Enhancement of Flotation Selectivity of Sphalerite Using Mineral-Stressed Paenibacillus polymyxa and Its Cellular Components

The selective flotation of sphalerite from a sphalerite-galena mineral mixture was achieved using cellular components of Paenibacillus polymyxa after adaptation to the above minerals. The soluble and insoluble fractions of the thermolysed bacterial cells adapted to sphalerite yielded higher flotation recoveries of sphalerite with selectivity indices ranging between 22 and 29. The protein profile for the unadapted and mineral-stressed cells was found to differ distinctly, attesting to variation in the yield and nature of extra-cellular polymeric substances. The changes induced in the bacterial cell wall components after adaptation to sphalerite or galena with respect to the contents of phosphate, uronic acid and acetylated sugars of P. polymyxa were quantified. In keeping with these changes, a marginal morphological transition of P. polymyxa from rods to spheres was observed. The role of the dissolved metal ions from the minerals as well as that of the constituents of extracellular secretions in modulating the surface potential of the mineral-stressed cells were demonstrated. These studies highlighted that, mineral stress led to qualitative and quantitative changes in the cellular components, which facilitated the enhancement of flotation selectivity of sphalerite.

Controlled release kinetics of p-aminosalicylic acid from biodegradable crosslinked polyesters for enhanced anti-mycobacterial activity

Unlike conventional polymeric drug delivery systems, where drugs are entrapped in polymers, this study focuses on the incorporation of the drug into the polymer backbone to achieve higher loading and sustained release. Crosslinked, biodegradable, xylitol based polyesters have been synthesized in this study. The bioactive drug moiety, p-aminosalicylic acid (PAS), was incorporated in xylitol based polyesters to impart its anti-mycobacterial activity. To understand the influence of the monomer chemistry on the incorporation of PAS and its subsequent release from the polymer, different diacids have been used. Controlled release profiles of the drug from these polyesters were studied under normal physiological conditions. The degradation of the polyesters varied from 48% to 76% and the release of PAS ranged from 54% to 65% of its initial loading in 7 days. A new model was developed to explain the release kinetics of PAS from the polymer that accounted for the polymer degradation and drug concentration. The thermal, mechanical, drug release and cytocompatibility properties of the polymers indicate their suitability in biomedical applications. The released products from these polymers were observed to be pharmacologically active against Mycobacteria. The high drug loading and sustained release also ensured enhanced efficacy. These polymers form biocompatible, biodegradable polyesters where the sustained release of PAS may be tailored for potential treatment of mycobacterial infections. Statement of significance In the present work, we report on novel polyesters with p-aminosalicylic acid (PAS) incorporated in the polymer backbone. The current work aims to achieve controlled release of PAS and ensures the delivered PAS is stable and pharmacologically active. The novelty of this work primarily involves the synthetic chemistry of polymerization and detailed analysis and efficacy of active PAS delivery. A new kinetic model has been developed to explain the PAS release profiles. These polymers are biodegradable, cytocompatible and anti-mycobacterial in nature. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Temperature-Dependent Photoluminescence of g-C3N4: Implication for Temperature Sensing

We report the temperature-dependent photoluminescence (PL) properties of polymeric graphite-like carbon nitride (g-C3N4) and a methodology for the determination of quantum efficiency along with the activation energy. The PL is shown to originate from three different pathways of transitions: sigma*-LP, pi*-LP, and pi*-pi, respectively. The overall activation energy is found to be similar to 73.58 meV which is much lower than the exciton binding energy reported theoretically but ideal for highly sensitive wide-range temperature sensing. The quantum yield derived from the PL data is 23.3%, whereas the absolute quantum yield is 5.3%. We propose that the temperature-dependent PL can be exploited for the evaluation of the temperature dependency of quantum yield as well as for temperature sensing. Our analysis further indicates that g-C3N4 is well-suited for wide-range temperature sensing.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Dual Drug Conjugate Loaded Nanoparticles for the Treatment of Cancer

Two antineoplastic agents, Imatinib (IM) and 5-Fluorouracil (FU) were conjugated by hydrolysable linkers through an amide bond and entrapped in polymeric Human Serum Albumin (HSA) nanoparticles. The presence of dual drugs in a common carrier has the advantage of reaching the site of action simultaneously and acting at different phases of the cell cycle to arrest the growth of cancer cells before they develop chemoresistance. The study has demonstrated an enhanced anticancer activity of the conjugate, and conjugate loaded stealth HSA nanoparticles (NPs) in comparison to the free drug in A-549 human lung carcinoma cell line and Zebra fish embryos (Danio rerio). Hydrolysability of the conjugate has also been demonstrated with complete hydrolysis being observed after 12 h. In vivo pharmacodynamics study in terms of tumor volume and pharmacokinetics in mice for conjugate (IM-SC-FU) and conjugate loaded nanoparticles showed significant anti-cancer activity. The other parameters evaluated were particle size (86nm), Poly Dispersive Index (PDI) (0.209), zeta potential (-49mV), drug entrapment efficiency (96.73%) and drug loading efficiency (89%). Being in stealth mode gives the potential for the NPs to evade Reticulo-Endothelial system (RES), achieve passive targeting by Enhanced Permeation Retention (EPR) effect with controlled release of the therapeutic agent. As the conjugate cleaves into individual drugs in the tumor environment, this promises better suppression of cancer chemoresistance by delivering dual drugs with different modes of action at the same site, thereby synergistically inhibiting the growth of cancerous tissue.

Three-dimensional plotted hydroxyapatite scaffolds with predefined architecture: comparison of stabilization by alginate cross-linking versus sintering

Scaffolds for bone tissue engineering are essentially characterized by porous three-dimensional structures with interconnected pores to facilitate the exchange of nutrients and removal of waste products from cells, thereby promoting cell proliferation in such engineered scaffolds. Although hydroxyapatite is widely being considered for bone tissue engineering applications due to its occurrence in the natural extracellular matrix of this tissue, limited reports are available on additive manufacturing of hydroxyapatite-based materials. In this perspective, hydroxyapatite-based three-dimensional porous scaffolds with two different binders (maltodextrin and sodium alginate) were fabricated using the extrusion method of three-dimensional plotting and the results were compared in reference to the structural properties of scaffolds processed via chemical stabilization and sintering routes, respectively. With the optimal processing conditions regarding to pH and viscosity of binder-loaded hydroxyapatite pastes, scaffolds with parallelepiped porous architecture having up to 74% porosity were fabricated. Interestingly, sintering of the as-plotted hydroxyapatite-sodium alginate (cross-linked with CaCl2 solution) scaffolds led to the formation of chlorapatite (Ca9.54P5.98O23.8Cl1.60(OH)(2.74)). Both the sintered scaffolds displayed progressive deformation and delayed fracture under compressive loading, with hydroxyapatite-alginate scaffolds exhibiting a higher compressive strength (9.5 +/- 0.5MPa) than hydroxyapatite-maltodextrin scaffolds (7.0 +/- 0.6MPa). The difference in properties is explained in terms of the phase assemblage and microstructure.

Corona Degradation of the Polymer Insulator Samples under Different Fog Conditions

Corona discharges resulting from the metal parts of insulators and the line hardware affect the long term performance of the polymeric insulators used for outdoor application and can lead to its eventual failure. The authors previous work, involved in developing a new methodology to evaluate the performance of polymeric shed materials subjected to corona stresses in the presence of natural fog condition, results revealed more surface hydroxylation thereby resulting in more loss of hydropobhicity. With the increase in industrialization, there is an increase in acidic component of the rain as well as the fog (moisture). The present work, reports the effect of acid fog on the corona performance of the polymeric insulators for both AC and DC excitation, interesting results are obtained. A comparison of the experimental investigations revealed that the acidic fog has more effect than that of the normal fog. This fact has been confirmed by physico-chemical analysis like the scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS) and contact angle measurement. The effect of DC corona is found to be lesser in comparison with the AC; however the hydroxylation induced by the DC corona under the presence of fog is similar with that of AC excitation.

Laboratory-scale fluidized bed rig for high-temperature tube wastage studies

As part of a study of the wear of candidate heat exchanger tube materials for use in fluidized bed combustors, two similar laboratory-scale rigs have been built and characterized. Specimens of selected alloys are carried on counter-rotating rotors immersed in a fluidized bed, and are exposed to particle impact velocities of up to approximately 3 ms-1 at temperatures up to 1000°C. The performance of this design of apparatus has been investigated in detail. The effects of several experimental variables have been studied, including angle of particle impact, specimen speed, position of the rotor within the fluidized bed, duration of exposure, bed material particle size, degradation of the bed material, degree of fluidization of the bed, and size of specimen. In many cases the results obtained with steel specimens at elevated temperatures are similar to those observed with polymeric specimens at low temperatures.

Deposition of carbon nitride films using an electron cyclotron wave resonance plasma source

Hydrogenated amorphous carbon nitride (a-C:N:H) has been synthesized using a high plasma density electron cyclotron wave resonance (ECWR) technique using N2 and C2H2 as source gases, at different ratios and a fixed ion energy (80 eV). The composition, structure and bonding state of the films were investigated and related to their optical and electrical properties. The nitrogen content in the film rises rapidly until the N2/C2H2 gas ratio reaches 2 and then increases more gradually, while the deposition rate decreases steeply, placing an upper limit for the nitrogen incorporation at 30 at%. For nitrogen contents above 20 at%, the band gap and sp3-bonded carbon fraction decrease from 1.7 to 1.1 eV and approximately 65 to 40%, respectively. Films with higher nitrogen content are less dense than the original hydrogenated tetrahedral amorphous carbon (ta-C:H) film but, because they have a relatively high band gap (1.1 eV), high resistivity (109 Ω cm) and moderate sp3-bonded carbon fraction (40%), they should be classed as polymeric in nature.

Nitrogen incorporation into tetrahedral hydrogenated amorphous carbon

Structural changes induced by the incorporation of nitrogen into ta-C : H films have been studied by Electron Energy Loss Spectroscopy, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy. ta-C:H films have been synthesised using a low pressure Electron Cyclotron Wave Resonance (ECWR) source which provides a plasma beam with a high degree of ionisation and dissociation. Nitrogen was incorporated by adding N2 to the C2H2 plasma used for the deposition of ta-C : H films. The N/C atomic ratio in the films rises rapidly until the N2/C2H2 gas ratio reaches three, and then increases more gradually, while the deposition rate decreases steeply. Chemical sputtering of the forming films and the formation of molecular nitrogen within the films limit the maximum nitrogen content to about N/C = 0.6. For low nitrogen content the films retain their diamond-like properties, however as N/C atomic ratio increases, a polymeric-like material is formed, with >C=N- structures and terminating C=N and NH groups that decrease the connectivity of the network.

Perturbation of the stability of amyloid fibrils through alteration of electrostatic interactions.

The self-assembly of proteins and peptides into polymeric amyloid fibrils is a process that has important implications ranging from the understanding of protein misfolding disorders to the discovery of novel nanobiomaterials. In this study, we probe the stability of fibrils prepared at pH 2.0 and composed of the protein insulin by manipulating electrostatic interactions within the fibril architecture. We demonstrate that strong electrostatic repulsion is sufficient to disrupt the hydrogen-bonded, cross-β network that links insulin molecules and ultimately results in fibril dissociation. The extent of this dissociation correlates well with predictions for colloidal models considering the net global charge of the polypeptide chain, although the kinetics of the process is regulated by the charge state of a single amino acid. We found the fibrils to be maximally stable under their formation conditions. Partial disruption of the cross-β network under conditions where the fibrils remain intact leads to a reduction in their stability. Together, these results support the contention that a major determinant of amyloid stability stems from the interactions in the structured core, and show how the control of electrostatic interactions can be used to characterize the factors that modulate fibril stability.

Microstructure, deformation and failure of polymer bonded explosives

Polymer bonded explosives (PBXs) are highly particle filled composite materials comprised of explosive crystals and a polymeric binder (ca. 5-10% by weight). The microstructure and mechanical properties of two pressed PBXs with different binder systems were studied in this paper. The initial microstructure of the pressed PBXs and its evolution under different mechanical aggressions were studied, including quasi-static tension and compression, ultrasonic wave stressing and long-pulse low-velocity impact. Real-time microscopic observation of the PBXs under tension was conducted by using a scanning electron microscope equipped with a loading stage. The mechanical properties under tensile creep, quasi-static tension and compression were studied. The Brazilian test, or diametrical compression, was used to study the tensile properties. The influences of pressing pressures and temperatures, and strain rates on the mechanical properties of PBXs were analyzed. The mesoscale damage modes in initial pressed samples and the samples insulted by different mechanical aggressions, and the corresponding failure mechanisms of the PBXs under different loading conditions were analyzed.

Advances in Click Chemistry for Single-Chain Nanoparticle Construction

Single-chain polymeric nanoparticles are artificial folded soft nano-objects of ultra-small size which have recently gained prominence in nanoscience and nanotechnology due to their exceptional and sometimes unique properties. This review focuses on the current state of the investigations of click chemistry techniques for highly-efficient single-chain nanoparticle construction. Additionally, recent progress achieved for the use of well-defined single-chain nanoparticles in some promising fields, such as nanomedicine and catalysis, is highlighted.

Metal-Free Polymethyl Methacrylate (PMMA) Nanoparticles by Enamine "Click" Chemistry at Room Temperature

"Click" chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the "metal-free" cross-linking of PMMA-precursor chains prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization containing beta-ketoester functional groups. Intramolecular collapse was performed by the one-pot reaction of beta-ketoester moieties with alkyl diamines in tetrahydrofurane at r.t. (i.e., by enamine formation). The collapsing process was followed by size exclusion chromatography and by nuclear magnetic resonance spectroscopy. The size of the resulting PMMA-NPs was determined by dynamic light scattering. Enamine "click" chemistry increases the synthetic toolbox for the efficient synthesis of metal-free, ultra-small polymeric NPs.