Biocompatible Gold Nanoparticles-Modified Fluorine Doped Tin Oxide Electrode for the Fabrication of Enzyme-Free Glucose Sensor.

This work demonstrates the use of jute stick extract as a reducing and stabilizing agent for the synthesis of spherical gold nanoparticles (AuNPs). In UV-Vis spectroscopy, peak at 550 nm was used to confirm the formation of AuNPs. The spherical surface morphology of AuNPs was determined through SEM and TEM analysis. While XRD investigation revealed the crystallinity of the prepared AuNPs. To ensure the biocompatibility of synthesized AuNPs, a bacterial investigation was conducted with negative results towards bacterial strain. The, modified FTO with AuNPs were able to detect glucose in CV analysis and the constructed sensor displayed a wide linear range of 50 µM to 40 mM with a detection limit of 20 µM. Scan rate analysis was performed to determine the charge transfer coefficient (0.42) and Tafel slope (102 mV/decade). Furthermore, the interfacial surface mechanism is illustrated to understand the interaction of glucose with the electrode surface in an alkaline medium and the product formation through the dehydrogenation and hydrolysis process. The prepared sensor also showed good stability, reproducibility, and anti-interference capabilities. In the case of real sample analysis, we used a blood serum sample. A low RSD value (<10 %) suggests the practical use of AuNPs/FTO in real-life applications.

Indocyanine Green (ICG) Fluorescence Is Dependent on Monomer with Planar and Twisted Structures and Inhibited by H-Aggregation.

The optical properties of indocyanine green (ICG) as a near-infrared (NIR) fluorescence dye depend on the nature of the solvent medium and the dye concentration. In the ICG absorption spectra of water, at high concentrations, there were absorption maxima at 700 nm, implying H-aggregates. With ICG dilution, the main absorption peak was at 780 nm, implying monomers. However, in ethanol, the absorption maximum was 780 nm, and the shapes of the absorption spectra were identical regardless of the ICG concentration, indicating that ICG in ethanol exists only as a monomer without H-aggregates. We found that emission was due to the monomer form and decreased with H-aggregate formation. In the fluorescence spectra, the 820 nm emission band was dominant at low concentrations, whereas at high concentrations, we found that the emission peaks were converted to 880 nm, suggesting a new form via the twisted intramolecular charge transfer (TICT) process of ICG. The NIR fluorescence intensity of ICG in ethanol was approximately 12- and 9-times brighter than in water in the NIR-I and -II regions, respectively. We propose an energy diagram of ICG to describe absorptive and emissive transitions through the ICG structures such as the monomer, H-aggregated, and TICT monomer forms.

Synthesis of a novel hydrazone-based compound applied as a fluorescence turn-on chemosensor for iron(iii) and a colorimetric sensor for copper(ii) with antimicrobial, DFT and molecular docking studies.

Hydrazone-hydrazide-based linkers perform a crucial role in environmental as well as biological fields. Such linkers are employed to detect exact metal ions at a minute level; hence, numerous probes are available. Even though thiophene-based molecules have a unique position in the medicinal arena, only very few chemosensors are reported based on such a moiety. In this current work, a novel hydrazide-hydrazone-based fluorogenic molecule 5-bromo-2-hydroxy-N'-[(1E)-1-(thiophen-2-yl)ethylidene]benzohydrazide (L) has been successfully designed and synthesized. The sensing studies of L demonstrated a ratio metric as well as turn-on-enhanced fluorescence and colorimetric response toward Fe3+ and Cu2+ ions, respectively and it was observed to be insensitive toward various metal ions. The Job plots revealed that the binding stoichiometry of L and metal ions is 2 : 1. In addition, density functional theory (DFT) results strongly suggested that L can be used as a powerful colorimetric sensor for the detection of Cu2+ ions. In vitro antimicrobial activities of L were evaluated by disk diffusion and results revealed good antibacterial activities against E. coli. Further, molecular docking was executed with DNA gyrase (PDB ID: 1KZN) of E. coli and the calculated interaction energy value was found to be -7.7 kcal mol-1. Finally, molecular docking, fluorescence, colorimetry and the HOMO-LUMO energy gap of the compound can provide new insights into developing drugs and detecting metals in biomolecules.

Interaction of mercury species with proteins: towards possible mechanism of mercurial toxicology.

The nature of the binding of mercurials (organic and inorganic) and their subsequent transformations in biological systems is a matter of great debate as several different hypotheses have been proposed and none of them has been conclusively proven to explain the characteristics of Hg binding with the proteins. Thus, the chemical nature of Hg-protein binding through the possible transportation mechanism in living tissues is critically reviewed herein. Emphasis is given to the process of transportation, and binding of Hg species with selenol-containing biomolecules that are appealing for toxicological studies as well as the advancement of environmental and biological research.

Synthesis, Characterization, and Studies on Photophysical Properties of Rhodamine Derivatives and Metal Complexes in Dye-Sensitized Solar Cells.

Rhodamine 6G dyes are low-cost, highly soluble fluorescent dyes frequently utilized as laser dyes, chemical sensors, and as tracer dyes in the determination of the direction and rate of flow of water. In this study, the photophysical properties of three rhodamine 6G dyes, bearing phenyl (P15), furan (P41), and 5-hydroxymethyl furan (P45), and their metal complexes were investigated using ultraviolet-visible (UV-vis) spectroscopy, fluorescence spectroscopy, fluorescence lifetime, and Fourier transform infrared (FTIR) measurements. Rhodamine 6G dyes and their complexes were subsequently applied as sensitizing dyes in the fabrication of dye-sensitized solar cells, and the solar to electric power efficiency and electrochemical impedance spectroscopy measurements were performed. The solar to electric power efficiency values of the metal complexes of the rhodamine 6G dyes were higher than those of the devices fabricated with only rhodamine dyes without copper (II). The most significant change was observed in rhodamine P41 with a 30% increase in solar to electric power efficiency when the dye was conjugated to the copper ion.

Energy Harvesting by Mesoporous Reduced Graphene Oxide Enhanced the Mediator-Free Glucose-Powered Enzymatic Biofuel Cell for Biomedical Applications.

Harnessing electrochemical energy in an engineered electrical circuit from biochemical substrates in the human body using biofuel cells is gaining increasing research attention in the current decade due to the wide range of biomedical possibilities it creates for electronic devices. In this report, we describe and characterize the construction of just such an enzymatic biofuel cell (EBFC). It is simple, mediator-free, and glucose-powered, employing only biocompatible materials. A novel feature is the two-dimensional mesoporous thermally reduced graphene oxide (rGO) host electrode. An additionally novelty is that we explored the potential of using biocompatible, low-cost filter paper (FP) instead of carbon paper, a conductive polymer, or gold as support for the host electrode. Using glucose (C6H12O6) and molecular oxygen (O2) as the power-generating fuel, the cell consists of a pair of bioelectrodes incorporating immobilized enzymes, the bioanode modified by rGO-glucose oxidase (GOx/rGO), and the biocathode modified by rGO-laccase (Lac/rGO). Scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX), transmission electron microscopy, and Raman spectroscopy techniques have been employed to investigate the surface morphology, defects, and chemical structure of rGO, GOx/rGO, and Lac/rGO. N2 sorption, SEM/EDX, and powder X-ray diffraction revealed a high Brunauer-Emmett-Teller surface area (179 m2 g-1) mesoporous rGO structure with the high C/O ratio of 80:1 as well. Results from the Fourier transform infrared spectroscopy, UV-visible spectroscopy, and electrochemical impedance spectroscopy studies indicated that GOx remained in its native biochemical functional form upon being embedded onto the rGO matrix. Cyclic voltammetry studies showed that the presence of mesoporous rGO greatly enhanced the direct electrochemistry and electrocatalytic properties of the GOx/rGO and Lac/rGO nanocomposites. The electron transfer rate constant between GOx and rGO was estimated to be 2.14 s-1. The fabricated EBFC (GOx/rGO/FP-Lac/rGO/FP) using a single GOx/rGO/FP bioanode and a single Lac/rGO/FP biocathode provides a maximum power density (Pmax) of 4.0 nW cm-2 with an open-circuit voltage (VOC) of 0.04 V and remains stable for more than 15 days with a power output of ∼9.0 nW cm-2 at a pH of 7.4 under ambient conditions.

Zero-Valent Iron Nanoparticles Induce Reactive Oxygen Species in the Cyanobacterium, Fremyella diplosiphon.

Nanoscale zero-valent iron nanoparticles (nZVIs) are known to boost biomass production and lipid yield in Fremyella diplosiphon, a model biodiesel-producing cyanobacterium. However, the impact of nZVI-induced reactive oxygen species (ROS) in F. diplosiphon has not been evaluated. In the present study, ROS in F. diplosiphon strains (B481-WT and B481-SD) generated in response to nZVI-induced oxidative stress were quantified and the enzymatic response determined. Lipid peroxidation as a measure of oxidative stress revealed significantly higher malondialdehyde content (p < 0.01) in both strains treated with 3.2, 12.8, and 51.2 mg L-1 nZVIs compared to untreated control. In addition, ROS in all nZVI-treated cultures treated with 1.6-25.6 mg L-1 nZVIs was significantly higher than the untreated control as determined by the 2',7'-dichlorodihydrofluorescein diacetate fluorometric probe. Immunodetection using densitometric analysis of iron superoxide dismutase (SOD) revealed significantly higher SOD levels in both strains treated with nZVIs at 51.2 mg L-1. In addition, we observed significantly higher (p < 0.001) SOD levels in the B481-SD strain treated with 6.4 mg L-1 nZVIs compared to 3.2 mg L-1 nZVIs. Validation using transmission electron microscopy equipped with energy-dispersive X-ray spectroscopy (EDS) revealed adsorption of nZVIs with a strong iron peak in both B481-WT and B481-SD strains. While the EDS spectra showed strong signals for iron at 4 and 12 days after treatment, a significant decrease in peak intensity was observed at 20 days. Future efforts will be aimed at studying transduction mechanisms that cause metabolic and epigenetic alterations in response to nZVIs in F. diplosiphon.

Photocatalytic performance, anti-bacterial activities and 3-chlorophenol sensor fabrication using MnAl2O4·ZnAl2O4 nanomaterials.

A MnAl2O4·ZnAl2O4 nanomaterial was synthesized by co-precipitation and characterized by XRD, SEM, EDS, TEM, AFM, FTIR, PL, CV and EIS. The photocatalytic activity of the nanocomposite against MV dye and its MDR anti-bacterial functions were studied. The nanocomposite shows excellent photocatalytic as well as anti-bacterial activity. A MnAl2O4·ZnAl2O4 nanomaterial/Nafion/GCE electrode was fabricated and implemented as the working electrode of a 3-CP sensor. The sensor exhibited good sensitivity, with the lowest detection limit, fast response time, large linear dynamic range (LDR), and long-term stability in the chemical environment. The estimated sensitivity is 70.07 µA mM-1 cm-2. The LDR, limit of detection (LOD), and limit of quantification (LOQ) are 0.1 nM to 0.01 M, 0.0014 ± 0.0001 nM, and 0.004 nM, respectively. The MnAl2O4·ZnAl2O4 nanomaterial/Nafion/GCE is a promising fabricated sensor probe for the selective detection of 3-CP for the environmental safety and healthcare fields on a large scale.

Enhancing the Performance of Dye Sensitized Solar Cells Using Silver Nanoparticles Modified Photoanode.

In this study, silver nanoparticles were synthesized, characterized, and applied to a dye-sensitized solar cell (DSSC) to enhance the efficiency of solar cells. The synthesized silver nanoparticles were characterized with UV-Vis spectroscopy, dynamic light scattering, transmission electron microscopy, and field emission scanning electron microscopy. The silver nanoparticles infused titanium dioxide film was also characterized by Fourier transform infrared and Raman spectroscopy. The performance of DSSC fabricated with silver nanoparticle-modified photoanode was compared with that of a control group. The current and voltage characteristics of the devices as well as the electrochemical impedance measurements were also carried out to assess the performance of the fabricated solar cells. The solar-to-electric efficiency of silver nanoparticles based DSSC was 1.76%, which is quite remarkable compared to the 0.98% realized for DSSC fabricated without silver nanoparticles.

Impact of Zero-Valent Iron Nanoparticles on Fremyella diplosiphon Transesterified Lipids and Fatty Acid Methyl Esters.

Efforts to enhance the transformative potential of biofuels is an important step to achieving an environment-friendly and sustainable energy source. Fremyella diplosiphon is an ideal third-generation biofuel agent due to its ability to produce lipids and desirable essential fatty acids. In this study, the impact of Nanofer 25s nanoscale zero-valent iron nanoparticles (nZVIs) on total lipid content and fatty acid composition of F. diplosiphon strains SF33 and B481 was investigated. We observed significant increases (P < 0.05) in the growth of F. diplosiphon treated with 0.2-1.6 mg L-1 Nanofer 25s, indicating that trace concentrations of nZVIs were not toxic to the organism. Chlorophyll a, carotenoids, and phycobiliprotein levels were not altered in F. diplosiphon treated with nZVIs ranging from 0.4 to 1.6 mg L-1, confirming that these concentrations did not negatively impact photosynthetic efficacy. In addition, Nanofer 25s ranging from 0.2 to 1.6 mg L-1 had an optimal impact on SF33 and B481 total lipid content. We identified significant increases in unsaturated fatty acid methyl esters (FAMEs) from F. diplosiphon Nanofer 25s-treated transesterified lipids. Theoretical chemical and physical biofuel properties revealed a product with elevated cetane number and oxidative stability for both strains. Scanning electron microscopy and energy-dispersive X-ray spectroscopy validated the localization of nZVIs. Our findings indicate that Nanofer 25s nZVIs significantly enhance F. diplosiphon total lipid content and essential FAMEs, thus offering a promising approach to augment the potential of the cyanobacterium as a large-scale biofuel agent.

Terahertz Reflectometry Imaging of Carbon Nanomaterials for Biological Application.

The multiwalled carbon nanotubes has a myriad of applications due to its unique electrical and mechanical properties. The biomedical application of multiwalled carbon nanotubes that have been reported include drug delivery, medical imaging, gene delivery, tissue regeneration, and diagnostics. Proper characterization is required to enhance the potential application of the multiwalled carbon nanotubes. Terahertz technology is a relatively unfamiliar spectrometric technique that show promise in efficiently characterizing multiwalled carbon nanotubes. In this paper, terahertz imaging was used to characterize multiwalled carbon nanotube in comparison with other characterization techniques, including transmission electron microscopy and field emission scanning electron microscopy. The average diameter of the carbon nanotubes from the reconstructed terahertz images was 48.54 nm, while the average length of a fiber was found to be approximately 1.2 µm. The multiwalled carbon nanotubes were additionally characterized by FTIR, Raman spectroscopy, and Energy-dispersive X-ray spectroscopy.

Set of Highly Stable Amine- and Carboxylate-Terminated Dendronized Au Nanoparticles with Dense Coating and Nontoxic Mixed-Dendronized Form.

The synthesis of a novel poly(propyleneimine) (PPI) dendron in gram scale as well as its use in the formation of a highly stable, dendronized gold nanoparticle (AuNP)-based drug delivery platform is described herein. The AuNP-based platform is composed of three complementary parts: (i) a 15 nm AuNP core, (ii) a heterofunctional thioctic acid-terminated tetraethylene glycol spacer, and (iii) a third-generation PPI dendron with a unique protonation profile and diverse end-group functionalization that allows for further derivatization. The prepared dendronized AuNPs are able to withstand several rounds of lyophilization cycles with no sign of aggregation, are stable in phosphate-buffered saline and Hanks' buffer as well as in serum, and are resistant to degradation by glutathione exchange reactions. This nanocarrier platform displays a dense coating, with >1400 dendrons/AuNPs, which will enable very high payload. Furthermore, while amine-terminated AuNPs expectedly showed cytotoxicity against the MCF-7 breast cancer cell line from a NP concentration of 1 nM, the mixed monolayer AuNPs (coated with 40/60 amine/carboxylate dendrons) interestingly did not exhibit any sign of toxicity at concentrations as high as 15 nM, similar to the carboxylate-terminated AuNPs. The described dendronized AuNPs address the current practical need for a stable NP-based drug delivery platform which is scalable and easily conjugable, has long-term stability in solution, and can be conveniently formulated as a powder and redispersed in desired buffer or serum.

Lipoic Acid Decorated Gold Nanoparticles and Their Application in the Detection of Lead Ions.

A simple colorimetric method has been developed for the detection of lead (Pb2+) in water samples using lipoic acid-functionalized gold nanoparticles. The lipoic acid-functionalized gold nanoparticles are induced to aggregate in the presence of the Pb2+ which results in a change in the color of the functionalized gold nanoparticles. The change in color and the amount of Pb2+ producing the change could be monitored via UV-visible spectrophotometry. A good correlation coefficient of 0.9927 was obtained for the calibration curve of the colorimetric method. The method was applied in the determination of Pb2+ in water samples and the results compared to that of measurement carried out with Atomic Absorption Spectroscopy.

Photophysical Studies of Ruthenium-Based Complexes and the Performance of Nanostructured TiO2 Based Dye Sensitized Solar Cells.

Dye-sensitized solar cells (DSSCs) have attracted enormous attention in the last couple of decades due to their relatively small size, low cost and minimal environmental impact. DSSCs convert solar energy to electrical energy with the aid of a sensitizing dye. In this work, two ruthenium-based dyes, tris(bipyridine)ruthenium(II) chloride (Rubpy) and ruthenium(II)2,2'-bis(benzimidazol-2-yl)-4,4'-bipyridine (RubbbpyH2), were synthesized, characterized, and investigated for use as dye sensitizers in the fabrication of DSSCs. The photovoltaic performance of the ruthenium-based DSSCs was assessed. The solar-to-electric power efficiency of the RubbbpyH2 DSSC was 0.2% and that of the Rubpy was 0.03%. The RubbbpyH2 was also deprotonated and analyzed to study the effect of deprotonation on the efficiency of the solar cell. The deprotonated species, Rubbbpy, recorded an average efficiency of 0.12%. Thus, a change in pH did not enhance the efficiency of the solar cell. The cells were further characterized by impedance measurements. The photocurrent-photovoltage results were not consistent with the absorption spectra since Rubbbpy showed a more prominent band than RubbbpyH2 but had a lower efficiency.

Dendrimer-based Nanoparticle for Dye Sensitized Solar Cells with Improved Efficiency.

Dye sensitized solar cells were fabricated with DyLight680 (DL680) dye and its corresponding europium conjugated dendrimer, DL680-Eu-G5PAMAM, to study the effect of europium on the current and voltage characteristics of the DL680 dye sensitized solar cell. The dye samples were characterized by using Absorption Spectroscopy, Emission Spectroscopy, Fluorescence lifetime and Fourier Transform Infrared measurements. Transmission electron microscopy imaging was carried out on the DL680-Eu-G5PAMAM dye and DL680-Eu-G5PAMAM dye sensitized titanium dioxide nanoparticles to analyze the size of the dye molecules and examine the interaction of the dye with titanium dioxide nanoparticles. The DL680-Eu-G5PAMAM dye sensitized solar cells demonstrated an enhanced solar-to-electric energy conversion of 0.32% under full light illumination (100 mWcm-2, AM 1.5 Global) in comparison with that of DL680 dye sensitized cells which recorded an average solar-to-electric energy conversion of only 0.19%. The improvement of the efficiency could be due to the presence of the europium that enhances the propensity of dye to absorb sunlight.

Fabrication, Optimization and Characterization of Natural Dye Sensitized Solar Cell.

The dyes extracted from pomegranate and berry fruits were successfully used in the fabrication of natural dye sensitized solar cells (NDSSC). The morphology, porosity, surface roughness, thickness, absorption and emission characteristics of the pomegranate dye sensitized photo-anode were studied using various analytical techniques including FESEM, EDS, TEM, AFM, FTIR, Raman, Fluorescence and Absorption Spectroscopy. Pomegranate dye extract has been shown to contain anthocyanin which is an excellent light harvesting pigment needed for the generation of charge carriers for the production of electricity. The solar cell's photovoltic performance in terms of efficiency, voltage, and current was tested with a standard illumination of air-mass 1.5 global (AM 1.5 G) having an irradiance of 100 mW/cm2. After optimization of the photo-anode and counter electrode, a photoelectric conversion efficiency (η) of 2%, an open-circuit voltage (Voc) of 0.39 mV, and a short-circuit current density (Isc) of 12.2 mA/cm2 were obtained. Impedance determination showed a relatively low charge-transfer resistance (17.44 Ω) and a long lifetime, signifying a reduction in recombination losses. The relatively enhanced efficiency is attributable in part to the use of a highly concentrated pomegranate dye, graphite counter electrode and TiCl4 treatment of the photo-anode.

Interaction of Sensitizing Dyes with Nanostructured TiO2 Film in Dye-Sensitized Solar Cells Using Terahertz Spectroscopy.

The objective of this investigation was to shed light on the nature of interaction of different organic dyes and an inorganic dye, Ruthenium (II) polypyridine complex, with TiO2 nanoparticles. TiO2 is commonly deployed as an efficient energy transfer electrode in dye sensitized solar cells. The efficiency of dye sensitized solar cells is a function of the interaction of a dye with the electrode material such as TiO2. To the best of our knowledge the present study is the first effort in the determination of terahertz absorbance signals, investigation of real-time dye permeation kinetics, and the surface profiling and 3D imaging of dye sensitized TiO2 films. Herein, we report that the terahertz spectra of the natural dye sensitized TiO2 films were distinctively different from that of the inorganic dye with prominent absorption of natural dyes occurring at approximately the same wavelength. It was observed that the permeation of the natural dyes were more uniform through the layers of the mesoporous TiO2 compared to the inorganic dye. Finally, defects and flaws on TiO2 film were easily recognized via surface profiling and 3D imaging of the films. The findings thus offer a new approach in characterization of dye sensitized solar cells.

Syntheses and characterization of lisinopril-coated gold nanoparticles as highly stable targeted CT contrast agents in cardiovascular diseases.

Lisinopril was used as the targeting moiety to prepare gold nanoparticle-based functional CT contrast agents. Pure lisinopril, thioctic acid-lisinopril conjugate, and reduced thioctic acid-lisinopril conjugate were used to obtain GNP-Lis, GNP-TA-Lis, and GNP-RTA-Lis, respectively, via ligand exchange reaction on citrate-coated gold nanoparticles (GNPs). These lisinopril-decorated GNPs were fully characterized, and their chemical stabilities in biological relevant media and in high salt concentration were compared. Their relative stabilities toward lyophilization and against cyanide-induced decomposition were also investigated. Because of their higher stability, GNP-TA-Lis were used to assess the targeting of angiotensin converting enzyme (ACE) using X-ray computed tomography (CT). The images obtained displayed high contrast in the region of the lungs and heart, clearly indicating the targeting of ACE, whose overexpression is associated with development of cardiac and pulmonary fibrosis. Thus, the new nanoprobes prepared here will serve as very useful tools for the monitoring of cardiovascular pathophysiologies using CT imaging.