Development of dye-sensitized solar cells using pigment extracts produced by Talaromyces atroroseus GH2.

The identification of more efficient, clean, secure, and competitive energy supply is necessary to align with the needs of sustainable devices. For this reason, a study for developing innovative dye-sensitized solar cells (DSSCs) based on microbial pigments is reported starting from Talaromyces atroroseus GH2. The fungus was cultivated by fermentation and the extracellular pigment extract was characterized by HPLC-DAD-ESI-MS analyses. The most abundant compound among the 22 azaphilone-type pigments identified was represented by PP-O. The device's behavior was investigated in relation to electrolyte and pH for verifying the stability on time and the photovoltaic performance. Devices obtained were characterized by UV-vis measurements to verify the absorbance intensity and transmittance percentage. Moreover, photovoltaic parameters through photo-electrochemical measurements (I-V curves) and impedance characteristics by Electrochemical Impedance Spectroscopy (EIS) were determined. The best microbial device showed a short-circuit current density (Jsc) of 0.69 mA/cm2, an open-circuit photo-voltage (Voc) of 0.27 V and a Fill Factor (FF) of 0.60. Furthermore, the power conversion efficiency (PCE) of the device was 0.11%. Thus, the present study demonstrated the potential of microbial origin pigments for developing DSSCs.

Fast gas chromatography-tandem mass spectrometry under milder electron ionization conditions for the assay of vitamin D metabolites in human serum.

The proposed research was focused on the development of a gas chromatography-tandem mass spectrometry (GC-QqQ-MS) method under milder electron ionization (EI) conditions for the assay of vitamin D metabolites in human serum. Efficiency of three different silylation agents was evaluated for the conversion of vitamin D species into trimethylsilyl (TMS) derivatives, among which N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA) proved to be the most effective. Indeed, the MSTFA reagent was able to convert in TMS ether even the 25-hydroxyl vitamin D derivative that, as known, possesses steric hindrance problems. The separation of vitamin D compounds was obtained in about 11.5 min using a narrow-bore column of dimensions 30 m × 0.25 mm ID × 0.10 µm df with a poly(5% diphenyl/95% dimethyl siloxane) stationary phase. The mass spectrometry ionization of the silylated derivatives was performed under milder EI conditions (20-eV energy) that, respect to common 70-eV energy, generated scan mass spectra with higher relative and absolute intensities of high-mass diagnostic ions, along with a reduced abundance of the low-mass. The signals of the ionized compounds were acquired in multi-reaction-monitoring (MRM) mode, thus enabling the obtainment of highly-sensitive and selective quantitative data. The developed method was validated in term of linearity, accuracy, limits of detection (LoD) and quantification (LoQ). In detail, regression coefficients of the calibration curves were between 0.9959 and 0.9999; LoDs ranged from 0.06 ng mL-1 to 0.73 ng mL-1 and LoQs from 0.16 ng mL-1 to 2.45 ng mL-1. With respect to accuracy, the serum SRM 972a certified reference material (Vitamin D metabolites in frozen human serum) (Levels 1-4) was analyzed.

A Curcumin-BODIPY Dyad and Its Silica Hybrid as NIR Bioimaging Probes.

In this paper we describe the synthesis of a novel bichromophoric system in which an efficient photoinduced intercomponent energy transfer process is active. The dyad consists of one subunit of curcumin and one of BODIPY and is able to emit in the far-red region, offering a large Stokes shift, capable of limiting light scattering processes for applications in microscopy. The system has been encapsulated in MCM-41 nanoparticles with dimensions between 50 and 80 nm. Both the molecular dyad and individual subunits were tested with different cell lines to study their effective applicability in bioimaging. MCM-41 nanoparticles showed no reduction in cell viability, indicating their biocompatibility and bio-inertness and making them capable of delivering organic molecules even in aqueous-based formulations, avoiding the toxicity of organic solvents. Encapsulation in the porous silica structure directed the location of the bichromophoric system within cytoplasm, while the dyad alone stains the nucleus of the hFOB cell line.

The online coupling of liquid chromatography to Fourier transform infrared spectroscopy using a solute-deposition interface: A proof of concept.

Hyphenated techniques combining chromatographic and spectroscopic methods are the gold standard to effectively handle the emerging challenges in the analysis of unknown chemical components in mixtures, and in this regard the coupling of liquid chromatography to Fourier transform infrared spectroscopy (LC-FTIR) is no exception. While earlier attempts to couple LC to IR spectroscopy relied almost entirely on offline techniques, clear motivations for implementing online LC-FTIR instrumentation emerged from the need for shorter analysis time, a higher degree of automation and sample throughput, better reproducibility, and reduced contamination. Most recent designs of LC-FTIR concepts have aimed to combine the advantages of both approaches by means of a solvent-elimination interface. The hyphenated instrumentation and method presented in this research are based on a pneumatically assisted LC-FTIR interface, relying on a small-scale self-regulating spray dryer to attain desolvation of the LC eluent stream while retaining the spatial and temporal resolution of the dissolved substrates. Focused deposition of the dried analytes occurs onto a ZnSe disc for continuous transmission mid-IR analysis at a resolution of 4 cm-1. The optimization of the LC-FTIR technique is discussed in terms of interface parameters, limits of detection, and limits of quantification for a pair of furanocoumarin isomers differing in the position (linear or angular type) of the furan ring fused to coumarin. Finally, confident discrimination between the two closely related molecules was attained by matching the experimental FTIR spectra in a dedicated library. The quality match factors obtained were higher than 99% for both molecules. The limit of identification (LOI) was determined experimentally as the minimum amount of substance yielding a library-searchable IR spectrum (affording a quality match factor higher than 90%). Specifically, LOI of 0.6 µg and 1.25 µg was determined for psoralen and angelicin, respectively.

Overcoming the lack of reliability associated to monodimensional gas chromatography coupled to isotopic ratio mass spectrometry data by heart-cut two-dimensional gas chromatography.

The use of IRMS as a GC detector has a history going back decades, however the critical issue of wrong δ13C measurements resulting from impure peaks has been often underestimated. To this regard, multidimensional separation techniques are effective tools to improve the reliability of the data, with respect to those obtained after monodimensional analysis. The present research aims to draw attention to one critical issue, related to the reliability of the δ13C data obtained by means of monodimensional GC-C-IRMS. Although already known from the literature, such aspect has been greatly overlooked, as is reflected in the few papers reporting the use of MDGC, among the plethora of published research dealing with GC-C-IRMS applications. Hereby, a set of natural samples of complex composition were analysed to investigate the presence of minor or even undetected coelutions, and to which extent it affected the isotope ratio determination. Apart from chromatographic effects, and issues related to analytes conversion to CO2 prior to IRMS measurement, unpredictable co-elutions with compounds, either resulting from oxidation or intentionally added in fraudulent practices, could also contribute to a shift of the δ13C data, up to 10‰ and higher. Last, the influence of column bleed was investigated, as affecting the determination of the δ13C data for compounds that were eluted at high temperatures. It was finally demonstrated by the selected key studies that implementation of MDGC separation is mandatory to prevent the aforementioned issues, aiming to guarantee accurate results. In the light of the above conclusions, and considering the level of automation of heart-cut devices nowadays available, routine practice of MDGC results highly recommendable in any IRMS applications.

Determination of multi-pesticide residues in vegetable products using a "reduced-scale" Quechers method and flow-modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry.

The aim of the present research was the development of an analytical method for the determination of multi-pesticide residues (88 target analytes) in four vegetable products (tomatoes, cucumbers, sweet red peppers and iceberg lettuce) using a "reduced-scale" QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method and flow-modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry. In particular, the suitability of flow modulation [with relatively high second-dimension gas flow conditions (8 mL min-1)] for trace analyte determination was evaluated. The samples were prepared according to the QuEChERS procedure as reported by the official European Union method, namely EN 15662:2018, based on the use of 3 g of vegetable product. Matrix-matched calibration processes were carried out for all the samples. The figures-of-merit determined were recovery, linearity, precision, limits of detection (LoDs), and limits of quantification (LoQs). Specifically, recoveries were in the 53-160% range, regression coefficients were between 0.9156 and 0.9999, the LoDs were in the 0.1-6.3 µg kg-1 range, the LoQs were in the 3.0-21.0 µg kg-1 range, and coefficients of variation were between 1 and 28% (at the 50 µg kg-1 level).

Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR.

Among the phencyclidine (PCP) and synthetic cathinone analogs present on the street market, 3-methoxyphencyclidine (3-MeO-PCP) is one of the most popular dissociative hallucinogen drugs, while 3-methylmethcathinone (3-MMC) is a commonly encountered psychostimulant. Numerous 3-MeO-PCP- and 3-MMC-related intoxication cases have been reported worldwide. Identification of the positional isomers of MeO-PCP and MMC families are particularly challenging for clinical and forensic laboratories; this is mostly due to their difficult chromatographic separation (particularly when using liquid chromatography-LC) and similar mass spectrometric behaviors. 3-MeO-PCP and 3-MMC were identified in two powders, detained by two subjects and seized by the police, by different analytical techniques, including liquid chromatography-high-resolution accurate-mass Orbitrap mass spectrometry (LC-HRAM-Orbitrap-MS), and solid deposition gas chromatography-Fourier transform infrared spectroscopy (sd-GC-FTIR). LC-HRAM-Orbitrap-MS allowed us to assign the elemental formulae C18H27NO (MeO-PCP) and C11H15NO (MMC) through accurate mass measurement of the two MH+ ions, and the comparison of experimental and calculated MH+ isotopic patterns. However, MH+ collision-induced product ions spectra were not conclusive in discriminating between the positional isomers [(3-MeO-PCP vs. 4-MeO-PCP) and (3-MMC vs. 4-MMC and 2-MMC)]. Likewise, sd-GC-FTIR easily allowed us to differentiate between the MeO-PCP and MMC positional isomers unambiguously, confirming the presence of 3-MeO-PCP and 3-MMC, due to the high-quality match factor of the experimental FTIR spectra against the target FTIR spectra of MeO-PCP and MMC isomers in a dedicated library. 3-MeO-PCP (in contrast to 3-MMC) was also detected in blood and urine samples of both subjects and analyzed in the context of routine forensic casework by LC-HRAM-Orbitrap-MS following a simple deproteinization step. In addition, this untargeted approach allowed us to detect dozens of phase I and phase II 3-MeO-PCP metabolites in all biological specimens. Analysis of the extracted samples by sd-GC-FTIR revealed the presence of 3-MeO-PCP, thus confirming the intake of such specific methoxy-PCP isomer in both cases. These results highlight the effectiveness of LC-HRAM-Orbitrap-MS and sd-GC-FTIR data in attaining full structural characterization of the psychoactive drugs, even in absence of reference standards, in both non-biological and biological specimens.

Synthesis of Curcumin Derivatives and Analysis of Their Antitumor Effects in Triple Negative Breast Cancer (TNBC) Cell Lines.

We analyzed antitumor effects of a series of curcumin analogues. Some of them were obtained by reaction of substitution involving the two phenolic OH groups of curcumin while the analogues with a substituent at C-4 was prepared following an original procedure that regards the condensation of benzenesulfenic acid onto the nucleophilic central carbon of the curcumin skeleton. We analyzed cytotoxic effects of such derivatives on two TNBC (triple negative breast cancer) cell lines, SUM 149 and MDA-MB-231, but only three of them showed an IC50 in a lower micromolar range with respect to curcumin. We also focused on these three derivatives that in both cell lines exhibited a higher or at least equivalent pro-apoptotic effect than curcumin. The analysis of molecular mechanisms of action of the curcumin derivatives under study has highlighted that they decreased NF-κB transcriptional factor activity, and consequently the expression of some NF-κB targets. Our data confirmed once again that curcumin may represent a very good lead compound to design analogues with higher antitumor capacities and able to overcome drug resistance with respect to conventional ones, even in tumors difficult to treat as TNBC.

Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products.

Sulfenic acids as small molecules are too unstable to be isolated and their transient nature offers the possibility to involve them in concerted processes that lead to the obtainment of functional groups such as sulfoxides, sulfones, and disulfides. All these functions are present in a number of natural and synthetic drugs and can represent structural motives inducing biologically relevant properties. In this small review the generation and reactions of sulfenic acid bearing naturally occurring residues are described. Carbohydrate and aminoacid-derived sulfenic acids have been used in concerted addition with triple bonds to obtain alliin derivatives and thiosugars in enantiomerically pure form. Glycoconjugates with sulfinyl, sulfonyl, and disulfane functional groups and pyridine-derived disulfides have been obtained from bis- and tris-sulfinyl precursors of sulfenic acids. Small families of such compounds have been subjected to preliminary biological tests. Starting from the evidence that the control of molecular architecture and the presence of suitable functional groups can play a significant role on the exhibition of biological properties, apoptotic effects on malignant cells by glycoconjugates and inhibitory activity against the important human pathogen S. aureus by pyrimidine-derived disulfides have been found.