Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu-Complex Immobilized on Graphitized Mesoporous Carbon.

The electrochemical reduction of carbon dioxide (CO2 ) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO2 to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO2 to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO2 in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.

Impact of obesity with impaired glucose tolerance on retinal degeneration in a rat model of metabolic syndrome.

PURPOSE: Metabolic syndrome (MetS) is associated with several degenerative diseases, including retinal degeneration. Previously, we reported on progressive retinal degeneration in a spontaneous obese rat (WNIN/Ob) model. In this study, we investigated the additional effect of impaired glucose tolerance (IGT), an essential component of MetS, on retinal degeneration using the WNIN/GR-Ob rat model. METHODS: The retinal morphology and ultrastructure of WNIN/GR-Ob and age-matched littermate lean rats were studied by microscopy and immunohistochemistry. The retinal transcriptome of WNIN/GR-Ob was compared with the respective lean controls and with the WNIN/Ob model using microarray analysis. Expression of selected retinal marker genes was studied via real-time PCR. RESULTS: Progressive loss of photoreceptor cells was observed in WNIN/GR-Ob rats with an onset as early as 3 months. Similarly, thinning of the inner nuclear layer was observed from 6 months in these rats. Immunohistochemical analysis showed decreased levels of rhodopsin and postsynaptic density protein-95 (PSD-95) proteins and increased levels of glial fibrillary acidic protein (GFAP), vascular endothelial growth factor (VEGF), and calretinin in WNIN/GR-Ob rats compared with the age-matched lean controls, further supporting cellular stress/damage and retinal degeneration. The retinal transcriptome analysis indicated altered expression profiles in both the WNIN/GR-Ob and WNIN/Ob rat models compared to their respective lean controls; these pathways are associated with activation of pathways like cellular oxidative stress response, inflammation, apoptosis, and phototransduction, although the changes were more prominent in WNIN/GR-Ob than in WNIN/Ob animals. CONCLUSIONS: WNIN/GR-Ob rats with added glucose intolerance developed retinal degeneration similar to the parent line WNIN/Ob. The severity of retinal degeneration was greater in WNIN/GR-Ob rats compared to WNIN/Ob, suggesting a possible role for IGT in this model. Hence, the WNIN/GR-Ob model could be a valuable tool for investigating the impact of MetS on retinal degeneration pathology.

Dietary ginger improves glucose dysregulation in a long-term high-fat high-fructose fed prediabetic rat model.

The rapid increase in global diabetes burden with its associated morbidity and mortality is a major health concern for humans. Prediabetes is a condition which predispose a person not only to diabetes but also to the associated complications including morbidity even in the absence of an apparant hyperglycemia. However, appropriate dietary intervention may not only prevent but also improve one's condition as diet is the major contributor to such metabolic disorders. Here, we investigated the effect of dietary ginger (Zingiber officinale Roscoe) on the markers of insulin resistance and pathophysiology in a diet-induced prediabetic rat model. Male Sprague-Dawley (SD) rats were fed the following diets: control (5% groundnut oil + 65 % corn starch), high fat high fructose (HFHF; 25% beef tallow + 35 % fructose) and HFHF with 3 % ginger (HFHFG) for eight months. Plasma markers of insulin resistance, lipid profile, oral glucose tolerance (OGTT; 2nd and 5th month), intraperitoneal insulin tolerance (ITT), plasma total antioxidant capacity (TAC), liver histology and pancreatic immunohistochemistry (IHC) were examined. The impaired OGTT, ITT and insulin sensitivity indices with observed hyperinsulinemia and hypertriglyceridemia suggest that HFHF feeding resulted in prediabetes in rats. HFHF feeding also decreased insulin secretion in the pancreas, increased lipid accumulation in liver and total oxidants in plasma. The effects of HFHF feeding on glucose regulation, pathophysiology of pancreas and liver; total oxidative stress were improved by ginger feeding. The present study demonstrated thatlong-term HFHF feeding induces prediabetes in experimental rats while dietary ginger neutralizes the HFHF induced impairment in glucose regulation, dyslipidemia, and oxidative stress.

Crystal structure of bis-(acetato-κO)di-aqua-(2,2'-bi-pyridine-κ(2) N,N')manganese(II).

In the title monomeric manganese(II) complex, [Mn(CH3COO)2(C10H8N2)(H2O)2], the metal ion is coordinated by a bidentate 2,2'-bi-pyridine (bpy) ligand, two water mol-ecules and two axial acetate anions, resulting in a highly distorted octa-hedral environment. The aqua ligands are stabilized by the formation of strong intra-molecular hydrogen bonds with the uncoordinated acetate O atoms, giving rise to pseudo-bridging arrangement of the terminal acetate groups. In the crystal, the mol-ecules form [010] zigzag chains via O-H⋯O hydrogen bonds involving the aqua ligands and acetate O atoms. Further, the water and bpy ligands are trans to each other, and are arranged in an off-set fashion showing inter-molecular π-π stacking between nearly parallel bi-py rings, the centroid-centroid separations being 3.8147 (12) and 3.9305 (13) Å.

In vitro and in silico approach towards antimicrobial and antioxidant behaviour of water-soluble chitosan dialdehyde biopolymers.

Chitosan dialdehyde (ChDA) was prepared from a three-step process initiated by thermal organic acid hydrolysis, periodate oxidization, and precipitation from native chitosan (NCh). The developed ChDA resulted in an aldehydic content of about 82 % with increased solubility (89 %) and maximum yield (97 %). The functional alteration of the aldehydic (-CHO) group in ChDA was established using vibrational stretching at 1744 cm-1. The increase in the zone of inhibition of ChDA compared to NCh has confirmed the inherent antimicrobial effect against bacterial and fungal species. ChDA showed better antioxidant activity of about 97.4 % (DPPH) and 31.1 % (ABTS) compared to NCh, measuring 45.3 % (DPPH) and 15.9 % (ABTS), respectively. The novel insilico predictions of the ChDA's biocidal activity were confirmed through molecular docking studies. The amino acid moiety such as ARG 110 (A), ASN 206 (A), SER 208 (A), THR 117 (B), ASN 118 (B), and LYS 198 (B) residues of 7B53 peptide from E. coli represents the binding pockets responsible for interaction with aldehyde group of ChDA. Whereas PHE 115 (E), ALA 127 (H), TYR 119 (C), GLN 125 (H), ASN 175 (E), ARG 116 (E), LYS 101 (H), and LYS 129 (H) of 1IYL A peptide from Candida albicans makes possible for binding with ChDA. Hence, the synergistic effect of ChDA as a biocidal compound is found to be plausible in the drug delivery system for therapeutic applications.

Benefits of early glycemic control by insulin on sensory neuropathy and cataract in diabetic rats.

While there is an emphasis on the early glycemic control for its long-term benefits in preventing microvascular complications of diabetes, the biochemical mechanisms responsible for the long-lasting effects are not clearly understood. Therefore the impact of early insulin (EI) versus late insulin (LI) treatment on diabetic sensory neuropathy and cataract in streptozotocin-induced diabetic Wistar male rats were evaluated. EI group received insulin (2.5 IU/animal, once daily) treatment from day 1 to 90 while LI group received insulin from day 60 to 90. Early insulin treatment significantly reduced the biochemical markers like glucose, triglyceride, glycated hemoglobin, thiobarbituric acid reactive substances, advanced glycation end products and ratio of reduced glutathione and oxidized glutathione in diabetic rats. The late insulin treatment failed to resist the biochemical changes in diabetic rats. Diabetic rats developed sensory neuropathy as evidenced by mechanical and thermal hyperalgesia and showed a higher incidence and severity of cataract as revealed by slit lamp examination. Early insulin treatment protected the rats from the development of neuropathy and cataract, but late insulin administration failed to do so. The results demonstrate the benefits of early glycemic control in preventing neuropathy and cataract development in diabetic rats.

Current nanotechnological strategies using lipids, carbohydrates, proteins and metal conjugates-based carrier systems for diagnosis and treatment of tuberculosis - A review.

Tuberculosis is a fatal disease caused by Mycobacterium tuberculosis with highest morbidity and mortality every year. The evolution of anti-TB drugs is promising in controlling and treating TB. Yet, the drug response varies depending on the bacterial load and host immunological profiles. The prolonged anti-TB treatment regimen and high pill burden leads to poor adherence to treatment and acquired drug resistance. In the clinical arena, sustainable nanotechnology improves the targeted strategies leading to enhance therapeutic recovery with minimum treatment duration and virtuous drug adherence. Determinants of nanosystems are the size, nature, formulation techniques, stable dosing patterns, bioavailability and toxicity. In the treatment of chronic illness, nanomedicines inclusive of biological macromolecules such as lipids, peptides, and nucleic acids occur to be a successive alternative to synthetic carriers. Most biological nanomaterials possess antimicrobial properties with other intrinsic characteristics. Recently, the pulmonary delivery of anti-TB drugs through polymeric nanocarrier systems is shown to be effective in achieving optimal drug levels in lungs for longer duration, enhanced tissue permeation and sustained systemic clearance. This thematic review provides a holistic insight into the nanodelivery systems pertinent to the therapeutic applications in pulmonary tuberculosis describing the choice of carriers, optimized process, metabolic action and excretion processes.

Molecular wiring of glucose oxidase enzyme with Mn polypyridine complex on MWCNT modified electrode surface and its bio-electrocatalytic oxidation and glucose sensing.

A simple method for molecular wiring of glucose oxidase (GOx) enzyme with a low cost Mn polypyridine complex, Mn(phen)2Cl2, carboxylic acid functionalized multiwalled carbon nanotube (f-MWCNT) and Nafion (Nf), which is useful for glucose oxidation and sensing application in pH 7 phosphate buffer solution, has been demonstrated. In the typical preparation, f-MWCNT, Mn(phen)2Cl2, Nafion and GOx solution/suspension were successfully drop-casted as layer-by-layer on a cleaned glassy carbon electrode and potential cycled using cylic voltametric (CV) technique. In this preparation procedure, the Mn(phen)2Cl2 complex is in-situ converted as a dimer complex, Mn2(phen)2(O)(Cl2). A cooperative interaction based on π-π, covalent, ionic, hydrophilic and hydrophobic are operated in the bioelectrode for molecular wiring and electron-transfer shutting reaction. The modified electrode is designated as GCE/f-MWCNT@Mn2(phen)2(O)(Cl2)-Nf@GOx. CV response of the bioelectrode showed a defined redox peak current signal at an apparent standard electrode potential, E°'=0.55V vs Ag/AgCl. Upon exposure of glucose, the modified electrode showed a current linearity in a range, 0-6mM with a current sensitivity value, 349.4µAmM-1cm-2 by CV and a current linearity in a window, 50-550µM with a current sensitivity, 316.8µAmM-1cm-2 at applied biased potential, 0.65V vs Ag/AgCl by amperometric i-t methods. Obtained glucose oxidation current sensitivity values are relatively higher than Os-complex based transducer systems.

Vitamin B12-Immobilized Graphene Oxide for Efficient Electrocatalytic Carbon Dioxide Reduction Reaction.

A naturally occurring water-soluble cobalt-complex cyanocobalamin (Vitamin B12) has been identified as a new and efficient electrocatalyst for the CO2 -to-CO reduction reaction in aqueous solution. Heterogeneous B12-electrocatalysts prepared by a simple electrochemical immobilization technique on graphene-oxide (GO)-modified glassy carbon and carbon paper (CP) electrodes, without any non-degradable polymer-binders, showed a highly stable and well-defined surface-confined redox peak at E'=-0.138 V vs. RHE with a surface-excess value, ΓB12 =4.28 nmol cm-2 . This new electrocatalyst exhibits 93 % Faradaic efficiency for CO2 -to-CO conversion at an electrolysis potential, -0.882 V vs. RHE (an optimal condition) with a high current density, 29.4 mA cm-2 and turn-over-frequency value, 5.2 s-1 , without any surface-fouling problem, in 0.5 m KHCO3 . In further, it follows an eco-friendly, sustainable and water-based approach with the involvement of biodegradable and non-toxic chemicals/materials like B12, GO and CP.

Improved Electrical Wiring of Glucose Oxidase Enzyme with an in-Situ Immobilized Mn(1,10-Phenanthroline)2Cl2-Complex/Multiwalled Carbon Nanotube-Modified Electrode Displaying Superior Performance to Os-Complex for High-Current Sensitivity Bioelectrocatalytic and Biofuel Cell Applications.

The search for a new and efficient transducer that can electrically connect enzyme active sites, like flavin adenine dinucleotide in glucose oxidase (GOx), with the electrode surface is a cutting-edge research area. Currently, Os(bpy)-complex pendent polyvinylpyridine/polyvinyl imidazole/pyridinium hydrogel based chemically modified electrodes have been widely used for this purpose (bpy = 2,2'-bipyridine). Herein, we report, a [Mn2III(phen)4(O)(Cl)2]2+ complex/Nafion-immobilized carboxylic acid-functionalized multiwalled carbon nanotube modified glassy carbon electrode (GCE/f-MWCNT@Mn2(Phen)4O(Cl)2-Nf, phen = 1,10-phenanthroline), prepared by an in-situ electrochemical method using the precursor, Mn(phen)2Cl2, as an efficient and low cost alternate to the Os-complex transducer, for the glucose oxidase enzyme (GOx) based bio-electro-catalytic system. The existence of the key active site, [Mn2III(phen)4(O)(Cl)2]2+, on the modified electrode was confirmed by physicochemical characterizations using transmission electron microscope, Raman, infrared, and UV-vis spectroscopes and electrospray ionization mass spectrometry techniques. The Mn-complex modified electrode showed a redox peak at E°' = 0.55 V vs Ag/AgCl in neutral solution with a surface excess (ΓMn) value of 5.6 × 10-9 mol cm-2. The GOx enzyme bioanode prepared by adsorbing GOx on the Mn-complex modified electrode has shown an efficient bioelectrocatalytic oxidation of glucose with a Tafel slope value of 111 mV dec-1. Amperometric i-t analysis of glucose showed a calibration plot in a linear range of 50-550 µM and with current sensitivity of 316.7 µA mM-1 cm-2. The current sensitivity value obtained here is about 2-80 000 times higher than that of the Os(bpy)-complex based transducers used for GOx based bio-electro-catalytic applications. Utilizing this new bioanode system along with a Pt-based oxygen reduction electrode, a new biofuel cell was constructed and achieved a power density value 7.5 µW cm-2.

Involvement of high-valent manganese-oxo intermediates in oxidation reactions: realisation in nature, nano and molecular systems.

Manganese plays multiple role in many biological redox reactions in which it exists in different oxidation states from Mn(II) to Mn(IV). Among them the high-valent manganese-oxo intermediate plays important role in the activity of certain enzymes and lessons from the natural system provide inspiration for new developments of artificial systems for a sustainable energy supply and various organic conversions. This review describes recent advances and key lessons learned from the nature on high-valent Mn-oxo intermediates. Also we focus on the elemental science developed from the natural system, how the novel strategies are realised in nano particles and molecular sites at heterogeneous and homogeneous reaction conditions respectively. Finally, perspectives on the utilisation of the high-valent manganese-oxo species towards other organic reactions are proposed.

Malnutrition: Modulator of Immune Responses in Tuberculosis.

Nutrition plays a major role in the management of both acute and chronic diseases, in terms of body's response to the pathogenic organism. An array of nutrients like macro- and micro-nutrients, vitamins, etc., are associated with boosting the host's immune responses against intracellular pathogens including mycobacterium tuberculosis (M.tb). These nutrients have an immunomodulatory effects in controlling the infection and inflammation process and nutritional deficiency of any form, i.e., malnutrition may lead to nutritionally acquired immunodeficiency syndrome, which greatly increases an individual's susceptibility to progression of infection to disease. This narrative review looks at the various mechanisms by which nutrition or its deficiency leads to impaired cell mediated and humoral immune responses, which in turn affects the ability of an individual to fight M.tb infection or disease. There is very little evidence in the literature that any specific food on its own or a specific quantity can alter the course of TB disease or be effective in the treatment of malnutrition. Further clinical trials or studies will be needed to recommend and to better understand the link between malnutrition, tuberculosis, and impaired immunity.

Differential effects of dietary saturated and trans-fatty acids on expression of genes associated with insulin sensitivity in rat adipose tissue.

OBJECTIVE: Trans-fatty acids (TFAs) are formed during partial hydrogenation of vegetable oils and are shown to be more atherogenic than saturated fatty acids (SFAs). Our previous study showed that dietary TFAs decrease adipose tissue insulin sensitivity to a greater extent than SFAs in rats. We hypothesized that the effects of these fatty acids on insulin sensitivity could be mediated through an alteration in gene expression. In the current study we have investigated the effects of dietary TFAs or SFAs on expression of genes associated with insulin sensitivity in rat adipose tissue. DESIGN AND METHODS: Male weanling Wistar/NIN rats were divided into four groups and fed one of the following diets containing 10% fat (g/100 g diet) differing only in the fatty acid composition for 3 months: control diet (3.7% linoleic acid (LA)), SFA diet (5% SFA), TFA diet 1 (1.5% TFA + 1% LA) and TFA diet 2 (1.5% TFA + 2% LA). The mRNA expression of peroxisome proliferator-activated receptor gamma (PPARgamma), lipoprotein lipase (LPL), glucose transporter-4 (GLUT4), resistin and adiponectin was analyzed in epididymal fat using RT-PCR. The effects of TFA were studied at two levels of LA to understand the beneficial effects of LA over the effects of TFA. RESULTS: Both dietary SFA and TFA upregulated the mRNA levels of resistin. Dietary SFA downregulated adiponectin and GLUT4 and upregulated LPL, while TFA downregulated PPARgamma and LPL. The effects of dietary TFA on PPARgamma and resistin were not counteracted by increased LA (TFA diet 2). CONCLUSION: The effects of SFAs on the aforementioned genes except PPARgamma could be extrapolated towards decreased insulin sensitivity, while only the alteration in the mRNA levels of PPARgamma and resistin could be associated with insulin resistance in TFA-fed rats. These findings suggest that dietary SFAs and TFAs alter the expression of different genes associated with insulin sensitivity in adipose tissue.

Biomimetic iron(III) complexes of facially and meridionally coordinating tridentate 3N ligands: tuning of regioselective extradiol dioxygenase activity in organized assemblies.

Four mononuclear iron(III) complexes of the type [Fe(L)Cl3] 1-4, where L is a tridentate 3N ligand such as (2-pyridin-2-ylethyl)(pyridin-2-ylmethyl)amine (L1), (methyl)(2-pyridin-2-ylethyl)(pyridin-2-ylmethyl)amine (L2), bis(pyridin-2-ylethyl)amine (L3), and (1-methyl-1H-imidazol-2-ylmethyl)(pyridin-2-ylethyl)amine (L4), have been isolated and studied as functional models for catechol dioxygenase enzymes. In [Fe(L2)Cl3] 2, the ligand L2 is coordinated facially to iron(III) whereas in [Fe(L1)Cl3] 1 and [Fe(L4)Cl3] 4 the ligands L1 and L4 are coordinated meridionally. In DCM, CH3CN and aqueous SDS, CTAB and TX-100 micellar media, the positions of both the low and high energy catecholate-to-iron(III) LMCT bands (465-530, 690-860 nm) observed for the 3,4-di-tert-butylcatecholate (DBC(2-)) adducts of the iron(III) complexes vary in the order 2 > 1 > 3 > 4, which reflects the influence of the stereoelectronic factors, mode of coordination and the chelate ring size formed by the tridentate ligands. Spectral and electrochemical studies disclose the formation and location of the cationic adducts as solvated [Fe(L)(DBC)(H2O)](+) species mostly in the aqueous micellar pseudophases of SDS and TX-100 and in the aqueous phase of CTAB micellar solution. The [Fe(L)(DBC)Cl] adducts of 1, 3 and 4, generated in situ, afford major amounts of intradiol cleavage products (17.0-70.0%) and smaller amounts of extradiol (1.2-4.2%) products with varying extradiol to intradiol cleavage product selectivity (E/I: 1, 0.08 : 1; 3, 0.02 : 1; 4, 0.3 : 1). On the other hand, interestingly, the adduct [Fe(L2)(DBC)Cl] of 2 generated in DCM yields a major amount of extradiol (54.0%) and a lower amount (18.3%) of the intradiol cleavage products (E/I, 3 : 1). Remarkably, in aqueous SDS micellar media, it shows exclusive extradiol cleavage products (79.4%) while all the other complexes show very low selectivity (E/I: 1, 0.03 : 1; 2, 79.4 : 0, 3, 0.06 : 1, 4, 0.06 : 1), suggesting the suitability of SDS medium for 2 to elicit exclusive extradiol cleavage. The TX-100 micellar medium also provides a suitable hydrophobic environment for 2 to elicit extradiol cleavage. However, in CTAB micellar medium, 2 shows cleavage selectivity lower than others. Also, the rate of dioxygenation is higher in SDS micellar medium than in DCM, and is dependent upon the chelate ring size.