Faraday efficiency and mechanism of electrochemical surface reactions: CO2 reduction and H2 formation on Pt(111).

An atomic scale model of the electrical double layer is used to calculate the mechanism and rate of electrochemical reduction of CO2 as well as H2 formation at a Pt(111) electrode. The water layer contains solvated protons and the electrode has excess electrons at the surface. Density functional theory within the generalized gradient approximation is used to describe the electronic structure while the mechanism and activation energy of the various elementary reactions is obtained by calculating minimum energy paths using the nudged elastic band method. The applied electrical potential is deduced from the calculated work function. The optimal reaction mechanism for CO2 reduction to either methane or methanol is found and the estimated rate compared with that of the competing reaction, H2 formation. When the free energy of only the intermediates and reactants is taken into account, not the activation energy, Pt(111) would seem to be a good electrocatalyst for CO2 reduction, significantly better than Cu(111). This, however, contradicts experimental findings. Detailed calculations reported here show that the activation energy for CO2 reduction is high for both Heyrovsky and Tafel mechanisms on Pt(111) in the relevant range of applied potential. The rate-limiting step of the Heyrovsky mechanism, *COOH + H+ + e- → *CO + H2O, is estimated to have an activation energy of 0.95 eV at -0.9 V vs. standard hydrogen electrode. Under the same conditions, the activation energy for H2 formation is estimated to be only 0.5 eV. This explains why attempts to reduce CO2 using platinum electrodes have produced only H2. A comparison is made with analogous results for Cu(111) [J. Hussain et al., Procedia Comput. Sci., 2015, 51, 1865] where a reaction mechanism with low activation energy for CO2 electroreduction to methane was identified. The difference between the two electrocatalysts is discussed.

In silico screening of molecular imprinting prepolymerization systems: oseltamivir selective polymers through full-system molecular dynamics-based studies.

All-component molecular dynamics studies were used to probe a library of oseltamivir molecularly imprinted polymer prepolymerization mixtures. Polymers included one of five functional monomers (acrylamide, hydroxyethylmethacrylate, methacrylic acid, 2-(triflouromethyl)acrylic acid, 4-vinylpyridine) and one of three porogens (acetonitrile, chloroform, methanol) combined with the crosslinking agent ethylene glycol dimethacrylate and initiator 2,2'-azobis(2-methylpropionitrile). Polymers were characterized by nitrogen gas sorption measurements and SEM, and affinity studies performed using radioligand binding in various media. In agreement with the predictions made from the simulations, polymers prepared in acetonitrile using either methacrylic or trifluoromethacrylic acid demonstrated the highest affinities for oseltamivir. Further, the ensemble of interactions observed in the methanol system provided an explanation for the morphology of polymers prepared in this solvent. The materials developed here offer potential for use in solid-phase extraction or for catalysis. The results illustrate the strength of this in silico strategy as a potential prognostic tool in molecularly imprinted polymer design.

Ilizarov Ankle Arthrodesis: A Simple Salvage Solution for Failed and Neglected Ankle Fractures.

Background: Infection around the ankle joint after fracture fixation, or septic arthritis with active discharging sinuses is often challenging to manage with conventional procedures of arthrodesis. The Ilizarov method of arthrodesis gives a better alternative for salvage in such cases. Methods: This was a retrospective study including 20 patients who were subjected to tibiotalar arthrodesis with Ilizarov method. The major pathologies included internal fixation of ankle fractures complicated by infection, posttraumatic infected ankle arthritis, and osteomyelitis. The patients were evaluated on the basis of Association for the Study and Application of the Method of Ilizarov (ASAMI) criteria. The aim of the surgery was to achieve plantigrade, stable, and painless foot with no signs of infection. Results: A total of 20 patients were operated and reviewed at our institute. The study comprised of 15 male and 5 female patients with a mean age of 43.9 years (range 33-55 years). Out of 20 patients, 4 patients had complications of pin-tract infection and one had wire breakage of the forefoot ring. According to the ASAMI criteria, 17 patients had excellent bone scores and 18 patients had good functional scores. Union was achieved in all patients with resolution of infection and the mean limb length discrepancy was 1.92 cm (range 1-2.5 cm). Conclusions: The Ilizarov fixator for ankle arthrodesis provides an excellent way for strong bone fusion, infection eradication, early weight-bearing, and the added benefits of compression at the arthrodesis site post-operatively.

Sodium alginate-f-GO composite hydrogels for tissue regeneration and antitumor applications.

Biopolymer-based composite hydrogels have attracted tremendous attention for tissue regeneration and antitumor applications. Since sodium alginate is a biopolymer, they offer excellent therapeutic options with long-term drug release and low side effects. To prepare multifunctional composite hydrogels with anticancer and tissue regeneration capabilities, sodium alginate (SA) and graphene oxide (GO) were covalently linked and crosslinked with tetraethyl orthosilicate (TEOS) by the solvothermal method. The structural and morphological results show that the hydrogels exhibit the desired functionality and porosity. The swelling of hydrogels in an aqueous and PBS medium was investigated. SGT-4 had the highest swelling in both aqueous and PBS media. Swelling and biodegradation of the hydrogel were inversely related. The drug release of SGT-4 was determined in different pH media (pH 6.4, 7.4, and 8.4) and the kinetics of drug release was determined according to the Higuchi model (R2 = 0.93587). Antibacterial activities were evaluated against severe infectious agents. Uppsala (U87) and osteoblast (MC3T3-E1) cell lines were used to determine the anticancer and biocompatibility of the composite hydrogels, respectively. These results suggest that the composite hydrogels could be used as potential biomaterials for tissue regeneration and antitumor applications.

Blood lead levels and cumulative blood lead index (CBLI) as predictors of late neurodevelopment in lead poisoned children.

OBJECTIVE: To find the best lead exposure assessment marker for children. METHODS: We recruited 11 children, calculated a cumulative blood lead index (CBLI) for the children, measured their concurrent BLL, assessed their development, and measured their bone lead level. RESULTS: Nine of 11 children had clinically significant neurodevelopment problems. CBLI and current blood lead level, but not the peak lead level, were significantly or marginally negatively associated with the full-scale IQ score. CONCLUSION: Lead exposure at younger age significantly impacts a child's later neurodevelopment. CBLI may be a better predictor of neurodevelopment than are current or peak blood lead levels.

Variations in Mineral/heavy Metals Profiling and Preventive Role of Trichomes in Peach Fruits Treated with CaC2.

BACKGROUND: Phytonutrients in peach fruits have health-promoting antioxidants against various chronic diseases. However, there is no extensive data to show the nutritional values of Local peach cultivars after post-harvest treatments. OBJECTIVE: Mainly this study was objective to determine the effect of calcium carbide on nutritional value and quality of fruits of Pakistani peach cultivars. METHODS: The peach fruits were collected from three different peach orchids of KPK and the fruits were divided into 4 groups while 5th group was collected from a local fruit shop. Each experimental group was treated with different concentrations of calcium carbide whereas control group was not treated. The peel and pulp samples were oven dried and ground to fine powder separately. The elemental compositions were determined using Particle Induced X-ray emission and Pelletron Tandem Accelerator. RESULTS: Sixteen elements were identified in peach fruits and the elements were Al, P, S, Cl, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, and Se. In peel, the concentration of some elements increased or decreased after treatment with CaC2 while in pulp the conc. of nearly all detected elements was increased in treated samples. We found a significantly higher amount of heavy metals traces, including As, Se, Co, Si, and P in peach fruits treated with CaC2 Interestingly, the presence of trichomes in peach skin prevents the transfer of these heavy metals deep into the pulp which was also verified by the elemental profiling of nectarines. CONCLUSION: Conclusively, the artificial ripening with CaC2 changed the nutritional value of peach fruits that has higher health risks if consume with the peel. According to our best knowledge, this is the first report that highlights the effects of CaC2 which deteriorate the nutritional value of peach fruits in Pakistan.

In Silico Structural, Functional, and Phylogenetic Analysis of Cytochrome (CYPD) Protein Family.

Cytochrome (CYP) enzymes catalyze the metabolic reactions of endogenous and exogenous compounds. The superfamily of enzymes is found across many organisms, regardless of type, except for plants. Information was gathered about CYP2D enzymes through protein sequences of humans and other organisms. The secondary structure was predicted using the SOPMA. The structural and functional study of human CYP2D was conducted using ProtParam, SOPMA, Predotar 1.03, SignalP, TMHMM 2.0, and ExPASy. Most animals shared five central motifs according to motif analysis results. The tertiary structure of human CYP2D, as well as other animal species, was predicted by Phyre2. Human CYP2D proteins are heavily conserved across organisms, according to the findings. This indicates that they are descended from a single ancestor. They calculate the ratio of alpha-helices to extended strands to beta sheets to random coils. Most of the enzymes are alpha-helix, but small amounts of the random coil were also found. The data were obtained to provide us with a better understanding of mammalian proteins' functions and evolutionary relationships.

Garlic (Allium sativum) based interplanting alters the heavy metals absorption and bacterial diversity in neighboring plants.

Heavy metals are naturally occurring elements that have a high atomic weight and let out in the environment by agriculture, industry, mining and therapeutic expertise and thrilling amassing of these elements pollutes the environment. In this study we have investigated the potential of garlic interplanting in promoting hyper accumulation and absorption of heavy metals to provide a basis for phytoremediation of polluted land. Monoculture and inter-plantation of garlic were conducted to investigate the absorption of cadmium and lead contamination in the land. A group of experiments with single planting (monoculture) of Lolium perenne, Conyza canadensis and Pteris vittata as accumulators were used. The results have shown that garlic has a potential as a hyper accumulate and absorb heavy metals. It was found that the accumulation of Cd and Pb was much higher with inter-planting. Garlic boosts up the absorption of heavy metals in Lolium perenne of Cd 66% and Pb 44% respectively. The Inter-planting of garlic with Pteris vittata promotes the Cd 26% and Pb 15%. While the maximum accumulation of Lead 87% and Cadmium 77% occurred in Conyza canadensis herb plant. The bacterial diversity in the soil was analyzed for each experimental soil and was found that the Proteobacteria, Acidobacteria, Actinobacteria, Firmicutes, and Planctomycetes were commonly abundant in both single planting (monoculture) of ryegrass and interplanting ryegrass with garlic habitats. Variances were observed in the bacterial floral composition of single (monoculture) and intercropping (interplant) soils. Relative abundance of bacterial taxa revealed that the proportion of Proteobacteria, Acidobacteria, and Actinobacteria in the inter-planting group was slightly higher, while Firmicutes and Planctomycetes were low. This study provides the evidence to control the heavy metals contaminated soils with weed species. Growth promotion and heavy metal uptake of neighboring plants proved the specific plant-plant and plant-microbial associations with garlic plants. This inter-planting strategy can be used to improve heavy metal absorption.

Why do RuO2 electrodes catalyze electrochemical CO2 reduction to methanol rather than methane or perhaps neither of those?

The electrochemical CO2 reduction reaction (CO2RR) on RuO2 and RuO2-based electrodes has been shown experimentally to produce high yields of methanol, formic acid and/or hydrogen while methane formation is not detected. This CO2RR selectivity on RuO2 is in stark contrast to copper metal electrodes that produce methane and hydrogen in the highest yields whereas methanol is only formed in trace amounts. Density functional theory calculations on RuO2(110) where only adsorption free energies of intermediate species are considered, i.e. solvent effects and energy barriers are not included, predict however, that the overpotential and the potential limiting step for both methanol and methane are the same. In this work, we use both ab initio molecular dynamics simulations at room temperature and total energy calculations to improve the model system and methodology by including both explicit solvation effects and calculations of proton-electron transfer energy barriers to elucidate the reaction mechanism towards several CO2RR products: methanol, methane, formic acid, CO and methanediol, as well as for the competing H2 evolution. We observe a significant difference in energy barriers towards methane and methanol, where a substantially larger energy barrier is calculated towards methane formation than towards methanol formation, explaining why methanol has been detected experimentally but not methane. Furthermore, the calculations show why RuO2 also catalyzes the CO2RR towards formic acid and not CO(g) and methanediol, in agreement with experimental results. However, our calculations predict RuO2 to be much more selective towards H2 formation than for the CO2RR at any applied potential. Only when a large overpotential of around -1 V is applied, can both formic acid and methanol be evolved, but low faradaic efficiency is predicted because of the more facile H2 formation.

Environmental evaluation of a child with developmental disability.

Children's health can be affected adversely by the environment in which they live. It is well recognized that some environmental chemicals are harmful to the brain, but the role these chemicals play in the development of specific disabilities such as attention deficit hyperactivity disorder and autism is not certain. Parents of children who have developmental disabilities often ask the primary care physician whether certain environmental toxicants might be the cause of the illness. A detailed environmental history and physical examination may help clarify whether there is a plausible relationship between an environmental toxicant and a child's disability.

Boerhaave's syndrome: a diagnostic dilemma in the emergency room.

Boerhaave's syndrome is a potential lethal condition which presents not only a diagnostic but also a therapeutic challenge. Errors in diagnosis are usually caused by unawareness of its varied and atypical presentations. All clinicians need to be aware of this lethal disease, its frequent unusual presentations and the importance of early diagnosis.

Au(III)-CTAB reduction by ascorbic acid: preparation and characterization of gold nanoparticles.

Upon addition of tetrachloroauric(III) (HAuCl(4)) to a solution of cetyltrimethylammonium bromide (CTAB), a perfect transparent yellow colored and yellowish-precipitate appears within the time of mixing, indicating the formation of a complex between HAuCl(4) and CTAB. Morphology of gold nanoparticles in situ via chemical reduction of title reaction has been determined by using conventional techniques. The position and shape of the surface plasmon resonance (SRP) band strongly depends on the [ascorbic acid], [HAuCl(4)], [CTAB] and mixing ratio of the reactants. Sub-, post- and dilution-micellar effects are accountable to the aggregation and/or adsorption of gold nanoparticles onto the surface of CTAB. The morphology of particles was altered by changing the [reactants] as well as [CTAB]. A mechanism of nanoparticle formation has been proposed comprising different steps of particle growth.

Starch-directed green synthesis, characterization and morphology of silver nanoparticles.

Silver nanoparticles were prepared by a simple chemical reduction method using ascorbic acid and starch as reducing and stabilizing agents, respectively. The effect of starch, silver ions and ascorbic acid was studied on the morphology of the silver nano-particles using UV-visible spectrophotometry. The initial reaction time min and amount of starch were important parameters for the growth of Ag-nanoparticles. The morphology was evaluated from transmission electron microscopy (TEM). The truncated triangle nano-plates (from 17 to 30 nm), polyhedron, spherical with some irregular shaped Ag-nanoparticles were formed in presence of starch. Particles are aggregated in an irregular manner, leads to the formation of butterfly-like structures of silver. Starch acts as a stabilizing, shape-directing and capping agent during the growth processes. Silver nanoparticles adsorbed electrostatically on the outer OH groups of amylose left-handed helical conformation in solution.

Shape-directing role of cetyltrimethylammonium bromide in the green synthesis of Ag-nanoparticles using Neem (Azadirachta indica) leaf extract.

The shape-directing role of cetyltrimethylammonium bromide, CTAB, is reported to the green synthesis of Ag-nanoparticles for the first time using Neem (Azadirachta indica) leaf extract. UV-vis spectroscopy, transmission electron microscopy (TEM), and selected area electron diffraction (SAED) patterns were used to monitor the growth kinetics, morphology and crystalline nature of Ag-nanoparticles, respectively. It was observed that the growths of Ag-nanoparticles are stopped within 40 min of reaction time. The Ag-nanoparticles are polydispersed spherical and exhibiting an interesting triangle, flat, plate-like hexagonal and some irregular morphology in presence of different [CTAB]. Hexagonal particles aggregated in a systematic manor, leads to produce a fine tiles-like arrangement of Ag-nanoparticles with dimensions between 10 and 37 nm. The nature of reaction-time curves to the reduction of Ag(+) ions by Neem leaf extract are much different than those observed by us in our earlier studies using different bio-reductants.

Effects of ionic surfactants on the morphology of silver nanoparticles using Paan (Piper betel) leaf petiole extract.

Stable silver nanoparticles were synthesized by the reduction of silver ions with a Paan (Piper betel) leaf petiole extract in absence and presence of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulphate (SDS). The reaction process was simple and convenient to handle, and was monitored using ultraviolet-visible spectroscopy. Absorbance of Ag-nanoparticles increases with the concentrations of Paan leaf extract, acts as reducing, stabilizing and capping agents. The polyphenolic groups of petiole extract are responsible to the rapid reduction of Ag(+) ions into metallic Ag(0). The results indicated that the shape of the spectra, number of peaks and its position strongly depend on the concentration of CTAB, which played a shape-controlling role during the formation of silver nanoparticles in the solutions, whereas SDS has no significant effect. The morphology (spherical, truncated triangular polyhedral plate and some irregular nanoparticles) and crystalline phase of the particles were determined from transmission electron microscopy (TEM) and selected area electron diffraction (SAED).

Silver nanoplates and nanowires by a simple chemical reduction method.

This paper describes a simple preparation of single-crystalline Ag-nanoparticles including plates, and wires in water by truncated triangular particles for the first time during the reduction of [Ag(NH3)2]⁺ complex with glucose at room temperature. Silver particles were characterized by means of the conventional transmission electron microscopy (TEM) and UV-VIS spectroscopy. Cetyltrimethylammonium bromide, CTAB, plays a number of roles during the redox process by solubilizing the reactants, controlling the nucleation and/or growth of nanoparticles, stabilizing the thus-prepared Ag-nanoparticles and minimizing the formation of Ag2O, AgCl, and AgBr precipitates. It was found that the rate constant and absorbance of silver nanoparticles were sigmoidal to the concentration of silver nitrate.

Infantile lead poisoning from an Asian tongue powder: a case report & subsequent public health inquiry.

INTRODUCTION: Lead poisoning from novel environmental sources continues to present a challenge to clinicians who treat infants and children. CASE REPORT: A 12 month old infant of Thai parents was found during well child care to have a venous blood lead concentration of 61 mcg/dL. He was hospitalized for parenteral chelation with CaNa2EDTA and subsequently managed as an outpatient with oral succimer, with a reduction in blood lead concentration to 23 mcg/dL. Chronic lead poisoning was attributed to the use of a Thai tongue powder by the parents for the first seven months of the infant's life. This ethnic remedy was applied to the tongue to absorb toxins, reduce white patches present after milk feedings, and preserve the infant's health. INVESTIGATIONS: Lead contaminated the powder at 109,000 ppm as measured by x-ray fluorescence spectrometry. Two poison centers in Thailand were contacted and initiated a public health inquiry with the Thai Food & Drug Administration (Thai FDA) to remove contaminated products from the marketplace. Their investigation found six additional contaminated tongue powders (of 10 tested) in a Bangkok shop offering Chinese remedies, some with lead levels > 9000 ppm. These products, unregistered with the Thai FDA, were confiscated and the shop closed. Local media attention and case-finding activities of health officials identified one additional infant suffering from lead poisoning due to tongue powders. CONCLUSIONS: Asian tongue powders can be a source of lead poisoning. Medical toxicologists, poison centers, and public health agencies can work together internationally to accomplish effective post-marketing product surveillance.