The Effects of Endogenous Non-Peptide Molecule Isatin and Hydrogen Peroxide on Proteomic Profiling of Rat Brain Amyloid-β Binding Proteins: Relevance to Alzheimer’s Disease?

The amyloid-β peptide is considered as a key player in the development and progression of Alzheimer’s disease (AD). Although good evidence exists that amyloid-β accumulates inside cells, intracellular brain amyloid-binding proteins remain poorly characterized. Proteomic profiling of rat brain homogenates, performed in this study, resulted in identification of 89 individual intracellular amyloid-binding proteins, and approximately 25% of them were proteins that we had previously identified as specifically binding to isatin, an endogenous neuroprotector molecule. A significant proportion of the amyloid-binding proteins (more than 30%) are differentially expressed or altered/oxidatively modified in AD patients. Incubation of brain homogenates with 70 µM hydrogen peroxide significantly influenced the profile of amyloid-β binding proteins and 0.1 mM isatin decreased the number of identified amyloid-β binding proteins both in control and hydrogen peroxide treated brain homogenates. The effects of hydrogen peroxide and isatin have been confirmed in optical biosensor experiments with purified glyceraldehyde-3-phosphate dehydrogenase, one of the known crucial amyloid-β binding proteins (also identified in this study). Data obtained suggest that isatin protects crucial intracellular protein targets against amyloid binding, and possibly favors intracellular degradation of this protein via preventing formation of amyloid-β oligomers described in the literature for some isatin derivatives.     

Solid Phase Extraction and Preconcentration of Trace Heavy Metal Ions in Natural Water with 2,2′‐Dithiobisaniline Modified Amberlite XAD‐2

Abstract

A solid phase extraction and preconcentration methodology utilizing a new chelating resin is described for the separation of Cd, Ni, Co, Cu, and Zn. The chelating resin matrix was prepared by covalently linking 2,2′‐dithiobisaniline synthesized from 2‐aminothiophenol with the benzene ring of polystyrene‐divinylbenzene resin Amberlite XAD‐2 through a –N?N– group. Its adsorption and preconcentration behavior for Cd, Ni, Co, Cu, and Zn in aqueous solution was studied using batch and column procedures in detail. The newly designed resin quantitatively adsorbs Cd, Ni, Co, Cu, and Zn above pH 5.0. Subsequent elution with 2 M HCl readily strips the sorbed metal ions from the resin. The sorption capacity is 360, 230, 170, 200, and 150 mol g^?1 for Cd, Ni, Co, Cu, and Zn, respectively. Their preconcentration factors are 80–200. The time for 80% sorption was less than 10 min for all five metal ions. The effects of electrolytes on the preconcentration were also investigated with the recoveries >95%. The procedure was validated by analysis of a standard reference river sediment material (GBW 08301 China). The developed method was successively utilized for the determination of Cd, Ni, Co, Cu, and Zn in tap water and river water by flame atomic absorption spectrometry (FAAS) after column SPE and preconcentration. The 3σ detection limits for these metal ions were found to be 0.10, 0.34, 0.42, 0.16, and 0.52 g L^?1, respectively. The relative standard deviation was <10% for the determination of 10 g each of Cd, Ni, Co, Cu, and Zn in a 100 mL water sample.     

Palladium Nanoparticles in Glycerol: A Versatile Catalytic System for C?X Bond Formation and Hydrogenation Processes

Palladium nanoparticles stabilised by tris(3‐sulfophenyl)phosphine trisodium salt in neat glycerol have been synthesised and fully characterised, starting from both Pd(II) and Pd(0) species. The versatility of this innovative catalytic colloidal solution has been proved by its efficient application in C X bond formation processes (X=C, N, P, S) and C C multiple bond hydrogenation reactions. The catalytic glycerol phase could be recycled more than ten times, preserving its activity and selectivity. The scope of each of these processes has demonstrated the power of the as‐prepared catalyst, isolating the corresponding expected products in yields higher than 90%. The dual catalytic behaviour of this glycerol phase, associated to the metallic nanocatalysts used in wet medium (molecular‐ and surface‐like behaviour), has allowed attractive applications in one‐pot multi‐step transformations catalysed by palladium, such as C C coupling followed by hydrogenation, without isolation of intermediates using only one catalytic precursor.

     

Electronic Metal–Support Interactions and the Production of Hydrogen Through the Water-Gas Shift Reaction and Ethanol Steam Reforming: Fundamental Studies with Well-Defined Model Catalysts

The electronic properties of Ni and Pt nanoparticles deposited on CeO₂(111) have been examined using core and valence photoemission. The results of valence photoemission point to a new type of metal–support interaction which produces large electronic perturbations for small Ni and Pt particles in contact with ceria. The Ni/CeO₂(111) and Pt/CeO₂(111) systems exhibited a density of metal d states near the Fermi level that was much smaller than that expected for bulk metallic Ni or Pt. The electronic perturbations induced by ceria on Ni made this metal a very poor catalyst for CO methanation, but transformed Ni into an excellent catalyst for the production of hydrogen through the water-gas shift and the steam reforming of ethanol. Furthermore, the large electronic perturbations seen for small Pt particles in contact with ceria significantly enhanced the ability of the admetal to adsorb and dissociate water made it a highly active catalyst for the water-gas shift. The behaviour seen for the Ni/CeO₂(111) and Pt/CeO₂(111) systems illustrates the positive effects derived from electronic metal–support interactions and points to a promising approach for improving or optimizing the performance of metal/oxide catalysts.     

Degradable Superhydrophilic Iron-Pillared Bentonite Doped with Polybutylene Adipate/Terephthalate Open-Cell Foam: Its Application in Dye Degradation,Removal of Heavy Metal Ions,and Oil–Water Separation

Development of industrialization has brought convenience to people's lives; however, it has also brought serious harm to the environment, where, water pollution is the most obvious. Here, a polybutylene adipate terephthalate (PBAT) open-cell foam doped with iron-pillared bentonite (IPB) is prepared by using sugar as a pore-forming agent and solution phase separation, and then combined with a solution dipping method to coat the foam surface with a polyacrylamide/SiO₂, which makes the PBAT foam superhydrophilic. The static adsorption effect of superhydrophilic IPB-doped PBAT open-cell foam on methylene blue (MB) and Cu²⁺ is studied. The adsorption isotherm fitting shows that the adsorption conforms to the Langmuir model and it has biased toward monolayer adsorption. The adsorption kinetics fitting confirms that the adsorption process is in line with the pseudo-second-order adsorption model, which is dominated by chemical adsorption. The modified PBAT open-cell foam has an adsorption effect on Cu²⁺; however, it has weak cyclic adsorption capacity. It shows a good cyclic adsorption ability for the cationic dye MB and it has >95% photodegradation efficiency of the MB after five time's cyclic adsorption. The superhydrophilicity makes the foam to have better applications in oil–water separation.     

Rhinacanthus nasutus Extracts Prevent Glutamate and Amyloid-β Neurotoxicity in HT-22 Mouse Hippocampal Cells: Possible Active Compounds Include Lupeol, Stigmasterol and β-Sitosterol

The Herb Rhinacanthus nasutus (L.) Kurz, which is native to Thailand and Southeast Asia, has become known for its antioxidant properties. Neuronal loss in a number of diseases including Alzheimer's disease is thought to result, in part, from oxidative stress. Glutamate causes cell death in the mouse hippocampal cell line, HT-22, by unbalancing redox homeostasis, brought about by a reduction in glutathione levels, and amyloid-β has been shown to induce reactive oxygen species (ROS) production. Here in, we show that ethanol extracts of R. nasutus leaf and root are capable of dose dependently attenuating the neuron cell death caused by both glutamate and amyloid-β treatment. We used free radical scavenging assays to measure the extracts antioxidant activities and as well as quantifying phenolic, flavonoid and sterol content. Molecules found in R. nasutus, lupeol, stigmasterol and β-sitosterol are protective against glutamate toxicity.     

An Oxidation System for Green Chemistry: The Oxidation of Alcohols and Hydrocarbons in the Presence of Metal–Polymer Complexes

Environmental and economic factors make the use of harmful oxidants increasingly unacceptable except on a small scale. Accordingly, we have investigated the use of dioxygen and hydrogen peroxide as oxidants. For this oxidation reaction of hydrocarbons, transition metal complexes and polymer-bound transition metal complexes were effective as catalysts. Earlier investigations indicated that the catalytic site was a bi- or multinuclear complex. Thus, several binuclear complexes of Cu and Mn [Eqs. (9)–(11)] were designed and their effectiveness in oxidizing phenols to biphenols and benzoquinones and in monooxygenase activity was demonstrated. In the oxidation of phenols, the system did not produce poly(phenylene oxide) since the intermediate phenoxy radical underwent C–C coupling to biphenol or underwent attack by hydroxyl radical to a hydroquinone that could be oxidized to a quinone. A reaction mechanism involving the binuclear complex for the oxidation is proposed.     

Effects of Ozonation on Natural Organic Matter Reactivity in Adsorption and Biodegradation Processes – A Case Study: The Úzquiza Reservoir Water

In this paper the influences of preozonation on the effectiveness of NOM adsorption and biodegradation processes are studied. Three different types of water have been used in this study: A natural water from the Úzquiza Reservoir (Burgos, Spain), synthetics waters prepared using natural humic substances (fulvic and humic acids extracted from the Úzquiza Reservoir) and a synthetic water prepared using a commercially supplied humic acid. The effect of preozonation on NOM adsorption by activated carbon is evaluated: adsorption of humic acids (hydrophobic, high molecular weight compounds) is improved following preozonation; however, for the fulvic acids (hydrophilic, low molecular weight compounds), no net appreciable effect of preozonation on adsorption was observed. Preozonation increases the biodegradability of NOM: biodegradable dissolved organic carbon (BDOC), which was determined using two different bioassays (Billen-Servais method and Joret-Lévi method), increases with increasing ozone dosage. A characterization of humic substances based on their adsorption and biodegradability properties is also reported, showing the effect of ozone.     

Disrupting Aryl-CH������O Interactions on Pt(111) Through the Coadsorption of Trifluoroacetic Acid and 2,2,2-Trifluoroacetophenone (TFAP): Inhibition of Competing Processes in Heterogeneous Asymmetric Catalysis

A study of the coadsorption of trifluoroacetic acid (TFA) and 2,2,2-trifluoroacetophenone (TFAP) on Pt(111) was carried out using scanning tunneling microscopy (STM) measurements. The investigation is based on literature reports that the conversion rate and the enantiomeric excess for the hydrogenation of TFAP on cinchona modified Pt/Al₂O₃ are very sensitive to the presence of small amounts of TFA in the solvent. As previously reported, STM and density functional theory (DFT) studies show that TFAP forms aryl-CH···O bonded dimers on Pt(111) at room temperature. In the present study, STM measurements show that TFA disrupts aryl-CH···O bonding through insertion into TFAP dimers to form isolated trimolecular and bimolecular assemblies. Structural models are proposed for the TFAP?CTFA aggregates. The implications of these structures for the rate and enantioselectivity of TFAP hydrogenation are discussed in terms of H-bonding activation of the carbonyl function. It is proposed that the acid additive operates on the enanantioselective hydrogenation of TFAP through the inhibition of the racemic reaction at sites remote from the chiral modifier. This action is assumed to occur in parallel with effects, already proposed in the literature, due to the formation of modifier?Cacid complexes and the protonation of the modifier.     

Stereo-Preference in the Degradation of the Erythro and Threo Isomers of β‐O‐4‐Type Lignin Model Compounds in Oxidation Processes: Part 1: In the Reaction with Active Oxygen Species Under Oxygen Delignification Conditions

We examined whether or not active oxygen species (AOS) stereo-preferentially attack the erythro or threo isomer of non-phenolic β-O-4 -type lignin model compounds under oxygen delignification conditions. When AOS were generated in situ by the reaction between O₂ and co-existing 4-hydroxy-3-methoxybenzyl alcohol (vanillyl alcohol), the obtained results could be explained on the basis of the hypothesis that an electrostatic repulsion exists between the negatively charged oxyl anion radical and the side-chain of the erythro isomer carrying the α-alkoxide anion. This repulsion prevents the reaction between the two species and, consequently, the erythro isomer is degraded less than the threo isomer. When 2,4,6-trimethylphenol (TMPh) was used to generate AOS, the reverse stereo-preference was observed. This reversal could be attributed to the neutral nature of a peroxyl radical that is an important AOS in the TMPh system and can attack the side-chain of the erythro isomer carrying the negatively charged α-alkoxide anion.     

The Role of Weak Intermolecular Interactions in the Assembly of a Series of d<Superscript>10</Superscript> Metal Coordination Polymers Based on <Emphasis Type="Italic">N,Nʹ</Emphasis>-Bis-Pyridin-3-Ylmethylene-Naphtalene-1,5-Diamine Ligand; Ultrasonic Synthesis,Spectroscopic and Structural Characterization

The motivation of this work is to highlight factors that influence the supramolecular structures of d¹⁰ metal coordination polymers. Two novel Hg(II) and Cd(II) 1D coordination polymers (CPs) have been constructed from metal iodide and a N,N′-bis-pyridin-3-ylmethylene-naphtalene-1,5-diamine ligand using conventional methods. Our analyses reveal the substantial role of weak hydrogen bonds and π–π stacking interactions in the assembly of these series of compounds. These compounds were studied using X-ray crystallography, infrared spectroscopy and X-ray powder diffraction. The supramolecular structures of these two compounds were compared with two structures that have been published recently. These coordination polymers in nano-size were synthesized under ultrasonication and their morphology were characterized using scanning electron microscopy (SEM).     

Metal catalysis with nanostructured metals supported on strongly acidic cross-linked polymer frameworks. Part I. The behaviour of M2+ ions (M = Ni,Pd, Pt,Cu) supported on Rohm & Haas’s resin A70 and Du Pont’s SAC-13, towards H2 in the solid state and NaBH4 in aqueous medium

The macroreticular Rohm & Haas resin A70 and the DuPont silica/nafion microcomposite SAC-13 undergo facile metalation with Ni^II, Pd^II, Pt^II, Cu^II cationic species to give materials that do react with both molecular hydrogen in the “dry” state and sodium borohydride in the aqueous phase. The distribution of the reduced species in the body of the support particles is sensitive to the reduction protocol.