A comprehensive HRMS methodology using LC-(ESI)-/GC-(APCI)-QTOF MS complementary platforms for wide-scope target screening of >750 pesticides in olive oil.

This study presents the development and validation of a comprehensive high-resolution mass spectrometry (HRMS) methodology for the detection of 771 pesticides in olive oil, using liquid chromatography with electrospray ionization, operating in positive and negative mode, and gas chromatography with atmospheric-pressure chemical ionization in positive mode, both coupled to quadrupole-time-of-flight mass spectrometry (LC-(ESI)-/GC-(APCI)-QTOF MS). Special reference is made to the post-acquisition evaluation step, in which all LC/GC-HRMS analytical evidence (i.e. mass accuracy, retention time, isotopic pattern, MS/MS fragmentation) is taken into account in order to successfully identify the compounds. The sample preparation of the method involves a QuEChERS-based protocol, common for both techniques, differentiated only on the reconstitution step, making the method highly applicable in routine analysis. A smart evaluation of method's performance was carried out, with 65 representative analytes comprising the validation set. The method was validated in terms of linearity, accuracy, matrix effect and precision, while the limits of detection and quantification of the method were estimated. Finally, twenty Greek olive oil samples were analysed in both analytical platforms and the findings included the pesticides lambda-cyhalothrin, chlorpyrifos, phosphamidon, pirimiphos-methyl and esprocarb at low ng g-1 level.

NMR-guided isolation of undescribed triterpenoid saponins from Lysimachia atropurpurea L.

Phytochemical investigation on aerial parts of Lysimachia atropurpurea L. (Myrsinaceae), guided by NMR methods, resulted in the isolation and characterization of three previously undescribed triterpenoid saponins named stralysaponins A-C along with five known compounds. Their structures were elucidated by 1D and 2D NMR spectroscopy and HR-ESI-MS. Stralysaponins A-C were categorized into 13ß-28-epoxyoleanane-type triterpenoid saponins, reaffirming their prevalent presence of this type in the Myrsinaceae family and the genus Lysimachia. The identified derivatives share a common four-unit branched sugar chain, with rhamnose as the terminal sugar linked at C-3 of the aglycone. The presence of triterpenoid saponins in L. atropurpurea is reported herein for the first time. This study enriched the chemical diversity of triterpenoid saponins of the genus Lysimachia. Additionally, it demonstrates the effectiveness of NMR-profiling in isolating previously undescribed triterpenoid saponins from Lysimachia spp.

Design, Characterization, and In Vivo Application of Multi-Conductive Layer Organic Electrocorticography Probes.

Biocompatible and plastic neural interface devices allow for minimally invasive recording of brain activity. Increasing electrode density in such devices is essential for high-resolution neural recordings. Superimposing conductive leads in devices can help multiply the number of recording sites while keeping probes width small and suitable for implantation. However, because of leads' vertical proximity, this can create capacitive coupling (CC) between overlapping channels, which leads to crosstalk. Here, we present a thorough investigation of CC phenomenon in multi-gold layer thin-film multi-electrode arrays with a parylene C (PaC) insulation layer between superimposed leads. We also propose a guideline on the design, fabrication, and characterization of such type of neural interface devices for high spatial resolution recording. Our results demonstrate that the capacitance created through CC between superimposed tracks decreases non-linearly and then linearly with the increase of insulation thickness. We identify an optimal PaC insulation thickness that leads to a drastic reduction of CC between superimposed gold channels while not significantly increasing the overall device thickness. Finally, we show that double gold layer electrocorticography probes with the optimal insulation thickness exhibit similar performances in vivo when compared to single-layer devices. This confirms that these probes are adequate for high-quality neural recordings.

In operando nanomechanical mapping of PEDOT:PSS thin films in electrolyte solutions with bimodal AFM.

Understanding the interplay between the nanomechanical properties of organic electronic materials and their electronic properties is central to developing sensors and transducers for applications ranging from immunosensing to e-skin. Controlling organic device operations in aqueous electrolyte solutions and their mechanical compliance with the host tissue or living systems, as for instance in active implants for the recording or stimulation of neural signals, is still largely unexplored. Here, we implemented bimodal AFM to map the nanomechanical and structural properties of thin films made from poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS), the most widely used conducting polymer blend, during operation as a microelectrode in an electrolyte solution. Nanomechanical maps showed the film consisting of a granular structure made from PEDOT:PSS regions embedded in the PSS matrix. The film swelled upon immersion in an aqueous solution. In operando bimodal AFM data obtained by applying a sequence of doping/de-doping bias cycles showed a significant decrease in the modulus (70%) that saturated after about 10 cycles. A similar sequence of biases at the opposite polarity did not significantly influence the mechanical behaviour of PEDOT:PSS. The decrease in the modulus was explained by the development of persistent hydration, which was enhanced by the cations trapped inside the organic electronic material.

Comparative Evaluation of Different Targeted and Untargeted Analytical Approaches to Assess Greek Extra Virgin Olive Oil Quality and Authentication.

Extra virgin olive oil (EVOO) is a key component of the Mediterranean diet, with several health benefits derived from its consumption. Moreover, due to its eminent market position, EVOO has been thoroughly studied over the last several years, aiming at its authentication, but also to reveal the chemical profile inherent to its beneficial properties. In the present work, a comparative study was conducted to assess Greek EVOOs' quality and authentication utilizing different analytical approaches, both targeted and untargeted. 173 monovarietal EVOOs from three emblematic Greek cultivars (Koroneiki, Kolovi and Adramytiani), obtained during the harvesting years of 2018-2020, were analyzed and quantified as per their fatty acids methyl esters (FAMEs) composition via the official method (EEC) No 2568/91, as well as their bioactive content through liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) methodology. In addition to FAMEs analysis, EVOO samples were also analyzed via HRMS-untargeted metabolomics and optical spectroscopy techniques (visible absorption, fluorescence and Raman). The data retrieved from all applied techniques were analyzed with Machine Learning methods for the authentication of the EVOOs' variety. The models' predictive performance was calculated through test samples, while for further evaluation 30 commercially available EVOO samples were also examined in terms of variety. To the best of our knowledge, this is the first study where different techniques from the fields of standard analysis, spectrometry and optical spectroscopy are applied to the same EVOO samples, providing strong insight into EVOOs chemical profile and a comparative evaluation through the different platforms.

Trapped Ion Mobility Incorporated in LC-HRMS Workflows as an Integral Analytical Platform of High Sensitivity: Targeted and Untargeted 4D-Metabolomics in Extra Virgin Olive Oil.

Trapped ion mobility spectrometry (TIMS) is a promising technique for the separation of isomers based on their mobility. In the present work, TIMS coupled to liquid chromatography (LC) and high-resolution mass spectrometry (HRMS) was applied as a comprehensive analytical platform to address authenticity challenges, focusing on extra virgin olive oil (EVOO). Isomers detected in EVOO's phenolic fraction, classified into secoiridoids group, were successfully separated. Thanks to parallel accumulation serial fragmentation (PASEF) acquisition mode, high-quality spectra were obtained, facilitating identification. Moreover, a four-dimensional (4D) untargeted metabolomics approach was implemented to evaluate EVOO's global profile in cases of both variety and geographical origin discrimination. Potential authenticity markers, attributed to isomers, were successfully identified through the proposed workflow that incorporates ion mobility information along with LC-HRMS analytical evidence (i.e., mass accuracy, retention time, isotopic pattern, MS/MS fragmentation). Our study establishes LC-TIMS-HRMS in food authenticity and highlights mobility-enhanced metabolomics in four dimensions.

Targeted and Untargeted Metabolomics as an Enhanced Tool for the Detection of Pomegranate Juice Adulteration.

Pomegranate juice is one of the most popular fruit juices, is well-known as a "superfood", and plays an important role in healthy diets. Due to its constantly growing demand and high value, pomegranate juice is often targeted for adulteration, especially with cheaper substitutes such as apple and red grape juice. In the present study, the potential of applying a metabolomics approach to trace pomegranate juice adulteration was investigated. A novel methodology based on high-resolution mass spectrometric analysis was developed using targeted and untargeted screening strategies to discover potential biomarkers for the reliable detection of pomegranate juice adulteration from apple and red grape juice. Robust classification and prediction models were built with the use of unsupervised and supervised techniques (principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA)), which were able to distinguish pomegranate juice adulteration to a level down to 1%. Characteristic m/z markers were detected, indicating pomegranate juice adulteration, and several marker compounds were identified. The results obtained from this study clearly demonstrate that Mass Spectrometry (MS)-based metabolomics have the potential to be used as a reliable screening tool for the rapid determination of food adulteration.

Beyond Donor-Acceptor (D-A) Approach: Structure-Optoelectronic Properties-Organic Photovoltaic Performance Correlation in New D-A1 -D-A2 Low-Bandgap Conjugated Polymers.

Low-bandgap near-infrared polymers are usually synthesized using the common donor-acceptor (D-A) approach. However, recently polymer chemists are introducing more complex chemical concepts for better fine tuning of their optoelectronic properties. Usually these studies are limited to one or two polymer examples in each case study so far, though. In this study, the dependence of optoelectronic and macroscopic (device performance) properties in a series of six new D-A1 -D-A2 low bandgap semiconducting polymers is reported for the first time. Correlation between the chemical structure of single-component polymer films and their optoelectronic properties has been achieved in terms of absorption maxima, optical bandgap, ionization potential, and electron affinity. Preliminary organic photovoltaic results based on blends of the D-A1 -D-A2 polymers as the electron donor mixed with the fullerene derivative [6,6]-phenyl-C71 -butyric acid methyl ester demonstrate power conversion efficiencies close to 4% with short-circuit current densities (J sc ) of around 11 mA cm-2 , high fill factors up to 0.70, and high open-circuit voltages (V oc s) of 0.70 V. All the devices are fabricated in an inverted architecture with the photoactive layer processed in air with doctor blade technique, showing the compatibility with roll-to-roll large-scale manufacturing processes.