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Adsorption of some bivalent heavy metal ions from aqueous solutions by manganese nodule leached residues.

The leached residue, generated after selective extraction of Cu, Ni, and Co in sulfur dioxide-ammonia leaching of manganese nodules, was characterized and batch isothermal adsorption experiments were conducted at ambient temperature to evaluate the effectiveness of the water-washed leached residue for removal of different bivalent metal ions from aqueous synthetic solutions. The effects of pH, initial metal ion concentrations, amount of adsorbent, interfering ions, and heat treatment were also investigated. The uptake of metal ions increased with increasing pH. Under identical conditions the adsorption capacity increased in the order Cd(2+)<Cu(2+)<Pb(2+). The adsorption kinetics was found to follow a first-order rate expression and the experimental equilibrium adsorption data fitted reasonably well to both Langmuir and Freundlich isotherm models. Various metal ions present in the leached residue were found to be released during adsorption of heavy metals, which decreased with increased pH and were practically negligible at pH approximately 6.0. Desorption of adsorbed metal ions from metal-loaded leached residue and its regeneration ability were also studied. The results obtained could be useful for considering the leached manganese nodules residue as adsorbent for removal of heavy metal ions from contaminated water bodies.

Journal Article↗

Wetting and electrical properties of the human hair surface: delipidation observed at the nanoscale.

The electrostatic properties and the wetting behaviour of the human hair surface at the nanometric scale have been investigated by using atomic force microscopy (AFM). Surface potential imaging was used to determine the electrostatic properties while non-contact mode AFM was used to investigate the wetting properties of a test liquid, squalane. We have studied natural hair and hair in which different covalently (18-methyleicosanoic acid) and non-covalently bound fatty acids present at the cuticle surface were selectively extracted. This study shows how the removal of these acids causes various profound changes in hair wettability at the cuticle scale.

Electrochemistry↗

Effects of a reactive barrier and aquifer geology on metal distribution and mobility in a mine drainage impacted aquifer.

The Nickel Rim aquifer has been impacted for five decades by a metal-rich plume generated from the Nickel Rim mine tailings impoundment. Metals released by the oxidation of pyrrhotite in the unsaturated zone of the tailings migrate into the downgradient aquifer, affecting both the groundwater and the aquifer solids. A reactive barrier has been installed in the aquifer to remove sulfate and metals from the groundwater. The effect of the reactive barrier on metal concentrations in the aquifer solids has not previously been studied. In this study, a series of selective extraction procedures was applied to cores of aquifer sediment, to ascertain the distribution of metals among various solid phases present in the aquifer. Extraction results were combined with groundwater chemistry, geochemical modelling and solid-phase microanalyses, to assess the potential mobility of metals under changing geochemical conditions. Reactions within the reactive barrier caused an increase in the solid-phase carbonate content downgradient from the barrier. The concentrations of poorly crystalline, oxidized phases of Mn and Fe, as well as concentrations of Cr(III) associated with oxidized Fe, and poorly crystalline Zn, are lower downgradient from the barrier, whereas total solid-phase metal concentrations remain constant. Iron and Mn accumulate as oxidized, easily extractable forms in a peat layer overlying the aquifer. Although these oxides may buffer reducing plumes, they also have the potential to release metals to the groundwater, should a reduced condition be imposed on the aquifer by remedial actions.

Biodegradation, Environmental↗

Composite membrane of bacterially-derived cellulose and molecularly imprinted polymer for use as a transdermal enantioselective controlled-release system of racemic propranolol.

A composite membrane for transdermal delivery of S-propranolol enantiomer was developed based on the controlled pore functionalization of bacterial cellulose membranes using a molecularly imprinted polymer (MIP) layer synthesis. The reactive pore-filling of an asymmetric porous cellulose membrane with a MIP thin-layer was effected using a silanized coupler as an additional anchor for the MIP. MIP thin-layers with specific binding sites for S-propranolol were synthesized by copolymerization of methacrylic acid with a cross-linker, ethylene glycol dimethacrylate in the presence of S-propranolol as the template molecule and the latter was subsequently extracted. Selective transport of S-propranolol through the MIP composite membrane was obtained, although this was determined mostly by the parent cellulose membrane with some ancillary contributory effect from the MIP layer. In addition, an enantioselectivity in the transport of propranolol prodrug enantiomers was found, suggesting that the shape and functional groups orientation, which are similar to that of the print molecule were essential for enantiomeric recognition of the MIP composite membrane. The enantioselectivity of S-MIP membranes was also shown when the release of propranolol enantiomers was studied in vitro using rat skin, with racemic propranolol contained in the donor compartment. The composite membrane of bacterially-derived cellulose and molecularly imprinted polymer may have great potential for use as a transdermal enantioselective controlled-release system for racemic propranolol.

Administration, Cutaneous↗

Transformation of heavy metal forms during sewage sludge bioleaching.

The transformation of heavy metal forms during sewage sludge bioleaching with elemental sulfur as substrate was investigated. The sequential selective extraction procedure was an effective way to reflect the variation in heavy metal forms. The exchangeable form of Cu, Pb and Zn after bioleaching accounted for 81.6, 40.2 and 75.8%, respectively. Cu at initial sludge mainly existed as sulfide precipitate form, most of which turned to exchangeable form during bioleaching, and was solubilized mostly by direct mechanism. The original forms of Pb and Zn were mainly carbonate precipitate and organically bound. Most of the carbonate precipitate Pb transformed into exchangeable form but a little of organically bound Pb. Pb was dissolved from the sludge due to transformation of carbonate precipitated and sulfide precipitated to exchangeable form by cooperation of both direct and indirect mechanisms. A majority of exchangeable Zn was transformed from organically bound and carbonate precipitated forms, and the bioleaching mechanism of Zn was mainly indirect. After bioleaching, the sewage sludge could be applied to land more safely because the heavy metals mainly existed in stable forms. The exchangeable Cu and Pb achieved an obvious increase at pH about 2, while exchangeable Zn showed higher percentage at pH about 3. The transformation of chemical forms for Cu had good relationship with ORP during bioleaching, but Zn was not influenced by ORP of sludge, which appeared to have high bioleaching efficiency at ORP less than 200 mV.

Hydrogen-Ion Concentration↗

Determination of naproxen in human urine by solid-phase microextraction coupled to liquid chromatography.

An SPME-LC-UV method for the determination of the non-steroidal anti-inflammatory drug (NSAID) naproxen and, after hydrolysis, its glucuronide in human urine samples was developed for the first time using a carbowax/templated resin (CW/TPR-100)-coated fibre. The procedure required a very simple sample pre-treatment, an isocratic elution, and provides a highly selective extraction. All the aspects influencing adsorption (extraction time, temperature, pH and salt addition) and desorption (desorption and injection time and desorption solvent mixture composition) of the analyte on the fibre have been investigated. The linear range investigated in urine was 0.2-20 microg/ml (that covers the typical naproxen urinary concentration) and almost quantitative recoveries were obtained. Within-day and between-days R.S.D.% in urine were 4.5 and 6.0, respectively. The LOD and LOQ in spiked urine were 0.03 and 0.20 microg/ml, well below the usual naproxen urinary level.

Adsorption↗

Control of antigen mass transfer via capture substrate rotation: an absolute method for the determination of viral pathogen concentration and reduction of heterogeneous immunoassay incubation times.

Immunosorbent assays are commonly employed as diagnostic tests in human healthcare, veterinary medicine and bioterrorism prevention. These assays, however, often require long incubation times, limiting sample throughput. As an approach to overcome this weakness, this paper examines the use of rotating capture substrates to increase the flux of antigen to the surface, thereby reducing the incubation time. To assess the capability of this approach, porcine parvovirus (PPV) was selectively extracted from solution by systematically varying the rotation rate of a gold substrate modified with a layer of anti-PPV monoclonal antibodies. The captured PPV were then directly imaged and quantified by atomic force microscopy. The benefits of substrate rotation are demonstrated by comparing an assay performed under stagnant conditions to one carried out with substrate rotation at 800 rpm, both for 10 min incubations at 25 degrees C. The use of rotation lowered the limit of detection to 3.4x10(4)TCID50/mL (approximately 80 fM) from 3.2x10(5)TCID50/mL (approximately 800 fM) under stagnant conditions. Results are also presented that show this strategy can be used: (1) to determine antigen concentrations without standards and (2) to establish the numerical relationship between quantal concentration units (e.g., 50% tissue culture infective dose (TCID50)) and quantitative concentration units (e.g., viruses/mL) The potential to broadly apply this technique to heterogeneous immunoassays is also briefly discussed.

Antibodies, Monoclonal↗

4-Alkyl- and 4-phenylcoumarins from Mesua ferrea as promising multidrug resistant antibacterials.

Supercritical CO2 selectively extracted a series of 4-alkyl and 4-phenyl 5,7-dihydroxycoumarins from Mesua ferrea blossoms. Chemical modifications of the isolated compounds allowed us to confirm the structures elucidated by spectroscopic means and to prepare new derivatives amenable to SAR studies and potential pharmaceutical development. Biological investigations towards the screening on a number of bacteria strains and Plasmodium falciparum, identified compounds 1-9 as weak antiprotozoal agents and potent antibacterials on resistant Gram-positive strains.

Animals↗

Effects of endocrine disruptors on the formation of prostaglandin and arachidonoyl-CoA formed from arachidonic acid in rabbit kidney medulla microsomes.

Under physiological conditions, small amounts of free arachidonic acid (AA) are released from membrane phospholipids, and cyclooxygenase (COX) and acyl-CoA synthetase (ACS) competitively act on this fatty acid to form prostaglandins (PGs) and arachidonoyl-CoA (AA-CoA). To explore the possible actions of endocrine disruptors on the metabolic fate of free AA into these two pathways, we investigated the effects of nonylphenol (NP), bisphenol A (BPA), di-n-butyl phthalate (DBP), benzyl-n-butyl phthalate (BBP) and di-2-ethylhexyl phthalate (DEHP) on the formation of PG and AA-CoA from 5 microM AA (close to the physiological concentration of the substrate) in rabbit kidney medulla microsomes. The kidney medulla microsomes were incubated with 5 microM [(14)C]-AA in 0.1 M Tris/HCl buffer (pH 8.0) containing cofactors of COX (reduced glutathione and hydroquinone) and cofactors of ACS (ATP, MgCl(2) and CoA). After incubation, PG (as total PGs) and AA-CoA were separated by selective extraction using petroleum ether and ethyl acetate. NP (1-200 microM) strongly enhanced the AA-CoA formation with a coincident decrease in the PG formation. BPA, DBP, BBP and DEHP failed to show any effect on the PG and AA-CoA formation up to 200 microM. Experiments utilizing 60 microM AA as the substrate concentration indicated that, under a low concentration of AA, NP decreases PG formation by inhibiting the COX activity, and reduces the AA flow into the COX pathway through inhibition on the COX activity, increasing availability of the substrate for the ACS and leading to enhanced AA-CoA formation. These results firstly show that NP has the potential to disturb the balance of PG and AA-CoA formations under normal physiological conditions.

Acyl Coenzyme A↗

15-Hydroperoxyeicosapentaenoic acid, but not eicosapentaenoic acid, shifts arachidonic acid away from cyclooxygenase pathway into acyl-CoA synthetase pathway in rabbit kidney medulla microsomes.

Under physiological conditions, small amounts of free arachidonic acid (AA) are released from membrane phospholipids, and cyclooxygenase (COX) and acyl-CoA synthetase (ACS) competitively act on this fatty acid to form prostaglandins (PGs) and arachidonoyl-CoA (AA-CoA). In the present study, we investigated the effects of eicosapentaenoic acid (EPA) and 15-hydroperoxyeicosapentaenoic acid (15-HPEPE) on the PG and AA-CoA formations from high and low concentrations of AA (60 and 5 microM) in rabbit kidney medulla microsomes. The kidney medulla microsomes were incubated with 60 or 5 microM [(14)C]-AA in 0.1M Tris/HCl buffer (pH 8.0) containing cofactors of COX (reduced glutathione and hydroquinone) and cofactors of ACS (ATP, MgCl(2) and CoA). After incubation, PG (as total PGs), AA-CoA and residual AA were separated by selective extraction using petroleum ether and ethyl acetate. EPA reduced the PG and AA-CoA formations from both 60 and 5 microM AA. In contrast, 15-HPEPE decreased the PG formation without affecting the AA-CoA formation from 60 microM AA, and increased the AA-CoA formation at the expense of PG formation when 5 microM AA was used as substrate concentration. The experiments utilizing Fe(2+) and an electron spin resonance (ESR) revealed that 15-HPEPE elicits these effects in the form of hydroperoxy adduct. These results suggest that 15-HPEPE, but not EPA, has the potential to shift AA away from COX pathway into ACS pathway at low substrate concentration (close to the physiological concentration of AA).

Animals↗

The regulation of formation of prostaglandins and arachidonoyl-CoA from arachidonic acid in rabbit kidney medulla microsomes by linoleic acid hydroperoxide.

Under physiological conditions, small amounts of free arachidonic acid (AA) are released from membrane phospholipids, and cyclooxygenase (COX) and acyl-CoA synthetase (ACS) competitively act on this fatty acid to form prostaglandins (PGs) and arachidonoyl-CoA (AA-CoA). In the present study, we investigated the effects of linoleic acid (LA) and 13-hydroperoxyoctadecadienoic acid (13-HPODE) on the PG and AA-CoA formation from high and low concentrations of AA (60 and 5 microM) in rabbit kidney medulla microsomes. The kidney medulla microsomes were incubated with 60 or 5 microM [(14)C]-AA in 0.1M Tris-HCl buffer (pH 8.0) containing cofactors of COX (reduced glutathione and hydroquinone) and cofactors of ACS (ATP, MgCl(2) and CoA). After incubation, PG (as total PGs), AA-CoA and residual AA were separated by selective extraction using petroleum ether and ethyl acetate. LA (10-50 microM) reduced only PG formation from both 60 and 5 microM AA. 13-HPODE (10-50 microM) also reduced PG formation from 60 and 5 microM AA, but the inhibitory potency was much stronger than that by LA. Furthermore, 13-HPODE had the potential to increase the AA-CoA formation with a decrease in the PG formation from 5 microM AA. These results suggest that 13-HPODE, but not LA, may shift AA away from COX pathway into ACS pathway under low substrate concentration (near physiological concentration of AA).

Acyl Coenzyme A↗

Immunocytochemical identification of the major exospore protein and three polar-tube proteins of the microsporidia Paranosema grylli.

Microsporidia are intracellular eukaryotic parasites that can infect a wide range of animal hosts with several genera causing opportunistic infections in immunodeficient patients. Their spore wall and their unique extrusion apparatus, which has the form of a long polar tube, confer resistance of these parasites against the environment and during host-cell invasion. In contrast to parasites of vertebrates, the spore-wall and polar-tube proteins of many microsporidia species still remain to be characterized, even though a great number of microsporidia infect invertebrates. Here, we have identified one spore-wall protein and three polar-tube proteins of the microsporidia Paranosema grylli that infects the cricket Gryllus bimaculatus. Incubation of intact spores with an alkaline-saline solution resulted in the selective extraction of a major 40 kDa protein. A wash of the discharged (or destroyed) spores with SDS and the following solubilization of their polar tubes with 50-75% 2-mercaptoethanol extracted a major protein of ca. 56 kDa. When the polar tubes were solubilized in the presence of SDS, two additional proteins of 46 and 34 kDa were extracted. Antibodies specific for these extracted proteins were generated and isolated by incubation of immune sera with the protein bands that had been transferred to nitrocellulose. Western blotting demonstrated the cross-reactivity of the anti-p46 and anti-p34 antibodies. Immuno-electron microscopy with the anti-p40 antibody revealed specific decoration of the microsporidia exospore. The 56, 46 and 34 kDa proteins were characterized as polar-tube components due to the clear antibody labeling of the polar filament.

Animals↗

Modified thoracic impedance plethysmography to monitor sleep apnea syndromes.

BACKGROUND AND PURPOSE: In order to identify sleep disorders by thoracic impedance plethysmography (TIP), we propose several new techniques: the application of an adaptive filter, a scaled Fourier linear combiner (SFLC) to eliminate cardiac-derived fluctuation in the impedance waveform, and the use of heart rate variability (HRV) to ascertain whether the airflow is obstructed. PATIENTS AND METHODS: Laboratory simulation experiments on four healthy individuals and actual overnight measurements on five patients with sleep disorders were carried out. Amplified thoracic impedance change (DeltaZ), ECG, a phonocardiograph, a pneumotachograph and a standard polysomnograph were recorded. The SFLC was applied to DeltaZ to selectively extract the cardiac-synchronous component (DeltaZ(CSC)), and the remainder of the waveform (DeltaZ(REM)) was low-pass filtered to estimate the waveform driven by respiration. The HRV was divided into respiratory synchronous (HRV(R)) and low frequency (HRV(L)) components. RESULTS: The SFLC could drastically extract DeltaZ(CSC) from DeltaZ and thereby demonstrate a DeltaZ(REM) pattern quite similar to the flow-volume curve of the pneumotachograph. Central sleep apnea could be identified as the cessation of DeltaZ(REM) and concomitant attenuation of HRV(R). Obstructive sleep apnea could be identified as the maintenance of rhythmic but attenuated variations of DeltaZ(REM) accompanied by asynchronous fluctuation of HRV(R) against DeltaZ(REM). Central hypopnea could be identified as a normal but attenuated waveform in both DeltaZ(REM) and HRV(R). A large fluctuation in HRV(L) was observed during repetitive appearances of apnea/hypopnea in the nocturnal experiments. CONCLUSION: The modified TIP together with HRV provides a superior tool for accurate and convenient definition of sleep apnea syndromes.

Heart Rate↗

Retention of inorganic arsenic by coryneform mutant strains.

The natural resistance mechanisms of corynebacteria to respond to the environments containing high levels of arsenic were successfully adopted to develop inexpensive and selective extractants for submicrogram amounts of arsenic. Kinetic and equilibrium characteristics were evaluated, and a preliminary exploration of the capability of these strains to be used for arsenic speciation was also made in this work. Three kinetics models were used to fit the experimental data. It was found that the pseudo-first-order kinetics model was not quite adequate to describe the retention process, while the intraparticle diffusion and the pseudo-second-order kinetics models provide the best fits. The equilibrium isotherm showed that the retention of arsenic was consistent with the Langmuir equation and that the Freundlich and Dubinin-Radushkevich models provided poorer fits to the experimental data. The maximum effective retention capacity for arsenic was about 15.4 ng As/mg biomass. The amount of arsenic retained was directly measured in the biomass by forward planning a slurry electrothermal atomic absorption spectrometric procedure.

Adsorption↗

Lipidic cubic phases as matrices for membrane protein crystallization.

This review provides detailed procedures for the crystallization of membrane proteins via the lipidic cubic phase method. Bacteriorhodopsin-specific, hands-on protocols are given for (i) the preparation of bacteriohordopsin from purple membrane by monomerization in octylglucoside and gel filtration chromatography or by selective extraction after pre-treatment with dodecyl-trimethylammonium bromide, (ii) the incorporation of bacteriorhodopsin into lipidic cubic phases by mixing in vials or within coupled syringes and, (iii) the crystallization of bacteriorhodopsin in the lipidic matrix by adding a solid salt or an overlaying with a solution. References for further useful procedures and materials are listed in order to provide biochemists and crystallographers with all information that is necessary to grow crystals of the membrane protein bacteriorhodopsin.

Bacteriorhodopsins↗

Dimerization of F0F1ATP synthase from bovine heart is independent from the binding of the inhibitor protein IF1.

Solubilization of heavy bovine heart mitochondria with Triton X-100 leads to the selective extraction of F0F1ATP synthase monomer and dimer in a 2:1 ratio, as revealed by blue native gel electrophoresis (BN-PAGE). Second dimensional SDS-PAGE and immunoblotting with IF1 and F1 antibodies following BN-PAGE show that both aggregation states of the ATP synthase contain IF1. The monomer/dimer ratio does not change in extracts from mitochondria subjected to different energy conditions accompanied by IF1 binding modulation or from submitochondrial particles differing in IF1 content. In addition, the usual monomer/dimer ratio is observed even in submitochondrial particles deprived of IF1. Histochemical staining for ATPase activity demonstrates that the dimer is inactive, irrespective of its IF1 content. It is concluded that in the membrane of bovine heart mitochondria the ATP synthase dimer is a stable inactive structure, whose formation is not mediated by IF1 binding.

Adenosine Triphosphate↗

Identification of F0 subunits in the rat liver mitochondrial F0F1-ATP synthase.

In order to identify the subunits constituting the rat liver F0F1-ATP synthase, the complex prepared by selective extraction from the mitochondrial membranes with a detergent followed by purification on a sucrose gradient has been compared to that obtained by immunoprecipitation with an anti-F1 serum. The subunits present in both preparations that are assumed to be authentic components of the complex have been identified. The results show that the total rat liver F0F1-ATP synthase contains at least 13 different proteins, seven of which can be attributed to F0. The following F0 subunits have been identified: the subunit b (migrating as a 24 kDa band in SDS-PAGE), the oligomycin-sensitivity-conferring protein (20 kDa), and F6 (9 kDa) that have N-terminal sequences homologous to the beef-heart ones; the mtDNA encoded subunits 6 (20 kDa) and 8 (less than 7 kDa) that can be synthesized in isolated mitochondria; an additional 20 kDa protein that could be equivalent to the beef heart subunit d.

Adenosine Triphosphatases↗

A novel photoprotein from oceanic squid (Symplectoteuthis oualaniensis) with sequence similarity to mammalian carbon-nitrogen hydrolase domains.

A 60-kDa photoprotein was selectively extracted from squid photogenic organ with 0.6 M KCl solution at pH 6 as luminescence-active forms. The photoprotein with fluorescence chromophore was eluted from size-exclusion HPLC mainly as oligomeric forms (about 200 kDa or more) with a trace amount of monomeric form of about 60 kDa. A limited tryptic digestion of the KCl-extract induced the cleavage into a 40-kDa fragment and a 16-kDa N-terminal fragment and the conversion to the monomeric form which still retained luminescence activity. Under UV light the 60-kDa protein and its 40-kDa fragment emitted fluorescence. Immunoblot analysis using specific antibody showed specific expression of the 60-kDa protein in the photogenic organ. Amino acid sequences of the 60-kDa photoprotein, its 40- and 16-kDa fragments, and six peptides from the Lys-C digest revealed no sequence similarity to known photoproteins but significant similarity to the carbon-nitrogen hydrolase domain found in mammalian biotinidase and vanin (pantetheinase).

Amidohydrolases↗