Biodegradation of Pyridine and Pyridine Derivatives by Soil and Subsurface Microorganisms

Abstract

Large amounts of aromatic compounds are produced by various industries and two thirds of these are heterocyclic chemicals. Compared with the extensive information available on microbial degradation of homocyclic aromatic compounds, relatively little is known on the transformation and biodegradation of heterocyclic chemicals in soil. Recent concerns about the persistence of hazardous pollutants have led to a renewed interest in the biodegradation of heterocyclic compounds. Hence, we investigated the microbial degradation of pyridine and some of its alkylated derivatives under aerobic and anaerobic conditions in groundwater, subsurface sediment, and soil. Results of the investigation revealed that these compounds were degraded predominantly under aerobic conditions and, to a lesser extent, under anaerobic conditions, with nitrate or sulfate serving as electron acceptors. In groundwater polluted with various pyridine derivatives, biodegradation was limited by the absence of oxygen. Therefore, we conclude that, under appropriate conditions, bioremediation is a potentially feasible method for the clean-up of environments contaminated with heterocyclic chemicals and, in particular, pyridine derivatives.     

Precise and accurate compound-specific carbon and nitrogen isotope analysis of RDX by GC-IRMS

A new analytical method is presented for the compound-specific carbon and nitrogen isotope ratio analysis of a thermo-labile nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by gas chromatograph coupled to an isotope ratio mass spectrometer (GC-IRMS). Two main approaches were used to minimise thermal decomposition of the compound during gas chromatographic separation: programmed temperature vaporisation (PTV) as an injection technique and a high-temperature ramp rate during the GC run. δ¹⁵N and δ¹³C values of RDX measured by GC-IRMS and elemental analyser (EA)-IRMS were in good agreement within a standard deviation of 0.3‰ and 0.4‰ for nitrogen and carbon, respectively. Application of the method for the isotope analysis of RDX during alkaline hydrolysis at 50°C revealed isotope fractionation factors ε _carbon?=??7.8‰ and ε _nitrogen?=??5.3‰.     

Remote dipolar interactions for objective density calibration and flow control of excitonic fluids

In this Letter we suggest a method to observe remote interactions of spatially separated dipolar quantum fluids, and in particular, of dipolar excitons in GaAs bilayer based devices. The method utilizes the static electric dipole moment of trapped dipolar fluids to induce a local potential change on spatially separated test dipoles. We show that such an interaction can be used for model-independent, objective fluid density measurements, an outstanding problem in this field of research, as well as for interfluid exciton flow control and trapping. For a demonstration of the effects on realistic devices, we use a full two-dimensional hydrodynamical model.     

Modulation of quinpirole-induced compulsive-like behavior in rats by environmental changes: Implications for OCD rituals and for exploration and navigation

Background  

Rats treated chronically with the D_2–3 dopamine agonist quinpirole were previously proposed as an animal model of obsessive-compulsive disorder (OCD) since their behavior is based on repeated, compulsive-like persistent traveling between a few places in the open field. The aim of the present study was to determine properties of the physical environment that shape such behavior. For this, quinpirole-treated rats were first exposed to an arena with an array of objects (landmarks) and after the development of compulsive-like behavior, the arena was manipulated by multiplying the number of objects, changing their spacing, relocating object array, or removing the objects.     

Marine inventory routing: shipments planning

This paper addresses a shipments-planning problem faced by producers of large volume liquid bulk products. Producing origins with limited tank storage capacity supply multiple products by ships (or barges) to consuming destinations that also have limited storage capacity. Timing, origin, destination, and product quantities of shipments have to be determined in a manner that minimizes costs and does not violate storage capacity constraints at both ends (neither stopping production at the origins, nor running out of stock at the destinations). A mixed integer-programming model is used to derive cost effective solutions within a few minutes. A cost-based heuristic algorithm is used to assure that acceptable solutions are obtained quickly.     

Temperature dependence of dimerization and dewetting of large-scale hydrophobes: a molecular dynamics study

We studied by molecular dynamics simulations the temperature dependence of hydrophobic association and drying transition of large-scale solutes. Similar to the behavior of small solutes, we found the association process to be characterized by a large negative heat capacity change. The origin of this large change in heat capacity is the high fragility of hydrogen bonds between water molecules at the interface with hydrophobic solutes; an increase in temperature breaks more hydrogen bonds at the interface than in the bulk. With increasing temperature, both entropy and enthalpy changes for association strongly decrease, while the change in free energy weakly varies, exhibiting a small minimum at high temperatures. At around T=Ts=360 K, the change in entropy is zero, a behavior similar to the solvation of small nonpolar solutes. Unexpectedly, we find that at Ts, there is still a substantial orientational ordering of the interfacial water molecules relative to the bulk. Nevertheless, at this point, the change in entropy vanishes due to a compensating contribution of translational entropy. Thus, at Ts, there is rotational order and translational disorder of the interfacial water relative to bulk water. In addition, we studied the temperature dependence of the drying-wetting transition. By calculating the contact angle of water on the hydrophobic surface at different temperatures, we compared the critical distance observed in the simulations with the critical distance predicted by macroscopic theory. Although the deviations of the predicted from the observed values are very small (8-23%), there seems to be an increase in the deviations with an increase in temperature. We suggest that these deviations emerge due to increased fluctuations, characterizing finite systems, as the temperature increases.     

Diazonium-functionalized horseradish peroxidase immobilized via addressable electrodeposition: direct electron transfer and electrochemical detection

A simple one-step procedure is introduced for the preparation of diazonium-enzyme adducts. The direct electrically addressable deposition of diazonium-modified enzymes is examined for electrochemical sensor applications. The deposition of diazonium-horseradish peroxidase leads to the direct electron transfer between the enzyme and electrode exhibiting a heterogeneous rate constant, ks, of 10.3 +/- 0.7 s-1 and a DeltaEp of 8 mV (v = 150 mV/s). The large ks and low DeltaEp are attributed to the intimate contact between enzyme and electrode attached by one to three phenyl molecules. Such an electrode shows high nonmediated catalytic activity toward H2O2 reduction. Future generations of arrayed electrochemical sensors and studies of direct electron transfer of enzymes can benefit from protein electrodes prepared by this method.     

Effect of ions on the hydrophobic interaction between two plates

We use molecular dynamics simulations to investigate the solvent mediated attraction and drying between two nanoscale hydrophobic surfaces in aqueous salt solutions. We study these effects as a function of the ionic charge density, that is, the ionic charge per unit ionic volume, while keeping the ionic diameter fixed. The attraction is expressed by a negative change in the free energy as the plates are brought together, with enthalpy and entropy changes that both promote aggregation. We find a strong correlation between the strength of the hydrophobic interaction and the degree of preferential binding/exclusion of the ions relative to the surfaces. The results show that amplification of the hydrophobic interaction, a phenomenon analogous to salting-out, is a purely entropic effect and is induced by high-charge-density ions that exhibit preferential exclusion. In contrast, a reduction of the hydrophobic interaction, analogous to salting-in, is induced by low-charge-density ions that exhibit preferential binding, the effect being either entropic or enthalpic. Our findings are relevant to phenomena long studied in solution chemistry, as we demonstrate the significant, yet subtle, effects of electrolytes on hydrophobic aggregation and collapse.     

Reagentless electrochemical immunoassay using electrocatalytic nanoparticle-modified antibodies

We describe a new approach for reagentless electrochemical immunoassay sensing in which Au/Pd NPs can be "loaded" onto antibodies to create an electrocatalytic antibody that is sensitive to the oxygen reduction reaction.     

Molecular Insight into Long‐Wavelength Fluorogenic Dye Design: Hydrogen Bond Induces Activation of a Dormant Acceptor

The detection of chemical or biological analytes in response to molecular changes relies increasingly on fluorescence methods. Therefore, there is a substantial need for the development of improved fluorogenic dyes. In this study, we demonstrated how an intramolecular hydrogen bond activates a dormant acceptor through a charge induction between phenolic hydrogen and a heteroaryl nitrogen moiety. As a result, a new fluorochrome is produced, and the molecule exhibits a strong fluorescent emission. When the strength of the hydrogen bonding was increased by conformational locking, the obtained dye emitted at longer wavelengths and fluoresced under physiological conditions. The dye was implemented in a turn‐ON system responsive to hydrogen peroxide. The molecular insight provided by this study should assist in the design of fluorescent dyes that are suitable for in vitro and in vivo applications.