Characterization of pyomelanin secreted by Shewanella sp. and their application in metal recovery.

Melanin is a biopolymer with versatile structural and functional properties and diverse applications in recovering toxic chemicals from water and wastewater, biomedical imaging, and as theragnostic agent. We report the structural characterization and biosynthetic pathway of an extracellular pyomelanin secreted by a sponge-associated bacterium, Shewanella sp. (Shewanella-melanin), and their potential application in metal recovery from liquid. Pyomelanin particles of > 50 µm size were found in the culture medium within 48 h of growth, which were formed through the self-polymerization of benzoquinone molecule produced through homogentisic acid pathway. The aspC and hppD genes involved in the biosynthetic pathway of pyomelanin were detected in the whole genome sequence of Shewanella sp. The FT-IR spectra of Shewanella-melanin, at ~ 3300-3420 cm-1 corresponding to the stretching vibration of -NH and -OH, was in good agreement with that of Sepia melanin, while its elemental composition (C/N/H/S of 29.2:8.23:6.41:1.58) was unique. Shewanella-melanin showed ~ 300 and ~ 950 times increased chelation of manganese and iron from a liquid medium supplemented with 2 mM of MnSO4 and FeSO4, respectively, compared to a control. The FT-IR spectrum showed the binding of metal ions to the carboxylic acid, hydroxyl, and amine groups of Shewanella-melanin. The Shewanella-melanin, with its excellent metal biosorption, could be a potential candidate for removing toxic compounds from water, in turn contributing to the fulfillment of sustainable development goal (SDG) 6.

Stimuli-Responsive Electrospun Piezoelectric Mats of Ethylene-co-vinyl Acetate-Millable Polyurethane-Nanohydroxyapatite Composites.

Piezoelectric materials have gained interest among materials scientists as body motion sensors and energy harvesters on account of their fast responsiveness and substantial output signals. In this work, piezoelectric polymer mats have been fabricated from ethylene-co-vinyl acetate-millable polyurethane/nanohydroxyapatite (EVA-MPU/nHA) composite systems by employing the electrospinning technique. The ferro-piezoelectric features of the samples were confirmed from the butterfly loops of electrostatic force microscopy (EFM) amplitude signals as well as through the hysteresis curves of the EFM phase recorded with the assistance of dynamic-contact EFM. Piezoelectric responses of the samples to random finger tapping were evaluated after fabricating a simple device prototype connected to an oscilloscope. The efficacy of the mats to generate a voltage in response to activities such as mechanical bending, movement of throat muscles while drinking, movement of elbow joints, air blowing, and so forth has also been investigated. The results suggest the promising possibility of fabricating user-friendly piezoelectric mats out of the EVA-MPU/nHA system for physiological motion-sensing applications.

Electrospun Poly(vinylidene fluoride-trifluoroethylene)-Based Polymer Nanocomposite Fibers for Piezoelectric Nanogenerators.

The present work deals with the preparation, characterization, and application of self-poled nanofibers using piezoelectric polymer poly(vinylidene fluoride-trifluoroethylene), zinc oxide, and exfoliated graphene oxide by electrospinning process. The characterization of nanofiber is carried by different techniques such as field emission scanning electron microscopy, Fourier transform Infrared spectroscopy, X-ray diffraction techniques, and dynamic contact mode electrostatic force microscopy. The nanofiber based piezoelectric nanoenergy generator devices are fabricated for analyzing the energy generating efficiency. Piezoelectric hybrid nanofibers are exhibiting better energy generating efficiency and identified as potential material for energy harvesting applications.

Extinction of Antimicrobial Resistant Pathogens Using Silver Embedded Silica Nanoparticles and an Efflux Pump Blocker.

Control measures against antimicrobial resistant bacterial pathogens are important challenges in our daily life. In this study, we discuss the sensitivity and resistance of four bacterial pathogens, Vibrio alginolyticus, Escherichia coli, Staphylococcus aureus, and Bacillus subtilis, to silver-silica hybrid nanoparticles. Successively, by combining with an efflux pump blocking agent Verapamil, we find that these hybrid nanoparticles induce complete mortality to even the most resistive S. aureus. The above pathogens are selected from a pool of 100 bacterial strains resistant to silver nitrate. While S. aureus shows increased resistance to the nanoparticles, the cell wall integrity and genetic stability of V. alginolyticus and E. coli are compromised in the presence of the hybrid nanoparticles. These studies suggest that the antimicrobial properties of the nanoparticles against Gram-negative pathogens originate from increased oxidative stress, which is confirmed by the blocking of reactive oxygen species (ROS) using scavengers such as ascorbic acid and observing DNA damage. The antimicrobial property of the nanoparticle when combined with its nontoxic nature to mammalian cells makes it a promising agent for controlling drug-resistant Gram-negative pathogens.

Water-Chloroform Interface Assisted Microstructure Tuning of Polypyrrole-Silver Sheets.

The liquid-liquid interface of two immiscible solvents remarkably controls the morphology of polymeric nanostructures as compared to the polymerization in single solvent systems. The polymerization of pyrrole in the water-chloroform medium using silver nitrate (AgNO3) as oxidant yields polypyrrole/silver (PPy/Ag) sheets. The water-chloroform interface acts as a template for the growth of PPy/Ag hybrids into sheets by preventing the secondary growth of silver associated pyrrole oligomers in a three-dimensional (3-D) manner. On the contrary, the 3-D growth of pyrrole oligomers into spherical shapes at the water-chloroform interface is observed when ammonium persulfate (APS) is used as the oxidant. Transmission electron microscopic and scanning electron microscopic images reveal the sheetlike morphology of PPy/Ag with a relatively uniform distribution of Ag NPs (∼100 nm) on PPy sheets. The ratio of aqueous-organic bisolvent and the concentration/type of oxidant have a distinct effect on morphology, crystallinity, and electrical properties of PPy/Ag sheets. The dispersed PPy/Ag sheets are stable in moderately polar solvents up to 2 weeks. The electrochemical behavior of PPy/Ag sheets is confirmed by H2O2 sensing capability through cyclic voltammetry experiments. The antibacterial activity toward E. coli and S. aureus is quantitatively assessed using the minimum bactericidal concentration (MBC) determination.

Unicellular cyanobacteria Synechocystis accommodate heterotrophic bacteria with varied enzymatic and metal resistance properties.

The interactions between heterotrophic bacteria and primary producers have a profound impact on the functioning of marine ecosystem. We characterized the enzymatic and metal resistance properties of fourteen heterotrophic bacteria isolated from a unicellular cyanobacterium Synechocystis sp. that came from a heavy metal contaminated region of Cochin estuary, southwest coast of India. Based on 16S rRNA gene sequence similarities, the heterotrophic bacteria were grouped into three phyla: namely Actinobacteria, Firmicute, and Proteobacteria. Overall Proteobacteria showed a higher level of enzyme expression while Actinobacteria and Firmicutes showed higher tolerance to heavy metals. Among Proteobacteria, an isolate of Marinobacter hydrocarbonoclasticus (MMRF-584) showed highest activities of ß-glucosidase (1.58 ± 0.2 µMml(-1) min(-1) ) and laminarinase (1170.17 ± 95.4 µgml(-1) min(-1) ), while other two isolates of M. hydrocarbonoclasticus, MMRF-578 and 581, showed highest phosphatase (44.71 ± 0.2 µMml(-1) min(-1) ) and aminopeptidase (33.22 ± 0 µMml(-1) min(-1) ) activities respectively. Among Firmicutes, the Virgibacillus sp. MMRF-571 showed exceptional resistance against the toxic heavy metals Cd (180 mM), Pb (150 mM), and Hg (0.5 mM). Bacillus cereus, MMRF-575, showed resistance to the highest concentrations of Co (250 mM), Cd (150 mM), Pb (180 mM), Hg (0.5 mM), Ni (280 mM), and Zn (250 mM) tested. Our results show that heterotrophic bacteria with varied enzymatic and metal resistance properties are associated with Synechocystis sp. Further studies to delineate the role of these heterotrophic bacteria in protecting primary producers from toxic effects of heavy metals and their potential application in bioremediation will be appreciated.