A voltammetric study of copper-ion binding to the cell surface of the marine alga

Abstract

The binding of copper ion to the surfaces of the marine diatom Phaeodactylum tricornutum was studied in seawater pH 8. The cell wall complexing capacity and the average surface complex formation constant were determined by voltammetric titration curves. The presence of biotic particles at a concentration of 2.7 X 10⁶ cells mL^?1 does not hinder the measurement of stripping currents and the voltammetric fraction of non-reducible copper is the same as the copper bound to the cell surfaces as measured by atomic absorption spectrometry.     

Kinetic and equilibrium studies of copper biosorption onto <Emphasis Type="Italic">Pseudomonas aeruginosa</Emphasis> base using direct determination of copper by a voltammetric method

This paper provided information on the use of linear sweep anodic stripping voltammetry for evaluating the process of copper biosorption onto Pseudomonas aeruginosa. This technique was suited to determine the concentration of free copper ion on site on the mercaptoethane sulfonate modified gold electrode surface without any pretreatment. It was in favor of the study of kinetic process as the fast changing kinetic data characteristic just after the beginning of biosorption could be accurately depicted. Based on the electrochemical results, the kinetics and equilibrium of biosorption were systematically examined. The pseudo-second-order kinetic model was used to correlate the kinetic experimental data and the kinetic parameters were evaluated. The Langmuir and Freundlich models were applied to describe the biosorption equilibrium. It was found that the Langmuir isotherm fitted the experimental data better than the Freundlich isotherm. Maximum adsorption capacity of copper ion onto Pseudomonas aeruginosa was 0.9355 μmol mg⁻¹ (about 59.4417 mg g⁻¹).     

Copper complexing capacity in fresh-waters using the catechol-cathodic stripping voltammetric method

Abstract

The catechol-cathodic stripping voltammetric (CSV) method for measurement of the copper complexing capacity of marine and estuarine waters, has been modified and applied to fresh-waters. The optimum catechol concentration needed was the major difference between the two methods. It was found necessary to separately optimise the catechol concentration for each of the three fresh-water samples tested, presumably because of the much greater differences in the concentration of complexing ligands in fresh-water compared with marine or estuarine waters. This limits the usefulness of the CSV method for the determination of the complexing capacity of fresh-waters.

The total ligand concentration ([L_t]) and conditional stability constants (*K) derived for the three fresh-waters are compared with similar data obtained using an anodic stripping voltammetric (ASV) method. The set of copper-binding ligands determined using the CSV method were slightly lower in concentration, but stronger binding, than those obtained using the ASV method (CSV: [L_t] 0.04–0.06 μM, log K(pH 6) 8.9–9.4; ASV: [L_t] 0.11–0.17 μM, log *K(pH 6) 7.9–8.1).     

Potentiometric Stripping analysis—a new technique for tissue analysis used to correlate chemical speciation with progress of wound healing

ABSTRACT

PSA has been adapted to the analysis of 20 mg samples of skin for copper at 12 and zinc at 33 ppb of dry mass. This technique can be applied to other metal analyses, can be extended to human samples and produces data which, used as input, will permit considerably more precise chemical speciation data reflecting bioavailabilities etc. Other methods of analysing such low levels are reviewed and all suffer from disadvantages compared with PSA when used in a hospital environment—extremely expensive, highly skilled technologists required, slow turn around of results, large sample volumes necessary, non-applicable to physiological concentrations. The PSA method can now be applied to assessing and monitoring treatment of copper and zinc levels for patients.     

超声定位腔镜深筋膜下交通支离断术联合湿性换药技术治疗下肢静脉性溃疡

目的:探讨彩超定位下的腔镜深筋膜下交通支离断术(SEPS)联合湿性换药技术治疗下肢静脉性溃疡(VU)的方法及效果。方法:回顾性分析了8例VU患者共8条C6级下肢SEPS手术联合湿性换药技术的方法和效果。术前用彩色多普勒超声对功能不全交通支(ICPV)行体表定位,进行SEPS+大隐静脉高位结扎剥脱术+硬化剂注射术,术后湿性换药技术溃疡换药。结果:超声准确定位下SEPS联合湿性换药术后所有C6级患肢VU均在短期内愈合,随访期间无溃疡复发。结论:SEPS联合湿性换药技术治疗VU术后安全,疗效确切,并发症少。     

Evaluation of the solubility of a range of copper sources and the effects of iron & sulphur on copper solubility under rumen simulated conditions

BackgroundAntagonisms exist in vivo which inhibit copper bioavailability in ruminants. Although the antagonism between iron, sulphur and copper has been well observed in vivo in practice the mechanism by which it acts has not yet been elucidated, nor the compound it creates identified. This results in problems when trying to optimise supplementation to prevent the interaction from occurring or provide a copper source which is able to negate its effects. This work aims to establish if the antagonism between sulphur, iron and copper could be elicited under in vitro rumen replicated conditions and using a range of copper sources to investigate any differences in their participation in the interaction.MethodsRumen simulated conditions were used to test solubility as a proxy for bioavailability of different copper sources. Sources from ionic, hydroxy and organic compounds were tested in de-ionised water and warmed, strained rumen fluid which mimicked duration, agitation, temperature and pH of the rumen.ResultsAll copper sources were less soluble in rumen fluid than in de-ionised water. The addition of sulphide, alone or as part of a sulphur mix with sulphate produced a pronounced reduction in solubility on each of the copper sources. The most soluble were the greatest affected.ConclusionThere was no indication that an in insoluble compound containing copper and iron was formed under these conditions. The intricacy of the in vivo rumen is required to elicit the reaction between copper, iron and sulphur.     

Detection of Lipid Degradation Products in the Water of a Reservoir During a Bloom of Synura uvella

A stripping method was used to determine the volatile compounds present in the raw water of a reservoir during a heavy bloom of Synura uvella. Besides numerous pollution products, a large number of previously unidentified algal excretion products were determined, including alkenes, alcohols, ketones, aldehydes, and nor-carotenoids. The approximate amounts of some important algal excretion products present in the raw water are stated. Their biosynthetic origin and possible function in the ecosystem are discussed. The offensive cod liver oil-like odor which Synura imparts to the raw water was traceable to trans,cis-deca-2,4-dienal and minor amounts of trans,cis-hepta-2,4-dienal.     

Old Iron, Young Copper: from Mars to Venus

Iron and copper are metals which play an important role in the living world. From a brief consideration of their chemistry and biochemistry we conclude that the early chemistry of life used water soluble ferrous iron while copper was in the water-insoluble Cu(I) state as highly insoluble sulphides. The advent of oxygen was a catastrophic event for most living organisms, and can be considered to be the first general irreversible pollution of the earth. In contrast to the oxidation of iron and its loss of bioavailability as insoluble Fe(III), the oxidation of insoluble Cu(I) led to soluble Cu(II). A new iron biochemistry became possible after the advent of oxygen, with the development of chelators of Fe(III), which rendered iron once again accessible, and with the control of the potential toxicity of iron by its storage in a water soluble, non-toxic, bio-available storage protein (ferritin). Biology also discovered that whereas enzymes involved in anaerobic metabolism were designed to operate in the lower portion of the redox spectrum, the arrival of dioxygen created the need for a new redox active metal which could attain higher redox potentials. Copper, now bioavailable, was ideally suited to exploit the oxidizing power of dioxygen. The arrival of copper also coincided with the development of multicellular organisms which had extracellular cross-linked matrices capable of resisting attack by oxygen free radicals. After the initial `iron age' subsequent evolution moved, not towards a `copper age', but rather to an `iron-copper' age. In the second part of the review, this symbiosis of iron and copper is examined in yeast. We then briefly consider iron and copper metabolism in mammals, before looking at iron-copper interactions in mammals, particularly man, and conclude with the reflection that, as in Greek and Roman mythology, a better understanding of the potentially positive interactions between Mars (iron) and Venus (copper) can only be to the advantage of our species.     

Comparison of Zinc Reduction with Platinum Reduction for Analysis of Deuterium‐Enriched Water Samples for the Doubly Labeled Water Technique

Objective: Isotope ratio mass spectrometry of hydrogen and oxygen is frequently used to determine total energy expenditure (TEE) using doubly labeled water. Conventionally, hydrogen isotope ratio is determined in hydrogen gas generated from water samples using zinc reduction. We compare this with a new automated platinum method to determine the ratios of hydrogen isotopes in deuterium‐enriched water samples. Research Methods and Procedures: The platinum method of sample preparation was compared with the zinc method in three ways: analytical variation in deuterium enrichment (within sample; n = 51), analytical variation in TEE estimates (within sample set; n = 10), and level of agreement of TEE estimates between both methods (n = 14). Results: For the zinc method, the standard deviation for multiple sets of triplicate ²H₂O sample analysis was ±4.36‰ and ±2.07‰ for platinum. The correlation between TEE estimates when sample sets were analyzed in duplicate was r = 0.89 for zinc and r = 0.83 for platinum. The intercept and slope of the regression line were significantly different from the line of identity for duplicate TEE estimates by zinc but were not different from the line of identity for platinum. After correction for the intra‐assay variation of each method, the correlation between zinc and platinum for TEE was 0.77, and the intercept, but not the slope, of the regression was significantly different from the line of identity. The mean difference between the zinc method and the platinum method was 56 kcal/day, and the 95% confidence interval was ?438 to 550 kcal/day. Discussion: These data suggest that the platinum method is at least as reliable as the zinc method as a sample preparation technique for isotope ratio mass spectrometry of deuterium‐enriched water samples. The platinum method is also less costly and less labor‐intensive than the zinc method.     

Calculating the target exposure index using a deep convolutional neural network and a rule base

PurposeThe objective of this study is to determine the quality of chest X-ray images using a deep convolutional neural network (DCNN) and a rule base without performing any visual assessment. A method is proposed for determining the minimum diagnosable exposure index (EI) and the target exposure index (EIt).MethodsThe proposed method involves transfer learning to assess the lung fields, mediastinum, and spine using GoogLeNet, which is a type of DCNN that has been trained using conventional images. Three detectors were created, and the image quality of local regions was rated. Subsequently, the results were used to determine the overall quality of chest X-ray images using a rule-based technique that was in turn based on expert assessment. The minimum EI required for diagnosis was calculated based on the distribution of the EI values, which were classified as either suitable or non-suitable and then used to ascertain the EIt.ResultsThe accuracy rate using the DCNN and the rule base was 81%. The minimum EI required for diagnosis was 230, and the EIt was 288.ConclusionThe results indicated that the proposed method using the DCNN and the rule base could discriminate different image qualities without any visual assessment; moreover, it could determine both the minimum EI required for diagnosis and the EIt.     

Copper exposure and the degeneration of olfactory receptors in rainbow trout (Oncorhynchus mykiss)

Abstract

Sublethal concentrations of copper in water cause the degeneration of olfactory receptors in rainbow trout (Oncorhynchus mykiss). Receptor cell loss has been correlated to the loss of olfaction in fish and may cause difficulties in olfactory mediated behaviors such as migration. This study investigated the effects of three levels of copper (100, 75 and 50 mg L^?1) on the olfactory epithelium of rainbow trout. Twenty fish randomly allocated between three exposure groups and one control were exposed for 24 hours under static renewal conditions. Light and scanning electron microscopic observations of olfactory tissue were taken to determine the extent of degeneration of receptors. In addition, levels of copper and zinc in the brain tissues were analyzed to determine if the olfactory route was a significant route of copper exposure and transfer to fish brain tissue. Results indicate that degeneration of receptors is related to the concentration of copper. Levels of copper in brain were found to be below detection of the instrument. Levels of zinc were extremely variable ranging from 52 to 132 ng zinc g^?1 brain tissue.     

Application of an unsupervised artificial neural network technique to multivariant surface water quality data

Surface water contamination from agricultural and urban runoff and wastewater discharges from industrial and municipal activities is of major concern to people worldwide. Classical models can be insufficient to visualise the results because the water quality variables used to describe dynamic pollution sources are complex, multivariable, and nonlinearly related. Artificial intelligence techniques with the ability to analyse multivariant water quality data by means of a sophisticated visualisation capacity can offer an alternative to current models. In this study, the Kohonen self-organising feature maps (SOM) neural network was initially applied to analyse the complex nonlinear relationships among multivariable surface water quality variables using the component planes of the variables to determine the complex behaviour of water quality parameters. The dependencies between water quality variables were extracted and interpreted using the pattern analysis visualised in component planes. For further investigation, the k-means clustering algorithm was used to determine the optimal number of clusters by partitioning the maps and utilising the Davies–Bouldin clustering index, leading to seven groups or clusters corresponding to water quality variables. The results reveal that the concentrations of Na, K, Cl, NH₄-N, NO₂-N, o-PO₄, component planes of organic matter (pV), and dissolved oxygen (DO) were significantly affected by seasonal changes, and that the SOM technique is an efficient tool with which to analyse and determine the complex behaviour of multidimensional surface water quality data. These results suggest that this technique could also be applied to other environmentally sensitive areas such as air and groundwater pollution.     

Absorption of copper and copper–histidine complexes across the apical surface of freshwater rainbow trout intestine

Bioavailability is integral in mediating the delicate balance between nutritive and potentially toxic levels of copper in fish diets. Brush-border membrane vesicles isolated from freshwater rainbow trout intestine were used to characterise apical copper absorption, and to examine the influence of the amino acid histidine on this process. In the absence of histidine, a low affinity, high capacity copper uptake mechanism was described. However, when expressed as a function of ionic copper (Cu²⁺), absorption was linear, rather than saturable, suggesting that the saturable curve was an artifact of copper speciation. Conversely, in the presence of l-histidine (780 μM) saturable uptake was characterised. The uptake capacity discerned (J _max of 354 ± 81 nmol mg protein⁻¹ min⁻¹) in the presence of histidine indicated a significantly reduced capacity for copper transport than that in the absence of histidine. To determine if copper uptake was achievable through putative histidine uptake pathways, copper and histidine were incubated in the presence of tenfold greater concentrations of amino acids proposed to block histidine transporters. Accounting for changes in copper speciation, significant inhibition of uptake by glycine and lysine were noted at copper levels of 699 and 1,028 μM. These results suggest that copper–histidine complexes may be transportable via specific amino acid-transporters in the brush-border membrane.     

The efficacy of respondent-driven sampling for the health assessment of minority populations

BackgroundRespondent driven sampling (RDS) is a relatively new network sampling technique typically employed for hard-to-reach populations. Like snowball sampling, initial respondents or “seeds” recruit additional respondents from their network of friends. Under certain assumptions, the method promises to produce a sample independent from the biases that may have been introduced by the non-random choice of “seeds.” We conducted a survey on health communication in Guam’s general population using the RDS method, the first survey that has utilized this methodology in Guam. It was conducted in hopes of identifying a cost-efficient non-probability sampling strategy that could generate reasonable population estimates for both minority and general populations.MethodsRDS data was collected in Guam in 2013 (n = 511) and population estimates were compared with 2012 BRFSS data (n = 2031) and the 2010 census data. The estimates were calculated using the unweighted RDS sample and the weighted sample using RDS inference methods and compared with known population characteristics.ResultsThe sample size was reached in 23 days, providing evidence that the RDS method is a viable, cost-effective data collection method, which can provide reasonable population estimates. However, the results also suggest that the RDS inference methods used to reduce bias, based on self-reported estimates of network sizes, may not always work. Caution is needed when interpreting RDS study findings.ConclusionsFor a more diverse sample, data collection should not be conducted in just one location. Fewer questions about network estimates should be asked, and more careful consideration should be given to the kind of incentives offered to participants.     

Copper biosorption in an aerobic bioreactor

Abstract

This study evaluates the biosorption of copper by aerobic biomass that was selected from surface waters of the San Pedro River in Sonora, Mexico. Using a batch system, 73% biosorption of copper was obtained in 75 minutes. Continuous biosorption assays were carried out for 133 days in an ascending flow aerobic reactor packed with zeolite (AFAR-PZ) that was inoculated with a bacterial consortium. Strains were grown until 1g L^?1 of biomass was obtained. Tests using continuous biosorption were performed as follows: (i) the addition of 50 mg Cu²⁺ L^?1 without recirculation of biomass; (ii) the addition of 20 mg Cu²⁺ L^?1without recirculation of biomass; and (iii) the biomass were recirculated with the addition of 20 mg Cu²⁺ L^?1 to pH 3 to 4. The fourth and fifth assays varied pH between 4 and 5, with 20 mg Cu²⁺ L^?1and the biomass recirculated. Biosorption capacity of the first and second assays was 96% on the first day of experimentation. During the third trial 97% of biosorption was obtained during 6 days and the process was improved by varying the pH. Copper biosorption equilibrium was investigated under the same operating conditions. Langmuir adsorption isotherms were used to fit experimental data. The biosorption capacity of aerobic biomass was 3.08 mmol g^?1. It was demonstrated that this biomass is capable of biosorbing copper and this method has potential for the treatment of industrial effluents contaminated with heavy metals.     

The antioxidant function of Sco proteins depends on a critical surface-exposed residue

BackgroundBesides their role in copper metabolism, Sco proteins from different organisms have been shown to play a defensive role against oxidative stress. In the present study, we set out to identify crucial amino acid residues for the antioxidant activity.MethodsNative and mutated Sco proteins from human, Arabidopsis thaliana and the yeast Kluyveromyces lactis were expressed in the model organism Saccharomyces cerevisiae. The oxidative stress resistance of the respective transformants was determined by growth and lipid peroxidation assays.ResultsA functionally important site, located 15 amino acids downstream of the well-conserved copper binding CxxxC motif, was identified. Mutational analysis revealed that a positive charge at this position has a detrimental effect on the antioxidant capacity. Bioinformatic analysis predicts that this site is surface-exposed, and according to Co-IP data it is required for binding of proteins that are connected to known antioxidant pathways.ConclusionThis study shows that the antioxidant capacity of eukaryotic Sco proteins is conserved and depends on the presence of functional site(s) rather than the extent of overall sequence homology.General significanceThese findings provide an insight into the conserved functional sites of eukaryotic Sco proteins that are crucial for combating oxidative stress. This capacity is probably not due to an enzymatic activity but rather is indirectly mediated by interaction with other proteins.     

Microscopies,spectroscopies and spectrometries applied to marine corrosion of copper

Used in combination, surface analytical techniques can resolve spatial relationships between bacteria and localized corrosion, determine specific corrosion mechanisms and differentiate between abiotic and biotic processes. Confocal laser scanning microscopy and scanning vibrating electrode microscopy were used to demonstrate that marine bacteria and anodic sites are co‐located. Environmental scanning electron microscopy coupled with energy dispersive X‐ray spectros‐copy was used to demonstrate dealloying of nickel from copper: nickel alloys. X‐ray absorption spectroscopy, and transmission electron microscopy equipped with electron energy loss spectrometry were used to determine the speciation of copper associated with corrosion products.     

Steady-state method for ka measurements in model systems

Summary A method to determine oxygen transfer coefficients is discussed. It is based on measuring steady-state values, which is considered to be most accurate. Although the method is very convenlent, it is seldom mentioned as possible technique. A defined flow is withdrawn from the reactor, de-aerated by stripping with nitrogen, and recirculated. From the flow and steady-state values of the oxygen tension in the reactor and the recirculation flow, the ka value can be calculated. Although generally applicable, this method is especially suitable for model systems without real oxygen consumption. In this paper it is illustrated for ka determination in a liquid-impelled loop reactor.     

The effect of the use of copper carbonate and copper nanoparticles in the diet of rats on the level of β-amyloid and acetylcholinesterase in selected organs

BackgroundCopper has an important role in nervous system function, as a cofactor of many enzymes and in the synthesis of neurotransmitters. Both the dose and the chemical form of copper can determine the impact of this element on metabolism, the neurological system and the immune system.AimsThe aim of the study was to determine whether and in what form the addition of copper changes the level of amyloid beta and acetylcholinesterase level in selected rat tissues.MethodsThirty, healthy, male, albino Wistar rats aged 7 weeks were randomly divided into 3 groups. Three experimental treatments were used to evaluate the effects of different levels and sources of Cu (6.5 mg kg of diet) in the diet: Cu₀ – rats fed a diet without Cu supplementation; Cu_salt – rats fed a diet with CuCO₃ (6.5 mg kg of diet) during two months of feeding; Cu_NPs - rats fed a diet with Cu nanoparticles (6.5 mg kg of diet) during two months of feeding. In blood serum and tissue homogenates there rated the indicators proving the potential neurodegenerative effect and epigenetic DNA damage induced by chemical form of copper or lack of additional copper supplementation in diet were determined. There were analysed: level of acetylcholinesterase, β-amyloid, low-density lipoprotein receptor-related protein 1, apyrimidinic endonuclease, thymidine glycosidase, alkylpurine-DNA-N-glycosylase and glycosylated acetylcholinesterase.ResultsIrrespective of the form of copper added, it was found to increase acetylcholinesterase level in the brain, spleen and liver, as well as in the blood plasma of the rats. Copper in the form of CuCO₃ was found to increase acetylcholinesterase level in the kidneys. The addition of both forms of copper caused a marked increase in the plasma concentration of β-amyloid in comparison with the diet with no added Cu. The addition of both forms of copper caused a marked increase in the plasma concentration of β-amyloid in comparison with the diet with no added Cu.ConclusionsA lack of added Cu in the diet of rats reduces the concentration of amyloid-β in the blood, whereas administration of copper, in the form of either CuNPs or CuCO₃, increases the level of this peptide in the blood. The use of copper in the form of CuNPs in the diet of rats does not increase the level of β-amyloid more than the use of the carbonate form of this element. The use of CuNPs or CuCO₃ in the diet of rats increases acetylcholinesterase level in the brain, spleen, liver, and blood. CuNPs in the diet of rats were not found to increase acetylcholinesterase level to a greater extent than Cu⁺² carbonate.     

Programa de entrenamiento de memoria para mayores con alteraciones de memoria: resultados y predictores

IntroductionDeficits in memory performance in later life are frequent and well documented. There are several terms that refer to this phenomenon and the most commonly used is age associated memory impairment (AAMI). Currently, cognitive or memory training programmes are increasingly being used to treat this deficit. The Department of Health of the City of Madrid has developed a multifactorial memory training programme for older people which is carried out in 13 City Health Centres.ObjectivesTo study the effects of this programme in a sample of users aged more than 65 years with memory impairment, to determine the persistence of the results after 6 months, and to investigate predictors of results.Patients and methodThe sample was composed of 1,083 subjects who underwent memory training. The subjects were assessed before and after training and after 6 months. Among other tests, the Mini Examen Cognoscitivo (MEC), the Rivermead Behavioural Memory Test (RBMT), the Geriatric Depression Scale (GDS), and Memory Failures of Everyday (MFE) were used. The training method used (UMAM method) was developed by the Memory Unit of the City of Madrid.ResultsObjective memory improvement for the entire group was 40% (Cohen’s «d», 0.95) and 77% of the subjects improved. Seventy- five percent of the subjects improved in subjective memory functioning (Cohen’s «d», 0.64). Improvement in mood was also observed. These changes were maintained after 6 months. The predictive variables were age, MEC, GHQ and GDS scores before training, but the percentage of explained variance was very low.ConclusionsThe multifactorial memory training programme, UMAM, improves objective and subjective memory functioning in older people with memory impairment and the benefits persist after 6 months. The predictive value of the variables studied is low.