Icosahedral gold nanoparticles decorated with hexon protein: a surrogate for adenovirus serotype 5.

The development of synthetic particles that emulate real viruses in size, shape, and chemical composition is vital to the development of imprinted polymer-based sorbent materials (molecularly imprinted polymers, MIPs). In this study, we address surrogates for adenovirus type 5 (Adv 5) via the synthesis and subsequent modification of icosahedral gold nanoparticles (iAuNPs) decorated with the most abundant protein of the Adv 5 (i.e., hexon protein) at the surface. CTAB-capped iAuNPs with dimensions in the range of 40-90 nm were synthesized, and then CTAB was replaced by a variety of polyethylene glycols (PEGs) in order to introduce suitable functionalities serving as anchoring points for the attachment of the hexon protein. The latter was achieved by non-covalent linking of the protein to the iAuNP surface using a PEG without reactive termination (i.e., methoxy PEG thiol, mPEG-SH, Mn=800). Alternatively, covalent anchoring points were generated by modifying the iAuNPs with a bifunctional PEG (i.e., thiol PEG amine, SH-PEG-NH2) followed by the addition of glutaraldehyde. X-ray photoelectron spectroscopy (XPS) confirmed the formation of the anchoring points at the iAuNP surface. Next, the amino groups present in the amino acids of the hexon protein interacted with the glutaraldehyde. iAuNPs before and after PEGylation were characterized using dynamic light scattering (DLS), XPS, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and UV-Vis spectroscopy, confirming the CTAB-PEG exchange. Finally, the distinct red shift obtained in the UV-Vis spectra of the pegylated iAuNPs in the presence of the hexon protein, the increase in the hydrodynamic diameter, the change in the zeta potential, and the selective binding of the hexon-modified iAuNPs towards a hexon-imprinted polymer (HIP) confirmed success in both the covalent and non-covalent attachment at the iAuNP surface.

Molecularly imprinted polymers for selective extraction/microextraction of cancer biomarkers: A review.

Over recent years, great efforts have been extensively documented in top scientific journals on the development of methods for early diagnosis, treatment, and monitoring of cancers which are prevalent critical diseases with a high mortality rate among men and women. The determination of cancer biomarkers using different optimum methodologies is one of the finest options for achieving these goals with more precision, speed, and at a lower cost than traditional clinical procedures. In this regard, while focusing on specific biomarkers, molecularly imprinted technology has enabled novel diagnostic techniques for a variety of diseases. Due to the well-known advantages of molecularly imprinted polymers (MIPs), this review focuses on the current trends of MIPs-based extraction/microextraction methods, specifically targeting cancer biomarkers from various matrices. These optimized methods have demonstrated high selectivity, accuracy, sorbent reusability, extraction recovery, and low limits of detection and quantification for a variety of cancer biomarkers, which are a powerful tool to provide early diagnosis, prognosis, and treatment monitoring, with potential clinical application expected soon. This review highlights the key progress, specific modifications, and strategies used for MIP synthesis. The future perspectives for cancer biomarkers purification and determination by fabricating MIP-based techniques are also discussed.

Plastic Antibodies Mimicking the ACE2 Receptor for Selective Binding of SARS-CoV-2 Spike.

Molecular imprinting has proven to be a versatile and simple strategy to obtain selective materials also termed "plastic antibodies" for a wide variety of species, i.e., from ions to macromolecules and viruses. However, to the best of the authors' knowledge, the development of epitope-imprinted polymers for selective binding of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is not reported to date. An epitope from the SARS-CoV-2 spike protein comprising 17 amino acids is used as a template during the imprinting process. The interactions between the epitope template and organosilane monomers used for the polymer synthesis are predicted via molecular docking simulations. The molecularly imprinted polymer presents a 1.8-fold higher selectivity against the target epitope compared to non-imprinted control polymers. Rebinding studies with pseudoviruses containing SARS-CoV-2 spike protein demonstrate the superior selectivity of the molecularly imprinted matrices, which mimic the interactions of angiotensin-converting enzyme 2 receptors from human cells. The obtained results highlight the potential of SARS-CoV-2 molecularly imprinted polymers for a variety of applications including chem/biosensing and antiviral delivery.

µOPTO: A microfluidic paper-based optoelectronic tongue as presumptive tests for the discrimination of alkaloid drugs for forensic purposes.

Natural and synthetic alkaloids are widely used for several applications, ranging from clinical purposes to criminal activities. Presumptive color tests are considered a leading tool to reveal on-scene substance identification via rapid chemical reactions that result in visual color changes. Colorimetric tests are popular due to their inherent simplicity, low cost, promptitude and portability; however, in many cases the results of such tests may not be predictable, partly because of the interference from similar species. In this proof-of-concept study, we present a paper-based microfluidic optoelectronic tongue - the so-called µOPTO - comprised of 6 indicators in lieu of one specific test and capable of discriminating 8 different alkaloid drugs (i.e. scopolamine, atropine, cocaine, morphine, ephedrine, caffeine, dipyrone and alprazolam) used for recreational, criminal and medical purposes. The wax printing method was employed to fabricate the microfluidic analytical device with six circular spots for reagent accommodation connected to a centered spot to enable simultaneous reactions with one sample injection. Digital images were obtained using an ordinary flatbed scanner, and the RGB information from before and after sample exposure was extracted using appropriate software. The color changes related to each spot were used to build differential maps with a unique fingerprint for each drug. The chemometric tools (i.e. PCA and HCA) showed suitable discrimination of all studied alkaloids in different quantities. To demonstrate a practical application, different alcoholic beverages spiked with scopolamine - a famous substance that causes drug abuse - were analyzed using the optoelectronic tongue. The results showed that small quantities of the drug were identified in different beverages, demonstrating that our device has the potential to be used in situ to prevent ingestion of contaminated samples.

Development and Characterization of Magnetic SARS-CoV-2 Peptide-Imprinted Polymers.

The development of new methods for the rapid, sensitive, and selective detection of SARS-CoV-2 is a key factor in overcoming the global pandemic that we have been facing for over a year. In this work, we focused on the preparation of magnetic molecularly imprinted polymers (MMIPs) based on the self-polymerization of dopamine at the surface of magnetic nanoparticles (MNPs). Instead of using the whole SARS-CoV-2 virion as a template, a peptide of the viral spike protein, which is present at the viral surface, was innovatively used for the imprinting step. Thus, problems associated with the infectious nature of the virus along with its potential instability when used as a template and under the polymerization conditions were avoided. Dopamine was selected as a functional monomer following a rational computational screening approach that revealed not only a high binding energy of the dopamine-peptide complex but also multi-point interactions across the entire peptide template surface as opposed to other monomers with similar binding affinity. Moreover, variables affecting the imprinting efficiency including polymerization time and amount of peptide and dopamine were experimentally evaluated. Finally, the selectivity of the prepared MMIPs vs. other peptide sequences (i.e., from Zika virus) was evaluated, demonstrating that the developed MMIPs were only specific for the target SARS-CoV-2 peptide.

Current overview and perspectives in environmentally friendly microextractions of carbamates and dithiocarbamates.

Carbamates and dithiocarbamates are two classes of pesticides widely employed in the agriculture practice to control and avoid pests and weeds, hence, the monitoring of the residue of those pesticides in different foodstuff samples is important. Thus, this review presents the classification, chemical structure, use, and toxicology of them. Moreover, it was shown the evolution of liquid- and solid-phase microextractions employed in the extraction of carbamates and dithiocarbamates in water and foodstuff samples. The classification, operation mode, and application of the microextractions of liquid-phase and solid-phase used in their extraction were discussed and related to the analytical parameters and guidelines of green analytical chemistry.

Chemical QR Code: A simple and disposable paper-based optoelectronic nose for the identification of olive oil odor.

Olive oil is an appreciated food product with high nutritional value, besides being an essential component in many culture diets. In this study, we present for the first time the application of a simple and non-invasive paper-based optoelectronic nose designed in a QR code configuration to evaluate the odor of olive oils. The chemical QR code was fabricated by the addition of 12 dyes, which provided high dimensional data resulting from the interaction between the volatile compounds and the colorimetric array. The color changes were employed to build differential maps with a unique fingerprint (i) to discriminate between olive oil and other edible oil samples; (ii) to quantify nonanaldehyde as an oxidation marker; and (iii) to identify oxidized oils through principal component analysis (PCA) and hierarchical component analysis (HCA). By developing suitable mobile apps, we anticipate the employment of the chemical QR code for portable, low-cost, and in-situ evaluation of food product quality.

Molecularly Imprinted Polymer Micro- and Nano-Particles. A review.

In recent years, molecularly imprinted polymers (MIPs) have become an excellent solution to the selective and sensitive determination of target molecules in complex matrices where other similar and relative structural compounds could coexist. Although MIPs show the inherent properties of the polymers, including stability, robustness, and easy/cheap synthesis, some of their characteristics can be enhanced, or new functionalities can be obtained when nanoparticles are incorporated in their polymeric structure. The great variety of nanoparticles available significantly increase the possibility of finding the adequate design of nanostructured MIP for each analytical problem. Moreover, different structures (i.e., monolithic solids or MIPs micro/nanoparticles) can be produced depending on the used synthesis approach. This review aims to summarize and describe the most recent and innovative strategies since 2015, based on the combination of MIPs with nanoparticles. The role of the nanoparticles in the polymerization, as well as in the imprinting and adsorption efficiency, is also discussed through the review.

Novel approaches for colorimetric measurements in analytical chemistry - A review.

Colorimetric techniques have been developed and used in routine analyses for over a century and apparently all their potentialities have been exhaustively explored. However, colorimetric techniques have gained high visibility in the last two decades mainly because of the development of the miniaturization concept, for example, paper-based analytical devices that mostly employ colorimetric reactions, and by the advances and popularity of image capture instruments. The impressive increase in the use of these devices was followed by the development and enhancement of different modes of color detection to meet the demands of making qualitative, semi-quantitative, and fully quantitative analyses of multiple analytes. Cameras, scanners, and smartphones are now being used for this purpose and have become suitable alternatives for different approaches to colorimetric analysis; this, in addition to advancements in miniaturized devices. On the other hand, recent developments in optoelectronics technologies have launched more powerful, more stable and cheaper light-emitting diodes (LEDs), which once again have become an interesting tool for the design of portable and miniaturized devices based on colored reactions. Here, we present a critical review of recent developments and challenges of colorimetric detection in modern analytical chemistry in the last five years, and present thoughts and insights towards future perspectives in the area to improve the use of colorimetric detection in different application approaches.

Two-dimensional separation by sequential injection chromatography.

Sequential injection chromatography (SIC) is an alternative for fast chromatographic separations with low consumption of organic solvents. However, its separation capacity is restricted by the use of short chromatographic columns and the limitations for gradient elution. The present work aimed to expand the analytical capacity of SIC by exploiting a multidimensional approach with two chromatographic columns, different in their separation mechanisms, which increased the selectivity and peak resolution. The viability of the proposal was demonstrated by separation of aromatic biogenic amines (histamine, tyramine, phenylethylamine, and tryptamine), whose unidimensional separation was not achieved either by using cyanopropyl or C18 chromatographic columns. In the two-dimensional approach, the fraction of the eluate unresolved in the first dimension (containing tyramine and phenylethylamine) was collected in a sampling loop and, subsequently, inserted in the second chromatographic dimension (heart-cutting mode). Under the optimized conditions, the first chromatographic dimension was based on a cyanopropyl monolithic column and an aqueous mobile phase composed of phosphoric acid solution, pH 2.5, while the second dimension employed a C18 superficially porous particle column and a mobile phase composed of acetonitrile and phosphoric acid aqueous solution, pH 2.5 (7:93, v/v). The total analysis time was 8 min, and a resolution of 1.72 was achieved between the nearest peaks (tyramine and phenylethylamine). Linear responses were obtained within 10 and 50 mg L-1 (r > 0.997), with detection limits estimated at 2.7, 7.7, 1.9, and 0.3 mg L-1, for histamine, tyramine, phenylethylamine, and tryptamine, respectively, and a coefficient of variation of 3.0% (n = 12).

Fast methods for simultaneous determination of arginine, ascorbic acid and aspartic acid by capillary electrophoresis.

Arginine (ARG), ascorbic acid (ASC) and aspartic acid (ASP) are very popular and widely consumed active ingredients used for fatigue treatment or improvement of physical performance. For this reason, these compounds are usually available in the same pharmaceutical formulation. In the current paper, we describe for the first-time methods for simultaneous determination of ARG, ASC and ASP using capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) and with UV spectrophotometric detection (CE-UV). The proposed methods are simple, rapid (78 and 23 injections h-1, respectively) and have low environmental impact (minimal waste generation). The separation by CE-C4D was achieved with a background electrolyte (BGE) composed by 20 mmol L-1 N-tris(hydroxymethyl)- methyl]-3-aminopropanesulfonic acid (TAPS) and 10 mmol L-1 of NaOH (pH 8.7). The limits of detection (LOD) were 0.01, 0.02 and 0.04 mmol L-1 for ARG, ASC and ASP, respectively. The proposed CE-UV method was optimized with a BGE composed by 10 mmol L-1 sodium tetraborate (pH 9.4). The limits of detection (LOD) were 0.03, 0.02 and 0.04 mmol L-1 for ARG, ASC and ASP, respectively. No statistically significant differences were observed (95% confidence level) between the results obtained by the developed CE methods and reference procedures (HPLC for ARG, iodometry for ASC and, acid-base titration for ASP).

Solid-phase extractions in flow analysis.

Coupling solid-phase extraction (SPE) to flow systems has promoted a synergistic development. Whereas SPE mechanization leads to improved precision and higher sample throughput, as well as diminishes systematic errors and contamination risks, analyte concentration and separation from the sample matrix provides a remarkable impact on detectability and selectivity in flow analysis. Historical aspects, main cornerstones, tips for system design, and recent applications are critically reviewed, in the context of analyte(s) separation/concentration, sample clean-up, and release of sorbed chemical species involving both packed (e.g. mini-columns, cartridges, and disks) or fluidized (e.g. beads and magnetic materials) particles. Novel (bio)sorbents, selective synthetic materials, and stationary phases for low-pressure chromatography are also discussed. Moreover, the feasibility of SPE for sample treatment before chromatographic separation, as well as the exploitation of direct measurements on the solid phase (optosensing) are emphasized.

Solid-phase extractions in flow analysis

ABSTRACT Coupling solid-phase extraction (SPE) to flow systems has promoted a synergistic development. Whereas SPE mechanization leads to improved precision and higher sample throughput, as well as diminishes systematic errors and contamination risks, analyte concentration and separation from the sample matrix provides a remarkable impact on detectability and selectivity in flow analysis. Historical aspects, main cornerstones, tips for system design, and recent applications are critically reviewed, in the context of analyte(s) separation/concentration, sample clean-up, and release of sorbed chemical species involving both packed (e.g. mini-columns, cartridges, and disks) or fluidized (e.g. beads and magnetic materials) particles. Novel (bio)sorbents, selective synthetic materials, and stationary phases for low-pressure chromatography are also discussed. Moreover, the feasibility of SPE for sample treatment before chromatographic separation, as well as the exploitation of direct measurements on the solid phase (optosensing) are emphasized.

Single-run capillary electrophoresis method for the fast simultaneous determination of amoxicillin, clavulanate, and potassium.

We report a new fast method for the simultaneous determination of amoxicillin, clavulanate, and potassium by capillary electrophoresis with capacitively coupled contactless conductivity detection. Samples containing potassium as the cation, and both amoxicillin and clavulanate as anions were determined simultaneously in a single run (in less than 45 s) using 10 mmol/L of both 2-amino-2-hydroxymethyl-propane-1,3-diol and 3-{[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]amino}-1-propanesulfonic acid (pH 8.4) as the background electrolyte. Limits of detection were 25.0, 5.0, and 4.0 µmol/L for amoxicillin, clavulanate, and potassium, respectively. The proposed method is inexpensive, simple, fast (75 injections h-1 ), environment friendly (minimal waste generation), and accurate (recovery values between 98 and 103%). The results obtained with the proposed method were statistically similar (95% confidence level) to those obtained by using high-performance liquid chromatography (amoxicillin and clavulanate) and flame photometry (potassium).

A sub-minute electrophoretic method for simultaneous determination of naphazoline and zinc.

This paper reports for the first time, a method for simultaneous determination of naphazoline (NPZ) and zinc (Zn) using an analytical separation technique (capillary electrophoresis with capacitively coupled contactless conductivity detection -CE-C4D). A single run is possible every 55s (sampling rate=65h-1). The separation by CE-C4D was achieved on a fused silica capillary (50cm length - 10cm effective, 50µm i.d.) with a background electrolyte (BGE) composed by 20mmolL-1 of 2-(morpholin-4-yl)ethane-1-sulfonic acid (MES) and 20mmolL-1 of histidine (HIS) (pH 6.0). Detection limits were estimated at 20 and 30µmolL-1 and recovery values for spiked samples were 98 and 102% for NPZ and Zn, respectively. The developed procedure was compared to HPLC (NPZ) and FAAS (Zn) and no statistically significant differences were observed (95% confidence level).

On-line hyphenation of solid-phase extraction to chromatographic separation of sulfonamides with fused-core columns in sequential injection chromatography.

On-line sample pretreatment (clean-up and analyte preconcentration) is for the first time coupled to sequential injection chromatography. The approach combines anion-exchange solid-phase extraction and the highly effective pentafluorophenylpropyl (F5) fused-core particle column for separation of eight sulfonamide antibiotics with similar structures (sulfathiazole, sulfanilamide, sulfacetamide, sulfadiazine, sulfamerazine, sulfadimidine, sulfamethoxazole and sulfadimethoxine). The stationary phase was selected after a critical comparison of the performance achieved by three fused-core reversed phase columns (Ascentis(®) Express RP-Amide, Phenyl-Hexyl, and F5) and two monolithic columns (Chromolith(®) High Resolution RP-18 and CN). Acetonitrile and acetate buffer pH 5.0 at 0.60 mL min(-1) were used as mobile phase to perform the separations before spectrophotometric detection. The first mobile phase was successfully used as eluent from SPE column ensuring transfer of a narrow zone to the chromatographic column. Enrichment factors up to 39.2 were achieved with a 500 µL sample volume. The developed procedure showed analysis time <10.5 min, resolutions >1.83 with peak symmetry ≤1.52, LODs between 4.9 and 27 µg L(-1), linear response ranges from 30.0 to 1000.0 µg L(-1) (r(2)>0.996) and RSDs of peak heights <2.9% (n=6) at a 100 µg L(-1) level and enabled the screening control of freshwater samples contaminated at the 100 µg L(-1) level. The proposed approach expanded the analytical potentiality of SIC and avoided the time-consuming batch sample pretreatment step, thus minimizing risks of sample contamination and analyte losses.

Flow analysis in Brazil: contributions over the last four decades.

The main contributions of Brazilian researchers to the field of flow analysis are reviewed, with an emphasis on historical developments, conceptual aspects, system design, and analytical applications. Contributions after the advent of flow injection analysis are highlighted. Novel approaches (e.g. zone merging, zone sampling, zone trapping, multi-site detection, and multi-commutation), flow modalities (e.g. monosegmented flow analysis, flow-batch analysis, multi-pumping flow analysis), as well as the pioneering implementation of different detection techniques (e.g. potentiometry, turbidimetry, flame atomic absorption spectrometry, inductively coupled plasma-optical emission spectrometry, and gravimetry) and analytical steps (e.g. titrations, membrane-less gas diffusion, and electrolytic dissolution) are highlighted. Strategies to improve analytical figures of merit and the use of the flow analyser as a tool for teaching purposes are also discussed. Contributions from Brazilian workers in the context of system miniaturization, "green" chemistry, analysis of complex samples, novel strategies and materials for in-line analyte separation/concentration, and proposals for expert systems are also highlighted. The large-scale analysis of samples of agronomical, environmental, industrial, and clinical relevance is emphasized.