A study on the DC-electrical and thermal conductivities of epoxy/ZnO composites doped with carbon black

Thermo-electrical characterizations of hybrid polymer composites, made of epoxy matrix filled with various zinc oxide (ZnO) concentrations (0, 4.9, 9.9, 14.9, and 19.9 wt%), and reinforced with conductive carbon black (CB) nanoparticles (0.1 wt%), have been investigated as a function of ZnO concentration and temperature. Both the measured DC-electrical and thermal conductivities showed ZnO concentration and temperature dependencies. Increasing the temperature and filler concentrations were reflected in a negative temperature coefficient of resistivity and enhancement of the electrical conductivity as well. The observed increase in the DC conductivity and decrease in the determined activation energy were explained based on the concept of existing paths and connections between the ZnO particles and the conductive CB nanoparticles. Alteration of ZnO concentration with a fixed content of CB nanoparticles and/or temperature was found to be crucial in the thermal conductivity behavior. The addition of CB nanoparticles to the epoxy/ZnO matrix was found to enhance the electrical conduction resulting from the electronic and impurity contributions. Also, the thermal conductivity enhancement was mostly attributed to the heat transferred by phonons and electrons hopping to higher energy levels throughout the thermal processes. Scanning electron microscopy and energy-dispersive spectroscopy were used to observe the morphology and elements’ distribution in the composites. The observed thermal conductivity behavior was found to correlate well with that of the DC-electrical conductivity as a function of the ZnO content. The overall enhancements in both the measured DC- and thermal conductivities of the prepared hybrid composites are mainly produced through mutual interactions between the filling conductive particles and also from electrons tunneling in the composite's bulk as well.     

Role of the velocity frame of reference in thermodiffusion in liquid mixtures

The role and significance of the velocity frame of reference in the interpretation, modeling and formulation of thermodiffusion in multicomponent liquid mixtures were investigated, focused on the nonequilibrium thermodynamics modeling approach. The effect of the velocity frame of reference on the phenomenological equations and thermodiffusion coefficients and expressions is explored. Theoretically and also by the aid of representative calculations, it is shown that while in binary mixtures transformation from one frame to another does not affect the sign and magnitude of the thermodiffusion coefficients, in multicomponent mixtures (ternary and higher), even the sign of the thermodiffusion coefficients may change when an alternative frame is used. This implies that in multicomponent mixtures for either experimental data or model estimations, the employed velocity frame for the thermodiffusion coefficients plays an important role in calculations. The Soret coefficients and the thermodiffusion factors are independent of the frame of reference.     

The Cytotoxic Effect of Apis mellifera Venom with a Synergistic Potential of Its Two Main Components—Melittin and PLA2—On Colon Cancer HCT116 Cell Lines

Colon carcinogenesis is ranked second globally among human diseases after cardiovascular failures. Bee venom (BV) has been shown to possess in vitro anticancer effects against several types of cancer cells. The two main biopeptides of Apis mellifera BV, namely, melittin (MEL) and phospholipase A2 (PLA2), are suspected to be the biomolecules responsible for the anticancer activity. The present work aims to evaluate the cytotoxic effect of the A. mellifera venom on human colon carcinoma cells (HCT116), and to assess the synergistic effect of MEL and PLA2 on these cells. After analyzing, through high-pressure liquid chromatography, the proportions of MEL and PLA2 on BV, we have established a cell viability assay to evaluate the effect of BV, MEL, PLA2, and a mixture of MEL and PLA2 on the HCT116 cells. Results obtained showed a strong cytotoxicity effect induced by the A. mellifera venom and to a lower extent MEL or PLA2 alone. Remarkably, when MEL and PLA2 were added together, their cytotoxic effect was greatly improved, suggesting a synergistic activity on HCT116 cells. These findings confirm the cytotoxic effect of the A. mellifera venom and highlight the presence of synergistic potential activities between MEL and PLA2, possibly inducing membrane disruption of HCT116 cancer cells. Altogether, these results could serve as a basis for the development of new anticancer treatments.     

Photochromism of dihydroindolizines. Part 16: Tuning of the photophysical behavior of photochromic dihydroindolizines in solution and in polymeric thin film

In this work, photochromic materials based on the dihydroindolizine (DHI) system were synthesized in multistep reactions using chemical and photochemical methods. Some of the synthesized photochromic dihydroindolizine derivatives were substituted on the fluorene (region A) and pyridazine (region C) moieties in order to provide the appropriate functionality for optimal tuning of the photochromic properties of the system. Irradiation of the photochromic DHIs with polychromatic light led to ring opened colored betaines, which underwent thermal 1,5-electrocyclization. The red to green colored betaines produced after UV irradiation returned back through 1,5-electrocyclization to the corresponding DHIs with different rate constants depending on the substituents in both fluorene and pyridazine regions. The kinetic measurements of the thermal 1,5-electrocyclization under different temperatures that ranged from −10 to 25 °C showed that the half-lives of the colored betaines fall in the second to hours domain. Interestingly, these materials showed a very good photochromic behavior not only in solution but also in the PMMA matrix. Irradiation of a slide prepared by the deep-coating method led to the formation of the colored betaine and the kinetics of the thermally reversible 1,5-electrocyclization and the AFM image of the film has been recorded. Indeed, the chemical and thermal stability of the investigated betaines in polymer (PMMA) will render such species useful for a plethora of new of applications.     

Hydrophobic AEROSIL®R972 Fumed Silica Nanoparticles Incorporated Monolithic Nano-Columns for Small Molecule and Protein Separation by Nano-Liquid Chromatography

A new feature of hydrophobic fumed silica nanoparticles (HFSNPs) when they apply to the preparation of monolithic nano-columns using narrow monolithic fused silica capillary columns (e.g., 50-µm inner diameter) was presented. The monolithic nano-columns were synthesized by an in-situ polymerization using butyl methacrylate (BMA) and ethylene dimethacrylate (EDMA) at various concentrations of AEROSIL^®R972, called HFSNPs. Dimethyl formamide (DMF) and water were used as the porogenic solvents. These columns (referred to as HFSNP monoliths) were successfully characterized by using scanning electron microscopy (SEM) and reversed-phase nano-LC using alkylbenzenes and polyaromatic hydrocarbons as solute probes. The reproducibility values based on run-to-run, column-to-column and batch-to-batch were found as 2.3%, 2.48% and 2.99% (n = 3), respectively. The optimized column also indicated promising hydrophobic interactions under reversed-phase conditions, while the feasibility of the column allowed high efficiency and high throughput nano-LC separations. The potential of the final HFSNP monolith in relation to intact protein separation was successfully demonstrated using six intact proteins, including ribonuclease A, cytochrome C, carbonic anhydrase isozyme II, lysozyme, myoglobin, and α-chymotrypsinogen A in nano-LC. The results showed that HFSNP-based monolithic nanocolumns are promising materials and are powerful tools for sensitive separations.     

Novel Disulfiram Derivatives as ALDH1a1-Selective Inhibitors

Aldehyde dehydrogenase-1a1 (ALDH1a1), the enzyme responsible for the oxidation of retinal into retinoic acid, represents a key therapeutic target for the treatment of debilitating disorders such as cancer, obesity, and inflammation. Drugs that can inhibit ALDH1a1 include disulfiram, an FDA-approved drug to treat chronic alcoholism. Disulfiram, by carbamylation of the catalytic cysteines, irreversibly inhibits ALDH1a1 and ALDH2. The latter is the isozyme responsible for important physiological processes such as the second stage of alcohol metabolism. Given the fact that ALDH1a1 has a larger substrate tunnel than that in ALDH2, replacing disulfiram ethyl groups with larger motifs will yield selective ALDH1a1 inhibitors. We report herein the synthesis of new inhibitors of ALDH1a1 where (hetero)aromatic rings were introduced into the structure of disulfiram. Most of the developed compounds retained the anti-ALDH1a1 activity of disulfiram; however, they were completely devoid of inhibitory activity against ALDH2.     

Capillary zone electrophoresis of derivatized acidic monosaccharides

A new and specific precolumn derivatization reaction for acidic monosaccharides was introduced and evaluated in the separation and sensitive detection of carbohydrates by capillary electrophoresis. The derivatization reaction involved the attachment of sulfanilic acid (a UV absorbing tag) or 7-aminonaphthalene-1,3-disulfonic acid (a UV absorbing and fluorescing tag) via a condensation reaction between the amino group of the derivatizing agent and the carboxyl group of the sugar in the presence of a water-soluble carbodiimide. The derivatization reaction replaced the weak carboxylic acid of the sugar by a strong sulfonic acid, which is fully ionized at all pH. This allowed the electrophoresis of the sugar derivatives over a wide pH range and permitted the determination of acidic carbohydrates at very low femtomole levels by UV and fluorescence detection.     

Remarkable activity of a novel cyclic seleninate ester as a glutathione peroxidase mimetic and its facile in situ generation from allyl 3-hydroxypropyl selenide

1,2-Oxaselenolane Se-oxide is a novel cyclic seleninate ester that functions as a remarkably efficient glutathione peroxidase mimetic by catalyzing the reduction of tert-butyl hydroperoxide to tert-butyl alcohol in the presence of benzyl thiol. The seleninate ester can be conveniently generated in situ by oxidation of allyl 3-hydroxypropyl selenide with tert-butyl hydroperoxide. Its catalytic activity surpasses that of several other known GPx mimetics containing cyclic selenenamide structures, which were also tested for comparison.     

Time-resolved resonance Raman analysis of chromophore structural changes in the formation and decay of rhodopsin's BSI intermediate

Time-resolved resonance Raman microchip flow experiments are performed to obtain the vibrational spectrum of the chromophore in rhodopsin's BSI intermediate and to probe structural changes in the bathorhodopsin-to-BSI and BSI-to-lumirhodopsin transitions. Kinetic Raman spectra from 250 ns to 3 micros identify the key vibrational features of BSI. BSI exhibits relatively intense HOOP modes at 886 and 945 cm(-1) that are assigned to C(14)H and C(11)H=C(12)H A(u) wags, respectively. This result suggests that in the bathorhodopsin-to-BSI transition the highly strained all-trans chromophore has relaxed in the C(10)-C(11)=C(12)-C(13) region, but is still distorted near C(14). The low frequency of the 11,12 A(u) HOOP mode in BSI compared with that of lumirhodopsin and metarhodopsin I indicates weaker coupling between the 11H and 12H wags due to residual distortion of the BSI chromophore near C(11)=C(12). The C=NH(+) stretching mode in BSI at 1653 cm(-1) exhibits a normal deuteriation induced downshift of 23 cm(-1), implying that there is no significant structural rearrangement of the Schiff base counterion region in the transition of bathorhodopsin to BSI. However, a dramatic Schiff base environment change occurs in the BSI-to-lumirhodopsin transition, because the 1638 cm(-1) C=NH(+) stretching mode in lumirhodopsin is unusually low and shifts only 7 cm(-1) in D(2)O, suggesting that it has essentially no H-bonding acceptor. With these data we can for the first time compare and discuss the room temperature resonance Raman vibrational structure of all the key intermediates in visual excitation.     

Affinity chromatography with monolithic capillary columns. II. Polymethacrylate monoliths with immobilized lectins for the separation of glycoconjugates by nano-liquid affinity chromatography

Monolithic capillary columns with surface bound lectin affinity ligands were introduced for performing lectin affinity chromatography (LAC) by nano-liquid chromatography (nano-LC). Two kinds of polymethacrylate monoliths were prepared, namely poly(glycidyl methacrylateco-ethylene dimethacrylate) and poly(glycidyl methacrylate-co-ethylene dimethacrylate-co-[2-(methacryloyloxy)ethyl]trimethyl ammonium chloride) to yield neutral and cationic macroporous polymer, respectively. Two lectins including concanavalin (Con A) and wheat germ agglutinin (WGA) were immobilized onto the monolithic capillary columns. The neutral monoliths with immobilized lectins exhibited lower permeability under pressure driven flow than the cationic monoliths indicating that the latter had wider flow-through pores than the former. Both types of monoliths with immobilized lectins exhibited strong affinity toward particular glycoproteins and their oligosaccharide chains (i.e., glycans) having sugar sequences recognizable by the lectin. Due to the strong binding affinity, the monoliths with surface bound lectins allowed the injection of relatively large volume (i.e., several column volumes) of dilute samples of glycoproteins and glycans thus allowing the concentration of the glycoconjugates and their subsequent isolation and detection at low levels (approximately 10(-8) M). To further exploit the lectin monoliths in the isolation of glycoconjugates, two-dimensional separation schemes involving LAC in the first dimension and reversed-phase nano-LC in the second dimension were introduced. The various interrelated methods established in this investigation are expected to play a major role in advancing the sciences of "nano-glycomics".