Alzheimer’s disease (AD) is the most common neurodegenerative disorder associated with cognitive decline and loss of memory. It is postulated that the generation of reactive oxygen species (ROS) in Fenton-like reaction connected with Cu(II)/Cu(I) redox cycling of the Cu(II)-aβ complex can play a key role in the molecular mechanism of neurotoxicity in AD. Semax (Met-Glu-His-Phe-Pro-Gly-Pro) is a synthetic regulatory peptide that possesses a high affinity for Cu(II) ions. The ability of the peptide Semax to inhibit the copper-catalyzed oxidation of aβ was studied in vitro and discussed. The results indicate that Semax is able to extract Cu(II) from Cu(II)-aβ species as well as to influence the redox cycling of the Cu(II)-aβ complex and decrease the level of associated ROS production. Finally, our data suggest that Semax shows cytoprotective properties for SH-SY5Y cells against oxidative stress induced by copper-catalyzed oxidation of the aβ peptide. This study provides valuable insights into the potential role of Semax in neurodegenerative disorders and into the design of new compounds with therapeutic potential for AD.

Tuning the surface chemistry of 3D graphene structures, such as hydrogels and aerogels, is critical for advancing their chemical and physical properties, which are essential for material design. Here, we present an innovative in-flow covalent functionalization approach based on diazonium salt chemistry to introduce new functionalities into the 3D graphene aerogel backbone while preserving its porous architecture. To achieve this, we designed a flow-based reactor tailored for the functionalization of macroscopic aerogel samples, addressing limitations of noncovalent methods including molecular slippage. Notably, the proposed method operates at room temperature, a significant advantage over existing techniques that often require high thermal conditions. Additionally, to overcome challenges associated with solid-state Raman analysis of graphene-based compounds, we proposed a statistical model to enhance the reproducibility of the process and rationalize I D/I G ratios post-treatment. This work demonstrates the feasibility of in-flow covalent functionalization of 3D graphene aerogels, opening new perspectives for the development of customizable porous carbon-based materials for various technological applications.

Melanin biosynthesis is a complex enzymatic process regulated by tyrosinase (TYR, EC 1.14.18.1) that initiates the process catalyzing the conversion of L-tyrosine to L-DOPA and L-DOPA to dopaquinone. The two transformations occur on the same active site of the enzyme composed of six histidine residues that coordinate two copper ions. TYR has been recognized as one of the most popular therapeutic targets for controlling melanin synthesis. Herein we report the synthesis of BODIPY-based piperazinyl phenol derivatives, that were designed to develop luminescent probes for the detection of TYR activity; additionally, these molecules might contemporarily act as TYR inhibitors through the piperazinyl phenolic fragment. Molecular docking studies pointed out the ability of the new compounds to bind the active site of Agaricus bisporus mushroom tyrosinase (AbTYR). Mitochondrial cytotoxic assay revealed that all the synthesized compounds were not cytotoxic up to 50 μM concentration. Their inhibitory effects were tested against monophenolase and diphenolase activities of AbTYR; as results two of the three new compounds provided to be more active than the starting reagent 4-(piperazin-1-yl)phenol for monophenolase activity. The most active inhibitor (IC50 value of 17.10 μM) was investigated through fluorescence spectroscopy and results corroborate the binding with AbTYR. Moreover, zebrafish embryos were used as a model organism for depigmentation studies and the introduction of fluorescent BODIPY moiety on the pharmacophoric fragment deeply improved its biocompatibility when compared to parent compounds and reflected its biodistribution.

Quantifying and monitoring the level of N-acylethanolamines (NAEs) in biological fluids is becoming increasingly important to better understand their role in health and disease. The complexity of biological matrices, however, poses significant challenges for accurate quantification, with traditional pretreatment methods often proving insufficient in certain cases. This study introduces a novel approach utilizing Online Solid Phase Extraction (SPE) to quantify NAEs in equine plasma, specifically Palmitoyl Ethanolamide (PEA) and Oleoyl Ethanolamide (OEA). In the original analytical method here developed and validated, established toluene liquid-liquid extraction was used to isolate the lipid-like fraction, followed by an innovative Time-Controlled Online SPE coupled to HPLC-MS/MS. This strategic temporal approach allows target analytes to rapidly elute to the analytical column while retaining lipidic interferents, preventing matrix contamination and ensuring selective analysis. The method validation demonstrated excellent linearity, while providing high recovery and suitable matrix effects. The limits of detection (LOD) and quantification (LOQ) were determined as 0.27 ng/mL and 0.83 ng/mL for PEA; 0.04 ng/mL and 0.11 ng/mL for OEA. The innovative approach here presented allowed for reliable NAE quantification in equine plasma and provided unprecedented data on the endogenous levels of PEA and OEA in this species. This method has potential applications for the analysis of other complex biological matrices with high levels of interferents that share chemical similarities with the target compounds. This novel approach significantly advances the understanding of the endocannabinoid system in equines and serves as a valuable tool for future research in this domain.

Lead leaching from perovskite solar cells remains a critical environmental concern, particularly in humid conditions that accelerate degradation. This study investigates the role of perfluorinated pyrene compounds in the Hole Transport Layer (HTL) as a promising strategy to reduce lead release from perovskite solar cells. For the first time, at the best of our knowledge, the tests were carried out by using the normalized condition dictated by standard UNI EN 12457-2. The Atomic Force Microscopy analyses reveal that the incorporation of perfluoroalkylated pyrene compounds reduced surface roughness and enhanced film uniformity, thereby preventing lithium salt aggregation and maintaining the structural integrity of the HTL without significantly altering the efficiency of the photovoltaic device. Moreover, a decrease in lead leaching was observed, from 5.5 to 3.0 mg/L, in the photovoltaic modules when Perfluoroalkylated Pyrenes were added. Furthermore, the hydrophobic nature of these compounds significantly limits lead leaching, by approximately 45 %, compared to conventional perovskite solar cells. As a result, the addition of perfluoroalkylated pyrene compounds effectively decreases lead leaching, contributing to improved environmental stability and device longevity. These findings highlight a promising strategy for reducing lead contamination in perovskite photovoltaics, paving the way for more sustainable and stable solar cell technologies.

Colorectal cancer (CRC) remains a significant global health burden, mainly due to late diagnosis and chemotherapy resistance. Macrophage migration inhibitory factor (MIF), a proinflammatory cytokine associated with tumor progression, has emerged as a promising biomarker in CRC. However, its clinical utility is limited by the lack of rapid and accessible detection methods. In this study, we report an electrochemical immunotechnology for the sensitive and selective quantification of MIF protein in CRC tissue samples. By combining magnetic microparticles (MMPs), antibody-based recognition, horseradish peroxidase (HRP) labeling, and amperometric transduction at disposable screen-printed carbon electrodes (SPCEs), the developed methodology displayed a linear dynamic range from 0.24 to 20 ng mL−1, enabling quantification across clinically relevant MIF levels, and achieving a low limit of detection (0.07 ng mL−1). In addition, the developed method is the only one reported for MIF assembled on MMPs and addresses its determination in a relevant oncological scenario (paired non-tumoral (NT) and tumoral (T) tissues from individuals diagnosed with CRC at different stages of the disease). The analysis, requiring only 100 ng of tissue extract, allowed efficient discrimination between NT and T paired tissues, and successfully differentiated between healthy, early (I–II) and advanced (III–IV) CRC stages, achieving these results in just 105 min.

The increase in food waste accumulation needs innovative valorization strategies that not only reduce environmental impacts but also provide functional applications. This study investigates the potential of almond hulls, an abundant agricultural by-product, as a source of bioactive compounds. For the first time, almond hull extract (AHE), was evaluated in terms of anti-adhesive and anti-biofilm activity against Staphylococcus aureus ATCC 29213 and Escherichia coli ATCC 9637. The extract was obtained by an optimized eco-friendly green technique using ultrasound-assisted extraction (UAE), and it was characterized for its main compounds by high-performance liquid chromatography–mass spectrometry (HPLC-MS) and nuclear magnetic resonance (NMR) analysis. Antimicrobial activity was evaluated on planktonic cells by minimum inhibitory/bactericidal concentration (MIC/MBC) and by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assays. Afterward, AHE activity was evaluated against the bacterial sessile phase, both against in-formation and mature biofilm. Finally, the toxicity of the extract was tested on normal human adult cells (HDFa) by an MTT test. The principal active compounds present in AHE belong to the polyphenol group, in particular, the phenolic acid (Hydroxycinnammic sub-class) and, more significantly, the flavonoid class. The results showed that the extract has a relevant antimicrobial activity against the planktonic cells of both tested strains. Moreover, it significantly inhibited bacterial adhesion and promoted biofilm removal, highlighting its potential as a sustainable antimicrobial agent. The MTT test on human fibroblasts showed that the extract is not toxic for normal human cells. This research highlights how food waste valorization could have a high potential in the antimicrobial field.

A luminescent calix[5]arene with a covalently linked dansyl chromophore substituent has been successfully used, both in solution and in the gas phase (ESI-MS), for the recognition of biogenic amines that contain linear alkylammonium structural unit. Binding constant values, determined by fluorescence spectroscopy, revealed a greater affinity for cadaverine, spermidine, and L-lysine, in which the terminal ammonium group allows for additional stabilizing interactions with the dansyl moiety.

The global spread of multi-drug-resistant (MDR) bacteria is rapidly increasing due to antibiotic overuse, posing a major public health threat and causing millions of deaths annually. The present study explored the potential of nanocarriers for delivering novel and alternative antibacterial agents using nanotechnology-based approaches to address the challenge of MDR bacteria. The purpose was to enhance the solubility, stability, and targeted delivery of berberine (BER) and its synthetic derivative NR16 using Styrene-co-Maleic Acid (SMA) nanoparticles. Characterization of the nanoparticles, including dynamic light scattering (DLS) analysis, TEM, and UV/Vis absorption spectroscopy, confirmed their suitability and high stability for passive drug delivery. Antibacterial and antifungal activities were evaluated against a panel of pathogens, revealing significant inhibitory effects on Gram-positive strains; particularly BER, SMA-BER, and NR16 were active against MRSA, MSSA, VR, and VS E. faecalis, and S. epidermidis. Additionally, SMA-BER and SMA-NR16 showed promising activity against biofilm formation of S. epidermidis; while the two free drugs contributed to S. epidermidis biofilm disruption activity. Hemolysis tests and in vitro studies on human embryonic kidney cells (HEK-293) confirmed the safety profiles of the nanoparticles and free drugs. Overall, this research highlighted the potential of nanotechnology in developing effective antibacterial agents with reduced toxicity, addressing the growing threat of MDR bacterial infections.

Herein, we describe the design, synthesis, and in vitro biological evaluation of HO-1 inducers endowed with cytotoxic effects mediated by ferroptosis activation. Using the natural HO-1 inducer caffeic acid phenethyl ester (CAPE) as a chemical scaffold, new derivatives were synthesized by performing modifications in the cathecol moiety and in the phenethyl ester aromatic ring. Biological assays aimed at evaluating an imbalanced activity of ferroptosis key players identified that 2-(1H-indol-3-yl)ethyl cinnamate (compound 24) possesses improved anticancer activity toward the MDA-MB 231 triple negative breast cancer cell line when compared to CAPE. Increased ROS and LOOH levels, reduced GSH levels, imbalanced mitochondrial activity, and restored cell viability after ferrostatin-1 treatment suggested a ferroptotic mechanism of action, which did not involve GPX4 inhibition. Compound 24 represents an intriguing hit compound useful for the identification of novel ferroptosis inducers

AbstractThree new chromophores based on difluoroborondipyrromethene dyes (Bodipy‐1, Bodipy‐2, and Bodipy‐3) are used as precursors to prepare luminescent solar concentrators (LSC) based on poly‐acrylate, following a thermally activated polymerization involving lauryl methacrylate as monomer, ethyl glycol dimethacrylate as cross‐linking agent, and lauroyl peroxide as initiator. The new dyes exhibit typical BODIPY absorption and emission properties in dichloromethane fluid solution, assigned to the lower‐lying singlet π–π∗ level, which in the case of Bodipy‐2 and Bodipy‐3, both containing diamino‐substituted styryl subunits in their structure, has a strong charge transfer contribution. The LSCs obtained starting from each of the three Bodipys are interfaced to silicon photovoltaic (PV) cells, and the PV light‐to‐energy conversion efficiencies ηopt for the three systems are calculated. The results yield ηopt of 4.53% for LSC‐Bodipy‐1, 5.26% for LSC‐Bodipy‐2, and 8.23% for LSC‐Bodipy‐3. The optical efficiency for LSC‐Bodipy‐3 is a remarkable value among the LSC based on organic dyes.

The supramolecular polymerization of a bis-pillar[5]arene dicarboxylic acid monomer (H) in the presence of a mixture of complementary bis-guests 1,12-dodecanediyl-bis-1,1 '-1H-imidazole (G1) and bis-N,N'-(6-(1H-imidazole)decyl)-perylene bisimide (G2), produces an AA/BB-type supramolecular copolymer H/G1/G2 that retains the properties of the parent bi-component systems, that is, H/G1 solubility and H/G2 photoresponsiveness. The supramolecular copolymer showed stimuli-responsiveness, reacting to the presence of the cancer marker, spermine (S), by disassemblying and releasing G2. Once released, the perylene bisimide monomer (quenched in the copolymer by host-to-guest electron transfer), showed a remarkable increase of emission intensity. ESI-MS data are fully consistent with the formation of the H/G1/G2 copolymer, and AFM investigations on films cast from H/G1/G2 and H/G1/G2 + S solutions demonstrated that the supramolecular copolymer sensing abilities are retained also in the solid state. A supramolecular copolymer, composed of a bis-pillar[5]arene diacid and complementary alkylidene- and perylene-bisimide-bis-imidazole comonomers, acts as an OFF/ON luminescent sensor for spermine.

The primary cause of poor and ambiguous results obtained from the bioanalytical process is the sample pre-treatment, especially in clinical analysis because it involves dealing with complex sample matrices, such as whole blood, urine, saliva, serum, and plasma. So, the aim of this review is to focus attention on the classical and new techniques of pre-treatment for biological samples used in the bioanalytical process. We discussed the methods generally used for these types of complex samples. Undoubtedly, it is a daunting task to deal with biological samples because the analyst may encounter a substantial loss of the analytes of interest, or the overall analysis may be too time-consuming. Nowadays, we are inclined to use green solvents for the environment, but without sacrificing analytical performance and selectivity. All the characteristics mentioned above should be added to the difficulty of the withdrawal of samples like blood because it can be an invasive practice. For these reasons, now we can also find in the literature the use of saliva as alternative biological samples and new techniques that do not require substantial sample pre-treatment, such as fabric phase sorptive extraction (FPSE). The text has been divided into the following two distinct parts: firstly, we described clinical applications under different subsections, such as anticancer drugs, antibiotics, vitamins, antivirals, non-steroidal anti-inflammatory drugs, statin, imidazoles, and triazoles. The second part is dedicated to sample preparation techniques for diagnostic purposes and is divided into the following different sample preparation techniques: solid-phase microextraction (SPME), microextraction by packed sorbent (MEPS), dispersive liquid–liquid microextraction (DDLME), and fabric phase sorptive extraction (FPSE).

The treatment of biological samples, especially from complex matrices, has consistently challenged analytical operators. The classic problems to be faced for any analysis, regardless of the origin of the sample, such as for example contamination and loss of analyte, in biological samples, are particularly emphasized. In particular, the main cause of the error is due to the degradation of the analyte which in several cases due to biological interaction. Many factors can influence the stability of drugs, chief among them the physicochemical properties of the drug, characteristics of the matrix, the tendency to conjugation/deconjugation, sample collection procedure, container characteristics (e.g., oxidation, adsorption), and the use of preservatives or other additives. The problem is severe in the toxicological and forensic fields, especially for analyzes considered ''non-repeatable.'' In this review, we will explore all the major problems in the pre-extraction phase for the chemical-analytical aspect in the pharmacotoxicological and forensic fields.

There is a growing interest for cost-effective and nondestructive analytical techniques in both research and application fields. The growing approach by near-infrared spectroscopy (NIRs) pushes to develop handheld devices devoted to be easily applied for in situ determinations. Consequently, portable NIR spectrometers actually result definitively recognized as powerful instruments, able to perform nondestructive, online, or in situ analyses, and useful tools characterized by increasingly smaller size, lower cost, higher robustness, easy-to-use by operator, portable and with ergonomic profile. Chemometrics play a fundamental role to obtain useful and meaningful results from NIR spectra. In this review, portable NIRs applications, published in the period 2019–2022, have been selected to indicate starting references. These publications have been chosen among the many examples of the most recent applications to demonstrate the potential of this analytical approach which, not having the need for extraction processes or any other pre-treatment of the sample under examination, can be considered the “true green analytical chemistry” which allows the analysis where the sample to be characterized is located. In the case of industrial processes or plant or animal samples, it is even possible to follow the variation or evolution of fundamental parameters over time. Publications of specific applications in this field continuously appear in the literature, often in unfamiliar journal or in dedicated special issues. This review aims to give starting references, sometimes not easy to be found.

One of the most discussed topics concerns the sample preparation before the analysis and, therefore, all the operations necessary to eliminate the interferents, clean up the specimens, and extract the analytes of interest, reducing the matrix effect. This review highlights the fundamental steps in the treatment of postmortem samples used in forensic analysis. Through critical literature research, it was possible to choose among the countless works that could provide a general overview of the state-of-the-art in this field. Different biological matrices have been considered; blood and urine (the traditional biological fluids) are used to investigate the presence of substances that may have caused death, whilst other body fluids, such as bile and oral fluids, are still under discussion for their usability (and suitability). In the second part of the review, all the solid matrices obtained after autopsy were further divided into conventional and unconventional matrices to facilitate proper understanding. The choice of literature was also made according to the most widely used pretreatment techniques and the most representative innovative techniques.

The study of the fractionation of the stable carbon isotopes 13 C and 12 C through the & delta;13 C value finds applications in various fields of science, from quality control in agribusiness to the study of the geographical origin of materials. At the plant level, this information is useful to prove which photosynthetic cycle a particular plant belongs to: C3, C4 or Crassulacean Acid Metabolism. In this work, the Isotopic Ratio Mass Spectrometry technique was used to shed light and investigate about the degradation due to aging of an ancient linen textile of Egyptian origins, in order to see whether degradation phenomena change the content of stable carbon isotopes, over time. For this purpose, the & delta;13 C values of the ancient sample were compared with contemporary Egyptian and French flax fibers samples. For the first time, it was observed that, contrary to what might have been expected, material degradation due to natural aging contributes to the phenomenon of the isotopic fractionation, due to the increasing in measured & delta;13 C values from contemporary to ancient samples.& COPY; 2023 The Author(s). Published by Elsevier Masson SAS on behalf of Consiglio Nazionale delle Ricerche (CNR).This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ )

Over the last few years, the study of the SARS-CoV-2 spike protein and its mutations has become essential in understanding how it interacts with human host receptors. Since the crystallized structure of the spike protein bound to the angiotensin-converting enzyme 2 (ACE2) receptor was released (PDB code 6M0J), in silico studies have been performed to understand the interactions between these two proteins. Specifically, in this study, heterocyclic compounds with different chemical characteristics were examined to highlight the possibility of interaction with the spike protein and the disruption of the interaction between ACE2 and the spike protein. Our results showed that these compounds interacted with the spike protein and interposed in the interaction zone with ACE2. Although further studies are needed, this work points to these heterocyclic push–pull compounds as possible agents capable of interacting with the spike protein, with the potential for the inhibition of spike protein–ACE2 binding.

Here we report the design and fabrication of an array-based sensor, containing functionalized Carbon Dots, Bodipy's and Naphthalimide probes, that shows high fluorescence emissions and sensitivity in the presence of low amounts of TNT explosive. In particular, we have fabricated the first sensor device based on an optical array for the detection of TNT in real samples by using a smartphone as detector. The possibility to use a common smartphone as detector leads to a prototype that can be also used in a real-life field application. The key benefit lies in the possibility of even a nonspecialist operator in the field to simply collect and send data (photos) to the trained artificial intelligence server for rapid diagnosis but also directly to the bomb disposal unit for expert evaluation. This new array sensor contains seven different fluorescent probes that are able to interact via noncovalent interactions with TNT. The interaction of each probe with TNT has been tested in solution by fluorescence titrations. The solid device has been tested in terms of selectivity and linearity toward TNT concentration. Tests performed with other explosives and other nitrogen-based analytes demonstrate the high selectivity for TNT molecules, thus supporting the reliability of this sensor. In addition, TNT can be detected in the range of 98 ng∼985 μg, with a clear different response of each probe to the different amounts of TNT.