Bacteriostatic Behavior of PLA-BaTiO3 Composite Fibers Synthesized by Centrifugal Spinning and Subjected to Aging Test.

The present work investigated the effect of Polylactic acid (PLA) fibers produced by centrifugal spinning with incorporated BaTiO3 particles to improve their bacteriostatic behavior. The PLA matrix and three composites, presenting three different amounts of fillers, were subjected to UV/O3 treatment monitoring the possible modifications that occurred over time. The morphological and physical properties of the surfaces were characterized by different microscopic techniques, contact angle, and surface potential measurements. Subsequently, the samples were tested in vitro with human dermal fibroblasts (HDF) to verify the cytotoxicity of the substrates. No significant differences between the PLA matrix and composites emerged; the high hydrophobicity of the fibers, derived by the polymer structure, represented an obstacle limiting the fibroblast attachment. Samples underwent bacterial exposure (Staphylococcus epidermidis) for 12 and 24 h. Increasing the concentration of BT, the number of living bacteria and their distribution decreased in comparison with the PLA matrix suggesting an effect of the inorganic filler, which generates a neutralization effect leading to reactive oxygen species (ROS) generation and subsequently to bacterial damages. These results suggest that the barium titanate (BT) fillers clearly improve the antibacterial properties of PLA fibers after aging tests made before bacterial exposure, representing a potential candidate in the creation of composites for medical applications.

Microbially Mediated Release of As from Mekong Delta Peat Sediments.

Peat layers within alluvial sediments are considered effective arsenic (As) sinks under reducing conditions due to the binding of As(III) to thiol groups in natural organic matter (NOM) and the formation of As-bearing sulfide phases. However, their possible role as sources of As for anoxic groundwaters remains unexplored. Here, we perform laboratory experiments to provide evidence for the role of a sediment peat layer in releasing As. Our results show that the peat layer, deposited about 8,000 years ago in a paleomangrove environment in the nascent Mekong Delta, could be a source of As to porewater under reducing conditions. X-ray absorption spectroscopy (XAS) analysis of the peat confirmed that As was bound to NOM thiol groups and incorporated into pyrite. Nitrate was detected in peat layer porewater, and flow-through and batch experiments evidenced the release of As from NOM and pyrite in the presence of nitrate. Based on poisoning experiments, we propose that the microbially mediated oxidation of arsenic-rich pyrite and organic matter coupled to nitrate reduction releases arsenic from this peat. Although peat layers have been proposed as As sinks in earlier studies, we show here their potential to release depositional- and/or diagenetically-accumulated As.

Arsenic Speciation in Mekong Delta Sediments Depends on Their Depositional Environment.

Arsenic contamination in groundwater is pervasive throughout deltaic regions of Southeast Asia and threatens the health of millions. The speciation of As in sediments overlying contaminated aquifers is poorly constrained. Here, we investigate the chemical and mineralogical compositions of sediment cores collected from the Mekong Delta in Vietnam, elucidate the speciation of iron and arsenic, and relate them to the sediment depositional environment. Gradual dissolution of ferric (oxyhydr)oxides with depth is observed down to 7 m, corresponding to the establishment of reducing conditions. Within the reduced sediment, layers originating from marine, coastal or alluvial depositional environments are identified and their age is consistent with a late Holocene transgression in the Mekong Delta. In the organic matter- and sulfur-rich layers, arsenic is present in association with organic matter through thiol-bonding and in the form of arsenian pyrite. The highest arsenic concentration (34-69 ppm) is found in the peat layer at 16 m and suggests the accumulation of arsenic due to the formation of thiol-bound trivalent arsenic (40-55%) and arsenian pyrite (15-30%) in a paleo-mangrove depositional environment (∼8079 yr BP). Where sulfur is limited, siderite is identified, and oxygen- and thiol-bound trivalent arsenic are the predominant forms. It is also worth noting that pentavalent arsenic coordinated to oxygen is ubiquitous in the sediment profile, even in reduced sediment layers. But the identity of the oxygen-bound arsenic species remains unknown. This work shows direct evidence of thiol-bound trivalent arsenic in the Mekong Delta sediments and provides insight to refine the current model of the origin, deposition, and release of arsenic in the alluvial aquifers of the Mekong Delta.

Arsenic Methylation Dynamics in a Rice Paddy Soil Anaerobic Enrichment Culture.

Methylated arsenic (As) species represent a significant fraction of the As accumulating in rice grains, and there are geographic patterns in the abundance of methylated arsenic in rice that are not understood. The microorganisms driving As biomethylation in paddy environments, and thus the soil conditions conducive to the accumulation of methylated arsenic, are unknown. We tested the hypothesis that sulfate-reducing bacteria (SRB) are key drivers of arsenic methylation in metabolically versatile mixed anaerobic enrichments from a Mekong Delta paddy soil. We used molybdate and monofluorophosphate as inhibitors of sulfate reduction to evaluate the contribution of SRB to arsenic biomethylation, and developed degenerate primers for the amplification of arsM genes to identify methylating organisms. Enrichment cultures converted 63% of arsenite into methylated products, with dimethylarsinic acid as the major product. While molybdate inhibited As biomethylation, this effect was unrelated to its inhibition of sulfate reduction and instead inhibited the methylation pathway. Based on arsM sequences and the physiological response of cultures to media conditions, we propose that amino acid fermenting organisms are potential drivers of As methylation in the enrichments. The lack of a demethylating capacity may have contributed to the robust methylation efficiencies in this mixed culture.

Allosteric control in a metalloprotein dramatically alters function.

Metalloproteins (MPs) comprise one-third of all known protein structures. This diverse set of proteins contain a plethora of unique inorganic moieties capable of performing chemistry that would otherwise be impossible using only the amino acids found in nature. Most of the well-studied MPs are generally viewed as being very rigid in structure, and it is widely thought that the properties of the metal centers are primarily determined by the small fraction of amino acids that make up the local environment. Here we examine both theoretically and experimentally whether distal regions can influence the metal center in the diabetes drug target mitoNEET. We demonstrate that a loop (L2) 20 Å away from the metal center exerts allosteric control over the cluster binding domain and regulates multiple properties of the metal center. Mutagenesis of L2 results in significant shifts in the redox potential of the [2Fe-2S] cluster and orders of magnitude effects on the rate of [2Fe-2S] cluster transfer to an apo-acceptor protein. These surprising effects occur in the absence of any structural changes. An examination of the native basin dynamics of the protein using all-atom simulations shows that twisting in L2 controls scissoring in the cluster binding domain and results in perturbations to one of the cluster-coordinating histidines. These allosteric effects are in agreement with previous folding simulations that predicted L2 could communicate with residues surrounding the metal center. Our findings suggest that long-range dynamical changes in the protein backbone can have a significant effect on the functional properties of MPs.

Assessing sigmoidal function on memristive maps.

Memristors offer a crucial element for constructing discrete maps that have garnered significant attention in complex dynamics and various potential applications. In this study, we have integrated memristive and sigmoidal function to propose innovative mapping techniques. Our research confirms that the amalgamation of memristor and sigmoidal functions represents a promising approach for creating both 2D and 3D maps. Particularly noteworthy are the chaotic maps featuring multiple sigmoidal functions and multiple memristors, as highlighted in our findings. Specifically focusing on the novel STMM1 map, we delve into its dynamics and assess its feasibility. Intriguingly, the introduction of sigmoidal functions leads to alterations in the quantity of fixed points and the symmetry of the map.

Groundwater in Southern Vietnam: Understanding geochemical processes to better preserve the critical water resource.

A thorough understanding of groundwater geochemical characteristics and dominant hydro(bio)geochemical processes in the aquifers is valuable for sustainable groundwater protection. With this respect, this study provides a comprehensive assessment of hydrogeochemical characteristics of groundwater in sedimentary aquifers of the Southern region of Vietnam. The dataset comprised 291 water samples collected in rainy and dry seasons from 155 wells, and their chemical compositions of dissolved ions (Ca2+, Mg2+, Na+, K+, HCO3-, Cl-, SO42-, NO3-, NH4+, Fe, total dissolved solids) and pH. We calculated the groundwater quality index to determine the suitability of groundwater for drinking purposes. Accordingly, about 47% of groundwater samples range from poor to unsuitable quality for drinking purposes, in which total dissolved solid (TDS) and high iron concentrations are primary factors. We also examined hydrogeochemical characteristics by multivariate statistical analyses (Hierarchical Cluster Analysis and Principal Component Analysis). The results demonstrated four groups of water: fresh groundwater (TDS < 1 g/L) in the highland (Group 1), lowland fresh-to-saline groundwater (2a), lowland saline groundwater (2b), and lowland saline/acidic groundwater (2c). Although the highland area is currently not impacted by salinization, the contamination by nitrate and chloride associated with a dense urban population and agricultural practices is deteriorating its fresh groundwater resources. On the other hand, the lowland area of Southern Vietnam is highly vulnerable to seawater intrusion (groups 2b and 2c). Only 34% out of 191 samples collected in the lowland area of southern Vietnam remained fresh. In this light, this study depicted the specific geographical location for various groundwater groups in Southern Vietnam. This finding is significant to assist water scientists and decision-makers in implementing targetted groundwater management measures as prevention and protection strategies should be tailored to groundwater geochemical characteristics and the dominant hydro(bio)geochemical processes.

Intensified salinity intrusion in coastal aquifers due to groundwater overextraction: a case study in the Mekong Delta, Vietnam.

Groundwater salinization is one of the most severe environmental problems in coastal aquifers worldwide, causing exceeding salinity in groundwater supply systems for many purposes. High salinity concentration in groundwater can be detected several kilometers inland and may result in an increased risk for coastal water supply systems and human health problems. This study investigates the impacts of groundwater pumping practices and regional groundwater flow dynamics on groundwater flow and salinity intrusion in the coastal aquifers of the Vietnamese Mekong Delta using the SEAWAT model-a variable-density groundwater flow and solute transport model. The model was constructed in three dimensions (3D) and accounted for multi-aquifers, variation of groundwater levels in neighboring areas, pumping, and paleo-salinity. Model calibration was carried for 13 years (2000 to 2012), and validation was conducted for 4 years (2013 to 2016). The best-calibrated model was used to develop prediction models for the next 14 years (2017 to 2030). Six future scenarios were introduced based on pumping rates and regional groundwater levels. Modeling results revealed that groundwater pumping activities and variation of regional groundwater flow systems strongly influence groundwater level depletion and saline movement from upper layers to lower layers. High salinity (>2.0 g/L) was expected to expand downward up to 150 m in depth and 2000 m toward surrounding areas in the next 14 years under increasing groundwater pumping capacity. A slight recovery in water level was also observed with decreasing groundwater exploitation. The reduction in the pumping rate from both local and regional scales will be necessary to recover groundwater levels and protect fresh aquifers from expanding paleo-saline in groundwater.

Chitosan-Functionalized Recycled Polyethylene Terephthalate Nanofibrous Membrane for Sustainable On-Demand Oil-Water Separation.

The preservation of marine ecosystems is one of the most severe challenges at present. In particular, oil-water separation from oil spills and oily wastewater is important. For this reason, a low-cost, effective, and sustainable polymeric solution is in high demand. In this work, a controlled-wettability membrane for selective separation of oil-water mixtures and emulsions is developed. The nanofibrous membrane is prepared via a facile and cost-effective electrospinning technique using environmentally sustainable materials, such as recycled polyethylene terephthalate and chitosan. The effect of different concentrations of chitosan on the morphology, chemical composition, mechanical properties, wettability, and separation performance of the membrane is evaluated. The membranes exhibited underoil superhydrophobic and underwater superoleophobic behavior, which is essential to perform the selective separation. In fact, the designed filter has competitive antifouling properties (oil intrusion pressure > 45 kPa) and showed high heavy- and light-oil/water separation efficiencies (>95%) both for emulsions and immiscible mixtures.

Associations between inorganic arsenic in rice and groundwater arsenic in the Mekong Delta.

There is growing concern regarding human dietary exposure to arsenic (As) via consumption of rice. The concentration and speciation of As in rice are highly variable, and models describing rice As speciation as a function of environmental covariates remain elusive. We conducted a survey of paddy rice and soil in the Mekong Delta with the objective of linking patterns in rice As content to soil chemical variables or hydrogeological parameters. The sum of As species (ΣAs) in husked rice averaged 243 µg/kg and the average inorganic As (iAs) content was 84%. There was no relationship found between rice As concentration or speciation and As levels in soil. However, mean As concentrations in groundwater near rice sampling locations were strongly correlated with grain ΣAs and iAs over a large part of the study region, despite the fact that groundwater is not commonly used for rice paddy irrigation in this region. We hypothesize that surficial sediments with high concentrations of soluble and plant-available As also serve as sources of arsenic to downgradient shallow aquifers, explaining the observed associations between rice and groundwater As. This study suggests that shallow groundwater As concentrations may serve as a useful indicator for locations at risk of elevated iAs concentrations in rice.

Regional heterogeneity and diversity in cytokine and chemokine production by astroglia: differential responses to HIV-1 Tat, gp120, and morphine revealed by multiplex analysis.

HIV-infected individuals who abuse opiates show a faster progression to AIDS and higher incidence of encephalitis. The HIV-1 proteins Tat and gp120 have been shown to cause neurodegenerative changes either in vitro or when injected or expressed in the CNS, and we have shown that opiate drugs can exacerbate neurotoxic effects in the striatum through direct actions on pharmacologically discrete subpopulations of mu-opioid receptor-expressing astroglia. Opiate coexposure also significantly enhances release of specific inflammatory mediators by astroglia from the striatum, and we theorize that astroglial reactivity may underlie aspects of HIV neuropathology. To determine whether astroglia from different regions of the central nervous system have distinct, intrinsic responses to HIV-1 proteins and opiates, we used multiplex suspension array analyses to define and compare the inflammatory signature of cytokines released by murine astrocytes grown from cerebral cortex, cerebellum, and spinal cord. Results demonstrate significant regional differences in baseline secretion patterns, and in responses to viral proteins. Of importance for the disease process, astrocytes from all regions have very limited inflammatory response to gp120 protein, as compared to Tat protein, either in the presence or absence of morphine. Overall, the chemokine/cytokine release is higher from spinal cord and cortical astroglia than from cerebellar astroglia, paralleling the relatively low incidence of HIV-related neuropathology in the cerebellum.

beta-Chemokine production by neural and glial progenitor cells is enhanced by HIV-1 Tat: effects on microglial migration.

Human immunodeficiency virus (HIV)-1 neuropathology results from collective effects of viral proteins and inflammatory mediators on several cell types. Significant damage is mediated indirectly through inflammatory conditions promulgated by glial cells, including microglia that are productively infected by HIV-1, and astroglia. Neural and glial progenitors exist in both developing and adult brains. To determine whether progenitors are targets of HIV-1, a multi-plex assay was performed to assess chemokine/cytokine expression after treatment with viral proteins transactivator of transcription (Tat) or glycoprotein 120 (gp120). In the initial screen, ten analytes were basally released by murine striatal progenitors. The beta-chemokines CCL5/regulated upon activation, normal T cell expressed and secreted, CCL3/macrophage inflammatory protein-1alpha, and CCL4/macrophage inflammatory protein-1beta were increased by 12-h exposure to HIV-1 Tat. Secreted factors from Tat-treated progenitors were chemoattractive towards microglia, an effect blocked by 2D7 anti-CCR5 antibody pre-treatment. Tat and opiates have interactive effects on astroglial chemokine secretion, but this interaction did not occur in progenitors. gp120 did not affect chemokine/cytokine release, although both CCR5 and CXCR4, which serve as gp120 co-receptors, were detected in progenitors. We postulate that chemokine production by progenitors may be a normal, adaptive process that encourages immune inspection of newly generated cells. Pathogens such as HIV might usurp this function to create a maladaptive state, especially during development or regeneration, when progenitors are numerous.

Leuco-Based Composite Resin Dosimeter Film.

A polystyrene (PS)-based composite resin dosimeter (CRD) film comprising 2-(phenylamino)-6-(dipentylamino)-3-methylspiro[9H-xanthene-9,3'-phthalide] (Black305) fluoran leuco dye, cerium-doped yttrium aluminum perovskite YAlO3:Ce (YAP:Ce) scintillator, and 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine (MBTT) photoacid generator was developed for the visualization of X-ray exposure doses in the range of 18-170 Gy. The color of the CRD film changed from yellow to black within this range based on the X-ray exposure dose. A CRD film based on Black305/YAP:Ce/MBTT/PS could be used to produce a dosimeter with various color change sensitivities by controlling the thermodynamic parameters of the constituent materials. A CRD film is a promising tool for measuring the X-ray exposure dose and can be used as an alternative to the existing radiochromic dosimeters.

Facile and Scalable Fabrication of Porous Polystyrene Fibers for Oil Removal by Centrifugal Spinning.

The demand for an efficient oil sorbent with high sorption capacity, low cost, scalable fabrication, and high selectivity for the cleanup of spreading oil on water is increasingly urgent due to the frequent occurrence of oil spill accidents in seawater all over the world. In this study, porous polystyrene (PS) fibers with high hydrophobicity and superoleophilicity were directly fabricated by a centrifugal spinning method (CS). The effect of solvents, tetrahydrofuran (THF), and dimethylformamide (DMF) on the morphology and porous structure of the polystyrene fibers was evaluated by using scanning electron microscopy and nitrogen adsorption-desorption experiments. The formation mechanism for the porous structure on the fibers was also evaluated. The oil sorption capacities of the PS fibers for silicon oil, pump oil, and vegetable oil were investigated. The highest oil sorption capacity was found in PS fibers fabricated from PS solution with a THF/DMF weight ratio of 1/3, which exhibited the highest specific surface area, pore volume, and porosity. The high productivity and highly porous structure of PS fibers indicate that CS is a promising method to fabricate porous fibers for the cleanup of oil spills.

Centrifugally Spun Recycled PET: Processing and Characterization.

Centrifugal spinning, which is a high-productivity fiber fabrication technique, was used to produce a value-added product from recycled poly(ethylene terephthalate) (rPET). In the present study, rPET fibers, with fiber diameters ranging from submicron to micrometer in scale, were fabricated by spinning a solution of rPET in a mixture of dichloromethane and trifluoroacetic acid. The influence of the polymer solution concentration (the viscosity), the rotational speed of the spinneret, and the inner diameter of the needles on the formation and morphology and mechanical properties of the fibers were examined through scanning electron microscopy and using a tensile testing machine. The thermal behaviors of fibrous mats with various average diameters were also investigated through differential scanning calorimetry. The smoothest and smallest fibers, with an average diameter of 619 nm, were generated using an rPET solution of 10 wt % under a rotation speed of 15,000 rpm using needles having an inner diameter of 160 µm. The fibrous mats have an average tensile strength and modulus of 4.3 MPa and 34.4 MPa, respectively. The productivity and the mechanical properties indicate that centrifugal spinning is an effective technique to fabricate high-value product from rPET.