Synthesis and application of imprinted polyvinylimidazole-silica hybrid copolymer for Pb2+ determination by flow-injection thermospray flame furnace atomic absorption spectrometry

A novel ion imprinted polyvinylimidazole-silica hybrid copolymer (IIHC) was synthesized and used as a selective solid sorbent for Pb(2+) ions preconcentration using an on-line solid phase extraction (SPE) system coupled to TS-FF-AAS. The ionic hybrid sorbent was prepared using 1-vinylimidazole and 3-(trimethoxysilyl)propylmethacrylate as monomers, Pb(2+) ions as template, tetraethoxysilane as reticulating agent and 2,2'-azobis-isobutyronitrile as initiator. The best on-line SPE conditions concerning sorption behavior, including sample pH (6.46), buffer concentration (9.0 mmol L(-1)), eluent (HNO(3)) concentration (0.5 mol L(-1)) and preconcentration flow rate (4.0 mL min(-1)), were optimized by means of full factorial design and Doehlert matrix. The analytical curve ranged from 2.5 to 65.0 μg L(-1) (r=0.999) with limit of detection of 0.75 μg L(-1); the precision (repeatability) calculated as relative standard deviation (n=10) was 5.0 and 3.6% for Pb(2+) concentration of 10.0 and 60.0 μg L(-1), respectively. From on-line breakthrough curve, column capacity was 3.5 mg g(-1). Preconcentration factor (PF), consumptive index (CI) and concentration efficiency (CE) were 128.0, 0.16 mL and 25.6 min(-1), respectively. The selective performance of the sorbent, based on relative selectivity coefficient, was compared to NIC (non imprinted copolymer) for the binary mixture Pb(2+)/Cd(2+), Pb(2+)/Cu(2+) and Pb(2+)/Zn(2+). The results showed that ion imprinted polyvinylimidazole-silica hybrid polymer had higher selectivity for Pb(2+) than NIC at 64.9, 16.0 and 8.8 folds. The developed method was successfully applied for highly sensitive and selective Pb(2+) determination in different kinds of water samples, parenteral solutions and urine. Accuracy was also assessed by analyzing certified reference fish protein (DORM-3) and marine sediment (MESS-3 and PACS-2) with satisfactory results.     

Axial coding in full-field microscopy using three-dimensional structured illumination implemented with no moving parts

We report a simple optical setup to produce both axial and lateral structured illumination through a single objective lens. With a minimum of six full-field images obtained without moving either the sample or the microscope objective, 100 nm diameter fluorescent beads can be localized axially with an accuracy of 50 nm in a 1.76-microm-thick layer. We show that this axial localization improvement can easily be combined with classical lateral structured illumination, so that lateral resolution enhancement by a factor of 2 is maintained.     

Full prediction of the broadband optical modulation performance of a twisted nematic liquid crystal cell

We present a procedure to obtain the physical parameters responsible of twisted nematic liquid crystal (LC) cells optical modulation. The novelty of our approach is based on the use of spectroscopic measurements of the light transmitted by the system polarizer-LC cell-analyzer, combined with a previously proposed simple physical model of the LC twist and tilt distribution along cell. The procedure involves two steps: the first one yields off-state parameters like the LC director orientation, the twist angle, and the optical path difference (cell gap); the second step yields the effective retardances of the central and edge LC layers. The use of a spectroscopic method provides a full characterization of the LC cell as a function of both the voltage and the wavelength. The complete procedure leads to a very accurate prediction of the transmitted light broadband spectrum, as well as the complex (amplitude and phase) modulation for any wavelength within the calibration range.     

Plasticity Effects in the Hole-Drilling Residual Stress Measurement in Peened Surfaces

The incremental hole-drilling technique (IHD) is a widely established and accepted technique to determine residual stresses in peened surfaces. However, high residual stresses can lead to local yielding, due to the stress concentration around the drilled hole, affecting the standard residual stress evaluation, which is based on linear elastic equations. This so-called plasticity effect can be quantified by means of a plasticity factor, which measures the residual stress magnitude with respect to the approximate onset of plasticity. The observed resultant overestimation of IHD residual stresses depends on various factors, such as the residual stress state, the stress gradients and the material’s strain hardening. In peened surfaces, equibiaxial stresses are often found. For this case, the combined effect of the local yielding and stress gradients is numerically and experimentally analyzed in detail in this work. In addition, a new plasticity factor is proposed for the evaluation of the onset of yielding around drilled holes in peened surface layers. This new factor is able to explain the agreement and disagreement found between the IHD residual stresses and those determined by X-ray diffraction in shot-peened steel surfaces.     

Theoretical Approach for the Luminescent Properties of Ir(III) Complexes to Produce Red–Green–Blue LEC Devices

With an appropriate mixture of cyclometalating and ancillary ligands, based on simple structures (commercial or easily synthesized), it has been possible to design a family of eight new Ir(III) complexes (1A, 1B, 2B, 2C, 3B, 3C, 3D and 3E) useful as luminescent materials in LEC devices. These complexes involved the use of phenylpyridines or fluorophenylpyridines as cyclometalating ligands and bipyridine or phenanthroline-type structures as ancillary ligands. The emitting properties have been evaluated from a theoretical approach through Density Functional Theory and Time-Dependent Density Functional Theory calculations, determining geometric parameters, frontier orbital energies, absorption and emission energies, injection and transport parameters of holes and electrons, and parameters associated with the radiative and non-radiative decays. With these complexes it was possible to obtain a wide range of emission colours, from deep red to blue (701–440 nm). Considering all the calculated parameters between all the complexes, it was identified that 1B was the best red, 2B was the best green, and 3D was the best blue emitter. Thus, with the mixture of these complexes, a dual host–guest system with 3D-1B and an RGB (red–green–blue) system with 3D-2B-1B are proposed, to produce white LECs.     

New PEPTIR-2.0 Peptide Designed for Use as Recognition Element in Electrochemical Biosensors with Improved Specificity towards E. coli O157:H7

The detection of pathogens through alternative methodologies based on electrochemical biosensors is being studied. These devices exhibit remarkable properties, such as simplicity, specificity, and high sensitivity in monitoring pathogens. However, it is necessary to continue conducting studies that adequately improve these characteristics, especially the recognition molecule. This work aims to design and evaluate a new peptide, named PEPTIR-2.0, as a recognition molecule in electrochemical biosensors to detect E. coli O157:H7 in water. PEPTIR-2.0 was obtained from modifications of the PEPTIR-1.0 peptide sequence, which was previously reported and exhibited excellent properties for detecting and quantifying this pathogenic microorganism. PEPTIR-1.0 is a peptide analogous to the TIR (Translocated Intimin Receptor) protein capable of interacting with the Intimin outer membrane. The basis of this study was to obtain, by using bioinformatics tools, a molecule analogous to PEPTIR-1.0 that maintains its three-dimensional structure but increases the hydrophobic interactions between it and Intimin, since these intermolecular forces are the predominant ones. The designed PEPTIR-2.0 peptide was immobilized on screen-printed electrodes modified with gold nanoparticles. The detection capacity of E. coli O157:H7 in water was evaluated using electrochemical impedance spectroscopy in the presence of other microorganisms, such as P. aeruginosa, S. aureus, and non-pathogenic E. coli. The results showed that PEPTIR-2.0 confers remarkable specificity to the biosensor towards detecting E. coli, even higher than PEPTIR-1.0.     

Biodegradable Nanoparticles Loaded with Levodopa and Curcumin for Treatment of Parkinson’s Disease

Background: Parkinson’s disease (PD) is the second most common age-related neurodegenerative disorder. Levodopa (L-DOPA) remains the gold-standard drug available for treating PD. Curcumin has many pharmacological activities, including antioxidant, anti-inflammatory, antimicrobial, anti-amyloid, and antitumor properties. Copolymers composed of Poly (ethylene oxide) (PEO) and biodegradable polyesters such as Poly (ε-caprolactone) (PCL) can self-assemble into nanoparticles (NPs). This study describes the development of NH₂–PEO–PCL diblock copolymer positively charged and modified by adding glutathione (GSH) on the outer surface, resulting in a synergistic delivery of L-DOPA curcumin that would be able to pass the blood–brain barrier. Methods: The NH₂–PEO–PCL NPs suspensions were prepared by using a nanoprecipitation and solvent displacement method and coated with GSH. NPs were submitted to characterization assays. In order to ensure the bioavailability, Vero and PC12 cells were treated with various concentrations of the loaded and unloaded NPs to observe cytotoxicity. Results: NPs have successfully loaded L-DOPA and curcumin and were stable after freeze-drying, indicating advancing into in vitro toxicity testing. Vero and PC12 cells that were treated up to 72 h with various concentrations of L-DOPA and curcumin-loaded NP maintained high viability percentage, indicating that the NPs are biocompatible. Conclusions: NPs consisting of NH₂–PEO–PCL were characterized as potential formulations for brain delivery of L-DOPA and curcumin. The results also indicate that the developed biodegradable nanomicelles that were blood compatible presented low cytotoxicity.     

Topotactical Route to Multiwalled Cerium Oxide Nanotubes from MWCNTs

The development of new strategies for synthesizing 1D cerium oxide (CeO₂) hollow nanostructures has attracted much attention in recent years due to the importance of their superior properties and highly anisotropic geometry. This study reports an unpublished route of fabricating novel multiwalled CeO_2-δ nanotubes (CeO_2-δ NTs) in which the entire volume of functionalized multiwalled carbon nanotubes (f-MWCNTs) is converted into the CeO_2-δ pseudomorph through oxidation and dehydration topotactic reactions. The stable CeO_2-δ (111) planes are topotactically grown on the curved C (002) planes, preferentially exposed along the nanotube axis. In their initial condition, the novel nanotubes consist of Ce oxyhydroxide (CeO_2-x(OH)_x) with residual carbon. When heating the air up to 500 °C, CeO_2-x(OH)_x transforms gradually by dehydration into CeO_2-δ, while the residual carbon is oxidized. Despite compositional changes, nanotubes maintain their multiwalled structural integrity up to ≈550 °C. The CeO_2-δ NTs exhibit an unusually high presence of Ce³⁺ ions and surface O vacancies, contributing to a low direct band gap ranging from 2.67 to 2.32 eV compared to their NPs counterparts (3.2 eV).     

Development of a selective graphene quantum dots based electrochemical sensor for the determination of estrone in different water matrices and synthetic urine

Estrone (E1) is associated with various health and environmental issues, necessitating the development of analytical methods for monitoring E1 in different matrices. In this context, the present study reports the development of a graphene quantum dot-based electrode (GQD/E) to detect estrone in water and urine samples. Voltammetric measurements under optimized conditions demonstrated the feasibility of using GQD/E to detect estrone at trace levels in aqueous samples. Two linear dynamic ranges were obtained at concentrations from 0.05 to 10.00 μmol L⁻¹, with limit of detection (LOD) and quantification (LOQ) of 28.0 and 96.0 nmol L⁻¹, respectively. Furthermore, the LOD value obtained in this study is one of the lowest ever reported in the literature for the electrochemical determination of E1. The method response showed no significant variation in the current intensity of E1 in the presence of the 16 interferents. The recovery values obtained by using GQD/E to quantify estrone in fortified samples of seawater, tap water, wastewater and synthetic urine ranged from 95.9 to 108.1 %, indicating that the method presents highly sensitive for detecting estrone in aqueous matrices.     

Retrosynthetic Analysis Applied to Clip-off Chemistry: Synthesis of Four Rh(II)-Based Complexes as Proof-of-Concept

Clip-off Chemistry is a synthetic strategy that our group previously developed to obtain new molecules and materials through selective cleavage of bonds. Herein, we report recent work to expand Clip-off Chemistry by introducing into it a retrosynthetic analysis step that, based on virtual extension of the products through cleavable bonds, enables one to define the required precursor materials. As proof-of-concept, we have validated our new approach by synthesising and characterising four aldehyde-functionalised Rh(II)-based complexes: a homoleptic cluster; a cis-disubstituted paddlewheel cluster; a macrocycle; and a crown.