Photoinduced energy and electron transfer processes in a supramolecular system combining a tetrapyrenylporphyrin derivative and arene-ruthenium metalla-prisms.

A supramolecular system, consisting of a tetrapyrenylporphyrinic core surrounded by arene-ruthenium prisms, has been assembled and characterized by means of electrochemical and photophysical techniques. The photophysical study shows that quantitative energy transfer from the peripheral pyrenyl units towards the central porphyrin core is operative in the tetrapyrenylporphyrinic system. Interestingly, encapsulation of the pyrenyl units into the ruthenium cages affects the photophysics of the central porphyrin component, since its emission quantum yield is reduced in the supramolecular array.

Assessing Cytotoxicity, Proteolytic Stability, and Selectivity of Antimicrobial Peptides: Implications for Orthopedic Applications.

In orthopedics, the use of anti-infective biomaterials is considered the most promising strategy to contrast the bacterial contamination of implant surfaces and reduce the infection rate. KSL, KSL-W, and Dadapin-1 are three antimicrobial peptides (AMPs) that possess significant antibacterial properties, making them promising candidates for producing anti-infective biomaterials not based on antibiotics. To fully assess their true potential, this study explores in detail their cytocompatibility on human osteoblast-like MG63 cells, murine fibroblastoid L929 cells, and hMSCs.

Uncovering Astrocyte Morphological Dynamics Using Optical Diffraction Tomography and Shape-Based Trajectory Inference.

Astrocytes, integral components of the central nervous system, are increasingly recognized for their multifaceted roles beyond support cells. Despite their acknowledged importance, understanding the intricacies of astrocyte morphological dynamics remains limited. Our study marks the first exploration of astrocytes using optical diffraction tomography (ODT), establishing a label-free, quantitative method to observe morphological changes in astrocytes over a 7-day in-vitro period.

Near-infrared phosphorescence in a ruthenium(II) complex equipped with a pyridyl-1,2-azaborine ligand.

The 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene molecule Hazab-py has been successfully used, for the first time, as a ligand in a ruthenium(II) polypyridine complex A (with the formula [Ru(dtbbpy)(azab-py)], where dtbbpy = 4,4'-di--butyl-2,2'-bipyridine). This compound was characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and its electrochemical and photophysical properties were fully investigated and compared to those of its homoleptic analogue [Ru(dtbbpy)] (B), an archetypical mono-cationic cyclometalated complex C (with the formula [Ru(dtbbpy)(ppy)], where Hppy = 2-phenylpyridine), and the more structurally similar analogue [Ru(dtbbpy)(naft-py)] (D), where the B-N unit of the azaborine ligand is replaced by a standard CC one, resulting in the 2-(naphthalen-2-yl)pyridine ligand (Hnaft-py). The presence of the novel 1,2-azaborine ligand induces a 0.

Long-chain surface-modified red-emitting carbon dots as fluorescent additives for 3D printing vat-photopolymerization.

Carbon dots have recently attracted tremendous scientific attention thanks to their enhanced luminescence properties, photostability and low toxicity. In particular, red-emitting carbon dots (RCDs) are assuming increasing importance in biomedical applications, such as bio-imaging and phototherapy. At the same time, the possibility to create functional and complex objects by means of vat-photopolymerization-based three-dimensional (3D) printing techniques is continuously growing.

Insights into SARS-CoV-2: Small-Molecule Hybrids for COVID-19 Treatment.

The advantages of a treatment modality that combines two or more therapeutic agents with different mechanisms of action encourage the study of hybrid functional compounds for pharmacological applications. Molecular hybridization, resulting from a covalent combination of two or more pharmacophore units, has emerged as a promising approach to overcome several issues and has also been explored for the design of new drugs for COVID-19 treatment. In this review, we presented an overview of small-molecule hybrids from both natural products and synthetic sources reported in the literature to date with potential antiviral -SARS-CoV-2 activity.

Towards Bacterial Resistance via the Membrane Strategy: Enzymatic, Biophysical and Biomimetic Studies of the Lipid cis-trans Isomerase of Pseudomonas aeruginosa.

The lipid cis-trans isomerase (Cti) is a periplasmic heme-c enzyme found in several bacteria including Pseudomonas aeruginosa, a pathogen known for causing nosocomial infections. This metalloenzyme catalyzes the cis-trans isomerization of unsaturated fatty acids in order to rapidly modulate membrane fluidity in response to stresses that impede bacterial growth. As a consequence, breakthrough in the elucidation of the mechanism of this metalloenzyme might lead to new strategies to combat bacterial antibiotic resistance.

Peroxyl Radical Trapping Antioxidant Activity of Essential Oils and Their Phenolic Components.

Essential oils (EOs) are gaining importance as sustainable food antioxidants, but kinetic data on peroxyl radical trapping are missing. Thirteen EOs from 11 botanical species were studied in the inhibited autoxidation of cumene by oxygen-uptake kinetics. EOs of , , , , , , and , containing 23-86% phenolic components by gas chromatography/mass spectrometry (GC-MS) analysis, afforded inhibition rate constants in the order of 10 M s at 30 °C similar to reference butylhydroxytoluene (2,6-di--butyl-4-methylphenol) (BHT).

Pro-aromatic Natural Terpenes as Unusual "Slingshot" Antioxidants with Promising Ferroptosis Inhibition Activity.

Ferroptosis is a cell death mechanism based on extensive cellular membrane peroxidation, implicated in neurodegenerative and other diseases. The essential oil component γ-terpinene, a natural monoterpene with a unique highly oxidizable pro-aromatic 1,4-cyclohexadiene skeleton, inhibits peroxidation of polyunsaturated lipid in model heterogeneous systems (micelles and liposomes). Upon H-atom abstraction, an unstable γ-terpinene-derived peroxyl radical is formed, that aromatizes to p-cymene generating HOO⋅ radicals.

Electrochemical sensors for fast classification of different Cannabis sativa L. samples according to total Δ-tetrahydrocannabinol content.

In this work, we investigated the ability of an electrochemical sensor to recognize Cannabis sativa L. samples with different total content of Δ-tetrahydrocannabinol (Δ-THC), determined by the levels of the psychoactive cannabinoid and of its biosynthetic precursor Δ-tetrahydrocannabinolic acid (Δ-THCA), using a multivariate approach. The voltammetric responses recorded with screen-printed electrodes modified with carbon black reflected the compositional differences from the different samples, in terms of cannabinoids of the vegetal material.

Directional Ring Translocation in a pH- and Redox-Driven Tristable [2]Rotaxane.

We describe the synthesis and characterization of a [2]rotaxane comprising a dibenzo-24-crown-8 (DB24C8) macrocyclic component and a thread containing three recognition sites: ammonium (AmH), bipyridinium (Bpy) and triazolium (Trz). AmH and Bpy are responsive to fully orthogonal stimuli, pH and electrochemical, which allows to precisely control the directional translation of the macrocycle along the axle. A better understanding of the processes driving the operation of the system was obtained thanks to an in-depth thermodynamic characterization.

Fully Bio-Based Blends of Poly (Pentamethylene Furanoate) and Poly (Hexamethylene Furanoate) for Sustainable and Flexible Packaging.

In the present study, bio-based polymeric blends have been prepared for applications in the field of sustainable food packaging, starting from two furan-based homopolymers, poly(hexamethylene 2,5-furanoate) (PHF) and poly(pentamethylene 2,5-furanoate) (PPeF). PHF and PPeF were synthesized by two-step melt polycondensation-a solvent-free synthetic strategy-and then binary physical mixtures, PHF/PPeF, with different weight compositions were prepared by dissolution in a common solvent. The blends were processed into compression-moulded films, and molecular, morphological, structural, thermal, and mechanical characterizations were subsequently carried out.

Molecules as Lubricants at the Nanoscale:Tunable Growth of Organic Structures from Nano- to Millimeter-Scale Using Solvent Vapour Annealing.

The creation of ordered structures of molecules assembled from solution onto a substrate is a fundamental technological necessity across various disciplines, spanning from crystallography to organic electronics. However, achieving macroscopic order poses significant challenges, since the process of deposition is inherently impacted by factors like solvent evaporation and dewetting flows, which hinder the formation of well-organized structures. Traditional methods like drop casting or spin coating encounter limitations due to the rapid kinetics of solvent evaporation, leading to limited control over final uniformity and order.

Organic super-reducing photocatalysts generate solvated electrons two consecutive photon induced processes.

Photocatalysts with extremely strong reducing potential are often thought to operate through a consecutive photoinduced electron transfer (ConPeT) mechanism, where a first photon generates the radical anion of the photocatalyst electron transfer and a second photon excites the radical anion into a super-reducing agent. Among them, 4CzIPN, (2,4,5,6-tetrakis(9H-carbazol-9-yl) isophthalonitrile) and the analogous 4DPAIPN (2,4,5,6-tetrakis(diphenylamino)isophthalonitrile) are supposed to operate following this principle, but the knowledge of the photophysical properties of the photogenerated radical anions is still very limited. An in-depth spectroscopic and computational study of their radical anions demonstrates that the excited states of 4CzIPN˙ and 4DPAIPN˙ are not behaving as super-reducing agents: they are very short lived ( 20 ps), not emissive and not quenched by common organic substrates.

Protocol for the simultaneous quantification of oxidative purine lesions in DNA using LC-MS/MS analysis.

Most DNA damages induced through oxidative metabolism are single lesions which can accumulate in tissues. Here, we present a protocol for the simultaneous quantification of oxidative purine lesions (cPu and 8-oxo-Pu) in DNA. We describe steps for enzymatic digestion of DNA and sample pre-purification, followed by quantification through liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis.

Evaluation of Anticancer Activity of Nucleoside-Nitric Oxide Photo-Donor Hybrids.

Herein, we report the synthesis of a new hybrid compound based on a 2'-deoxyuridine nucleoside conjugated with a NO photo-donor moiety (dU-t-NO) via CuAAC click chemistry. Hybrid dU-t-NO, as well as two previously reported 2'-deoxyadenosine based hybrids (dAdo-S-NO and dAdo-t-NO), were evaluated for their cytotoxic and cytostatic activities in selected cancer cell lines. dAdo-S-NO and dAdo-t-NO hybrids displayed higher activity with respect to dU-t-NO.

Kinetic study of the reaction of thiophene-tocopherols with peroxyl radicals enlightenings the role of O˙⋯S noncovalent interactions in H-atom transfer.

Three new α-tocopherol thiophene derivatives were efficiently synthesized, characterized and used for the first time as chain-breaking antioxidants for the inhibition of the autoxidation of reference oxidizable substrates. The rate constant of the reaction with alkylperoxyl (ROO˙) radicals and the stoichiometry of radical trapping () for the thiophene-tocopherol compounds were determined by measuring the oxygen consumption during the autoxidation of styrene or isopropylbenzene, using a differential pressure transducer. The measurement of the reaction with ROO˙ radicals in an apolar solvent at 30 °C showed inhibition rate constants () in the order of 10 M s.

Corrigendum: HSA-nanobinders crafted from bioresponsive prodrugs for combined cancer chemoimmunotherapy-an exploration.

[This corrects the article DOI: 10.3389/fchem.2024.

Electrochemical Synthesis of Itaconic Acid Derivatives via Chemodivergent Single and Double Carboxylation of Allenes with CO.

Leveraging electrochemistry, a new synthesis of non-natural derivatives of itaconic acid is proposed by utilizing carbon dioxide (CO) as a valuable C1 synthon. An electrochemical cross-electrophile coupling between allenoates and CO was targeted, allowing for the synthesis of both mono- and di-carboxylation products in a catalyst- and additive-free environment (yields up to 87 %, 30 examples). Elaboration of the model mono-carboxylation product, and detailed cyclovoltammetric, as well as mechanistic analyses complete the present investigation.

Keratin-PNIPAM Hybrid Microgels: Preparation, Morphology and Swelling Properties.

Combinations of synthetic polymers, such as poly(N-isopropylacrylamide) (PNIPAM), with natural biomolecules, such as keratin, show potential in the field of biomedicine, since these hybrids merge the thermoresponsive properties of PNIPAM with the bioactive characteristics of keratin. This synergy aims to produce hybrids that can respond to environmental stimuli while maintaining biocompatibility and functionality, making them suitable for various medical and biotechnological uses. In this study, we exploit keratin derived from wool waste in the textile industry, extracted via sulfitolysis, to synthesize hybrids with PNIPAM microgel.

HSA-nanobinders crafted from bioresponsive prodrugs for combined cancer chemoimmunotherapy-an exploration.

Introduction: Triple-negative breast cancer (TNBC) is an aggressive subtype of breast cancer still lacking effective treatment options. Chemotherapy in combination with immunotherapy can restrict tumor progression and repolarize the tumor microenvironment towards an anti-tumor milieu, improving clinical outcome in TNBC patients. The chemotherapeutic drug paclitaxel has been shown to induce immunogenic cell death (ICD), whereas inhibitors of the indoleamine 2,3- dioxygenase 1 (IDO1) enzyme, whose expression is shared in immune regulatory and tumor cells, have been revealed to enhance the anti-tumor immune response.

Association between Albumin Alterations and Renal Function in Patients with Type 2 Diabetes Mellitus.

Diabetic kidney disease (DKD) is a major cause of morbidity and mortality in individuals with type 2 diabetes mellitus (T2DM). The aim of this study was to investigate whether albumin structural alterations correlate with DKD severity and evaluate whether native and reduced albumin concentrations could complement the diagnosis of DKD. To this end, one hundred and seventeen T2DM patients without ( = 42) and with ( = 75) DKD (DKD I-III upon KDIGO classification) were evaluated; the total albumin concentration (tHA) was quantified by a bromocresol green assay, while structural alterations were profiled via liquid chromatography-high-resolution mass spectrometry (LC-HRMS).