Mechanistic studies of the photocatalytic oxidation of microcystin-LR: An investigation of byproducts of the decomposition process

Microcystins (cyclic heptapeptides) are produced by a number of freshwater cyanobacteria and cause concern in potable water supplies due to their acute and chronic toxicity. The present study reports the structural characterization of the degradation products of the photocatalytic oxidation of microcystin-LR, so aiding the mechanistic understanding of this process. TiO₂ photocatalysis is a promising technology for removal of these toxins from drinking water. However, before it can be adopted in any practical application it is necessary to have a sufficient knowledge of degradation byproducts and their potential toxicity. Liquid chromatography-mass spectrometry analysis demonstrated that the major destruction pathway of microcystin appears to be initiated via three mechanisms: UV irradiation, hydroxyl radical attack, and oxidation. UV irradiation caused geometrical isomerization of microcystin converting the (4E), (6E) of the Adda configuration to (4E), 6(Z) or 4(Z), 6(E). Hydroxyl radical attack on the conjugated diene structure of Adda moiety produced dihyroxylated products. Further oxidation cleaved the hydroxylated 4-5 and/or 6-7 bond of Adda to form aldehyde or ketone peptide residues, which then were oxidized into the corresponding carboxylic acids. Photocatalysis also hydrolyzed the peptide bond on the ring structure of microcystin to form linear structures although this appeared to be a minor pathway.

Mechanistic and toxicity studies of the photocatalytic oxidation of microcystin-LR

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however, a variety of by-products were generated. In this paper, we report a mechanistic study of the photocatalytic destruction of microcystin-LR. In particular, the toxicity by-products of the process have been studied using both brine shrimp and protein phosphatase bioassays. 

Hydrogen peroxide enhanced photocatalytic oxidation of microcystin-lR using titanium dioxide

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however non-toxic by-products were detected. It has been shown that photocatalytic reactions are enhanced by utilisation of alternative electron acceptors. We report here enhanced photocatalytic degradation of microcystin-LR following the addition of hydrogen peroxide to the system. It was also found that hydrogen peroxide with UV illumination alone was capable of decomposing microcystin-LR although at a much slower rate than found for TiO₂. No HPLC detectable by-products were found when the TiO₂/UV/H₂O₂ system was used indicating that this method is more effective than TiO₂/UV alone. Results however indicated that only 18% mineralisation occurred with the TiO₂/UV/H₂O₂ system and hence undetectable by-products must still be present. At higher concentrations hydrogen peroxide was found to compete with microcystin-LR for surface sites on the catalyst but at lower peroxide concentrations this competitive adsorption was not observed. Toxicity studies showed that both in the presence and absence of H₂O₂ the microcystin solutions were detoxified. These findings suggest that hydrogen peroxide greatly enhances the photocatalytic oxidation of microcystin-LR.

Detoxification of microcystins (cyanobacterial hepatotoxins) using TiO2 photocatalytic oxidation

TiO₂ photocatalysis has been used to destroy microcystin-LR in aqueous solution. The destruction of this toxin was monitored by HPLC, and the disappearance was accompanied by the appearance of seven UV detectable compounds. Spectral analysis revealed that some of these compounds retained spectra similar to the parent compound suggesting that the Adda moiety, thought to be responsible for the characteristic spectrum, remained intact whereas the spectra of some of the other products was more radically altered. Six of the seven observed reaction products did not appear to undergo further degradation during prolonged photocatalysis (100 min). The degree to which microcystin-LR was mineralized by photocatalytic oxidation was determined. Results indicated that less than 10% mineralization occurred. Mass spectral analysis of the photocatalyzed microcystin-LR allowed tentative characterization of the reaction process and products. Reduction in toxicity due to the photocatalytic oxidation was evaluated using an invertebrate bioassay, which demonstrated that the disappearance of microcystin-LR was paralleled by a reduction in toxicity. These findings suggest that photocatalytic destruction of microcystins may be a suitable method for the removal of these potentially hazardous compounds from drinking water.

Hyperglycemia and Diabetes Downregulate the Functional Expression of TRPV4 Channels in Retinal Microvascular Endothelium

Retinal endothelial cell dysfunction is believed to play a key role in the etiology and pathogenesis of diabetic retinopathy. Numerous studies have shown that TRPV4 channels are critically involved in maintaining normal endothelial cell function. In the current paper, we demonstrate that TRPV4 is functionally expressed in the endothelium of the retinal microcirculation and that both channel expression and activity is downregulated by hyperglycaemia. Quantitative PCR and immunostaining demonstrated molecular expression of TRPV4 in cultured bovine retinal microvascular endothelial cells (RMECs). Functional TRPV4 activity was assessed in cultured RMECs from endothelial Ca2+-responses recorded using fura-2 microfluorimetry and electrophysiological recordings of membrane currents. The TRPV4 agonist 4α-phorbol 12,13-didecanoate (4-αPDD) increased [Ca2+]i in RMECs and this response was largely abolished using siRNA targeted against TRPV4. These Ca2+-signals were completely inhibited by removal of extracellular Ca2+, confirming their dependence on influx of extracellular Ca2+. The 4-αPDD Ca2+-response recorded in the presence of cyclopiazonic acid (CPA), which depletes the intracellular stores preventing any signal amplification through store release, was used as a measure of Ca2+-influx across the cell membrane. This response was blocked by HC067047, a TRPV4 antagonist. Under voltage clamp conditions, the TRPV4 agonist GSK1016790A stimulated a membrane current, which was again inhibited by HC067047. Following incubation with 25mM D-glucose TRPV4 expression was reduced in comparison with RMECs cultured under control conditions, as were 4αPDD-induced Ca2+-responses in the presence of CPA and ion currents evoked by GSK1016790A. Molecular expression of TRPV4 in the retinal vascular endothelium of 3 months' streptozotocin-induced diabetic rats was also reduced in comparison with that in age-matched controls. We conclude that hyperglycaemia and diabetes reduce the molecular and functional expression of TRPV4 channels in retinal microvascular endothelial cells. These changes may contribute to diabetes induced endothelial dysfunction and retinopathy.

Efficacy of instant hand sanitizers against foodborne pathogens compared to hand washing with soap and water in food preparation settings: a systematic review

Hands can be a vector for transmitting pathogenic microorganisms to foodstuffs and drinks, and to the mouths of susceptible hosts. Hand washing is the primary barrier to prevent transmission of enteric pathogens via cross contamination from infected persons. Conventional hand washing involves the use of warm water, soap and friction to remove dirt and microorganisms. Over recent years there has been an increasing availability of hand sanitizing products for use when water and soap are unavailable. The aim of this systematic review was to collate scientific information on the efficacy of hand sanitizers compared to hand washing with soap and water for the removal of foodborne pathogens from the hands of food handlers. An extensive literature search was carried out using three electronic databases - Web of Science, Scopus and PubMed. Twenty-eight scientific publications were ultimately included in the review. Analysis of the literature showed various limitations in the scientific information due to the absence of a standardized protocol to evaluate efficacy of hand products, and variation in experimental conditions applied in different studies. Despite the existence of conflicting results, scientific evidence seems to support the historical scepticism about the use of water-less hand sanitizers in food preparation settings. Water and soap appear to achieve greater removal of soil and microorganisms than water-less products from hands. None of the hand sanitizers tested in the literature seemed to achieve complete inactivation or removal of all foodborne pathogens tested, and the presence of food debris significantly affected inactivation rates of hand products.

Assessment of the Activity of Photocatalytic Paint Using a Simple Smart Ink Designed for High Activity Surfaces

The use of an acid violet 7 (AV7) smart ink to assess the activity of photocatalytic paint is demonstrated. A linear correlation is established between the change in oxidized dye concentration, as measured by diffuse reflectance, and the change in the green component of the RGB color values, obtained using a portable hand-held scanner, suggesting that such tests can be monitored easily using an inexpensive piece of hand-held office equipment, as opposed to an expensive lab-based instrument, such as a diffuse reflectance UV/vis spectrophotometer. The bleaching of the AV7 follows first order kinetics, at a rate that is linearly dependent upon the UVA irradiance (0.30–3.26 mW cm–2). A comparison of relative rate of bleaching of the AV7 ink with the relative rate of removal of NOx, as determined using the ISO test (ISO 22197-1:2007), established a linear relationship between the two sets of results and the relevance of this correlation is discussed briefly.

A randomized clinical trial of ascorbic acid in open abdominal aortic aneurysm repair

BACKGROUND: Open AAA repair is associated with ischaemia-reperfusion injury where systemic inflammation and endothelial dysfunction can lead to multiple organ injury including acute lung injury. Oxidative stress plays a role that may be inhibited by ascorbic acid.

METHODS: A double blind, allocation concealed, randomized placebo-controlled trial was performed to test the hypothesis that a single bolus dose (2g) of intra-operative parenteral ascorbic acid would attenuate biomarkers of ischaemia-reperfusion injury in patients undergoing elective open AAA repair.

RESULTS: Thirty one patients completed the study; 18 received placebo and 13 ascorbic acid. Groups were comparable demographically. Open AAA repair caused an increase in urinary Albumin:Creatinine Ratio (ACR) as well as plasma IL-6 and IL-8. There was a decrease in exhaled breath pH and oxygenation. Lipid hydroperoxides were significantly higher in the ascorbic acid group following open AAA repair. There were no other differences between the ascorbic acid or placebo groups up to 4 hours after removal of the aortic clamping.

CONCLUSIONS: Open AAA repair caused an increase in markers of systemic endothelial damage and systemic inflammation. Administration of 2g parenteral ascorbic acid did not attenuate this response and with higher levels of lipid hydroperoxides post-operatively a pro-oxidant effect could not be excluded.

TRIAL REGISTRATION: ISRCTN27369400.

Ionic liquid solvents of perhalide type for metals for extraction radioactive metals from mineral ores.

The invention relates to a process for dissolving metals (e.g., Al, Cu, Fe, Cr, Sb, Ti, and W) in perhalide contg. ionic liqs. having the formula (I), and to the extn. of metals from mineral ores; the remediation of materials contaminated with heavy, toxic, or radioactive metals; and to the removal of heavy and toxic metals from hydrocarbon streams. In the formula (I), [X] comprises at least one perhalide anion selected from [I3]-, [BrI2]-, [Br2I]-, [ClI2]-, [ClBr2]-, [BrCl2]-, or [ICl2]-, [ClI3]-. The (Cat+) is a cationic species selected from: ammonium, azaannulenium, azathiazolium, benzimidazolium, benzofuranium, benzotriazolium, borolium, cinnolinium, diazabicyclodecenium, diazabicyclononenium, diazabicyclo- undecenium, dithiazolium, furanium, guanidinium, imidazolium, indazolium, indolinium, indolium, morpholinium, oxaborolium, oxaphospholium, oxazinium, oxazolium, iso-oxazolium, oxathiazolium, pentazolium, phospholium, phosphonium, phthalazinium, piperazinium, piperidinium, pyranium, pyrazinium, pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolium, quinazolinium, quinolinium, isoquinolinium, quinoxalinium, selenozolium, sulfonium, tetrazolium, iso-thiadiazolium, thiazinium, thiazolium, thiophenium, thiuronium, triazadecenium, triazinium, triazolium, iso-triazolium, and uronium. [on SciFinder(R)]

Simultaneous biosorption of methylene blue and trivalent chromium onto olive stone

In this work, olive stone (OS) was utilized to investigate its capacity as biosorbent for methylene blue (MB) and Cr(III), which are usually present in textile industry effluents. Equilibrium and kinetic experiments were performed in batch experiments. The biosorption process followed pseudo-second-order kinetics. The equilibrium data were fitted with several models, but Langmuir and Sips models best reproduced the experimental results. Maximum biosorption capacities were 3.296 mg/g (0.0116 mmol/g) and 4.990 mg/g (0.0960 mmol/g) for MB and Cr(III), respectively. Several operation variables, such as
biosorbent mass, flow rate, and initial concentration on the removal of dye and metal, were evaluated in column system. The removal efficiency improved as OS mass increased and decreased when flow rate and initial concentration increased. Also, MB uptake was substantially decreased by increasing the initial concentration of Cr(III), ranging from 6.09 to 2.75 mg/g. These results show that the presence of Cr(III) significantly modifies the biosorption capacity of MB by the OS. These results suggest that OS is a potential low-cost food industry waste for textile industry wastewater treatment.

Molecular Medicine and Molecular Pathology for Haematologists:I. Gene Speak made Easy: An Overview of Genes and Gene Expression

Molecular Medicine and Molecular Pathology are integral parts of Haematology as we enter the new millennium. Their origins can be linked to fundamental developments in the basic sciences, particularly genetics, chemistry and biochemistry. The structure of DNA and the genetic code that it encrypts are the critical starting points to our understanding of these new disciplines. The genetic alphabet is a simple one, consisting of just 4 letters, buts its influence is crucial to human development and differentiation. The concept of a gene is not a new one but the Human Genome Project (a joint world-wide effort to characterise our entire genetic make-up) is providing an invaluable understanding of how genes function in normal cellular processes and pinpointing how disruption of these processes can lead to disease. Transcription and translation are the key events by which our genotype is converted to our phenotype (via a messenger RNA intermediate), producing the myriad proteins and enzymes which populate the cellular factory of our body. Unlike the bacterial or prokaryotic genome, the human genome contains a large amount of non coding DNA (less than 1% of our genome codes for proteins), and our genes are interrupted, with the coding regions or exons separated by non coding introns. Precise removal of the intronic material after transcription (though a process called splicing) is critical for efficient translation to occur. Incorrect splicing can lead to the generation of mutant proteins, which can have a dilaterious effect on the phenotype of the individual. Thus the 100,000-200,000 genes which are present in each cell in our body have a defined control mechanism permitting efficient and appropriate expression of proteins and enzymes and yet a single base change in just one of those genes can lead to diseases such as haemophilia or fanconis anaemia.

Impacts of culling and exclusion of browsers on vegetation recovery across New Zealand forests

Introduced browsing animals negatively impact New Zealand's indigenous ecosystems. Eradicating introduced browsers is currently unfeasible at large scales, but culling since the 1960s has successfully reduced populations to a fraction of their earlier sizes. Here we ask whether culling of ungulates has allowed populations of woody plant species to recover across New Zealand forests. Using 73 pairs of permanent fenced exclosure and unfenced control plots, we found rapid increases in sapling densities within exclosures located in disturbed forests, particularly if a seedling bank was already present. Recovery was slower in thinning stands and hampered by dense fern cover. We inferred ungulate diet preference from species recovery rates inside exclosures to test whether culling increased abundance of preferred species across a national network of 574 unfenced permanent forest plots. Across this network, saplings were observed irrespective of their preference to ungulates in the 1970s, but preferred species were rarer within disturbed sites in the 1990s after long-term culling and despite nationwide increases in sapling densities. This indicates that preferred species are relatively heavily affected by browsing after culling, presumably because remaining animals will increase consumption of preferred species as competition is reduced. Our results clearly suggest that culling will not return preferred plants to the landscape immediately, even given suitable conditions for regeneration. Complete removal of ungulates rather than simply reducing their densities may be required for recovery in heavily browsed temperate forests, but since this is only feasible at small spatial scales, management efforts must target sites of high conservation value. © 2012 Elsevier Ltd.

Efficiency of starfish mopping in reducing predation on cultivated benthic mussels (Mytilus edulis Linnaeus)

The starfish, Asterias rubens, preys on mussels (Mytilus edulis), which are relaid during benthic cultivation processes. Starfish mops, a modified dredge used to remove starfish from mussel cultivation beds, are used in several fisheries today but few studies have attempted to quantify the effectiveness of this method in removing starfish. This study tested the effectiveness of starfish mopping to reduce starfish numbers on mussel beds in Belfast Lough, Northern Ireland. Video surveys to determine starfish densities on mussel beds were conducted between October 2013 and December 2014 using a GoPro™ camera attached to starfish mops. This allowed us to firstly test whether starfish density varied among mussel beds and to investigate how fluctuations in starfish numbers may vary in relationship to starfish ecology. We then estimated the efficiency of mops at removing starfish from mussel beds by comparing densities of starfish on beds, as determined using video footage, with densities removed by mops. Starfish abundance was similar among different mussel beds during this study. The efficiency of mops at removing estimated starfish aggregations varied among mussel beds (4–78%) and the mean reduction in starfish abundance was 27% (± SE 3.2). The effectiveness of mops at reducing starfish abundance was shown to decline as the initial density of starfish on mussel beds increased. It can be recommended that the exact deployment technique of mops on mussel beds should vary depending on the density of starfish locally. The area of mussel bed covered by mops during a tow, for example, should be less when starfish densities are high, to maintain efficiencies throughout the full length of tows and to optimise the removal of starfish from mussel beds. This strategy, by reducing abundance of a major predator, could assist in reducing losses in the mussel cultivation industry.

Factors that impact on the use of mechanical ventilation weaning protocols in critically ill adults and children: a qualitative-evidence synthesis

Background:
Prolonged mechanical ventilation is associated with a longer intensive care unit (ICU) length of stay and higher mortality. Consequently, methods to improve ventilator weaning processes have been sought. Two recent Cochrane systematic reviews in ICU adult and paediatric populations concluded that protocols can be effective in reducing the duration of mechanical ventilation, but there was significant heterogeneity in study findings. Growing awareness of the benefits of understanding the contextual factors impacting on effectiveness has encouraged the integration of qualitative evidence syntheses with effectiveness reviews, which has delivered important insights into the reasons underpinning (differential) effectiveness of healthcare interventions.

Objectives:
1. To locate, appraise and synthesize qualitative evidence concerning the barriers and facilitators of the use of protocols for weaning critically-ill adults and children from mechanical ventilation;

2. To integrate this synthesis with two Cochrane effectiveness reviews of protocolized weaning to help explain observed heterogeneity by identifying contextual factors that impact on the use of protocols for weaning critically-ill adults and children from mechanical ventilation;

3. To use the integrated body of evidence to suggest the circumstances in which weaning protocols are most likely to be used.

Search methods:
We used a range of search terms identified with the help of the SPICE (Setting, Perspective, Intervention, Comparison, Evaluation) mnemonic. Where available, we used appropriate methodological filters for specific databases. We searched the following databases: Ovid MEDLINE, Embase, OVID, PsycINFO, CINAHL Plus, EBSCOHost, Web of Science Core Collection, ASSIA, IBSS, Sociological Abstracts, ProQuest and LILACS on the 26th February 2015. In addition, we searched: the grey literature; the websites of professional associations for relevant publications; and the reference lists of all publications reviewed. We also contacted authors of the trials included in the effectiveness reviews as well as of studies (potentially) included in the qualitative synthesis, conducted citation searches of the publications reporting these studies, and contacted content experts.

We reran the search on 3rd July 2016 and found three studies, which are awaiting classification.

Selection criteria:
We included qualitative studies that described: the circumstances in which protocols are designed, implemented or used, or both, and the views and experiences of healthcare professionals either involved in the design, implementation or use of weaning protocols or involved in the weaning of critically-ill adults and children from mechanical ventilation not using protocols. We included studies that: reflected on any aspect of the use of protocols, explored contextual factors relevant to the development, implementation or use of weaning protocols, and reported contextual phenomena and outcomes identified as relevant to the effectiveness of protocolized weaning from mechanical ventilation.

Data collection and analysis:
At each stage, two review authors undertook designated tasks, with the results shared amongst the wider team for discussion and final development. We independently reviewed all retrieved titles, abstracts and full papers for inclusion, and independently extracted selected data from included studies. We used the findings of the included studies to develop a new set of analytic themes focused on the barriers and facilitators to the use of protocols, and further refined them to produce a set of summary statements. We used the Confidence in the Evidence from Reviews of Qualitative Research (CERQual) framework to arrive at a final assessment of the overall confidence of the evidence used in the synthesis. We included all studies but undertook two sensitivity analyses to determine how the removal of certain bodies of evidence impacted on the content and confidence of the synthesis. We deployed a logic model to integrate the findings of the qualitative evidence synthesis with those of the Cochrane effectiveness reviews.

Main results:
We included 11 studies in our synthesis, involving 267 participants (one study did not report the number of participants). Five more studies are awaiting classification and will be dealt with when we update the review.

The quality of the evidence was mixed; of the 35 summary statements, we assessed 17 as ‘low’, 13 as ‘moderate’ and five as ‘high’ confidence. Our synthesis produced nine analytical themes, which report potential barriers and facilitators to the use of protocols. The themes are: the need for continual staff training and development; clinical experience as this promotes felt and perceived competence and confidence to wean; the vulnerability of weaning to disparate interprofessional working; an understanding of protocols as militating against a necessary proactivity in clinical practice; perceived nursing scope of practice and professional risk; ICU structure and processes of care; the ability of protocols to act as a prompt for shared care and consistency in weaning practice; maximizing the use of protocols through visibility and ease of implementation; and the ability of protocols to act as a framework for communication with parents.

Authors' conclusions:
There is a clear need for weaning protocols to take account of the social and cultural environment in which they are to be implemented. Irrespective of its inherent strengths, a protocol will not be used if it does not accommodate these complexities. In terms of protocol development, comprehensive interprofessional input will help to ensure broad-based understanding and a sense of ‘ownership’. In terms of implementation, all relevant ICU staff will benefit from general weaning as well as protocol-specific training; not only will this help secure a relevant clinical knowledge base and operational understanding, but will also demonstrate to others that this knowledge and understanding is in place. In order to maximize relevance and acceptability, protocols should be designed with the patient profile and requirements of the target ICU in mind. Predictably, an under-resourced ICU will impact adversely on protocol implementation, as staff will prioritize management of acutely deteriorating and critically-ill patients.