Modulating temperature for Cu2ZnSnS4 (CZTS) synthesis via hot injection method and studying the photocatalytic efficiencies for the degradation of Rhodamine 6G and Methylene blue pollutants.

Cu2ZnSnS4 (CZTS) was synthesized following hot injection method and the process was optimized by varying temperature conditions. Four samples at different temperatures viz., 200, 250, 300 and 350°C were prepared and analyzed using different characterization techniques. Based on the correlation between XRD, Raman and XPS, we conclude that the formation of ZnS and SnS2 occurs at 3500C but at 2000C there is no breakdown of the complex as per XRD. According to Raman and XPS analysis, as the temperature rises, the bonds between the metals become weaker, which is visibly seen in Raman and XPS due to the minor peaks of copper sulfide. Scanning electron microscopic analysis confirmed nanometric particles which increase in size with temperature. The photocatalytic evaluation showed that CZTS synthesized at 2000C performed efficiently in the removal of the two colorants, methylene blue and Rhodamine 6G, achieving 92.80% and 90.65%, respectively. The photocatalytic degradation efficiencies decreased at higher temperatures due to bigger sized CZTS particles as confirmed by SEM results. Computational simulations confirm that CZTS has a highly negative energy -25,764 Ry, confirming its structural stability and higher covalent than ionic character.

Probing the influence of crosslinkers on the properties, response, and degradation of enzymatic hydrogels for electrochemical glucose biosensing through fluorescence analysis.

Drop-cast crosslinked hydrogels are a common platform for enzymatic electrochemical biosensors. Despite the widespread use of these complex systems, there are still several questions about how their physicochemical properties affect their performance, stability, and reproducibility. In this work, first-generation faradaic biosensors composed of glucose oxidase and branched polyethyleneimine (BPEI) are prepared using either glutaraldehyde (GA) or ethylene glycol diglycidyl ether (EGDGE) as crosslinkers. While EGDGE gels present an increasing electrochemical response with increasing crosslinker concentration, the current of GA gels decreases at high crosslinker concentration probably due to the hampered diffusion on tightly networked gels. We compared different strategies to use fluorescence microscopy to gain insight into the gel structure either by labeling the gel components with fluorophores or taking advantage of the intrinsic fluorescence of the imines formed upon crosslinking with GA. By monitoring the fluorescence of the crosslinking bonds and the electrochemical response, we demonstrate that hydrolysis, a common hydrogel degradation mechanism, is not responsible for the loss of electrical current over time in gels prepared with glutaraldehyde. Most hydrogel-based electrochemical biosensor studies do not perform specific experiments to determine the cause of the degradation and instead just infer it from the dependence of the current on the preparation conditions (most commonly concentrations). We show that, by taking advantage of several analytical techniques, it is possible to gain more knowledge about the degradation mechanisms and design better enzymatic biosensors.

Abiotic, Hybrid, and Biological Electrocatalytic Materials Applied in Microfluidic Fuel Cells: A Comprehensive Review.

This article provides an overview of the work reported in the past decade in the field of microfluidic fuel cells. To develop appropriate research, the most commonly used electrocatalytic materials were considered and a new classification was proposed based on their nature: abiotic, hybrid, or biological. This classification allowed the authors to discern the information collected. In this sense, the types of electrocatalysts used for the oxidation of the most common fuels in different environments, such as glucose, ethanol, methanol, glycerol, and lactate, were presented. There are several phenomena presented in this article. This information gives an overview of where research is heading in the field of materials for electrocatalysis, regardless of the fuel used in the microfluidic fuel cell: the synthesis of abiotic and biological materials to obtain hybrid materials that allow the use of the best properties of each material.

Development of a Redox-Polymer-Based Electrochemical Glucose Biosensor Suitable for Integration in Microfluidic 3D Cell Culture Systems.

The inclusion of online, in situ biosensors in microfluidic cell cultures is important to monitor and characterize a physiologically mimicking environment. This work presents the performance of second-generation electrochemical enzymatic biosensors to detect glucose in cell culture media. Glutaraldehyde and ethylene glycol diglycidyl ether (EGDGE) were tested as cross-linkers to immobilize glucose oxidase and an osmium-modified redox polymer on the surface of carbon electrodes. Tests employing screen printed electrodes showed adequate performance in a Roswell Park Memorial Institute (RPMI-1640) media spiked with fetal bovine serum (FBS). Comparable first-generation sensors were shown to be heavily affected by complex biological media. This difference is explained in terms of the respective charge transfer mechanisms. Under the tested conditions, electron hopping between Os redox centers was less vulnerable than H2O2 diffusion to biofouling by the substances present in the cell culture matrix. By employing pencil leads as electrodes, the incorporation of these electrodes in a polydimethylsiloxane (PDMS) microfluidic channel was achieved simply and at a low cost. Under flow conditions, electrodes fabricated using EGDGE presented the best performance with a limit of detection of 0.5 mM, a linear range up to 10 mM, and a sensitivity of 4.69 µA mM-1 cm-2.

Poly-L-lysine-modified with ferrocene to obtain a redox polymer for mediated glucose biosensor application.

Ferrocene-based polymers as redox mediators are considered versatile and important in the study of glucose biosensors. Poly-L-lysine (PLL), as a cationic polymer, possesses good properties including biocompatibility, biodegradation and water solubility. In this work, PLL was modified with ferrocene carboxylate in a very simple way by activating the carboxyl group of Fc, which reacted with the amino groups of the polymer. The resulting product was analysed by FTIR. Performance as a redox mediator (Fc-PLL) with the enzyme glucose oxidase was tested by cyclic voltammetry and showed an increase in the oxidation current in the presence of glucose in PBS pH 7.4. Additionally, performance as a biosensor was evaluated by amperometry and gave a linear range of 0-10 mM, a limit of detection of 23 µM, a sensitivity of 6.55 µA/cm2 mM and high selectivity. To evaluate the charged regions of Fc-PLL/GOx on the electrode surface, analysis by scanning electrochemical microscopy showed remarkable activity. The Fc-PLL redox polymer as a glucose biosensor has been well accepted as this kind of material, and the results showed remarkable activity as an electron transfer mediator between the redox polymer and the GOx enzyme.

Biological Synthesis of PbS, As3S4, HgS, CdS Nanoparticles using Pseudomonas aeruginosa and their Structural, Morphological, Photoluminescence as well as Whole Cell Protein Profiling Studies.

Metal sulfide nanoparticles are semi-conductors that possess many applications in optics, optoelectronics and magnetic devices. There are physical and chemical methods for their synthesis but such methods involve toxic precursors as well as many obnoxious by-products. Hence, biological synthesis of metal sulfide nanoparticles are efficient enough to transform toxic metals to non-toxic ones. Pseudomonas aeruginosa, isolated from textile effluent and tolerant of high levels of heavy metals, was used for the green synthesis of metal sulfide (HgS, As3S4, CdS and PbS) nanoparticles. The optical, structural and morphological nature of metal sulfide nanoparticles was also determined. FTIR (Fourier Transform Infra-red) analysis showed spectral changes when P. aeruginosa was grown in medium containing heavy metals viz. Hg, As, Pb and Cd indicating that there are functional groups viz. carboxyl, hydroxyl, phosphate, amino and amide, that exists on the surface of the bacteria, thus facilitating binding of metals on its surface. The bacterial samples which were treated with different metals at different concentrations, were subjected to whole cell protein analysis using SDS-PAGE (Sodium dodecyl Sulphate- Polyacrylamide gel electrophoresis) and protein profiling. The total protein estimation revealed that there was an increase in the protein concentration in the presence of heavy metals and a significant change in the banding pattern was observed which showed induction of a set of proteins under heavy metal stress especially mercury.

Synthesis, Characterization and Magnetic Hyperthermia of Monodispersed Cobalt Ferrite Nanoparticles for Cancer Therapeutics.

Magnetic nanoparticles such as cobalt ferrite are investigated under clinical hyperthermia conditions for the treatment of cancer. Cobalt ferrite nanoparticles (CFNPs) synthesized by the thermal decomposition method, using nonionic surfactant Triton-X100, possess hydrophilic polyethylene oxide chains acting as reducing agents for the cobalt and iron precursors. The monodispersed nanoparticles were of 10 nm size, as confirmed by high-resolution transmission electron microscopy (HR-TEM). The X-ray diffraction patterns of CFNPs prove the existence of cubic spinel cobalt ferrites. Cs-corrected scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) of CFNPs confirmed their multi-twinned crystallinity due to the presence of atomic columns and defects in the nanostructure. Magnetic measurements proved that the CFNPs possess reduced remnant magnetization (MR/MS) (0.86), which justifies cubic anisotropy in the system. Microwave-based hyperthermia studies performed at 2.45 GHz under clinical conditions in physiological saline increased the temperature of the CFNP samples due to the transformation of radiation energy to heat. The specific absorption rate of CFNPs in physiological saline was 68.28 W/g. Furthermore, when triple-negative breast cancer cells (TNBC) in the presence of increasing CFNP concentration (5 mg/mL to 40 mg/mL) were exposed to microwaves, the cell cytotoxicity was enhanced compared to CFNPs alone.

Triple-Negative Breast Cancer: A Review of Conventional and Advanced Therapeutic Strategies.

Triple-negative breast cancer (TNBC) cells are deficient in estrogen, progesterone and ERBB2 receptor expression, presenting a particularly challenging therapeutic target due to their highly invasive nature and relatively low response to therapeutics. There is an absence of specific treatment strategies for this tumor subgroup, and hence TNBC is managed with conventional therapeutics, often leading to systemic relapse. In terms of histology and transcription profile these cancers have similarities to BRCA-1-linked breast cancers, and it is hypothesized that BRCA1 pathway is non-functional in this type of breast cancer. In this review article, we discuss the different receptors expressed by TNBC as well as the diversity of different signaling pathways targeted by TNBC therapeutics, for example, Notch, Hedgehog, Wnt/b-Catenin as well as TGF-beta signaling pathways. Additionally, many epidermal growth factor receptor (EGFR), poly (ADP-ribose) polymerase (PARP) and mammalian target of rapamycin (mTOR) inhibitors effectively inhibit the TNBCs, but they face challenges of either resistance to drugs or relapse. The resistance of TNBC to conventional therapeutic agents has helped in the advancement of advanced TNBC therapeutic approaches including hyperthermia, photodynamic therapy, as well as nanomedicine-based targeted therapeutics of drugs, miRNA, siRNA, and aptamers, which will also be discussed. Artificial intelligence is another tool that is presented to enhance the diagnosis of TNBC.

Composite Sulfonated Polyether-Ether Ketone Membranes with SBA-15 for Electrochemical Energy Systems.

The aim of this work is the evaluation of a Sulfonated Poly Ether-Ether Ketone (S-PEEK) polymer modified by the addition of pure Santa Barbara Amorphous-15 (SBA-15, mesoporous silica) and SBA-15 previously impregnated with phosphotungstic acid (PWA) fillers (PWA/SBA-15) in order to prepare composite membranes as an alternative to conventional Nafion® membranes. This component is intended to be used as an electrolyte in electrochemical energy systems such as hydrogen and methanol Proton Exchange Membrane Fuel Cell (PEMFC) and Electrochemical Hydrogen Pumping (EHP). The common requirements for all the applications are high proton conductivity, thermomechanical stability, and fuel and oxidant impermeability. The morphology of the composite membranes was investigated by Scanning Electron Microscopy- Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis. Water Uptake (Wup), Ion Exchange Capacity (IEC), proton conductivity, methanol permeability and other physicochemical properties were evaluated. In PEMFC tests, the S-PEEK membrane with a 10 wt.% SBA-15 loading showed the highest performance. For EHP, the inclusion of inorganic materials led to a back-diffusion, limiting the compression capacity. Concerning methanol permeability, the lowest methanol crossover corresponded to the composites containing 5 wt.% and 10 wt.% SBA-15.

Gold-Iron oxide yolk-shell nanoparticles (YSNPs) as magnetic probe for fluorescence-based detection of 3 base mismatch DNA.

Seed-mediated Gold-Iron oxide yolk-shell nanoparticles (YSNPs) were synthesized and functionalized with cy5 attached- thiolated single strand DNA probe for the detection of mutated DNA. The optimum concentration of thiolated DNA determined from a bathochromic shift of surface plasmon resonance (SPR) peak, was 0.177µM. The effect of pH (2-10), temperature (4, 37, 60 and 100 °C), and ionic strengths (1 M to 4 M) on the stability of ssDNA probe tethered YSNPs, studied with the assistance of flocculation parameter. The detection of mutation in DNA was possible using such ssDNA probe functionalized and stabilized nanoparticles. The hybridization of the oligonucleotide probe with the complementary, non-complementary and mutated DNA strands are determined via their respective intensities of the fluorescence of cy5, an efficient fluorescent marker. The intensities help in the comprehension of the specificity of the system. The report predicts controlled efficiency of hybridization with the aid of Hamaker constant, which is determined as 1.15 × 10-20 J for DNA functionalized YSNPs. The minimum concentration of target DNA detected using this methodology was 1.2 × 10-11 mol/L.

Synthesis and evaluation of HfO2 as a prospective filler in inorganic-organic hybrid membranes based on Nafion for PEM fuel cells.

Hybrid inorganic-organic Nafion membranes modified with metal oxides (typically TiO2, ZrO2, WO3) are a good alternative for fuel cell applications. However, one of their main limitations is associated with their relative low proton conductivity at temperatures above 80 °C. In this work, we overcome this issue using HfO2 as a filler. HfO2 was prepared by a sol-gel method, and it was compared with a recast Nafion membrane (named as recast). Deconvolved XPS spectra confirmed the presence of hafnia, while EDS analysis was used to determine its weight content resulting in a 1.88 wt%. FT-IR ATR experiments indicated that the HfO2 hybrid membrane possess a higher capability to retain water than the recast. Thus, the water uptake, swelling degree, conductivity tests and fuel cell evaluations were performed. The water uptake analysis revealed that the hybrid membrane presented a higher retention percentage at 100 °C (61%) than recast (29%). This improvement enabled a higher ionic conductivity at 80 °C and 100 °C. The hybrid membrane displayed a higher conductivity at 100 °C than the recast membrane (112 versus 82 mS cm-1), increasing the cell performance to 0.36 W cm-2; being this performance almost two-fold higher to that obtained for the recast membrane. In summary, herein we demonstrated that HfO2 can be considered as an excellent substitute to conventional fillers.

Evaluation of single and stack membraneless enzymatic fuel cells based on ethanol in simulated body fluids.

The purpose of this work is to evaluate single and double-cell membraneless microfluidic fuel cells (MMFCs) that operate in the presence of simulated body fluids SBF, human serum and blood enriched with ethanol as fuels. The study was performed using the alcohol dehydrogenase enzyme immobilised by covalent binding through an array composed of carbon Toray paper as support and a layer of poly(methylene blue)/tetrabutylammonium bromide/Nafion and glutaraldehyde (3D bioanode electrode). The single MMFC was tested in a hybrid microfluidic fuel cell using Pt/C as the cathode. A cell voltage of 1.035V and power density of 3.154mWcm-2 were observed, which is the highest performance reported to date. The stability and durability were tested through chronoamperometry and polarisation/performance curves obtained at different days, which demonstrated a slow decrease in the power density on day 10 (14%) and day 20 (26%). Additionally, the cell was tested for ethanol oxidation in simulated body fluid (SBF) with ionic composition similar to human blood plasma. Those tests resulted in 0.93V of cell voltage and a power density close to 1.237mWcm-2. The double cell MMFC (Stack) was tested using serum and human blood enriched with ethanol. The stack operated with blood in a serial connection showed an excellent cell performance (0.716mWcm-2), demonstrating the feasibility of employing human blood as energy source.

Copper-palladium core-shell as an anode in a multi-fuel membraneless nanofluidic fuel cell: toward a new era of small energy conversion devices.

A membraneless nanofluidic fuel cell with flow-through electrodes that works with several fuels (individually or mixed): methanol, ethanol, glycerol and ethylene-glycol in alkaline media is presented. For this application, an efficient Cu@Pd electrocatalyst was synthesized and tested, resulting outstanding performance until now reported, opening the possibility of power nano-devices for multi-uses purposes, regardless of fuel re-charge employed.

A nanofluidic direct formic acid fuel cell with a combined flow-through and air-breathing electrode for high performance.

The use of three-dimensional flow-through nanoporous electrodes and the merging of a flow-through and air-breathing cathode were explored and successfully applied in a formic acid air-breathing nanofluidic fuel cell. The effects of fuel concentration, reaction stoichiometry and catalyst mass loading were investigated, resulting in power densities ranging from 28 to 100 mW cm(-2).

Hybrid microfluidic fuel cell based on Laccase/C and AuAg/C electrodes.

A hybrid glucose microfluidic fuel cell composed of an enzymatic cathode (Laccase/ABTS/C) and an inorganic anode (AuAg/C) was developed and tested. The enzymatic cathode was prepared by adsorption of 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and Laccase on Vulcan XC-72, which act as a redox mediator, enzymatic catalyst and support, respectively. The Laccase/ABTS/C composite was characterised by Fourier Transform Infrared (FTIR) Spectroscopy, streaming current measurements (Zeta potential) and cyclic voltammetry. The AuAg/C anode catalyst was characterised by Transmission electron microscopy (TEM) and cyclic voltammetry. The hybrid microfluidic fuel cell exhibited excellent performance with a maximum power density value (i.e., 0.45 mW cm(-2)) that is the highest reported to date. The cell also exhibited acceptable stability over the course of several days. In addition, a Mexican endemic Laccase was used as the biocathode electrode and evaluated in the hybrid microfluidic fuel cell generating 0.5 mW cm(-2) of maximum power density.

AuPd/polyaniline as the anode in an ethylene glycol microfluidic fuel cell operated at room temperature.

AuPd/polyaniline was used for the first time, for ethylene glycol (EG) electrooxidation in a novel microfluidic fuel cell (MFC) operated at room temperature. The device exhibits high electrocatalytic performance and stability for the conversion of cheap and fully available EG as fuel.

Novel electro-fenton approach for regeneration of activated carbon.

An electro-Fenton-based method was used to promote the regeneration of granular activated carbon (GAC) previously adsorbed with toluene. Electrochemical regeneration experiments were carried out using a standard laboratory electrochemical cell with carbon paste electrodes and a batch electrochemical reactor. For each system, a comparison was made using FeSO4 as a precursor salt in solution (homogeneous system) and an Fe-loaded ion-exchange resin (Purolite C-100, heterogeneous system), both in combination with electrogenerated H2O2 at the GAC cathode. In the two cases, high regeneration efficiencies were obtained in the presence of iron using appropriate conditions of applied potential and adsorption-polarization time. Consecutive loading and regeneration cycles of GAC were performed in the reactor without great loss of the adsorption properties, only reducing the regeneration efficiency by 1% per cycle during 10 cycles of treatment. Considering that, in the proposed resin-containing process, the use of Fe salts is avoided and that GAC cathodic polarization results in efficient cleaning and regeneration of the adsorbent material, this novel electro-Fenton approach could constitute an excellent alternative for regenerating activated carbon when compared to conventional methods.

Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment.

Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO2 semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO2 based photoanode using an optic fiber support. The novel arrangement of a TiO2 layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 microm thickness SnO2:Sb films on which the photoactive TiO2 layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO2:Sb and TiO2 showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H(2)O(2) close to 50% as compared to different types of TiO2 films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L(-1)) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.