Building a High-Potential Silver-Sulfur Redox Reaction Based on the Hard-Soft Acid-Base Theory.

Sulfur holds immense promise for battery applications owing to its abundant availability, low cost, and high capacity. Currently, sulfur is commonly combined with alkali or alkaline earth metals in metal-sulfur batteries. However, these batteries universally face challenges in cycling stability due to the inevitable issue of polysulfide dissolution and shuttling. Additionally, the inferior stability of metal sulfide discharge compounds results in low S0/S2- redox potentials (<-0.41 V vs SHE). Herein, we leverage the principle of the hard-soft acid-base theory to introduce a novel silver-sulfur (Ag-S) battery system, which operates on the reaction between the soft acid of Ag+ and the soft base of S2-. Due to their high reaction affinity, the discharge compound of silver sulfide (Ag2S) is intrinsically insoluble and fundamentally stable. This not only resolves the polysulfide dissolution issue but also leads to a predominantly high S0/S2- redox potential (+1.0 V vs. SHE). We thus exploit the Ag-S reaction for a primary zinc battery application, which exhibits a high capacity of ∼620 mAh g-1 and a high voltage of ∼1.45 V. This work offers valuable insights into the application of classic chemistry theories in the development of innovative energy storage devices.

Optimizing Sustainable Energy Generation in Ethanol Fuel Cells: An Exploration of Carrageenan with TiO2 Nanoparticles and Ni/CeO2 Composites.

Based on the search for new biodegradable materials that are low cost and easy to synthesize by environmentally friendly methods, we report the use of carrageenan membranes (mixture of κ and λ carrageenans) with different concentrations of titanium dioxide nanoparticles (TiO2 NPs) and Ni/CeO2 (10 wt % Ni) for the fabrication of a novel fuel cell electrode for the oxidation of ethanol. Each membrane was characterized to determine its physicochemical properties using X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) spectroscopy. Using impedance spectroscopy (IS), a maximum value of 2.08 × 10-4 S/cm in ionic conductivity was found for the carrageenan nanocomposite with a concentration of 5 wt % TiO2 NPs (CR5%). Due to its high conductivity values, the CR5% membrane was mixed with Ni/CeO2 to prepare the working electrode for cyclic voltammetry measurements. Using a solution of 1 M ethanol and 1 M KOH, the oxidation of ethanol over CR5% + Ni/CeO2 resulted in peak current density values at forward and reverse scan voltages of 9.52 and 12.22 mA/cm2, respectively. From our results, the CR5% + Ni/CeO2 membrane proves to be more efficient in the oxidation of ethanol compared with commercially available Nafion membranes containing Ni/CeO2.

Microalgae Peptide-Stabilized Gold Nanoparticles as a Versatile Material for Biomedical Applications.

Microalgae peptides have many medical and industrial applications due to their functional properties. However, the rapid degradation of peptides not naturally present in biological samples represents a challenge. A strategy to increase microalgae peptide stability in biological samples is to use carriers to protect the active peptide and regulate its release. This study explores the use of gold nanoparticles (AuNPs) as carriers of the Chlorella microalgae peptide (VECYGPNRPQF). The potential of these peptide biomolecules as stabilizing agents to improve the colloidal stability of AuNPs in physiological environments is also discussed. Spectroscopic (UV-VIS, DLS) and Microscopic (TEM) analyses confirmed that the employed modification method produced spherical AuNPs by an average 15 nm diameter. Successful peptide capping of AuNPs was confirmed with TEM images and FTIR spectroscopy. The stability of the microalgae peptide increased when immobilized into the AuNPs surface, as confirmed by the observed thermal shifts in DSC and high zeta-potential values in the colloidal solution. By optimizing the synthesis of AuNPs and tracking the conferred chemical properties as AuNPs were modified with the peptide via various alternative methods, the synthesis of an effective peptide-based coating system for AuNPs and drug carriers was achieved. The microalgae peptide AuNPs showed lower ecotoxicity and better viability than the regular AuNPs.

Porous Cellulose Acetate/Block Copolymer Membranes for the Recovery of Polyphenolic Compounds from Aquatic Environments.

Polyphenols are natural compounds with strong antioxidant properties synthesized by plants and widely distributed in plant tissues. They compose a broad class of compounds that are commonly employed for multiple applications such as food, pharmaceutical, adhesives, biomedical, agricultural, and industrial purposes. Runoffs from these sources result in the introduction of polyphenols into aquatic environments where they further transform into highly toxic pollutants that can negatively affect aquatic ecosystems and humans. Therefore, the development of extraction and remediation methods for such compounds must be addressed. This study describes the identification and operation of a method to recover polyphenolic compounds from water environments by utilizing membrane-based separation. Composite membranes derived from electrospun cellulose acetate (CA) fibers and diblock copolymer (DiBCP) PEO-b-P4VP were prepared to evaluate the adsorption of polyphenolic compounds from aqueous environments. The highly porous CA fibers were developed using the electrospinning technique, and the fabricated DiBCP/CA membranes were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) spectroscopy, and tensile testing. Finally, the ability of the composite membranes to adsorb the soluble polyphenolic compounds catechol (CAT) and gallic acid (GA), from a wetland environment, was studied via batch adsorption experiments and by solid-phase extraction (SPE). Results revealed a successful recovery of both polyphenols, at concentrations within the parts per million (ppm) range, from the aqueous media. This suggests a novel approach to recover these compounds to prevent their transformation into toxic pollutants upon entrance to water environments.

Comparison of chemical compounds associated with sclerites from healthy and diseased sea fan corals (Gorgonia ventalina).

BACKGROUND: The roles of gorgonian sclerites as structural components and predator deterrents have been widely studied. Yet their role as barriers against microbes has only recently been investigated, and even less is known about the diversity and roles of the chemical compounds associated with sclerites. METHODS: Here, we examine the semi-volatile organic compound fraction (SVOCs) associated with sclerites from healthy and diseased Gorgonia ventalina sea fan corals to understand their possible role as a stress response or in defense of infection. We also measured the oxidative potential of compounds from diseased and healthy G. ventalina colonies. RESULTS: The results showed that sclerites harbor a great diversity of SVOCs. Overall, 70 compounds were identified, the majority of which are novel with unknown biological roles. The majority of SVOCs identified exhibit multiple immune-related roles including antimicrobial and radical scavenging functions. The free radical activity assays further confirmed the anti-oxidative potential of some these compounds. The anti-oxidative activity was, nonetheless, similar across sclerites regardless of the health condition of the colony, although sclerites from diseased sea fans display slightly higher anti-oxidative activity than the healthy ones. DISCUSSION: Sclerites harbor great SVOCs diversity, the majority of which are novel to sea fans or any other corals. Yet the scientific literature consulted showed that the roles of compounds found in sclerites vary from antioxidant to antimicrobial compounds. However, this study fell short in determine the origin of the SVOCs identified, undermining our capacity to determine the biological roles of the SVOCs on sclerites and sea fans.

Metalized Nanocellulose Composites as a Feasible Material for Membrane Supports: Design and Applications for Water Treatment.

Herein, we study the feasibility of using nanocellulose (NC)-based composites with silver and platinum nanoparticles as additive materials to fabricate the support layer of thin film composite (TFC) membranes for water purification applications. In brief, the NC surface was chemically modified and then was decorated with silver and platinum nanoparticles, respectively, by chemical reduction. These metalized nanocellulose composites (MNC) were characterized by several techniques including: FTIR, XPS, TGA, XRD, and XANES to probe their integrity. Thereafter, we fabricated the MNC-TFC membranes and the support layer was modified to improve the membrane properties. The membranes were thoroughly characterized, and the performance was evaluated in forward osmosis (FO) mode with various feed solutions: nanopure water, urea, and wastewater samples. The fabricated membranes exhibited finger-like pore morphologies and varying pore sizes. Interestingly, higher water fluxes and solute rejection was obtained with the MNC-TFC membranes with wastewater samples. The overall approach of this work provides an effort to fabricated membranes with high water flux and enhanced selectivity.

Catalytic effect of ultrananocrystalline Fe3O4 on algal bio-crude production via HTL process.

We report a comprehensive quantitative study of the production of refined bio-crudes via a controlled hydrothermal liquefaction (HTL) process using Ulva fasciata macroalgae (UFMA) as biomass and ultrananocrystalline Fe3O4 (UNCFO) as catalyst. X-ray diffraction and electron microscopy were applied to elucidate the formation of the high-quality nanocatalysts. Gas chromatography-mass spectroscopy (GC-MS) and CHNS analyses showed that the bio-crude yield and carbon/oxygen ratios increase as the amount of UNCFO increases, reaching a peak value of 32% at 1.25 wt% (a 9% increase when compared to the catalyst-free yield). The bio-crude is mainly composed of fatty acids, alcohols, ketones, phenol and benzene derivatives, and hydrocarbons. Their relative abundance changes as a function of catalyst concentration. FTIR spectroscopy and vibrating sample magnetometry revealed that the as-produced bio-crudes are free of iron species, which accumulate in the generated bio-chars. Our findings also indicate that the energy recovery values via the HTL process are sensitive to the catalyst loading, with a threshold loading of 1.25 wt%. GC-MS studies show that the UNCFO not only influences the chemical nature of the resulting bio-crudes and bio-chars, but also the amount of fixed carbons in the solid residues. The detailed molecular characterization of the bio-crudes and bio-chars catalyzed by UNCFO represents the first systematic study reported using UFMA. This study brings forth new avenues to advance the highly-pure bio-crude production employing active, heterogeneous catalyst materials that are recoverable and recyclable for continuous thermochemical reactions.

Assembly of a Cost-Effective Anode Using Palladium Nanoparticles for Alkaline Fuel Cell Applications.

Nanotechnology allows the synthesis of nanoscale catalysts, which offer an efficient alternative for fuel cell applications. In this laboratory experiment, the student selects a cost-effective anode for fuel cells by comparing three different working electrodes. These are commercially available palladium (Pd) and glassy carbon (GC) electrodes, and a carbon paste (CP) electrode that is prepared by the students in the laboratory. The GC and CP were modified with palladium nanoparticles (PdNP) suspensions. The electrodes efficiencies were studied for ethanol oxidation in alkaline solution using cyclic voltammetry techniques. The ethanol oxidation currents obtained were used to determine the current density using the geometric and surface area of each electrode. Finally, students were able to choose the best electrode and relate catalytic activity to surface area for ethanol oxidation in alkaline solution by completing a critical analysis of the cyclic voltammetry results. With this activity, fundamental electrochemical concepts were reinforced.

Chemically glycosylation improves the stability of an amperometric horseradish peroxidase biosensor.

We constructed a biosensor by electrodeposition of gold nano-particles (AuNPs) on glassy carbon (GC) and subsequent formation of a 4-mercaptobenzoic acid self-assembled monolayer (SAM). The enzyme horseradish peroxidase (HRP) was then covalently immobilized onto the SAM. Two forms of HRP were employed: non-modified and chemically glycosylated with lactose. Circular dichroism (CD) spectra showed that chemical glycosylation did neither change the tertiary structure of HRP nor the heme environment. The highest sensitivity of the biosensor to hydroquinone was obtained for the biosensor with HRP-lactose (414 nA µM(-1)) compared to 378 nA µM(-1) for the one employing non-modified HRP. The chemically glycosylated form of the enzyme catalyzed the reduction of hydroquinone more rapidly than the native form of the enzyme. The sensor employing lactose-modified HRP also had a lower limit of detection (74 µM) than the HRP biosensor (83 µM). However, most importantly, chemically glycosylation improved the long-term stability of the biosensor, which retained 60% of its activity over a four-month storage period compared to only 10% for HRP. These results highlight improvements by an innovative stabilization method when compared to previously reported enzyme-based biosensors.

Detection of fatty acid ethyl esters in skin surface lipids as biomarkers of ethanol consumption in alcoholics, social drinkers, light drinkers, and teetotalers using a methodology based on microwave-assisted extraction followed by solid-phase microextraction and gas chromatography-mass spectrometry.

Fatty acid ethyl esters (FAEE) are known to be a direct alcohol marker and are mainly investigated in hair samples for their ability to be incorporated into this matrix from sebum. The present study used an already developed methodology to provide and confirm information about the use of FAEEs in skin surface lipids as markers of alcohol consumption. The skin surface lipids were collected with Sebutapes(®) from the foreheads of teetotalers, light drinkers, social drinkers, and alcoholics. The samples were analyzed by direct solid-phase microextraction and gas chromatography-mass spectrometry for ethyl myristate, ethyl palmitate, ethyl oleate, and ethyl stearate. Relative FAEE/sebum allowed an evaluation of alcohol consumption. The ranges obtained for relative FAEEs in each category were as follows, teetotalers (0-13.85 pg/mg), light drinkers (11.10-26.80 pg/mg), social drinkers (20.55-86.55 pg/mg), and alcoholics (109.00-1243.40 pg/mg). A social drinker volunteer was monitored during a period of two months. The highest m(FAEE)/m(sebum) were generally detected 7-9 days after the days of high alcohol consumption. From these results, a clear distinction of teetotalers, social drinkers, and alcoholics could be established with the methodology used.

Optimization of microwave-assisted extraction followed by solid phase micro extraction and gas chromatography-mass spectrometry detection for the assay of some semi volatile organic pollutants in sebum.

Methodology using MAE/SPME/GC-MS is being pursued for the analysis of organic pollutants in sebum. The microwave-assisted extraction (MAE) of standards of semi volatile organic pollutants from sebum was optimized. All compounds were extracted from sebum with recoveries analyzed by GC/MS ranging from 94% to 100% under the optimum MAE conditions: 10mL acetone-hexane (2:1), 60 degrees C, and 10 min microwave heating. To improve the detection limits a SPME procedure was optimized. Linearity ranged from 0.70 ppb to 25 ppb. R.S.D. were in the range of 1-23% for the SPME step. Preliminary real samples were analyzed and a range of compounds was detected. The optimized MAE/SPME/GC-MS methodology promises to be useful for different applications.