Green Bioanalytical Applications of Graphene Oxide for the Extraction of Small Organic Molecules

Bioanalysis is the scientific field of the quantitative determination of xenobiotics (e.g., drugs and their metabolites) and biotics (e.g., macromolecules) in biological matrices. The most common samples in bioanalysis include blood (i.e., serum, plasma and whole blood) and urine. However, the analysis of alternative biosamples, such as hair and nails are gaining more and more attention. The main limitations for the determination of small organic compounds in biological samples is their low concentration in these matrices, in combination with the sample complexity. Therefore, a sample preparation/analyte preconcentration step is typically required. Currently, the development of novel microextraction and miniaturized extraction techniques, as well as novel adsorbents for the analysis of biosamples, in compliance with the requirements of Green Analytical Chemistry, is in the forefront of research in analytical chemistry. Graphene oxide (GO) is undoubtedly a powerful adsorbent for sample preparation that has been successfully coupled with a plethora of green extraction techniques. GO is composed of carbon atoms in a sp² single-atom layer of a hybrid connection, and it exhibits high surface area, as well as good mechanical and thermal stability. In this review, we aim to discuss the applications of GO and functionalized GO derivatives in microextraction and miniaturized extraction techniques for the determination of small organic molecules in biological samples.     

Honey Phenolic Compound Profiling and Authenticity Assessment Using HRMS Targeted and Untargeted Metabolomics

Honey consumption is attributed to potentially advantageous effects on human health due to its antioxidant capacity as well as anti-inflammatory and antimicrobial activity, which are mainly related to phenolic compound content. Phenolic compounds are secondary metabolites of plants, and their content in honey is primarily affected by the botanical and geographical origin. In this study, a high-resolution mass spectrometry (HRMS) method was applied to determine the phenolic profile of various honey matrices and investigate authenticity markers. A fruitful sample set was collected, including honey from 10 different botanical sources (n = 51) originating from Greece and Poland. Generic liquid–liquid extraction using ethyl acetate as the extractant was used to apply targeted and non-targeted workflows simultaneously. The method was fully validated according to the Eurachem guidelines, and it demonstrated high accuracy, precision, and sensitivity resulting in the detection of 11 target analytes in the samples. Suspect screening identified 16 bioactive compounds in at least one sample, with abscisic acid isomers being the most abundant in arbutus honey. Importantly, 10 markers related to honey geographical origin were revealed through non-targeted screening and the application of advanced chemometric tools. In conclusion, authenticity markers and discrimination patterns were emerged using targeted and non-targeted workflows, indicating the impact of this study on food authenticity and metabolomic fields.     

A Novel Glass Fiber Coated with Sol–Gel Poly-Diphenylsiloxane Sorbent for the On-Line Determination of Toxic Metals Using Flow Injection Column Preconcentration Platform Coupled with Flame Atomic Absorption Spectrometry

A novel simple and sensitive, time-based flow injection solid phase extraction system was developed for the automated determination of metals at low concentration. The potential of the proposed scheme, coupled with flame atomic absorption spectrometry (FAAS), was demonstrated for trace lead and chromium(VI) determination in environmental water samples. The method, which was based on a new sorptive extraction system, consisted of a microcolumn packed with glass fiber coated with sol–gel poly (diphenylsiloxane) (sol–gel PDPS), which is presented here for the first time. The analytical procedure involves the on-line chelate complex formation of target species with ammonium pyrrolidine dithiocarbamate (APDC), retention onto the hydrophobic sol–gel sorbent coated surface of glass fibers, and finally elution with methyl isobutyl ketone prior to atomization. All main chemical and hydrodynamic factors, which affect the complex formation, retention, and elution of the metal, were optimized thoroughly. Furthermore, the tolerance to potential interfering ions appearing in environmental samples was also explored. Enhancement factors of 215 and 70, detection limits (3 s) of 1.1 μg·L⁻¹ and 1.2 μg·L⁻¹, and relative standard deviations (RSD) of 3.0% (at 20.0 μg·L⁻¹) and 3.2% (at 20.0 μg·L⁻¹) were obtained for lead and chromium(VI), respec tively, for 120 s preconcentration time. The trueness of the developed method was estimated by analyzing certified reference materials and spiked environmental water samples.     

Utilizing Recyclable Task-Specific Ionic Liquid for Selective Leaching and Refining of Scandium from Bauxite Residue

Ionic liquids (ILs) have attracted great interest in the field of extractive metallurgy mainly because they can be utilized in low temperature leaching processes where they exhibit selectivity and recyclability. A major drawback in mixed aqueous-IL systems, is IL dissolution in the aqueous phase, which leads to IL losses, increasing the overall processing cost. This study advances the method for recovering scandium (Sc) from bauxite residue (BR) using as leaching agent the IL betainium bistriflimide, [Hbet][Tf₂N] mixed with water, which has been reported in previous publications. Ionic liquid leachate (IL-PLS) was prepared by leaching BR with a mixture of [Hbet][Tf₂N]-H₂O and subjected to different stripping experiments using hydrochloric acid. The advancement, presented in this work, is related with the optimization of the metal extraction (stripping) from the IL-PLS, where an aqueous solution with high Sc concentration and minimum metal impurities and minimum IL co-extraction is produced. It is further proven that the metal cation extraction is defined by the stoichiometry of the acidic solution and the dissolution (losses) of the IL in the aqueous phase can be minimized by adjusting the volume ratio and the acid concentration. A two-step stripping process described, achieves the selective increase of Sc concentration by 8 times in the aqueous solution, while maintaining cumulative IL losses to similar levels as the optimum 1 step non-Sc selective stripping process.     

Classification of Greek Olive Oils from Different Regions by Machine Learning-Aided Laser-Induced Breakdown Spectroscopy and Absorption Spectroscopy

In the present work, the emission and the absorption spectra of numerous Greek olive oil samples and mixtures of them, obtained by two spectroscopic techniques, namely Laser-Induced Breakdown Spectroscopy (LIBS) and Absorption Spectroscopy, and aided by machine learning algorithms, were employed for the discrimination/classification of olive oils regarding their geographical origin. Both emission and absorption spectra were initially preprocessed by means of Principal Component Analysis (PCA) and were subsequently used for the construction of predictive models, employing Linear Discriminant Analysis (LDA) and Support Vector Machines (SVM). All data analysis methodologies were validated by both “k-fold” cross-validation and external validation methods. In all cases, very high classification accuracies were found, up to 100%. The present results demonstrate the advantages of machine learning implementation for improving the capabilities of these spectroscopic techniques as tools for efficient olive oil quality monitoring and control.     

Green-Light Activatable BODIPY and Coumarin 5’-Caps for Oligonucleotide Photocaging

We synthesized two green-light activatable 5’-caps for oligonucleotides based on the BODIPY and coumarin scaffold. Both bear an alkyne functionality allowing their use in numerous biological applications. They were successfully incorporated in oligonucleotides via solid-phase synthesis. Copper-catalyzed alkyne-azide cycloaddition (CuAAC) using a bisazide photo-tether gave cyclic oligonucleotides that could be relinearized by activation with green light and were shown to exhibit high stability against exonucleases. Chemical ligation as another example for bioconjugation yielded oligonucleotides with an internal strand break site. Irradiation at 530 nm or 565 nm resulted in complete photolysis of both caging groups.     

Effect of clay modification on structure–property relationships and thermal degradation kinetics of β-polypropylene/clay composite materials

Journal of Thermal Analysis and Calorimetry - The influence of neat and organically modified montmorillonite on the structure–property relationships of a β-nucleated polypropylene matrix...     

On the Nonlinear Continuum Theory of Dislocations: A Gauge Field Theoretical Approach

A nonlinear continuum theory of material bodies with continuously distributed dislocations is presented, based on a gauge theoretical approach. Firstly, we derive the canonical conservation laws that correspond to the group of translations and rotations in the material space using Noether’s theorem. These equations give us the canonical Eshelby stress tensor as well as the total canonical angular momentum tensor. The canonical Eshelby stress tensor is neither symmetric nor gauge-invariant. Based on the Belinfante-Rosenfeld procedure, we obtain the gauge-invariant Eshelby stress tensor which can be symmetric relative to the reference configuration only for isotropic materials. The gauge-invariant angular momentum tensor is obtained as well. The decomposition of the gauge-invariant Eshelby stress tensor in an elastic and in a dislocation part gives rise to the derivation of the famous Peach-Koehler force.