Enzymatic oxidation of mercury vapor by erythrocytes

The formation of glutathione radicals, the evolution of nascent oxygen or the peroxidatic reaction with catalase complex I are considered as possible mechanisms for the oxidation of mercury vapor by red blood cells. To select among these, the uptake of atomic mercury by erythrocytes from different species was studied and related to their various activities of catalase (hydrogenperoxide : hydrogen-peroxide oxidoreductase, EC 1.11.1.6) and glutathione peroxidase (glutathione : hydrogen-peroxide oxidoreductase, EC 1.11.1.9). A slow and continuous infusion of diluted H2O2 was used to maintain steady concentrations of complex I. 1% red cell supsensions were found most suitable showing high rates of Hg uptake and yielding still enough cells for subsequent determinations. The results indicate that the oxidation of mercury depends upon the H2O2-generation rate and upon the specific acticity of red-cell catalase. The oxidation occurred in a range of the catalase-H2O2 reaction where the evolution of oxygen could be excluded. Compounds reacting with complex I were shown to be effective inhibitors of the mercury uptake. GSH-peroxidase did not participate in the oxidation but rather, was found to inhibit it by competing with catalase for hydrogen peroxide. These findings support the view that elemental mercury is oxidized in erythrocytes by a peroxidatic reaction with complex I only.     

Laminar airflow and nanoparticle or vapor deposition in a human nasal cavity model

The transport and deposition of nanoparticles, i.e., dp = 1-2 nm, or equivalent vapors, in the human nasal cavities is of interest to engineers, scientists, air-pollution regulators, and healthcare officials alike. Tiny ultrafine particles, i.e., dp < or = 5 nm, are of special interest because they are most rapidly absorbed and hence have an elevated toxic or therapeutic impact when compared to larger particles. Assuming transient laminar 3-D incompressible flow in a representative human nasal cavity, the cyclic airflow pattern as well as local and overall nanoparticle depositions were computationally simulated and analyzed. The focus was on transient effects during inhalation/exhalation as compared to the steady-state assumption typically invoked. Then, an equation for a matching steady-state inhalation flow rate was developed that generates the same deposition results as cyclic inhalation. Of special interest is the olfactory region where the narrow channel surfaces receive only about one-half of a percent of the inhaled nanoparticles because the airflow bypasses these recesses located in the superior-most portions in the geometrically complex nasal cavities.     

Regulation of silk material structure by temperature-controlled water vapor annealing

We present a simple and effective method to obtain refined control of the molecular structure of silk biomaterials through physical temperature-controlled water vapor annealing (TCWVA). The silk materials can be prepared with control of crystallinity, from a low content using conditions at 4 °C (α helix dominated silk I structure), to highest content of ～60% crystallinity at 100 °C (β-sheet dominated silk II structure). This new physical approach covers the range of structures previously reported to govern crystallization during the fabrication of silk materials, yet offers a simpler, green chemistry, approach with tight control of reproducibility. The transition kinetics, thermal, mechanical, and biodegradation properties of the silk films prepared at different temperatures were investigated and compared by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), uniaxial tensile studies, and enzymatic degradation studies. The results revealed that this new physical processing method accurately controls structure, in turn providing control of mechanical properties, thermal stability, enzyme degradation rate, and human mesenchymal stem cell interactions. The mechanistic basis for the control is through the temperature-controlled regulation of water vapor to control crystallization. Control of silk structure via TCWVA represents a significant improvement in the fabrication of silk-based biomaterials, where control of structure-property relationships is key to regulating material properties. This new approach to control crystallization also provides an entirely new green approach, avoiding common methods that use organic solvents (methanol, ethanol) or organic acids. The method described here for silk proteins would also be universal for many other structural proteins (and likely other biopolymers), where water controls chain interactions related to material properties.     

Uptake of mercury vapor by wheat: an assimilation model

Using a whole-plant chamber and ²⁰³Hg-labeled mercury, a quantitative study was made of the effect of environmental parameters on the uptake, by wheat (Triticum aestivum), of metallic mercury vapor, an atmospheric pollutant. Factors were examined in relation to their influence on components of the gas-assimilation model, [Formula: see text]     

Solvolysis of wood and pure cellulose by anhydrous hydrogen fluoride vapor

The solvolysis of bigtooth aspen wood and pure cellulose (filter paper) by anhydrous hydrogen fluoride (HF) vapor was investigated. Each substrate was exposed to a 100% HF vapor stream at 0·101 MPa and 27°C to 77°C for a given reaction time. The water-soluble reaction products were then post-hydrolyzed in 2 n trifluoroacetic acid for 1 h at 121°C. With this two-step hydrolysis, maximum glucose yields of 85% from wood and 94% from pure cellulose were obtained. HPLC analysis of the water-soluble reaction products obtained before post-hydrolysis revealed that glucose and glucosyl fluoride repolymerized to oligomers during vapor-phase HF solvolysis of cellulose. The oligosaccharide product distribution was dependent on reaction time, temperature and sample water content.     

Biofiltration of methanol vapor

Biofiltration of solvent and fuel vapors may offer a costeffective way to comply with increasingly strict air emission standards. An important step in the development of this technology is to derive and validate mathematical models of the biofiltration process for predictive and scaleup calculations. For the study of methanol vapor biofiltration, an 8-membered bacterial consortium was obtained from methanol-exposed soil. The bacteria were immobilized on solid support and packed into a 5-cm-diameter, 60-cm-high column provided with appropriate flowmeters and sampling ports. The solid support was prepared by mixing two volumes of peat with three volumes of perlite particles (i.e., peat-perlite volume ratio 2:3). Two series of experiments were performed. In the first, the inlet methanol concentration was kept constant while the superficial air velocity was varied from run to run. In the second series, the air flow rate (velocity) was kept constant while the inlet methanol concentration was varied. The unit proved effective in removing methanol at rates up to 112.8 g h(-1) m(-3) packing. A mathematical model has been derived and validated. The model described and predicted experimental results closely. Both experimental data and model predictions suggest that the methanol biofiltration process was limited by oxygen diffusion and methanol degradation kinetics. (c) 1993 John Wiley & Sons, Inc.     

Inhalation toxicity of soman vapor in non-anesthetized rats: A preliminary assessment of inhaled bronchodilator or steroid therapy

Respiratory toxicity, injury and treatment following vapor inhalational exposure to the chemical warfare nerve agent (CWNA) soman (GD) were examined in non-anesthetized rats. This study exposed male Sprague–Dawley rats (250–300 g) to 520, 560, 600, 825 or 1410 mg × min/m³ of soman in a customized head-out inhalation system. Signs of CWNA-induced cholinergic crises were observed in all soman-exposed animals. The LCt50 of vaporized soman as determined by probit analysis was 593.1 mg × min/m³. All animals exposed to 825 and 1410 mg × min/m³ developed severe convulsions and died within 4–8 min post-exposure. Edema measured by wet/dry weight ratio of the left lung lobe increased in a dose-dependent manner in all soman-exposed animals. Bronchoalveolar lavage (BAL) fluid and blood acetylcholinesterase (AChE) activities were inhibited dose-dependently in soman-exposed groups at 24 h. A significant increase in total BAL protein was observed in soman-exposed animals at all doses. AChE activity was inhibited in lung and whole brain tissues in all soman-exposed animals. Histopathological analysis of the lungs of animals exposed to 600 mg × min/m³ of soman revealed prominent morphological changes including alveolar histiocytosis, hemorrhage and inflammation consisting of neutrophilic exudate. Exposure of animals to 600 mg × min/m³ of soman followed by treatment with two actuations for 10 s of Combivent (21 μg of ipratropium bromide and 120 μg of albuterol sulfate) and Symbicort (80 μg budesonide and 4.5 μg formoterol) by inhalation into a modified metered dose inhaler (MDI) 10 min post-exposure resulted in increased minute volume, but did not decrease mortality. These results indicate that inhalation exposure to soman vapor causes acute respiratory toxicity and injury in untreated, un-anesthetized rats and that inhalation treatment with Combivent or Symbicort did improve the respiratory outcomes, but did not influence lethality.     

Highly protective alkalinization by ammonia vapor diffusion in viscosimetric DNA damage assessment

A method for the measurement of viscosities correlated to DNA alterations in alkaline homogenate suspensions is described. The alkaline pH shift to afford cell lysis, DNA unfolding, and denaturation is attained by gaseous ammonia diffusion, thus avoiding shear stress from mechanical mixing. At the same time a stabilizing density gradient is established. This solution is run through a plastic measuring tube that is wide enough to minimize the influence of uneven swelling of the lysing DNA-containing components. Flow times under a carefully controlled water head are registered, and their ratios to control solutions are evaluated. The relative viscosities show a strong and irreversible dependence on shear and on DNase treatment and therefore are considered as essentially DNA derived. The time dependence of the lysate viscosities with and without the DNA-damaging agent bleomycin is given and the dose:activity curves of this agent with sponge homogenates from two orders of Porifera are given with their 50% effective concentration values. The dose:activity curve of an extract from a polluted marine point source is demonstrated. The concentration changes in sponges exposed at differently polluted marine sites are shown. The idea of alkalinization through gaseous diffusion in conjunction with a simple measuring device has already proven a sensitive, reliable, and specific tool in the assessment of DNA damage produced under both laboratory and field conditions.     

Treatment of mercury vapor toxicity by combining deferasirox and deferiprone in rats

The hypothesis that combination of deferasirox and deferiprone chelators might be more efficient as combined therapy than single therapy in removing mercury from the body was considered. Male Wistar rats were exposed to mercury vapor for 2 weeks. After mercury administration some abnormal clinical signs such as red staining around the eyes, greenish mottling on the liver, weakness, loss of hair and weight, were observed in animals. Chelators were given orally after mercury vapor application for 2 weeks. Mercury toxicity symptoms in rats decreased after drug administration. After chelation therapy, these rats were anesthetized with ether vapor and immobilized by cervical dislocation and then their heart, liver, kidneys, intestine, spleen and testicles were sampled for determination of mercury and iron concentration. The combined chelation therapy results showed that these chelators are able to remove mercury from the body and toxicity symptoms decreased.     

An examination of the oxidation of mercury vapor by rat brain homogenate

The oxidation of mercury vapor (Hg degrees) to divalent inorganic mercury (Hg2+) was studied in rat brain homogenates. By using a "degassing" method, it was possible to speciate the mercury present in the homogenate and, for the first time, to measure the rate of oxidation as a function of the substrate (Hg degrees) concentration. Mercury oxidation was first-order with respect to substrate concentration at all concentrations tested, and the first-order rate constant for the oxidation process was proportional to homogenate concentration. The role of catalase compound I in mercury vapor oxidation by brain homogenate was examined by observing the effects of two inhibitors of catalase (catalase compound I) on homogenate mercury-oxidizing activity and catalase activity. Sodium azide (50 mM) completely inhibited both mercury-oxidizing activity and catalase activity. Aminotriazole (3-amino-1H-1,2,4-triazole) (50 mM) completely inhibited only mercury-oxidizing activity; some residual catalase activity was found in the aminotriazole-treated homogenate. It was concluded that catalase compound I plays a major role in the oxidation of Hg degrees, but the possibility that catalase-independent pathways make a minor contribution cannot be excluded.     

Improving protein crystal quality by decoupling nucleation and growth in vapor diffusion

A simple method for growing protein crystals in the metastable zone using the vapor diffusion technique is described. The coverslips holding the hanging drops are transferred, after being incubated for some time at conditions normally giving many small crystals, over reservoirs at concentrations that normally yield clear drops. Fewer, much larger and better diffracting crystals are obtained, compared with conventional crystallization at similar conditions. To our knowledge, this is the first report of a significant crystal improvement due to "backing off" from nucleation conditions, using the hanging drop method. A correlation of the transfer time with published results for vapor diffusion equilibration of poly(ethylene glycol) solutions is also presented.     

Removal of ethylacetate vapor from waste gases by a trickle-bed air biofilter

Biofilter system is a relatively new process that has been proven to be more cost-effective than traditional technologies such as carbon adsorption, liquid scrubbing, condensation, thermal incineration, and catalytic incineration for removing low-strength volatile organic compounds from waste gases. The trickle-bed air biofilter (TBAB) performance for ethylacetate (EA) removal was evaluated under different influent loadings. In the pseudo-steady states, the elimination capacity increased, but the removal efficiency decreased with increased influent loading. More than 95 and 90% removal efficiencies could be achieved for EA loadings below 490 and 810 g m(-3) h(-1), respectively. The TBAB appears to be very effective for controlling EA emission under low to high loading conditions, and the effectiveness could be maintained over 190 days of laboratory operation.     

Preparation and characterization of chitin hydrogels by water vapor induced gelation route

A novel method of chitin hydrogel preparation, called vapor induced gelation, using exposure of chitin/N-methyl-pyrrolidone/LiCl solution to water vapors is presented. Compared to gelation induced by direct immersion in water, hydrogels are characterized by smaller deformation during gelation (area shrinkage is 20% instead of 65%), larger water volume fraction (75 instead of 62%, v/v) and 10 times higher apparent compression moduli. Their nanostructure consists of thicker and larger crystalline platelets network (thickness=37?, apparent coherent crystalline size L(020)=145?) comparatively to direct immersion gels (25? and L(020)=95?). Drug delivery potential of chitin hydrogels was determined for non-interactive low molecular molecules.     

Detection of sister-chromatid exchanges in human peripheral lymphocytes induced by ethylene dibromide vapor

A method using sister-chromatid exchanges (SCEs) for genotoxic testing of gaseous compounds is described. Human peripheral lymphocyte cultures previously stimulated with phytohemagglutinin were placed in sterile dialysis tubing and then put in an enclosed flask containing additional culture media. Air, with or without ethylene dibromide (EDB), was bubbled through the flask for up to 8 h. The cultures were harvested 75 h after culture initiation, and second-division cells were scored for induction of SCEs according to established procedures. The SCE frequency was approximately doubled in cultures treated with EDB. A similar experiment with air alone resulted in only slight increases in SCEs. The results indicate that this system is potentially useful for detecting genotoxicity of gases and vapors and may be useful for the detection of genotoxic agents in occupational settings.