Hydroxyapatite and ionic liquid coupled with hybrid membranes for toxic pollutant removal and remediation.

Access to clean water is the mandatory requirement for every living being to sustain life. So, membrane-based integrated approach of adsorption and separation technology has recently been preferred by scientists over other conventional techniques, for wastewater treatment. Current research focused on the synthesis of novel imidazolium (A1) based IL, which was further functionalized with hydroxyapatite (HAp; extracted from Labeo rohita scales), to create possible solutions towards environmental remediation. Cellulose acetate (CA) was used for the fabrication of three different ionic liquid membranes. All the synthesized products were characterized by FTIR, XRD and TGA. Two dyes of different nature, i.e., congo red (anionic) and crystal violet (cationic) were selected because of their highly toxic and carcinogenic effects, for batch adsorption experiments. Antibacterial activity of the synthesized membranes was also evaluated against S. aureus. Results of the study revealed that CA-HA1 1:2 acted as the best adsorbent towards the removal of crystal violet, exhibiting removal efficiency of 98% with the contact time of 24 h while in case of congo red adsorption, CA-HA1 (1:2) proved as prime adsorbent with the removal efficiency of 96% for the same preceding contact time. Considering the antibacterial character of the synthesized membranes, CA-A1 (1:1) emerged as very efficient antibacterial agent with the inhibition zone of 50 mm after 48 h. The overall behavior of monolayer and multilayer adsorption was witnessed for both dyes while kinetic studies favored the pseudo-second order reaction for all adsorbents.

Investigation of structural, electronic and optical properties of two-dimensional MoS2-doped-V2O5 composites for photocatalytic application: a density functional theory study.

In the present research, the structural, electronic and optical properties of transition metal dichalcogenide-doped transition metal oxides MoS2-doped-V2O5 with various doping concentrations (x = 1-3%) of MoS2 atoms are studied by using first principles calculation. The generalized gradient approximation Perdew-Burke-Ernzerhof simulation approach is used to investigate the energy bandgap (Eg) of orthorhombic structures. We examined the energy bandgap (Eg) decrement from 2.76 to 1.30 eV with various doping (x = 1-3%) of molybdenum disulfide (MoS2) atoms. The bandgap nature shows that the material is a well-known direct bandgap semiconductor. MoS2 doping (x = 1-3%) atoms in pentoxide (V2O5) creates the extra gamma active states which contribute to the formation of conduction and valance bands. MoS2-doped-V2O5 composite is a proficient photocatalyst, has a large surface area for absorption of light, decreases the electron-hole pairs recombination rate and increases the charge transport. A comprehensive study of optical conductivity reveals that strong peaks of MoS2-doped-V2O5 increase in ultraviolet spectrum region with small shifts at larger energy bands through increment doping x = 1-3% atoms of MoS2. A significant decrement was found in the reflectivity due to the decrement in the bandgap with doping. The optical properties significantly increased by the decrement of bandgap (Eg). Two-dimensional MoS2-doped-V2O5 composite has high energy absorption, optical conductivity and refractive index, and is an appropriate material for photocatalytic applications.

An eco-sustainable approach towards heavy metals remediation by mangroves from the coastal environment: A critical review.

Mangroves provide various ecosystem services, carbon sequestration, biodiversity depository, and livelihoods. They are most abundant in marine and coastal ecosystems and are threatened by toxic contaminants like heavy metals released from various anthropogenic activities. However, they have significant potential to survive in salt-driven environments and accumulate various pollutants. The adverse effects of heavy metals have been extensively studied and recognized as toxic to mangrove species. This study sheds light on the dynamics of heavy metal levels, their absorption, accumulation and transport in the soil environment in a mangrove ecosystem. The article also focuses on the potential of mangrove species to remove heavy metals from marine and coastal environments. This review concludes that mangroves are potential candidates to clean up contaminated water, soil, and sediments through their phytoremediation ability. The accumulation of toxic heavy metals by mangroves is mainly through roots with limited upward translocation. Therefore, promoting the maintenance of biodiversity and stability in the coastal environment is recommended as an environmentally friendly and potentially cost-effective approach.

Rational synthesis and characterization of highly water stable MOF@GO composite for efficient removal of mercury (Hg2+) from water.

The present study is aimed at adsorptive removal of Mercury (Hg2+) using highly functionalized nanomaterials based on Graphene Oxide Zeolitic Imidazolate Framework composite (ZIF-67@GO). Solvothermal methodology was used to synthesize ZIF-67@GO composite. Synthesized compounds were confirmed by FTIR, SEM, PXRD and EDX analysis. The as-prepared ZIF-67@GO was tested as efficient adsorbent for effective removal of Mercury (Hg2+) from aquatic environment. The atomic adsorption spectrophotometer was used to monitor the process of adsorption of Hg+2 on ZIF-67@GO. From the adsorption data, the maximum removal efficiency achieved was 91.1% using 10 mg amount of composite for 50 mL using 20 ppm Mercury (Hg2+) solution. Different parameters like pH, contact time, concentration, adsorption kinetics and isotherm were also examined to explore adsorption process. Adsorption data fitted well for Freundlich Model having R2 value of 0.9925 than Langmuir Isotherm with R2 value of 0.9238. Kinetics were rapid and excellently described via 2nd order model with R2 = 0.99946 than 1st order model with R2 value of 0.8836. Freundlich and pseudo 2nd order models validated that multilayer chemisorption occurs during adsorption process due to the presence of highly functionalized sites on ZIF-67@GO composite. The synthesized composite material has shown excellent reusability. Thus, water stable ZIF-67@GO composites can efficiently be used for Mercury (Hg2+) confiscation from water.

Synergetic effect of bismuth vanadate over copolymerized carbon nitride composites for highly efficient photocatalytic H2 and O2 generation.

The development of copolymerized carbon nitride (CN)-based photocatalysts may support advances in photocatalytic overall water splitting. However, the recombination of charge carriers is the main bottleneck that reduces its overall photocatalytic activity. To overcome this problem, the construction of heterojunction technology has emerged as an effective approach to reduce the charge carrier recombination, thereby improving charge separation and transport efficiency. In this work, an innovative heterojunction was prepared between Quinolinic acid (QA) modified CN (CN-QAx) and novel nanorod-shaped bismuth vanadate (BiVO4) (BiVO4/CN-QAx) for overall water splitting through a simple in-situ solvent evaporation technique. The obtained results show that the synthesized samples have efficient and improved activities for releasing H2 (862.1 µmol/h) and O2 (31.58 µmol/h) under visible light irradiation. Furthermore, an exceptional apparent quantum yield (AQY) of 64.52 % has been recorded for BiVO4/CN-QA7.0 at 420 nm, which might be due to the substantial isolation of photoinducedcharge carriers. Therefore, this work opens up a new channel toward efficient CN-based photocatalysts in the sustainable energy production processes.

Antifungal Activity of Soft Tissue Extract from the Garden Snail Helix aspersa (Gastropoda, Mollusca).

Gastropods comprise approximately 80% of molluscans, of which land snails are used variably as food and traditional medicines due to their high protein content. Moreover, different components from land snails exhibit antimicrobial activities. In this study, we evaluated the antifungal activity of soft tissue extracts from Helix aspersa against Candida albicans, Aspergillus flavus, and Aspergillus brasiliensis by identifying extract components using liquid chromatography-tandem mass spectrometry (LC-MS-MS). Two concentrations of three extracts (methanol, acetone, and acetic acid) showed antifungal activity. Both acetone (1 g/3 mL) and acetic acid extracts (1 g/mL) significantly inhibited C.albicans growth (p = 0.0001, 5.2 ± 0.2 mm and p = 0.02, 69.7 ± 0.6 mm, respectively). A. flavus and A. brasiliensis growth were inhibited by all extracts at 1 g/mL, while inhibition was observed for acetic acid extracts against A. brasiliensis (p = 0.02, 50.3 ± 3.5 mm). The highest growth inhibition was observed for A. flavus using acetic acid and acetone extracts (inhibition zones = 38 ± 1.7 mm and 3.1 ± 0.7 mm, respectively). LC-MS-MS studies on methanol and acetone extracts identified 11-α-acetoxyprogesterone with a parent mass of 372.50800 m/z and 287.43500 m/z for luteolin. Methanol extracts contained hesperidin with a parent mass of 611.25400 m/z, whereas linoleic acid and genistein (parent mass = 280.4 and 271.48900 m/z, respectively) were the main metabolites.

Manganese Ferrite-Hydroxyapatite Nanocomposite Synthesis: Biogenic Waste Remodeling for Water Decontamination.

Environmental pollution, especially water pollution caused by dyes, heavy metal ions and biological pathogens, is a root cause of various lethal diseases in human-beings and animals. Water purification materials and treatment methods are overpriced. Consequently, there is an imperative outlook observance for cheap materials for the purification of wastewaters. In order to fill up the projected demand for clean water, the present study aimed to make use of cost-effective and environmentally friendly methods to convert bone-waste from animals such as cows into novel composites for the decontamination of water. The bone-waste of slaughtered cows from the Najran region of Saudi Arabia was collected and used for the synthesis of hydroxyapatite based on the thermal method. The synthesized hydroxyapatite (Ca10(PO4)6(OH)2) was utilized to prepare a manganese ferrite/hydroxyapatite composite. The nanocomposite was categorized by diverse sophisticated procedures, for instance XRD, FE-SEM, EDX, TEM, UV, PL and FT-IR. This composite possesses outstanding photocatalytic activity against methylene blue dye, which is a common pollutant from industrial wastes. Moreover, the synthesised composite revealed exceptional bacteriostatic commotion towards E. coli and S. aureus bacteria, which are accountable for acute waterborne infections. The outcome of this study demonstrated that the integration of manganese ferrite into hydroxyapatite significantly intensified both antimicrobial and photocatalytic actions when compared to the virgin hydroxyapatite.

Electrocatalytic hydrogen generation using tripod containing pyrazolylborate-based copper(ii), nickel(ii), and iron(iii) complexes loaded on a glassy carbon electrode.

Three transition metal complexes (MC) namely, [TpMeMeCuCl(H2O)] (CuC), [TpMeMeNiCl] (NiC), and [TpMeMeFeCl2(H2O)] (FeC) {TpMeMe = tris(3,5-dimethylpyrazolyl)borate} were synthesized and structurally characterized. The three complexes CuC, NiC, and FeC-modified glassy carbon (GC) were examined as molecular electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution (0.1 M KOH). Various GC-MC electrodes were prepared by loading different amounts (ca. 0.2-0.8 mg cm-2) of each metal complex on GC electrodes. These electrodes were used as cathodes in aqueous alkaline solutions (0.1 M KOH) to efficiently generate H2 employing various electrochemical techniques. The three metal complexes' HER catalytic activity was assessed using cathodic polarization studies. The charge-transfer kinetics of the HER at the (GC-MC)/OH- interface at a given overpotential were also studied using the electrochemical impedance spectroscopy (EIS) technique. The electrocatalyst's stability and long-term durability tests were performed employing cyclic voltammetry (repetitive cycling up to 5000 cycles) and 48 h of chronoamperometry measurements. The catalytic evolution of hydrogen on the three studied MC surfaces was further assessed using density functional theory (DFT) simulations. The GC-CuC catalysts revealed the highest HER electrocatalytic activity, which increased with the catalyst loading density. With a low HER onset potential (E HER) of -25 mV vs. RHE and a high exchange current density of 0.7 mA cm-2, the best performing electrocatalyst, GC-CuC (0.8 mg cm-2), showed significant HER catalytic performance. Furthermore, the best performing electrocatalyst required an overpotential value of 120 mV to generate a current density of 10 mA cm-2 and featured a Tafel slope value of -112 mV dec-1. These HER electrochemical kinetic parameters were comparable to those measured here for the commercial Pt/C under the same operating conditions (-10 mV vs. RHE, 0.88 mA cm-2, 108 mV dec-1, and 110 mV to yield a current density of 10 mA cm-2), as well as the most active molecular electrocatalysts for H2 generation from aqueous alkaline electrolytes. Density functional theory (DFT) simulations were used to investigate the nature of metal complex activities in relation to hydrogen adsorption. The molecular electrostatic surface potential (MESP) of the metal complexes was determined to assess the putative binding sites of the H atoms to the metal complex.

Correction: Electrocatalytic hydrogen generation using tripod containing pyrazolylborate-based copper(ii), nickel(ii), and iron(iii) complexes loaded on a glassy carbon electrode.

[This corrects the article DOI: 10.1039/D1RA08530A.].

Ligustrum lucidum Leaf Extract-Assisted Green Synthesis of Silver Nanoparticles and Nano-Adsorbents Having Potential in Ultrasound-Assisted Adsorptive Removal of Methylene Blue Dye from Wastewater and Antimicrobial Activity.

Present study was conducted to investigate the adsorption and ultrasound-assisted adsorption potential of silver nanoparticles (AgNPs) and silver nanoparticles loaded on chitosan (AgCS composite) as nano-adsorbents for methylene blue (MB) removal. AgNPs were synthesized using leaf extract of Ligustrum lucidum, which were incorporated on the chitosan's surface for modification. UV−Vis Spectroscopy, FTIR, XRD, SEM, and EDX techniques were used to confirm the synthesis and characterization of nanomaterials. Batch adsorption and sono-adsorption experiments for the removal of MB were executed under optimal conditions; for fitting the experimental equilibrium data, Langmuir and Freundlich's isotherm models were adopted. In addition, the antimicrobial potential of the AgNPs and AgCS were examined against selected bacterial and fungal strains. UV−Vis spectroscopy confirmed AgNPs synthesis from the leaf extract of L. lucidum used as a reducer, which was spherical as exposed in the SEM analysis. The FTIR spectrum illustrated phytochemicals in the leaf extract of L. lucidum functioning as stabilizing agents around AgNPs and AgCS. Whereas, corresponding crystalline peaks of nanomaterial, including a signal peak at 3 keV indicating the presence of silver, were confirmed by XRD and EDX. The Langmuir model was chosen as an efficient model for adsorption and sono-adsorption, which exposed that under optimum conditions (pH = 6, dye initial concentration = 5 mg L−1, adsorbents dosage = 0.005 g, time = 120 min, US power 80 W), MB removal efficiency of AgNPs was >70%, using ultrasound-assisted adsorption compared to the non-sonicated adsorption. Furthermore, AgNPs exhibited promising antibacterial potential against Staphylococcus aureus with the maximum zone of inhibition (14.67 ± 0.47 mm). It was concluded that the green synthesis approach for the large-scale production of metallic nanoparticles is quite effective and can be recommended for efficient and cost-effective way to eradicate dyes, particularly from textile wastewater.

Integrated hydrothermal and deep eutectic solvent-mediated fractionation of lignocellulosic biocomponents for enhanced accessibility and efficient conversion in anaerobic digestion.

Effective fractionation of lignocellulosic biocomponents of lignocellulosic biomass can increase its utilization in anaerobic digestion for high yield biomethane production. A hydrothermal process was optimized and integrated with a deep eutectic solvent (DES) pretreatment to preferentially fractionate hemicellulose, cellulose, and lignin in rice straw. The optimized hydrothermal process resulted in 96% hemicellulose solubilization at moderately low combined pretreatment severity (log S = 2.26), allowing increased hemicellulosic sugar recovery with minimal formation of inhibitory byproducts. Subsequent DES pretreatment resulted in highly bioaccessible cellulosic pulp, removing 81.3% of lignin that can be recovered and converted into value-added products. Anaerobic digestion of hemicellulosic fraction and cellulosic pulp using a microbial methanogenic consortium seed acclimatized to the lignocellulosic inhibitors resulted in a 33.4% higher yield of methane (467.84 mL g-1 VSinitial) than with anaerobic digester sludge seed. This integrated approach can facilitate and maximize the targeted utilization of different biocomponents through sustainable biorefining.

Dark fermentative biohydrogen production from vinicultural biomass without exogenous inoculum in a semi-batch reactor: A kinetic study.

This work employed a unique kind of vinicultural biomass (grape residues) to generate fermentative hydrogen. This form of biomass serves two purposes (contains substrate and inoculum). Four mathematical model methods were established; these models were used to represent the fluctuation of hydrogen generation and other fermentation products (organic acids, alcohols), the consumption of substrates included in biomass, and bacterial growth. One of these models was verified using experimental data and used to represent all of the metabolic pathways of bacteria contained in the medium and the interaction between products and substrates. The optimal biomass load, 60 g COD (Chemical Oxygen Demand)/L with a concentration of 0.22 mol of hexose and 0.0444 mol of tartrate offers the best hydrogen yield.

Design and Characterization of Electrochemical Sensor for the Determination of Mercury(II) Ion in Real Samples Based upon a New Schiff Base Derivative as an Ionophore.

The present paper provides a description of the design, characterization, and use of a Hg2+ selective electrode (Hg2+-SE) for the determination of Hg2+ at ultra-traces levels in a variety of real samples. The ionophore in the proposed electrode is a new Schiff base, namely 4-bromo-2-[(4-methoxyphenylimino)methyl]phenol (BMPMP). All factors affecting electrode response including polymeric membrane composition, concentration of internal solution, pH sample solution, and response time were optimized. The optimum response of our electrode was obtained with the following polymeric membrane composition (% w/w): PVC, 32; o-NPOE, 64.5; BMPMP, 2 and NaTPB, 1.5. The potentiometric response of Hg2+-SE towards Hg2+ ion was linear in the wide range of concentrations (9.33 × 10-8-3.98 × 10-3 molL-1), while, the limit of detection of the proposed electrode was 3.98 × 10-8 molL-1 (8.00 µg L-1). The Hg2+-SE responds quickly to Hg2+ ions as the response time of less than 10 s. On the other hand, the slope value obtained for the developed electrode was 29.74 ± 0.1 mV/decade in the pH range of 2.0-9.0 in good agreement with the Nernstian response (29.50 mV/decade). The Hg2+-SE has relatively less interference with other metal ions. The Hg2+-SE was used as an indicator electrode in potentiometric titrations to estimate Hg2+ ions in waters, compact fluorescent lamp, and dental amalgam alloy and the accuracy of the developed electrode was compared with ICP-OES measurement values. Moreover, the new Schiff base (BMPMP) was synthesized and characterized using ATR-FTIR, elemental analysis, 1H NMR, and 13C NMR. The PVC membranes containing BMPMP as an ionophore unloaded and loaded with Hg(II) are reported by scanning electron microscope images (SEM) along with energy-dispersive X-ray spectroscopy (EDX) spectra.

NDM Production as a Dominant Feature in Carbapenem-Resistant Enterobacteriaceae Isolates from a Tertiary Care Hospital.

The worldwide spread and increasing prevalence of carbapenem-resistant Enterobacteriaceae (CRE) is of utmost concern and a problem for public health. This resistance is mainly conferred by carbapenemase production. Such strains are a potential source of outbreaks in healthcare settings and are associated with high rates of morbidity and mortality. In this study, we aimed to determine the dominance of NDM-producing Enterobacteriaceae at a teaching hospital in Karachi. A total of 238 Enterobacteriaceae isolates were collected from patients admitted to Jinnah Postgraduate Medical Centre (Unit 4) in Karachi, Pakistan, a tertiary care hospital. Phenotypic and genotypic methods were used for detection of metallo-ß-lactamase. Out of 238 isolates, 52 (21.8%) were CRE and 50 isolates were carbapenemase producers, as determined by the CARBA NP test; two isolates were found negative for carbapenemase production by CARB NP and PCR. Four carbapenemase-producing isolates phenotypically appeared negative for metallo-ß-lactamase (MBL). Of the 52 CRE isolates, 46 (88.46%) were blaNDM positive. Most of the NDM producers were Klebsiella pneumoniae, followed by Enterobacter cloacae and Escherichia coli. In all the NDM-positive isolates, the blaNDM gene was found on plasmid. These isolates were found negative for the VIM and IPM MBLs. All the CRE and carbapenem-sensitive isolates were sensitive to colistin. It is concluded that the NDM is the main resistance mechanism against carbapenems and is dominant in this region.

The Influence of Microstructure on the Passive Layer Chemistry and Corrosion Resistance for Some Titanium-Based Alloys.

The effect of microstructure and chemistry on the kinetics of passive layer growth and passivity breakdown of some Ti-based alloys, namely Ti-6Al-4V, Ti-6Al-7Nb and TC21 alloys, was studied. The rate of pitting corrosion was evaluated using cyclic polarization measurements. Chronoamperometry was applied to assess the passive layer growth kinetics and breakdown. Microstructure influence on the uniform corrosion rate of these alloys was also investigated employing dynamic electrochemical impedance spectroscopy (DEIS). Corrosion studies were performed in 0.9% NaCl solution at 37 °C, and the obtained results were compared with ultrapure Ti (99.99%). The different phases of the microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Chemical composition and chemistry of the corroded surfaces were studied using X-ray photoelectron spectroscopy (XPS) analysis. For all studied alloys, the microstructure consisted of α matrix, which was strengthened by ß phase. The highest and the lowest values of the ß phase's volume fraction were recorded for TC21 and Ti-Al-Nb alloys, respectively. The susceptibility of the investigated alloys toward pitting corrosion was enhanced following the sequence: Ti-6Al-7Nb < Ti-6Al-4V << TC21. Ti-6Al-7Nb alloy recorded the lowest pitting corrosion resistance (Rpit) among studied alloys, approaching that of pure Ti. The obvious changes in the microstructure of these alloys, together with XPS findings, were adopted to interpret the pronounced variation in the corrosion behavior of these materials.