Electroanalytical sensing of dyes and colorants

Color is an important element of the final product of many industries, including the textile, leather, food, cosmetic, pharmaceutical, plastic, and fuel-marking industries. Dyes are complex organic substances with chromophore and auxochromic groups, which can be electrochemically oxidized and/or reduced; this constitutes the basis of their electroanalytical determination. Despite some controversies, dyes pose risks to living organisms, especially after biotransformation, as the metabolites can be more toxic, mutagenic, or carcinogenic than the original dyes. The present work provides a brief overview of the recent progress in electrochemical sensors used for dye detection in diversified matrices. Sensors developed over the recent years are characterized by high sensitivity and selectivity, besides being economically advantageous once they allow the use of little or no clean-up samples in portable and miniaturized systems.     

Heart-cutting two-dimensional (size exclusion × reversed phase) liquid chromatography–mass spectrometry analysis of flavonol glycosides from leaves of Maytenus ilicifolia

Two-dimensional liquid chromatography–electrospray ionization mass spectrometry was employed to analyze flavonol glycosides present in leaves of Maytenus ilicifolia, frequently used in traditional Brazilian medicine. Since they contain many flavonol glycosides, including isomers, one-dimensional liquid chromatography did not give complete separation and identification, yielding overlapping of compounds with different molecular weights. Thus, employing size exclusion chromatography in the first and reversed phase in the second dimension, a great number of flavonol glycosides could be identified and its relative abundances determined. The majority of glycosides contained kaempferol or quercetin as aglycones, and glycosides with previously unreported structures were also present and characterized.     

Absorption Spectra of 4‐Nitrophenolate Ions Measured in Vacuo and in Solution

From blue to red: While four π‐conjugated nitrophenolates absorb within a relatively narrow region in solution, they cover the entire visible spectrum when isolated in vacuo (see picture). The work combines gas‐ and solution‐phase spectroscopy and provides the first benchmark of theoretical excitation energies for nitrophenolates.

     

Optimization of aircraft structural components by using nature-inspired algorithms and multi-fidelity approximations

In this work, a flat pressure bulkhead reinforced by an array of beams is designed using a suite of heuristic optimization methods (Ant Colony Optimization, Genetic Algorithms, Particle Swarm Optimization and LifeCycle Optimization), and the Nelder-Mead simplex direct search method. The compromise between numerical performance and computational cost is addressed, calling for inexpensive, yet accurate analysis procedures. At this point, variable fidelity is proposed as a tradeoff solution. The difference between the low-fidelity and high-fidelity models at several points is used to fit a surrogate that corrects the low-fidelity model at other points. This allows faster linear analyses during the optimization; whilst a reduced set of expensive non-linear analyses are run “off-line,” enhancing the linear results according to the physics of the structure. Numerical results report the success of the proposed methodology when applied to aircraft structural components. The main conclusions of the work are (i) the variable fidelity approach enabled the use of intensive computing heuristic optimization techniques; and (ii) this framework succeeded in exploring the design space, providing good initial designs for classical optimization techniques. The final design is obtained when validating the candidate solutions issued from both heuristic and classical optimization. Then, the best design can be chosen by direct comparison of the high-fidelity responses.     

Automated microcolumn-switching system for drug analysis by direct injection of human plasma

This study presents the application of a system that joins the known advantages of capillary liquid chromatography (e.g., higher concentration of the analytes and lower consumption of mobile phase) with those of column-switching using restricted access material (RAM) (sample clean up and extraction) to the analysis of fluoxetine in plasma samples. Automatically, the system loads the biological sample, while a RAM-BSA-C18 column (50 mm x 520 microm) excludes the macromolecules and focuses the analytes; afterwards, a second mobile phase elutes the analytes, in backflush mode, and provides the separation in a C18 analytical column (100 mm x 520 microm). We optimized the procedure for a total analysis time of 25 min. Using this approach the calibration curve shows r=0.998 with a linearity range from 20 to 500 ng ml(-1). Precision, calculated as relative standard deviation (RSD), was<20%. The developed miniaturized system showed to be adequate and attractive, demonstrating a large potential for sample preparation.     

Novel adsorbent based on silkworm chrysalides for removal of heavy metals from wastewaters

In this contribution, maximum capacity for adsorption of Pb(2+), Ni(2+), and Cu(2+) by silkworm chrysalides (SC) was determined. The raw silkworm chrysalides (SC(r)) and chrysalides after acidic washing (SC(w)) were used. Chitin (CT), extracted from SC, and chitosan (CS), with 85% deacetylation, were employed as reference samples. Adsorption tests showed that all the studied adsorbents exhibited excellent performance in removal of metals. The choice of a more appropriate adsorbent is related to its efficiency for removal of a specific metal. The studied materials presented different intensities for metal adsorption as follows: (i) Ni(2+)>Cu(2+)>Pb(2+) for SC(r); (ii) Pb(2+)>Cu(2+)>Ni(2+) for SC(w); (iii) Ni(2+)>Cu(2+)>Pb(2+) for CT; and (iv) Cu(2+)>Pb(2+)>Ni(2+) for CS. Metal adsorption onto SC(r) and CS was analyzed by Freundlich and Langmuir isotherm equations. Adsorption values for CS-Pb and SC(r)-Ni were provided by the Freundlich model, while the adsorption values for CS-Cu, CS-Ni, SC(r)-Pb, and SC(r)-Cu were provided by the Langmuir model. The studied adsorbents are suitable for use in treatment of wastewater. From the economic point of view, the use of SC(r) as an adsorbent of heavy metals (mainly Ni(2+)) on the large industrial scale would be more appropriate.     

Broadband measurement of true transverse relaxation rates in systems with coupled protons: application to the study of conformational exchange

Accurate measurement of transverse relaxation rates in coupled spin systems is important in the study of molecular dynamics, but is severely complicated by the signal modulations caused by scalar couplings in spin echo experiments. The most widely used experiments for measuring transverse relaxation in coupled systems, CPMG and PROJECT, can suppress such modulations, but they also both suppress some relaxation contributions, and average relaxation rates between coupled spins. Here we introduce a new experiment which for the first time allows accurate broadband measurement of transverse relaxation rates of coupled protons, and hence the determination of exchange rate constants in slow exchange from relaxation measurements. The problems encountered with existing methods are illustrated, and the use of the new method is demonstrated for the classic case of hindered amide rotation and for the more challenging problem of exchange between helical enantiomers of a gold(i) complex.

Existing methods for measuring transverse relaxation give incorrect results in coupled spin systems. Measuring true relaxation rates extends their utility.     

Lipid-based nanoparticles as drug delivery system for paclitaxel in breast cancer treatment

Paclitaxel (PTX) is a well-known antitumor drug, widely utilized in the treatment of breast, ovarian, head, and neck tumors, among others. The low aqueous solubility (< 1.0 μg/mL; log P = 3.96) limits its use by intravenous route, and alternatives found for the marketed products are associated with high toxicity. Incorporation of PTX into lipid nanocarriers has been considered an interesting nontoxic alternative for this route, but drug loading is usually low. This study aimed to analyze the influence of the lipid composition and three different lipid nanosystems—solid lipid nanoparticles, nanostructured lipid carriers (NLCs), and nanoemulsion—in PTX encapsulation and its biological response. The three proposed systems were prepared by hot melt homogenization followed by ultrasonication. Among the blank formulations first prepared, NLC had the smallest size (74 ± 1 nm), with negative zeta potential (? 11.4 ± 0.1 mV). The incorporation of 0.10 mg/mL PTX into this NLC formulation yielded high and stable encapsulation (0.089 ± 0.003 mg/mL), also supported by polarized light microscopy and differential scanning calorimetry curves. NLC-PTX was very effective against MCF-7 (IC50 25.33 ± 3.17 nM) and MDA-MB-231 breast cancer cell lines (IC50 2.13 ± 0.21 nM), compared to free PTX (IC50 > 500 nM). In addition, no significant cytotoxicity was found against fibroblast cells. Taken together, these results demonstrated that PTX was successfully incorporated into NLC with appropriate physicochemical characteristics for intravenous administration, suggesting that the use of NLC as vehicle to incorporate PTX may be a promising strategy in the treatment of breast cancer.     

Solvent and concentration effects on the visible spectra of tri-para-dialkylamino-substituted triarylmethane dyes in liquid solutions

We have characterized the spectroscopy properties of crystal violet (CV+) and ethyl violet (EV+) in liquid solutions as a function of the solvent type and dye concentration. The analysis of how solvent properties and dye concentration affects the electronic spectra of these tri-para-dialkylamino substituted tryarylmethane (TAM+) dyes was performed on the basis of two spectroscopic parameters, namely the difference in wavenumber (deltanu) between the maximum and the shoulder that appears in the short-wavelength side of the respective maximum visible band (deltanu = 1/lambda(shoulder)-1/lambda(max) cm(-1)), and the wavelength of the maximum absorption (lambda(max)). The solvent and the concentration effects on lambda(max) and deltanu have indicated that both solute/solute (ion-pairing and dye aggregation) and solute/solvent (H-bonding type) interactions modulate the shape of the visible electronic spectra of these dyes in solution. In solvent with small dieletric constant (epsilon < approximately 10), the formation of ion-pairs represents a major contribution to the shaping of these spectra. Upon increasing dye concentration the formation of ion-pairs was characterized by an increase in deltanu observed concomitantly with a red shift in lambda(max) In chloroform and chlorobenzene the ion-pair association constant of CV+ and EV+ with Cl- ions were found to be in the order of 10(6) and 10(5) M(-1), respectively. In trichloroethylene the association constant for the CV+Cl- pair was 10(8) M(-1). In water, dye aggregation instead of ion-pairing represents a major contribution to the shaping of the visible spectra of CV+ and EV+. Dye aggregation was indicated by an increase in deltanu observed concomitantly with a blue shift in lambda(max) upon increasing dye concentration. The distinct behavior of deltanu for dye aggregation and ion-pairing as a function of dye concentration can therefore assist in the characterization of these two distinct phenomena. The solute/solvent interactions were studied in a series of polar solvents in which solute/solute interactions do not occur in any detectable extent. The dependence found for deltanu as a function of the Kamlet-Tafts solvatochromic parameters (alpha, beta and pi*) is in keeping with previous inferences indicating that the splitting in the overlapped absorption band of CV+ and EV+ in hydroxilated solvents arises from a perturbation in the molecular symmetry induced by hydrogen bonding (donor-acceptor) type interactions with solvent molecules. A distinction between the effects of solute/solute and solute/solvent interactions on the visible spectra of these dyes is provided.     

The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes--a computational study

Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications.