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PubMed1987

A calorimetric study of the interaction of synthetic phospholipid liposomes with lipid-soluble small molecules used as dental materials and devices.

The interaction of 22 lipid-soluble small molecules, widely used in dental materials and devices, with synthetic phospholipid liposomes, was investigated by the application of differential scanning calorimetry (DSC), in order to clarify the mechanism of small molecules in biological systems. Dimyristoyl phosphatidyl choline (DMPC) and dipalmitoyl phosphatidyl choline (DPPC) were used as lipids. The interaction of various monomers with liposomes has been reported by us in this journal. In this experiment, various compounds such as redox-initiator, photo-initiator or photo-sensitizer, inhibitor, root-canal disinfectant, cement-base materials (eugenol and 2-ethoxybenzoic acid) etc., were investigated. From changes in the phase transition temperature (T), enthalpy (delta H kcal mol-1) and H/HHW values of both DMPC and DPPC liposomes induced by these molecules, it was concluded that aromatic tertiary amine, benzoyl peroxide and hydroquinone monomethyl ether had a relatively large effect on liposomes, and that in phenol derivatives, m-cresol and p-chlorophenol had a large effect on liposomes compared to phenol. Eugenol used as dental cement also had a large effect on liposomes due to its high hydrophobicity. Changes in the transition properties of liposomes induced by small molecules (characterized by shift of T to a lower temperature, an increase or decrease in cooperativity (H/HHW), and a decrease in delta H of a endothermic peak) seemed to be related to biological activities.

Calorimetry, Differential Scanning↗
PubMed2006

Impact of freeze-drying on ionization of sulfonephthalein probe molecules in trehalose-citrate systems.

"pH memory," i.e., correlation between pH of solution before freeze-drying and chemical reactivity in the freeze-dried state, has been reported in many systems. In this study, the "pH memory" is explored by comparing the extent of protonation of sulfonephthalein probe molecules, bromophenol blue, bromocresol green, and chlorophenol red, in aqueous solution in the pH range of 3.4-6.0 and in the resulting freeze-dried amorphous matrix (lyophile) containing trehalose and sodium citrate buffer. The protonation of the probe molecules was measured in the lyophiles by diffuse reflectance visible spectroscopy, and compared with that in the solution before drying. The protonation of the indicators in the amorphous matrix correlated with solution pH, that is, an increase in solution pH resulted in a progressive decrease in the indicator protonation in the corresponding lyophile. However, the protonation was consistently higher in the lyophile than in the corresponding solution. The Hammett acidity function of lyophiles was calculated based on the extent of protonation of the probe molecules. Protonation of the probe molecules and the Hammett acidity function depended not only on prelyophilization solution pH, but also on the residual water content and the presence of amorphous sugar in the lyophile.

Bromcresol Green↗
PubMed1978

Simultaneous programmed temperature GLC assay of phenol, chloroxylenol, and lidocaine hydrochloride in topical antiseptic cream.

A simultaneous programmed temperature GLC assay for the active ingredients in a topical antiseptic cream is described. The sample is extracted directly using a dimethyl sulfoxide solution of p-cresol, 4-chlorophenol, and 2-amino-4-phenylthiazole as internal standards for phenol, chloroxylenol, and lidocaine hydrochloride, respectively. The resulting solution is chromatographed by temperature programming on an OV-225 column from 90 to 225 degrees. The internal standard calculation is accomplished using peak heights or peak areas. The relative standard deviation of all assays is less than 2%.

Anti-Infective Agents, Local↗
PubMed1994

A substrate recycling assay for phenolic compounds using tyrosinase and NADH.

A substrate recycling assay for phenolic compounds was developed using tyrosinase, a copper-containing enzyme, in excess NADH. The reaction of various phenols with the enzyme produced an o-quinone, which was then detected by recycling between reactions with the enzyme and NADH. The recycling of quinones by excess NADH to their original reduced forms prevented the problems of subsequent quinone polymerization and product inactivation which occur in nonrecycling assays. Absorbance measurements of the NADH consumption rate enhanced the assay sensitivity for catechol 100-fold compared to nonrecycling o-quinone detection, giving a detection limit of 240 nM. Fluorescence NADH monitoring permitted a 10-fold improvement over absorbance, with a detection limit of 23 nM. The recycling reaction was selective for o-quinones, and no interference was noted for p-quinones or quinoneimines. The two-step oxidation of phenols was observed as an initial lag phase (ca. 10 min), requiring a higher enzyme concentration to achieve the same sensitivity as that for catechol. The procedure was most useful for assaying catechol, 4-chlorocatechol, phenol, p-cresol, and 4-chlorophenol and may provide selective detection of these components in mixtures. Several other derivatives of catechols, including amine derivatives, were also detected, with relative sensitivity being related to substrate activity of the enzyme.

Catechols↗
PubMed1998

Effect of specific inhibitors on the anaerobic reductive dechlorination of 2,4,6-trichlorophenol by a stable methanogenic consortium.

The transformation of 2,4,6-trichlorophenol (TCP) into 4-chlorophenol (4CP) was studied using a stable methanogenic enrichment culture derived from an anaerobic fixed bed reactor. Using acetate as a growth substrate, different inhibitors of methanogenesis exhibited distinct effects on TCP dechlorination. Whereas reductive dechlorination activity was not affected by 2% ethylene in the gas phase, 25 mM bromoethanesulfonic acid (BESA) had a direct inhibitory effect on this process. The choice of BESA as a specific inhibitor for identifying the subpopulations involved in reductive dechlorination of chloroaromatics is thus questionable. Inhibitors of sulfate reduction such as molybdate (20 mM) and selenate (20 mM) had a direct inhibitory effect on reductive dechlorination independently of the presence of sulfate in the medium supplemented with acetate as growth substrate. Consequently much more care must also be taken with these inhibitors to prove that reductive chlorination is coupled to sulfate reduction.

Journal Article↗
PubMed1994

A field study of environmental impacts at a bleached kraft pulp mill site on the Baltic Sea coast.

The rate of technical development in bleaching of chemical pulp and the upgrading of process control and wastewater treatment systems in the pulp industry have been extremely rapid over the past few years. When assessing the environmental impacts of bleached kraft pulp mill effluents (BKMEs), it is therefore more important than ever to carefully characterize the bleaching process, the composition of the treated effluent, and the degree of exposure of sensitive target organisms in the receiving water body. These requirements have not always been fulfilled in previous reports on biological effects of BKMEs in Scandinavia. This work presents the results of a comprehensive field study of the impacts of a 350,000-tonne kraft mill, bleaching softwood and hardwood pulp in campaigns according to the sequence O(D25,C70+D5)(EOP)D(EP)D. The effluent is treated in an aerated lagoon with a mean retention time of 8-9 days, practically eliminating chlorate and resin acids, and reducing the discharge of adsorbable organic halogen (AOX) to an average of 1 t/day (1.3 and 0.4 kg/ADt for softwood and hardwood, respectively). The treated effluent is discharged through a 1.3-km-long diffuser, at a water depth of 9-12 m, into a well ventilated coastal area, giving a 1000-fold dilution within 3-4 km from the diffuser. The actual exposure of the coastal ecosystem to BKME components was determined by analysis of extractable organic chlorine in suspended solids and of conjugates of chlorophenolics in the bile of feral perch. Despite a major damage to the benthic communities that occurred about 10 years ago, and was due to large chlorate discharges at the time, no direct detrimental effects on benthic flora and fauna could be ascribed to the present BKME discharge. Instead, a clear recovery of the Fucus community, although not yet completed, could be demonstrated. Studies of the composition, abundance and biomass of the fish community, the recruitment and survival of fish fry, and the physiological status of perch, using a set of biomarkers, revealed that even in the most BKME-exposed area, only minor effects were detected. These effects were related to eutrophication/enrichment rather than to the action of toxic substances. The general effect picture, thus, was essentially of a different type than the one recorded in previous studies of mills, which used older technology and less effective process and effluent treatment control, and which were discharging into enclosed, shallow bays of the Baltic Sea.

Animals↗
PubMed2000

Pseudomonas pickettii: a common soil and groundwater aerobic bacteria with pathogenic and biodegradation properties.

Pseudomonas pickettii is an aerobic, nonfermentative, Gram-negative rod-shaped, bacterium that has been isolated from soil, water, humans, and recently the bovine intestinal tract. It belongs to the rRNA group II of the genus Pseudomonas and has three biovars: Va-1, Va-2, and biovar 3/thomasii. P. pickettii can cause pneumonia, meningitis, endocarditis, and osteomyelitis in humans. It frequently is associated with nosocomial infections that often are linked to contaminated injectable solutions. P. pickettii exhibits remarkable ability to degrade a variety of toxic compounds such as chlorophenols, aromatic hydrocarbons, 2,4-dichlorophenoxyacetic acid, and pentacyclic triterpeniod compounds. The genes that encode for these properties are chromosome- and plasmid-associated. Strains of the organism also have demonstrated resistance to heavy metals, such as cadmium, copper, and zinc. This species can survive in a nutrient-poor environment and use a variety of toxic compounds as carbon and energy sources, making it an ideal candidate for study in the biodegradation of toxic compounds found in wastewater and soils.

Aerobiosis↗
PubMed1997

Equilibrium Adsorption Studies of Some Aromatic Pollutants from Dilute Aqueous Solutions on Activated Carbon at Different Temperatures

Aqueous solutions of phenol, p-chlorophenol, and p-nitrophenol have been used to determine the adsorption isotherm for single solute systems on activated carbon at different temperatures. The experimental program has been conducted to investigate the influence of concentration and temperature. All the reported equilibrium isotherm equations have been tried on present and published experimental data. A generalized isotherm equation which was proposed by Khan et al. (6, 10) and tested for bi-solute adsorption data has been modified for single-solute system. The temperature dependency has also been incorporated into a generalized equation. It has been noticed that the Radke and Prausnitz (7) and generalized isotherm equations could represent the entire data with a minimum average percentage error. The influence of different adsorbents, sorbate concentrations, and pH of aqueous solutions has also been discussed in detail. The temperature dependency has been investigated using both the Dubinin-Astakov (13) and the modified generalized equation. The generalized equation describes the experimental and published data adequately and provides a single value of differential molar heat of adsorption, DeltaHads, for a single solute adsorption system. The Dubinin-Astakov isotherm equation has shown an increasing trend of DeltaHads as the loading of adsorbent has increased. Copyright 1997 Academic Press. Copyright 1997Academic Press

Journal Article↗
PubMed2000

Adsorption of Gemini and Conventional Cationic Surfactants onto Montmorillonite and the Removal of Some Pollutants by the Clay.

The adsorption of a series of gemini surfactants, [C(n)H(2n+1)N(+) (CH(3))(2)-CH(2)CH(2)](2).2Br(-), where n = 10, 12, 14, and 16, on clay (Na-montmorillonite) from their aqueous solution in 0.01 M KBr and the effect of this adsorption on the removal of 2-naphthol and 4-chlorophenol have been studied. Compared to those of conventional cationic surfactants with similar single hydrophilic and hydrophobic groups (C(n)H(2n+1)N(+)(CH(3))(3).Br(-), where n = 10, 12, 14, and 16), the molar adsorptions of the gemini and conventional surfactants are almost identical. This indicates that only one of the hydrophilic groups in the gemini molecule is adsorbed onto the clay and that the second hydrophilic is presumably oriented toward the aqueous phase, in contrast to the adsorption of the conventional surfactants, where the hydrophobic group is oriented toward the aqueous phase. Stability studies on dispersions of clay treated with the two types of surfactants confirm this. The slight increase in the moles of surfactant to values above the CEC of the clay with an increase in the carbon number of the hydrophobic chain indicates that adsorption through hydrophobic group interaction occurs in addition to the major ion exchange. Adsorption studies of the pollutants onto the clay treated by either the gemini or the conventional surfactants show that the former are both more efficient and more effective at removing the pollutants from the aqueous phase. Copyright 2000 Academic Press.

Journal Article↗
PubMed2000

Mechanism of Adsorption of Dyes and Phenols from Water Using Activated Carbons Prepared from Plum Kernels.

The kinetics and mechanism of adsorption of two commercial dyes (BR22, AB25), phenol, and 3-chlorophenol from water on activated carbons were studied at 30 degrees C. The activated carbons were prepared from plum kernels, and the activation temperature and time tested were in the ranges 750-900 degrees C and 1-4 h, respectively. Three simplified kinetic models including a pseudo-first-order, a pseudo-second-order, and an intraparticle diffusion model were tested. It was shown that the adsorption of both phenols could be fitted to a pseudo-second-order rate law, and that of both dyes could be fitted to an intraparticle diffusion model. Kinetic parameters were calculated and correlated with the physical properties of the adsorbents. Copyright 2000 Academic Press.

Journal Article↗
PubMed2001

Organic Pillared Clays.

Commonly used organophilic clays are modified by alkylammonium cations which hold apart the aluminosilicate layers permanently. The cations fill the interlayer space and are contemplated as flexible pillars, resulting from the mobility of the alkyl chains. Therefore, the interlayer distance varies depending on the layer charge and on the alkyl chain length. Contrary to these cations, rigid pillaring cations guarantee a constant interlayer distance without occupying the interlayer by themselves and show special adsorption properties such as hydrophilic behavior contrary to the generally hydrophobic ones. Smectites were modified by flexible organic cations, e.g., dimethyldioctadecylammonium, and by rigid ones, e.g., tetraphenylphosphonium. Their adsorption properties are compared. Our investigations showed improved adsorption properties for rigid organic cations on smectites using 2-chlorophenol as pollutant. Best adsorption results are achieved using pillaring cations in combination with low charged smectites, especially at low pollutant concentrations. The properties of organic modified smectites are discussed by a pollution intercalation model. The intercalation process of an organic pollutant into an organic modified smectite is expressed by a two-step Born-Haber cycle process: (i) the formation of an adsorbing position by layer expansion and (ii) the occupation of the adsorbing position by the pollutant. The first step of the formation of the adsorbing position is an endothermal transition state which lowers the total intercalation energy and therefore worsens the adsorption behavior. Thus, an already expanded organophilic smectite will show improved adsorption behavior. The formed adsorbing position state on organic modified smectites is comparable to the pillared state of inorganic pillared clays. Copyright 2001 Academic Press.

Journal Article↗
PubMed1998

Polychlorinated diphenylethers: origin, analysis, distribution, and toxicity in the marine environment.

PCDEs are present as impurities in chlorophenol preparations, which are often used as wood preservatives. Other sources of PCDEs such as municipal waste incinerators seem to be of minor importance. It is estimated that, worldwide 250-2500 metric tons of PCDEs have been produced, which is a lesser amount compared to the production figures of polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs), or polychlorinated naphthalenes (PCNs). The required analytical methods are rather complex and are comparable to methods used for polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs). Gas chromatography with low resolution or high resolution mass spectrometry or with electron-capture detection is recommended for the final determination of PCDEs. There is only limited information on the presence of PCDEs in the marine environment. High concentrations of PCDEs were found in Baltic white-tailed sea eagles (up to 13 mg/kg lipid weight per congener). Total PCDE concentrations of 50-300 micrograms/kg were reported in cod liver oil samples. PCDEs are immunotoxic and show a clear potency as inducers of hepatic microsomal AHH and EROD activity. Although PCDE concentrations in marine organisms are expected to be lower than those of PCBs, PBDEs, and PCNs, because of their toxic properties, persistence, and hydrophobic and bioaccumulative character and because of the limited information on these concentrations in marine organisms, further research on these concentrations in marine organisms is recommended.

Animals↗
PubMedDate not supplied

Toxicity of chlorobenzene on Pseudomonas sp. strain RHO1, a chlorobenzene-degrading strain.

Pseudomonas sp. strain RHO1 able to use chloro- and 1,4-dichlorobenzene as growth substrates was tested towards sensitivity against chlorobenzene. Concentrations of chlorobenzene higher than 3.5 mM were found to be toxic to cells independent of pregrowth with chlorobenzene or nutrient broth. Below this concentration, sensitivity towards chlorobenzene depended on the precultivation of the cells, i.e. type of growth substrate (chlorobenzene or nutrient broth) and the concentration of chlorobenzene as the growth substrate. Cells grown in continuous culture were especially sensitive with a threshold concentration of 2.5 mM chlorobenzene. In addition to chlorobenzene, metabolites also seem to function as toxic compounds. 2-Chlorophenol and 3-chlorocatechol were isolated from cell extracts. Cleavage of 3-chlorocatechol by catechol 1,2-dioxygenase seems to be the critical step in the metabolism of chlorobenzene.

Biodegradation, Environmental↗
PubMed1990

Isolation and characterization of a 2-(2,4-dichlorophenoxy) propionic acid-degrading soil bacterium.

The 2-(2,4-dichlorphenoxy)propionic acid (2,4-DP)-degrading bacterial strain MH was isolated after numerous subcultivations of a mixed culture obtained by soil-column enrichment and finally identified as Flavobacterium sp. Growth of this strain was supported by 2,4-DP (maximum specific growth rate 0.2 h-1) as well as by 2,4-dichlorophenoxyacetic acid (2,4-D), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), and 2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) as sole sources of carbon and energy under aerobic conditions. 2,4-DP-Grown cells (10(8] of strain MH degraded 2,4-dichlorophenoxyalkanoic acids, 2,4-dichlorophenol (2,4-DCP), and 4-chlorophenol at rates in the range of 30 nmol/h. Preliminary investigations indicate that cleavage of 2,4-DP results in 2,4-DCP, which is further mineralized via ortho-hydroxylation and ortho-cleavage of the resulting 3,5-dichlorocatechol.

2,4-Dichlorophenoxyacetic Acid↗
PubMed1984

Noninvasive assessment of microsomal enzyme activity in occupational medicine: present state of knowledge and future perspectives.

The activity of the hepatic microsomal enzyme system, which may be of great importance for metabolic activation and deactivation of hepatotoxic agents and carcinogens, is changed by exposure to commonly used industrial chemicals. The antipyrine test is the most widely used method for assessing microsomal enzyme activity in man. The clearance of antipyrine can be accurately calculated from one sample of saliva obtained about 24 h after an oral dose of the drug. By measuring antipyrine metabolism during exposure to industrial chemicals and at the end of 3-4 weeks free from exposure, the impact of industrial chemicals on antipyrine metabolism can be estimated, provided the chemicals are eliminated within 3-4 weeks. This test can be performed by skilled and unskilled workers using written instructions. This has broadened the application of the test. Other noninvasive indices of microsomal enzyme activity include the aminopyrine and caffeine breath tests and the urinary excretion of 6-beta-hydroxycortisol and D-glucaric acid. These tests probably reflect the activity of different but overlapping parts of the microsomal enzyme system and may be of value in research in occupational medicine. Previous studies indicate that chlorinated hydrocarbon insecticides, phenoxyacids, chlorophenols, polychlorinated biphenyles, some organic solvents and high concentrations of inhalation anaesthetics may stimulate microsomal enzyme activity, while styrene, toluene and inhalation anaesthetics in concentrations at about the allowed safety limit values have no effect. Lead, chemicals used by spray painters, and carbon disulphide probably inhibit the activity. While the short-term consequences of these changes include altered metabolism of hormones, vitamins, drugs, and other microsomally metabolized compounds, the possible impact on health on a long-term scale is unknown. It is now possible to study this with the use of the available noninvasive simple indices of microsomal enzyme activity. The potentially useful applications include biological monitoring of environmental carcinogenesis and hepatotoxicity.

Aminopyrine↗
PubMed1980

Histochemical staining of cadmium with benzothiazolylazophenol derivatives.

As part of the continuous developmental research for a highly sensitive chelating agent for cadmium, benzothiazolylazophenol derivatives (BTAP) were synthesized and their staining properties for cadmium were examined. The compounds synthesized for this study were identified as being BTAP by analysis of their melting points and C,H,N,S content. Benzothiazolylazo-p-methoxyphenol, -p-chlorophenol and -p-cresol stained cadmium with the highest optical density and the most precise localization amongst dyestuffs reported to date. Differential sequestration by pyrophosphate makes it possible to distinguish cadmium masked by the presence of zinc. With the modification of a chelating agent to increase sensitivity, the improvement in molar absorptivity was also considered theoretically.

Animals↗
PubMed1993

Malignant lymphomas and leukemias, and exposures in the wood industry: an industry-based case-referent study.

Jobs and exposures in woodwork may entail an elevated risk of lymphomas and leukemias. Exposures occurring in woodwork were scrutinized in a small industry-based case-referent study of four cases of Hodgkin's disease, eight cases of non-Hodgkin's lymphoma, 12 cases of leukemia, and 152 matched referents, all from the Finnish wood industry. Past exposures to wood dust, chlorophenols, terpenes, and engine exhaust, individually reconstructed through plant- and period-specific job exposure matrices, were unrelated to lymphoma/leukemia risk. Exposures to various solvents were associated with an odds ratio (OR) of 5.6 (95% confidence interval 1.0-32.0). The OR for formaldehyde was 2.5 (nonsignificant). The results are interpreted as providing limited evidence of the role of exposure to some as yet unidentified organic solvents in increasing the risk of malignant lymphomas. Formaldehyde may be another woodwork-related risk factor for some lymphomas, but the power of the study was too low for empirical confirmation of this possibility. Leukemias did not seem to be associated with any of the exposures studied.

Air Pollutants, Occupational↗
PubMed1996

Introduction of a de novo bioremediation activity into anaerobic granular sludge using the dechlorinating bacterium DCB-2.

The strictly anaerobic, pentachlorophenol (PCP) degrading bacterium DCB-2 was immobilized in an Upflow Anaerobic Sludge Blanket (UASB) reactor containing sterile granules. PCP and lactate were fed to the reactor and the concentration of chlorophenols in the effluent were monitored for 641 days. PCP was found to be degraded and transformed into 3,4,5-trichlorophenol in the reactor where DCB-2 introduced PPCP was still transformed to 3,4,5-trichlorophenol when the hydraulic retention time was decreased to six hours which was much lower than the generation time of DCB-2 insuring no free living cells in the reactor. This indicated that DCB-2 was immobilized in the granular layer. A control reactor that contained only sterile granules did not dechlorinate PCP indicating that the performance in the inoculated reactor was only due to the introduced bacteria. Immobilization of DCB-2 in the granules was further demonstrated by adding an antibody raised against DCB-2 to sliced granules. Bacteria thus visualized formed a net structure inside the granules. No DCB-2 bacteria could be found in granules from the control reactor. When lactate was omitted from the influent, the reactor still dechlorinated PCP in accordance with our findings that lactate was not used by DCB-2. This suggested that the reducing equivalents for reductive dechlorination were derived from the granules themselves. The reactor performance was 120 mumol.l reactor-1.day-1, comparable to the best described performance of a UASB-reactor and to aerobic reactors. Our study demonstrates that granules can be constructed which possess specific abilities such as a dechlorinating activity and at the same time be high performing. This result have implications for eco-engineering of granules for anaerobic treatment of contaminated waters.

Bacteria, Anaerobic↗