Innovative Non-Enzymatic Electrochemical Quantification of Cholesterol.

The use of the Liebermann-Burchard reaction in this study has been explored in the development of a simple, reliable, and robust quantitative electrochemical method to assay cholesterol, and hence provide a good alternative to colorimetric methods. The optimization of batch mode operation for electrochemical oxidation of cholesterol in the Liebermann-Burchard reagents included the applied potential and acidic volume. Tested using chronoamperometry, the developed method showed a high sensitivity (14.959 µA mM-1) and low detection limit (19.78 nM) over a 0.025-3 mM concentration range, with remarkable linearity (R2 = 0.999), proving an analytical performance either higher or comparable to most of the cholesterol sensors discussed in literature. The influence of possible interfering bioactive agents, namely, glucose, uric acid, ascorbic acid, KCl and NaCl, has been evaluated with no or negligible effects on the measurement of cholesterol. Our study was directed at finding a new approach to chemical processing arising from the use of external potential as an additional level of control for chemical reactions and the transfer of electrons between surfaces and molecules. Finally, the optimized method was successfully applied for the determination of cholesterol content in real blood samples.

Cyclodextrin Encapsulated pH Sensitive Dyes as Fluorescent Cellular Probes: Self-Aggregation and In Vitro Assessments.

We have designed and synthesized a series of novel, supramolecular, long-lived fluorescent probes based on the host-guest inclusion complexes formation between fluorescent indolizinyl-pyridinium salts and ß-cyclodextrin. Fluorescence and electrospray ionisation mass spectrometry experiments, supported by theoretical molecular docking studies, were utilized in the monitoring of the inclusion complexes formation, evidencing the appearance of corresponding 1:1 and 1:2 species. Additionally, the influence of the guest molecule over the aggregation processes of the cyclodextrin inclusion complexes was investigated by transmission electron microscopy. The absence of cytotoxicity, cellular permeability, long-lived intracellular fluorescence, and in time specific accumulation within acidic organelles identified the investigated supramolecular entities as remarkable candidates for intracellular fluorescence probes. Co-staining experiments using specific organelle markers revealed the fact that, after a 24-h incubation period, the inclusion complexes accumulate predominantly in lysosomes rather than in mitochondria. This study opens new possibilities for a broad range of fluorescent dyes with solubility and high toxicity issues, able to form inclusion complexes with ß-cyclodextrin, to be tested as intracellular fluorescence probes.

Zinc Oxide Spherical-Shaped Nanostructures: Investigation of Surface Reactivity and Interactions with Microbial and Mammalian Cells.

Two ZnO materials of spherical hierarchical morphologies, with hollow (ZnOHS) and solid cores (ZnOSS), were obtained through the hydrolysis of zinc acetylacetonate in 1,4-butanediol. The nature of the defects and surface reactivity for the two ZnO materials were investigated through photoluminescence, X-ray photoelectron spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy proving the coexistence of shallow and deep defects and, also, the presence of polyol byproducts adsorbed on the outer layers of the ZnO samples. The EPR spectroscopy coupled with the spin-trapping technique showed that the surface of the ZnO samples generates reactive oxygen species (ROS) like hydroxyl (•OH) and singlet oxygen (1O2) as well as carbon-centered radicals. The ZnO materials exhibited a wide spectrum of antimicrobial activity, being active against Gram-positive, Gram-negative, and fungi strains, both in planktonic and, more importantly, adherent growth states. The decrease of antimicrobial efficiency in the presence of a ROS scavenger (mannitol) and the decrease of the cell viability with the ROS level suggest that one of the mechanisms that governs both the antimicrobial and cytotoxic activities on human liver cells is ROS-mediated. However, at active antimicrobial concentrations, the biocompatibility of the tested materials is very good.

Sustainable one-pot integration of ZnO nanoparticles into carbon spheres: manipulation of the morphological, optical and electrochemical properties.

ZnO-carbon composite spheres were synthesized via starch hydrothermal carbonization (HTC) in the presence of a soluble zinc salt (acetate), followed by thermal processing under an argon atmosphere. Besides sustainability, the one-pot procedure represents a scalable synthesis of tailored carbon-metal oxide spheres with a structurally-ordered carbon matrix obtained at a relatively low temperature (700 °C). The ability of zinc cations to develop different linkages with starch's hydrophilic functional groups and to act as external nucleators determines an increase in HTC yield; the effect is obvious even in the presence of small concentrations of zinc in the reaction medium (0.005 M), thus providing a way to improve the carbonization process efficiency. It is also shown that zinc content is the control vector of the spherical composite's properties: a variation from 0.3 to 4.8 at% not only induces a variation in their size (200 nm-10 µm), interconnectivity (from disperse spheres to necklace-like aggregations), surface area and connected porosity (from micro- to mesoporosity), but also of their electrochemical and white light adsorption and emission features. Since the variation in zinc content is made by a simple adjustment of the raw material concentrations, the functionality of these carbon-based materials can be modulated in a straightforward manner.

Dynameric G-quadruplex-dextran hydrogels for cell growth applications.

Hybrid dextran-G-quartet produces tunable biocompatible three-dimensional thixotropic hydrogels, able to support cell growth.

Deciphering the role of water and a zinc-doping process in a polyol-based approach for obtaining Zn/Co/Al-based spinels: toward "green" mesoporous inorganic pigments.

Two new families of zinc/cobalt/aluminum-based pigments, with a unique composition, were obtained through the polyol method. The hydrolysis process of a mixture of Co(CH3COO)2, Zn(acac)2 and Al(acac)3 (acac- = acetylacetonate ion) in 1,4-butanediol afforded dark blue gels (wPZnxCo1-xAl), in the presence of a supplementary amount of water, and light green powders (PZnxCo1-xAl), respectively, for the water-free procedure (x = 0, 0.2, 0.4). The calcination of the precursors yielded dark green (wZnxCo1-xAl) and blue (ZnxCo1-xAl) products. XRD measurements and Rietveld refinement indicate the co-existence of three spinel phases, in different proportions: ZnxCo1-xAl2O4, Co3O4 and the defect spinel, γ-Al2.67O4. The Raman scattering and XPS spectra are in agreement with the compositions of the samples. The morphology of wZnxCo1-xAl consists of large and irregular spherical particle aggregates (ca. 5-100 mm). Smaller agglomerates (ca. 1-5 mm) with a unique silkworm cocoon-like hierarchical morphology composed of cobalt aluminate cores covered with flake-like alumina shells are formed for ZnxCo1-xAl. TEM and HR-TEM analyses revealed the formation of crystalline, polyhedral particles of 7-43 nm sizes for wZnxCo1-xAl, while for ZnxCo1-xAl, a duplex-type morphology, with small (7-13 nm) and larger (30-40 nm) particles, was found. BET assessment showed that both series of oxides are mesoporous materials, with different pore structures, with the water-free samples exhibiting the largest surface areas due, most likely, to the high percent of aluminum oxide. A chemical mechanism is proposed to highlight the role of the water amount and the nature of the starting compounds in the hydrolysis reaction products and, further, in the morpho-structural features and composition of the resulting spinel oxides. The CIE L*a*b* and C* colorimetric parameters indicate that the pigments are bright, with a moderate degree of luminosity, presenting an outstanding high blueness.

Ag-Decorated Iron Oxides-Silica Magnetic Nanocomposites with Antimicrobial and Photocatalytic Activity.

Nanotechnology offers unlimited possibilities for creating effective hybrid materials, which combine functional performance in environment depollution and antimicrobial defense with a lack of toxicity, biocompatibility, biodegradability, and natural availability. This paper presents the silver effect on photocatalytic and antibacterial activities of double-coated iron oxide nanoparticles (NPs), Fe3O4@SiO2/ZnO-Ag. The structural, morphological, and textural information of the, core-shell iron oxides-based superparamagnetic nanoparticles (IOMNPs) decorated with 5% Ag by ultrasound-assisted synthesis were evaluated by scanning electron microscopy with energy dispersive spectroscopy (SEM-EDX), X-ray diffraction, Raman spectroscopy, and Brunauer-Emmett-Teller physisorption measurements. Although two synthesis temperatures of 95 and 80 °C were used for the co-precipitated iron oxide cores, the XRD patterns revealed the formation of a single magnetite, Fe3O4, phase. The sorption-photocatalytic activities under dark and UV irradiation encountered a maximum removal efficiency of the MB (90.47%) for the Fe3O4@SiO2/ZnO-Ag sample with iron oxide core obtained at 80 °C. The rate constant for the second-order kinetics was 0.0711 min-1 for 2 h, and the correlation coefficient R2 closed to unity. Two samples with Ag-decorated hybrid SiO2/ZnO shell and hierarchically interconnected porous structure with large surface area (328.8 and 342.5 m2g-1) exhibited the best disk diffusion antimicrobial activity against four microorganisms, especially gram-positive Staphylococcus aureus.

Magnetic Core-Shell Iron Oxides-Based Nanophotocatalysts and Nanoadsorbents for Multifunctional Thin Films.

In recent years, iron oxides-based nanostructured composite materials are of particular interest for the preparation of multifunctional thin films and membranes to be used in sustainable magnetic field adsorption and photocatalysis processes, intelligent coatings, and packing or bio-medical applications. In this paper, superparamagnetic iron oxide (core)-silica (shell) nanoparticles suitable for thin films and membrane functionalization were obtained by co-precipitation and ultrasonic-assisted sol-gel methods. The comparative/combined effect of the magnetic core co-precipitation temperature (80 and 95 °C) and ZnO-doping of the silica shell on the photocatalytic and nano-sorption properties of the resulted composite nanoparticles were investigated by ultraviolet-visible (UV-VIS) spectroscopy monitoring the discoloration of methylene blue (MB) solution under ultraviolet (UV) irradiation and darkness, respectively. The morphology, structure, textural, and magnetic parameters of the investigated powders were evidenced by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) measurements, and saturation magnetization (vibrating sample magnetometry, VSM). The intraparticle diffusion model controlled the MB adsorption. The pseudo- and second-order kinetics described the MB photodegradation. When using SiO2-shell functionalized nanoparticles, the adsorption and photodegradation constant rates are three-four times higher than for using starting core iron oxide nanoparticles. The obtained magnetic nanoparticles (MNPs) were tested for films deposition.

Electrochemical behaviour of piperine. Comparison with control antioxidants.

Piperine, as the most abundant alkaloid in pepper, gained a lot of attention for possible antioxidant and therapeutic properties. Electrochemical techniques were applied to widely evaluate the redox behavior of piperine by comparison to that of well-known antioxidants: ascorbic acid, protocatechuic acid, syringic acid, tyrosine and capsaicin used as controls. Also, electrochemistry was involved in an innovative way to investigate the potential antioxidant properties of piperine combined with different in vitro peroxidation and reducing assays: (i) 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging; (ii) 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) scavenging; (iii) ferric ions (Fe3+) reducing power; (iv) hydrogen peroxide (H2O2) scavenging. Results show that piperine readily reacts with highly oxidizing radicals and bind redox-active metal ions in a similar manner as antioxidants used as model.

Rational Functionalization Towards Redox-Active TEMPO Stable Free-Radical-Hydrochar Composites.

Although both stable free organic radicals and biomass-derived hydrochars have emerged as appealing, green, multifunctional materials, their association has not been explored. In this study, strength is found to lie in their union, which primarily leads to stable redox-active free-radical-hydrochar composites that can generate unexpected opportunities for the development of advanced metal-free sustainable materials. The composites are obtained by a straightforward green one-pot hydrothermal procedure. The loading of stable free radicals of nitroxide type and their localization is engineered by the nature of the carbohydrate and the reaction status; vigorous reaction parameters promote faster nucleation and growth kinetics of the hydrochar products, leading to a covalent immobilization of redox species on the surface of the carbonaceous microspherical aggregates. The nitroxide free-radical-hydrochar materials demonstrate enhancements in terms of both electrocatalytic activity and capacitive features.

Eco-friendly synthesized spherical ZnO materials: Effect of the core-shell to solid morphology transition on antimicrobial activity.

ZnO materials with spherical morphology, core-shell and solid, disperse or interconnected, were obtained by a completely green synthesis via a carbohydrate-template route. Morphology, structure and optical properties, as well as antimicrobial potential and cytocompatibility were investigated. The antimicrobial efficiency of the obtained materials was screened against a large spectrum of reference and clinical microbial strains, both susceptible and exhibiting resistance phenotypes of clinical and epidemiological interest, in planktonic and biofilm state. Their biocidal activity is strongly dependent of material's characteristics and target microorganism. One of the most valuable findings of our study is the good antibiofilm activity of the obtained nanostructures, which in some cases was superior to that noted against planktonic cells, despite the well-known high tolerance of biofilm-embedded cells to different stressor agents. Another important finding is the excellent efficiency against three Gram-negative, respectively Pseudomonas aeruginosa, Acinetobacter baumannii, and Klebsiella pneumoniae and two Gram-positive species, i.e. Staphylococcus aureus and Enteroccus faecium included in the ESKAPE list of the most dangerous resistant pathogens, requiring global surveillance and urgent need for the development of novel antimicrobial agents. Our study offers the first insight regarding the high therapeutic potential of ZnO nanoparticles against the fearful nosocomial pathogen A. baumannii. The cytocompatibility of the developed materials in terms of cell morphology, viability and proliferation, revealed a comparable dose-dependent cellular response, at the active antimicrobial concentrations, only a low effect on cell viability is evidenced. Overall, our data demonstrated the potential of the materials for antimicrobial applications and also that their biotoxicity can be modulated directly through their morpho-structural characteristics.

Self-assembled zinc oxide hierarchical structures with enhanced antibacterial properties from stacked chain-like zinc oxalate compounds.

Single ZnO crystallites assembled into porous hierarchical structures have been prepared by topotactic thermal decomposition of in situ obtained zinc oxalate precursors, whose synthesis involves a redox reaction between 1,2-ethanediol and nitrate ion. For the first time it was demonstrated that post-synthesis protocols of the precursors (e.g. ultrasound irradiation, hydrolytic decomposition) master the hydrogen bonds formed between oxalate chains, allowing that way the adjustment of materials properties (morphology, porosity and optical) and a rational introduction of different dopants (Eu3+/Er3+). The ZnO surface reactivity is confirmed by the significant biocidal activity of the obtained materials against Gram-positive and Gram-negative planktonic and biofilm-embedded cells, superior to those reported in the literature for other ZnO-based materials or antibiotics, associated also with a good biocompatibility.

Facile, high yield ultrasound mediated protocol for ZnO hierarchical structures synthesis: Formation mechanism, optical and photocatalytic properties.

Hierarchical flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method performed in a ordinary ultrasonic bath using an ammonia solution and zinc acetate, in the absence of any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the materials obtained at different ultrasound irradiation times were characterized by infrared, UV-Vis and photoluminescence spectroscopy, X-ray diffraction, scanning and transmission electron microscopy investigations. It was proved that the ultrasound irradiation time manipulates both the defect content (implicit the photoluminescent properties) and morphology of the ZnO materials: shorter irradiation times leads to the synthesis of high-defected ZnO structures of flower morphology with triangular-shaped petals, while higher irradiation times favours the formation of low-defected ZnO structures with tipped rod-like petals. A plausible growth mechanism of the architectures that implies aggregation via oriented attachment followed by an Ostwald ripening is advanced based on these results. The ZnO flower-like structures present high photocatalytic activities, a total phenol mineralization being registered in the case of visible light experiments. Electron-spin resonance measurements demonstrate the generation of reactive oxygen species, namely hydroxyl radicals but also C centred radicals adducts derived most probable from the residual acetate adsorbed on ZnO surface.

Tunable ZnO spheres with high anti-biofilm and antibacterial activity via a simple green hydrothermal route.

A family of distinct ZnO morphologies - hollow, compartmented, core-shell and full solid ZnO spheres, dispersed or interconnected - is obtained by a simple hydrothermal route, in the presence of the starch biopolymer. The zinc-carbonaceous precursors were characterized by infrared spectroscopy, thermal analysis and scanning electron microscopy, while the ZnO spheres, obtained after the thermal processing, were investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, UV-VIS spectroscopy, photoluminescence measurements, antimicrobial, anti-biofilm and flow cytometry tests. The formation mechanism proposed for this versatile synthesis route is based on the gelling ability of amylose, one of the starch template constituents, responsible for the effective embedding of zinc cations into starch prior to its hydrothermal carbonization. The simple variation of the raw materials concentration dictates the type of ZnO spheres. The micro-sized ZnO spheres exhibit high antibacterial and anti-biofilm activity against Gram-positive (Staphylococcus aureus, Bacillus subtilis) and Gram-negative (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa) reference and methicillin resistant clinical strains especially for Gram-negative biofilms (P. aeruginosa), demonstrating great potential for new ZnO anti-biofilm formulations.

Biopolymer starch mediated synthetic route of multi-spheres and donut ZnO structures.

A starch-assisted synthetic methodology of multispheres ZnO-starch biocomposites was developed. An additional thermal processing of the ZnO-starch composites induces the formation of ZnO with donut-like morphology. The synthesis of single-phase zinc oxide with a spherical morphology is conditioned by the presence of starch, which acts as template, stabilizing/capping agent. The synthesized structures present significant photocatalytic activities; a total phenol mineralization is attained with the donut-like ZnO photocatalyst under visible light irradiation, due to a cumulative effect of the its relatively large specific surface area, high crystallinity and favorable combination of defects for band narrowing, which together permit an enhanced utilization rate of the light.

A general, eco-friendly synthesis procedure of self-assembled ZnO-based materials with multifunctional properties.

A bioinspired one-pot approach for the synthesis of ZnO-carbohydrate hierarchical architectures was developed. The synergy between a saccharide (mono-, di- or polysaccharide) that contains d-glucose units and triethanolamine is the key parameter of the synthetic methodology. The morphology of the ZnO composites is dictated by the saccharide used, and rod, spindle, solid and hollow spherical-like ZnO structures are obtained by varying the carbohydrate. The synthesized composites present good photocatalytic and antimicrobial activity.