Aromatic l-amino acid decarboxylase : histochemical localization in rat kidney and lack of effect of dietary potassium or sodium loading on enzyme distribution

Utilizing a mono-specific antiserum produced in rabbits to hog kidney aromatic L-amino acid decarboxylase (AADC), the enzyme was localized in rat kidney by immunoperoxidase staining. AADC was located predominantly in the proximal convoluted tubules; there was also weak staining in the distal convoluted tubules and collecting ducts. An increase in dietary potassium or sodium intake produced no change in density or distribution of AADC staining in kidney. An assay of AADC enzyme activity showed no difference in cortex or medulla with chronic potassium loading. A change in distribution or activity of renal AADC does not explain the postulated dopaminergic modulation of renal function that occurs with potassium or sodium loading.

Characterisation and source apportionment of polycyclic aromatic hydrocarbons in the sediments of Brisbane River

The thesis was a step forward in predicting the levels and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of Brisbane river, especially after the Brisbane floods in 2011. It employed different statistical techniques to provide valuable information that may assist source control and formulation of pollution mitigation measures for the river.

Reaction of Aromatic Peroxyl Radicals with Alkynes: A Mass Spectrometric and Computational Study Using the Distonic Radical Ion Approach

The reaction of the aromatic distonic peroxyl radical cations N-methyl pyridinium-4-peroxyl (PyrOO center dot+) and 4-(N,N,N-trimethyl ammonium)-phenyl peroxyl (AnOO center dot+), with symmetrical dialkyl alkynes 10?ac was studied in the gas phase by mass spectrometry. PyrOO center dot+ and AnOO center dot+ were produced through reaction of the respective distonic aryl radical cations Pyr center dot+ and An center dot+ with oxygen, O2. For the reaction of Pyr center dot+ with O2 an absolute rate coefficient of k1=7.1X10-12 cm3 molecule-1 s-1 and a collision efficiency of 1.2?% was determined at 298 K. The strongly electrophilic PyrOO center dot+ reacts with 3-hexyne and 4-octyne with absolute rate coefficients of khexyne=1.5X10-10 cm3 molecule-1 s-1 and koctyne=2.8X10-10 cm3 molecule-1 s-1, respectively, at 298 K. The reaction of both PyrOO center dot+ and AnOO center dot+ proceeds by radical addition to the alkyne, whereas propargylic hydrogen abstraction was observed as a very minor pathway only in the reactions involving PyrOO center dot+. A major reaction pathway of the vinyl radicals 11 formed upon PyrOO center dot+ addition to the alkynes involves gamma-fragmentation of the peroxy O?O bond and formation of PyrO center dot+. The PyrO center dot+ is rapidly trapped by intermolecular hydrogen abstraction, presumably from a propargylic methylene group in the alkyne. The reaction of the less electrophilic AnOO center dot+ with alkynes is considerably slower and resulted in formation of AnO center dot+ as the only charged product. These findings suggest that electrophilic aromatic peroxyl radicals act as oxygen atom donors, which can be used to generate alpha-oxo carbenes 13 (or isomeric species) from alkynes in a single step. Besides gamma-fragmentation, a number of competing unimolecular dissociative reactions also occur in vinyl radicals 11. The potential energy diagrams of these reactions were explored with density functional theory and ab initio methods, which enabled identification of the chemical structures of the most important products.

Anionic migration reactions in aromatic systems effected by collisional activation : Deprotonated anilides containing methoxycarbonyl substituents

Long-range cross-ring reactions are of minor importance in the collision-induced mass spectra (MS/MS) of [M - H]- ions of CH2OCO-C6H4-NHCOR systems: e.g. the loss of 'CD3CO2CH3' from CH3OCO-C6H4-(N) over bar COCD3. Major processes involve (i) losses of radicals to form stable radical anions, e.g. loss of a ring hydrogen atom and losses from the ester (CH3 ., CH3O . and . CO2CH3), (ii) losses of neutral molecules from the amide moiety [e.g. CO (R = H) and CH2CO (R = CH3), and proximity effects when the two substituents are ortho [e.g. loss of (CH3OD+CO2) from o-CH3OCO-C6H4 (N) over bar COCD3].

Anionic migration in aromatic systems effected by collisional activation. Unusual fragmentations of deprotonated anilides containing methoxyl and ethoxyl substituents

Long-range cross-ring reactions occur when (M - H)(-) ions of methoxy- and ethoxy-C6H4-(-)NCOR (R = H, CH3, C6H5 and CH3O) are subjected to collisional activation, These reactions are generally minor processes: a particular example is the cross-ring elimination p-C2H5O-C6H4-(NCOCH3)-N-- --> [CH3-(p-C2H5O-C6H4-NCO)] --> p-(O--)-C6H4-NCO + C2H4 + CH4. Major processes of these (M - H)(-) ions involve (i) losses of radicals to form stabilised radical anions, e.g. (a) loss of a ring H-. or (b) CH3. (or C2H5.) from the alkoxy group, and (ii) proximity effects when the two substituents are ortho, e.g. loss of CH3OH from o-CH3O-C6H4-(NCHO)-N-- yields deprotonated benzoxazole. Another fragmentation of an arylmethoxyl anion involves loss of CH2O. It is proposed that losses of CH2O are initiated by anionic centres but the actual mechanisms in the cases studied depend upon the substitution pattern of the methoxyanilide: o- and p-methoxyanilides may undergo ipso proton transfer/elimination reactions, whereas the in-analogues undergo proton transfer reactions to yield an o-CH3O substituted aryl carbanion followed by proton transfer from CH3O to the carbanion site with concomitant loss of CH2O.

Flammability and thermal properties of novel semi aromatic polyamide/organoclay nanocomposite

The development of semi aromatic polyamide/organoclays nanocomposites (PANC) is reported in this communication. New polyamide (PA) was successfully synthesized through direct polycondensation reaction between bio-based diacid and aromatic diamine. PA exhibited strong UV vis absorption band at 412 nm. Its photoluminescence spectrum showed maximum band at 511 nm in the green region. The surface modification of montmorillonite was carried out through ion-exchange reaction using 1,4-bis[4-aminophenoxy]butane (APB) as a modifier. Then PANCs containing 3 and 6 wt.% of the modified montmorillonite (MMT-APB) were prepared. Flammability and thermal properties of PA and the nanocomposites were studied by microscale combustion calorimeter (MCC), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA results in both air and nitrogen atmospheres indicated improving in thermal properties of PANCs compared to the neat PA. According to MCC analysis, a 31.6% reduction in pHRR value has been achieved by introducing 6 wt.% of the organoclay in PA matrix.

Influence of traffic characteristics on polycyclic aromatic hydrocarbon build-up on urban road surfaces

Traffic is one of the prominent sources of polycyclic aromatic hydrocarbons (PAHs) and road surfaces are the most critical platform for stormwater pollution. Build-up of pollutants on road surfaces was the focus of this research study. The study found that PAHs build-up on road surfaces primarily originate from traffic activities, specifically gasoline powered vehicles. Other sources such as diesel vehicles, industrial oil combustion and incineration were also found to contribute to the PAH build-up. Additionally, the study explored the linkages between concentrations of PAHs and traffic characteristics such as traffic volume, vehicle mix and traffic flow. While traffic congestion was found to be positively correlated with 6- ring and 5- ring PAHs in road build-up, it was negatively correlated with 3-ring and 4 ring PAHs. The absence of positive correlation between 3-ring and 4-ring PAHs and traffic parameters is attributed to the propensity of these relatively volatile PAHs to undergo re-suspension and evaporation. The outcomes of this study are expected to contribute effective transport and land use planning for the prevention of PAH pollution in the urban environment.

Biomonitoring of polycyclic aromatic hydrocarbons exposure in small groups of residents in Brisbane, Australia and Hanoi, Vietnam, and those travelling between the two cities

Exposure to polycyclic aromatic hydrocarbons (PAHs) has been associated with adverse health outcomes. Concentrations of urinary PAH metabolites (OH-PAHs) provide an integrated measure of human exposure to PAHs but measurement of urinary OH-PAHs has not been done in Australia and rarely in Vietnam, where air pollution is of concern. In this study, we assessed exposure to PAHs in 16 participants living in Brisbane, Australia and Hanoi, Vietnam, with 4 participants travelling between the two cities during the monitoring period. A total of 312 first morning urine samples were collected over 10 weeks and were analysed for nine OH-PAHs. Concentrations of the urinary OH-PAHs were 2–10 times higher in participants from Hanoi than those from Brisbane. For example, the median concentrations of 1-hydroxypyrene were 292 pg/mL in Hanoi, compared to 64 pg/mL in Brisbane. For participants travelling from Brisbane to Hanoi and back, differences in exposure to PAHs in these two cities resulted in corresponding changes of urinary OH-PAH concentrations, demonstrating that the more polluted environment in Hanoi was likely the source for higher PAH exposure there.

Visible light enhanced oxidant free dehydrogenation of aromatic alcohols using Au-Pd alloy nanoparticle catalysts

We find that visible light irradiation of gold–palladium alloy nanoparticles supported on photocatalytically inert ZrO2 significantly enhances their catalytic activity for oxidant-free dehydrogenation of aromatic alcohols to the corresponding aldehydes at ambient temperatures. Dehydrogenation is also the dominant process in the selective oxidation of the alcohols to the corresponding aldehydes with molecular oxygen. The alloy nanoparticles strongly absorb light and exhibit superior catalytic and photocatalytic activity when compared to either pure palladium or gold nanoparticles. Analysis with a free electron gas model for the bulk alloy structure reveals that the alloying increases the surface charge heterogeneity on the alloy particle surface, which enhances the interaction between the alcohol molecules and the metal NPs. The increased surface charge heterogeneity of the alloy particles is confirmed with density function theory applied to small alloy clusters. Optimal catalytic activity was observed with a Au : Pd molar ratio of 1 : 186, which is in good agreement with the theoretical analysis. The rate-determining step of the dehydrogenation is hydrogen abstraction. The conduction electrons of the nanoparticles are photo-excited by the incident light giving them the necessary energy to be injected into the adsorbed alcohol molecules, promoting the hydrogen abstraction. The strong chemical adsorption of alcohol molecules facilitates this electron transfer. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive the dehydrogenation. These findings provide useful insight into the design of catalysts that utilize light for various organic syntheses at ambient temperatures.

An infrared spectroscopic study of the phase transitions of crystalline aromatic donor-acceptor complexes involving a pseudoplastic state

Variable temperature i.r. spectroscopic studies of weak pi-donor-pi-acceptor complexes in the crystalline state indicate that the complexes undergo order-disorder transitions, the disorder being caused by molecular motion. Thermodynamic data on the phase transitions along with the spectral data suggest that the high-temperature crystalline forms of the complexes are likely to be pseudoplastic.

Enzyme-catalysed non-oxidative decarboxylation of aromatic acids: I.Purification and spectroscopic properties of 2,3 dihydroxybenzoic acid decarboxylase from Image Image

In order to understand the molecular mechanism of non-oxidative decarboxylation of aromatic acids observed in microbial systems, 2,3 dihydroxybenzoic acid (DHBA) decarboxylase from Image Image was purified to homogeneity by affinity chromatography. The enzyme (Mr 120 kDa) had four identical subunits (28 kDa each) and was specific for DHBA. It had a pH optimum of 5.2 and Km was 0.34mM. The decarboxylation did not require any cofactors, nor did the enzyme had any pyruvoyl group at the active site. The carboxyl group and hydroxyl group in the Image -position were required for activity. The preliminary spectroscopic properties of the enzyme are also reported.

Atmospheric polycyclic aromatic hydrocarbons in the urban environment: Occurrence, toxicity and source apportionment

Polycyclic Aromatic Hydrocarbons (PAHs) represent a major class of toxic pollutants because of their carcinogenic and mutagenic characteristics. People living in urban areas are regularly exposed to PAHs because of abundance of their emission sources. Within this context, this study aimed to: (i) identify and quantify the levels of ambient PAHs in an urban environment; (ii) evaluate their toxicity; and (iii) identify their sources as well as the contribution of specific sources to measured concentrations. Sixteen PAHs were identified and quantified in air samples collected from Brisbane. Principal Component Analysis – Absolute Principal Component Scores (PCA- APCS) was used in order to conduct source apportionment of the measured PAHs. Vehicular emissions, natural gas combustion, petrol emissions and evaporative/unburned fuel were the sources identified; contributing 56%, 21%, 15% and 8% of the total PAHs emissions, respectively, all of which need to be considered for any pollution control measures implemented in urban areas.

X-Ray Structure Of A Ternary Metal-Complex - Copper(Ii) Inosine 5'-Monophosphate Imidazole - Metal-Binding To The N(7) Atom Of The Nucleotide In A Mixed-Ligand System Containing An Aromatic Amine

A ternary metal-nucleotide complex, Na2[Cu(5’-IMP)2(im)o,8(H20)l,2(H20)2h]as~ 1be2e.n4 pHr2ep0a,r ed and its structure analyzed by X-ray diffraction (5’-IMP = inosine 5’-monophos hate; im = imidazole). The complex crystallizes in space group C222, with a = 8.733 (4) A, b = 23.213 (5) A, c = 21.489 (6) 1, and Z = 4. The structure was solved by the heavy-atom method and refined by full-matrix least-squares technique on the basis of 2008 observed reflections to a final R value of 0.087. Symmetry-related 5’-IMP anions coordinate in cis geometry through the N(7) atoms of the bases. The other cis positions of the coordination plane are statistically occupied by nitrogen atoms of disordered im groups and water oxygens with occupancies 0.4 and 0.6, respectively. Water oxygens in axial positions complete the octahedral coordination of Cu(I1). The complex is isostructural with C~S-[P~(S’-IMP),(NH~)~a] m”,o del proposed for Pt(I1) binding to DNA. The base binding observed in the present case is different from the typical ”phosphate only” binding shown from earlier studies on metal-nucleotide complexes containing various other ?r-aromatic amines.

Applications of the Vilsmeier reaction. 13. Vilsmeier approach to polycyclic aromatic hydrocarbons

The Synthesis of three typical polycyclic hydrocarbons (PAH) has been described, wherein the Vilsmeier reaction plays a major role. Vilsmeier reaction of the tetraloll gives the dihydronaphthaldehyde 2 which on cyclodehydration gives the dihydroarene 3. Ita dehydrogenation affords 3-methoxybenz[a]anthracene (4). Vilsmeier reaction on the dimethoxydihydronaphthalene 5 gives the versatile dimethoxydihydronaphthaldehyde 6 which has been converted to the dimethoxybenzo[c]fluorene 7 by direct cyclodehydration and the fulvene 10 by cyclodehydration of allylic alcohol 8 derived from 6 followed by dehydrogenation. The saturated alcohol 12 corresponding to 8 undergoes cyclodehydration to give the dimethoxyhexahydrobenzo[c]phenanthrene (13). Some of the advantages of the Vilsmeier approach to PAH have been pointed out.

Reinvestigation of the antifungal activities of some aromatic N-oxides

Dinitroquinoline-N-oxide, 4-nitroquinoline N-oxide and a series of 4-substituted pyridine N-oxides have been subjected toMINDO/3 treatment in order to understand their antifungal activities. The photoelectron spectra and the nature of the N-oxide bond are discussed.