distance is similar to 3.5 angstrom. The Fe-O-Fe unit is essentially linear, giving a bond angle of similar to 172 degrees. The complexes showed irreversible cyclic voltammetric cathodic response near -0.1 V vs. SCE in H2O-0.1 M KCl. The binuclear units displayed antiferromagnetic interaction between two high-spin (S = 5/2) iron(III) centers giving a -J value of -110 cm(-1). The complexes showed good DNA binding propensity giving a binding constant value of similar to 10(5) M-1. Isothermal titration calorimetric data indicated single binding mode to the DNA. The binding was found to be driven by negative free energy change and enthalpy. The dpq complex 3 showed oxidative double-strand DNA cleavage on exposure to UV-A and visible light. The phen complex 2 displayed single-strand photocleavage of DNA. The DNA double-strand breaks were rationalized from theoretical molecular docking calculations. Mechanistic investigations showed formation of hydroxyl radicals as the reactive species through photodecarboxylation of the L-histidine ligand. The complexes exhibited good binding propensity to bovine serum albumin (BSA) protein in Tris-HCl/NaCl buffer medium. The dpq complex 3 showed UV-A light-induced site-specific oxidative BSA cleavage forming fragments of similar to 45 kDa and similar to 20 kDa molecular weights via SOH pathway.

Structure of 4-Hydroxymonophenylbutazone

4-Butyl-4-hydroxy-l-phenyl-3,5-pyrazolidinedione, ClaH16N20 a, Mr=248.3, monoclinic, P21/n, a = 22.357 (5), b = 5.014 (2), c = 11.350 (4)/~,, //=91.88(3) °, V=1272(1)A 3, Z=4, D,,=1.296(3), D x = 1.297 Mg m -3, 2(Cu Ka) = 1.5418/~, a = 0.777 mm -~, F(000) = 528, T= 293 K. Final R - 0.059 for 1668 observed reflections. The hetero nitrogen which carries the six-membered ring is planar in the structure while the other unsubstituted one is pyramidal. The five- and six-membered rings are almost coplanar. The crystal is made up of infinite columns of hydrogen-bonded molecules.

Laser flash photolysis study of triplets of cyclobutanethiones

Five cyclobutanethiones with different chromophores at the 3-position were examined for triplet state behaviour in benzene using laser excitation into their low lying nπ*1 band systems. A weak transient absorption attributable to the triplet state is observed in all these cases. Results concerning triplet lifetimes, intersystem crossing yields (S1 → T1), self-quenching kinetics and kinetics of energy transfer to all-trans-1,6-diphenyl-1,3,5-hexatriene and oxygen and quenching by di-t-butyl nitroxide (DTBN) are presented. Intersystem crossing yields estimated with reference to p,p′-dimethoxythiobenzophenone are roughly unity in all five cases. Self-quenching rates are found to be less than diffusion limited and this is attributed to steric crowding at the α positions (dimethyl group). The rates of oxygen and DTBN quenching compare well with those reported for several other thiones in the literature. No transients other than the triplet were detected in the above cyclobutane-thiones.

Structural studies of analgesics and their interactions. VII. Stereoisomerism and disorder in the structure of oxyphenbutazone monohydrate

Oxyphenbutazone, C19H20N203, a metabolite and perhaps the active form of phenylbutazone, is a widely used non-narcotic analgesic and anti-inflammatory pyrazolidinedione derivative. The monohydrate of the compound crystallizes in the triclinic space group Pi with two molecules in a unit cell of dimensions a -- 9.491 (4), b = 10.261 (5), c = 11.036 (3)A and ¢~ = 72.2 (1), fl = 64.3 (1), 7 = 73.0 (1) °. The structure was solved by direct methods and refined to an R value of 0.107 for 1498 observed reflections. The butyl group in the molecule is disordered. The hydroxyl group occupies two sites with unequal occupancies. On account of the asymmetry at the two N atoms and one of the C atoms in the central five-membered ring, the molecule can exist in eight isomeric states, of which four are sterically unfavourable. The disorder in the position of the hydroxyl group can be readily explained on the basis of the existence, with unequal abundances, of all four sterically favourable isomers.The bond lengths and angles in the molecule are similar to those in phenylbutazone. The crystal structure is stabilized by van der Waals interactions, and O-H... O hydrogen bonds involving the carbonyl and the hydroxyl groups as well as a water molecule.

Oxidations of thio ketones by singlet and triplet oxygen

Oxidation of di-tert-butyl thioketone (1) and 2,2,4,4-tetramethylcyclobutylth ioketone (2) by singlet oxygen yields the corresponding sulfine and ketone; in the case of 1 the sulfine is the major product, whereas in 2 it is the ketone. 1,2,3-Dioxathietane has been suggested as the precursor for the ketones, and the zwitterionic/diradid peroxide is believed to be a common primary intermediate for both sulfine and ketone. Steric influence is felt both during primary interaction between singlet oxygen and thioketone and during the partitioning of the peroxide intermediate. Steric interaction is suggested as the reason for variations in the product distribution between 1 and 2. Singlet oxygen is also generated through energy transfer from the triplet state of thioketones. These excited states also directly react with oxygen to yield ketone.

A vanadate-stimulated NADH oxidase in erythrocyte membrane generates hydrogen peroxide

Oxidation of NADH by rat erythrocyte plasma membrane was stimulated by about 50-fold on addition of decavanadate, but not other forms of vanadate like orthovanadate, metavanadate aad vanadyl sulphate. The vanadate-stimulated activity was observed only in phosphate buffer while other buffers like Tris, acetate, borate and Hepes were ineffective. Oxygen was consumed during the oxidation of NADH and the products were found to be NAD+ and hydrogen peroxide. The reaction had a stoichiometry of one mole of oxygen consumption and one mole of H2O2 production for every mole of NADH that was oxidized. Superoxide dismutase and manganous inhibited the activity indicating the involvement of superoxide anions. Electron spin resonance in the presence of a spin trap, 5, 5prime-dimethyl pyrroline N-oxide, indicated the presence of superoxide radicals. Electron spin resonance studies also showed the appearance of VIV species by reduction of VV of decavanadate indicating thereby participation of vanadate in the redox reaction. Under the conditions of the assay, vanadate did not stimulate lipid peroxidation in erythrocyte membranes. Extracts from lipid-free preparations of the erythrocyte membrane showed full activity. This ruled out the possibility of oxygen uptake through lipid peroxidation. The vanadate-stimulated NADH oxidation activity could be partially solubilized by treating erythrocyte membranes either with Triton X-100 or sodium cholate. Partially purified enzyme obtained by extraction with cholate and fractionation by ammonium sulphate and DEAE-Sephadex was found to be unstable.

Photooxidative and pyrolytic degradation of methyl methacrylate-alkyl acrylate copolymers

Different compositions of poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA) copolymers were synthesized and characterized. The photocatalytic oxidative degradation of all these copolymers were studied in presence of two different catalysts namely Degussa P-25 and combustion synthesized titania using azobis-iso-butyronitrile and benzoyl peroxide as oxidizers. Gel permeation hromatography (GPC) was used to determine the molecular weight distribution of the samples as a function of time. The GPC chromatogram indicated that the photocatalytic oxidative degradation of all these copolymers proceeds by both random and chain end scission.Continuous distribution kinetics was used to develop a model for photocatalytic oxidative degradation considering both random and specific end scission. The degradation rate coefficients were determined by fitting the experimental data with the model. The degradation rate coefficients of the copolymers decreased with increase in the percentage of alkyl acrylate in the copolymer. This indicates that the photocatalytic oxidative stability of the copolymers increased with increasing percentage of alkyl acrylate. From the degradation rate coefficients, it was observed that the photocatalytic oxidative stability follows the order PMMABA > PMMAEA > PMMAMA. The thermal degradation of the copolymers was studied by using thermogravimetric analysis (TGA). The normalized weight loss and differential fractional weight loss profiles indicated that the thermal stability of the copolymer increases with an increase in the percentage of alkyl acrylate and the thermal stability of poly(methyl methacrylate-co-alkyl acrylate)s follows the order PMMAMA > PMMAEA > PMMABA. The observed contrast in the order of photostability and thermal stability of the copolymers was attributed to different mechanisms involved for the scission of polymer chain and formation of different products in both the processes.

Oxidations of thio ketones by singlet and triplet oxygen

Oxidation of di-tert-butyl thioketone (1) and 2,2,4,4-tetramethylcyclobutylth ioketone (2) by singlet oxygen yields the corresponding sulfine and ketone; in the case of 1 the sulfine is the major product, whereas in 2 it is the ketone. 1,2,3-Dioxathietane has been suggested as the precursor for the ketones, and the zwitterionic/diradid peroxide is believed to be a common primary intermediate for both sulfine and ketone. Steric influence is felt both during primary interaction between singlet oxygen and thioketone and during the partitioning of the peroxide intermediate. Steric interaction is suggested as the reason for variations in the product distribution between 1 and 2. Singlet oxygen is also generated through energy transfer from the triplet state of thioketones. These excited states also directly react with oxygen to yield ketone.

Mechanism of aromatic hydroxylation *1, , *2, , *3: Properties of a model for pyridine nucleotide-dependent flavoprotein hydroxylases

A model (NADH-phenazine methosulfate-O2) formally similar to pyridine nucleotide-dependent flavoprotein hydroxylases catalyzed the hydroxylation of several aromatic compounds. The hydroxylation was maximal at acid pH and was inhibited by ovine Superoxide dismutase, suggesting that perhydroxyl radicals might be intermediates in this process. The stoichiometry of the reaction indicated that a univalent reduction of oxygen was occurring. The correlation between the concentration of semiquinone and hydroxylation, and the inhibition of hydroxylation by ethanol which inhibited semiquinone oxidation, suggested the involvement of phenazine methosulfate-semiquinone. Activation of hydroxylation by Fe3+ and Cu2+ supported the contention that univalently reduced species of oxygen was involved in hydroxylation. Catalase was without effect on the hydroxylation by the model, ruling out H2O2 as an intermediate. A reaction sequence, involving a two-electron reduction of phenazine methosulfate to reduced phenazine methosulfate followed by disproportionation with phenazine methosulfate to generate the semiquinone, was proposed. The semiquinone could donate an electron to O2 to generate O2 which could be subsequently protonated to form the perhydroxyl radical.

Structural studies of analgesics and their interactions. Part 4. Crystal structures of phenylbutazone and a 2 : 1 complex between phenylbutazone and piperazine

The X-ray crystal structures of 4-butyl-1,2-diphenylpyrazolidine-3,5-dione (phenylbutazone)(I). and its 2 : 1 complex (II) with piperazine have been determined by direct methods and the structures refined to R 0.096 (2 300 observed reflections measured by diffractometer) and 0.074 (2 494 observed reflections visuallyestimated). Crystals are monoclinic, space group P21/c; for (I)a= 21.695(4), b= 5.823(2), c= 27.881(4)Å, = 108.06 (10)°, Z= 8, and for (II)a= 8.048(4), b= 15.081(4), c= 15.583(7)Å, = 95.9(3)°, Z= 2. The two crystallographically independant molecules in the structure of (I) are similar except for the conformation of the butyl group, which is disordered in one of the molecules. In the pyrazolidinedione group, the two C–C bonds are single and the two C–O bonds double. The two nitrogen atoms in the five-membered ring are pyramidal with the attached phenyl groups lying on the opposite sides of the mean plane of the ring. The phenylbutazone molecule in (II) exists as a negative ion owing to deprotonation of C-4. C-4 is therefore trigonal and the orientation of the Bu group with respect to the pyrazolidinedione group is considerably different from that in (I); there is also considerable electron delocalization along the C–O and C–C bonds. These changes in geometry and electronic structure may relate to biological activity. The doubly charged cationic piperazine molecule exists in the chair form with the nitrogen atoms at the apices. The crystal structure of (II) is stabilized by ionic interactions and N–H O hydrogen bonds.

Continuous Distribution Kinetics for Photopolymerization of Alkyl Methacrylates

The photopolymerization of methyl,ethyl,butyl, and hexyl methacrylates in solution was studied. The effect of initial initiator and monomer concentrations on the time evolution of polymer concentration (M) over bar (n) and PDI was examined. The reversible chain addition and beta-scission, and primary radical termination steps were included in the mechanism along with the classical steps. The rate equations were derived using continuous distribution kinetics and solved numerically to fit the experimental data. The regressed rate coefficients compared well with the literature data. The model predicted the instantaneous increase in (M) over bar (n) and PDI to steady state values. The rate coefficients exhibited a linear increase with the size of alkyl chain of the alkyl methacrylates.

Ultrasonic degradation of poly(methyl methacrylate-co-alkyl acrylate) copolymers

The copolymers, poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA), of different compositions were synthesized and characterized. The effect of alkyl acrylate content, alkyl group substituents and solvents on the ultrasonic degradation of these copolymers was studied. A model based on continuous distribution kinetics was used to study the kinetics of degradation. The rate coefficients were obtained by fitting the experimental data with the model. The linear dependence of the rate coefficients on the logarithm of the vapor pressure of the solvent indicated that vapor pressure is the crucial parameter that controls the degradation process. The rate of degradation increases with an increase in the alkyl acrylate content. At any particular copolymer composition, the rate of degradation follows the order: PMMAMA > PMMAEA > PMMABA. It was observed that the degradation rate coefficient varies linearly with the mole percentage of the alkyl acrylate in the copolymer.