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Modern isothermal titration calorimetry instruments give great precision, but for comparable accuracy they require chemical calibration. For the heat factor, one recommended process is HCl into the weak base TRIS. In studying this reaction with a VP-ITC and two Nano-ITCs, we have encountered some problems, most importantly a titrant volume shortfall Δv ≈ 0.3 μL, which we attribute to diffusive loss of HCl in the syringe tip. This interpretation is supported by a mathematical treatment of the diffusion problem. The effect was discovered through a variable-v protocol, which thus should be used to properly allow for it in any reaction that similarly approaches completion. We also find that the effects from carbonate contamination and from OH - from weak base hydrolysis can be more significant that previously thought. To facilitate proper weighting in the least-squares fitting of data, we have estimated data variance functions from replicate data. All three instruments have low-signal precision of σ ≈ 1 μJ; titrant volume uncertainty is a factor of ∼2 larger for the Nano-ITCs than for the VP-ITC. The final heat factors remain uncertain by more than the ∼1 % precision of the instruments and are unduly sensitive to the HCl concentration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Group (IV) metal oxo clusters represent a unique family of molecular species that are increasingly being utilized in applications ranging from catalysis and materials chemistry to electronics, and sensors. These clusters exhibit distinctive structural features, chemical reactivity, and electronic structure. Nevertheless, their full potential has yet to be fully realized due to the lack of deeper understanding regarding their structure and formation mechanisms, inherent traits, and intricacies in their design, which could ultimately enable significant customization of their properties and overall behaviour. Considering the recently observed reignited interest in the chemistry of group IV molecular species, the scope of this article is to bring to the readers the main chemical characteristics of the family of titanium, zirconium, and hafnium-based clusters, their structural features and their potential in future applications.

The initial use of 2-(pyridin-2-yl)propane-1,3-diol (pypdH 2 ) in Mn cluster chemistry has afforded two new mixed-valence polynuclear Mn clusters, namely, [Mn 8 Ο 5 (pypd)(hmp) 3 (O 2 CCMe 3 ) 8 ] ( 1 ) and [Mn 16 Ο 10 (N 3 ) 2 (pypd) 2 {(py) 2 CO 2 } 4 (O 2 CEt) 12 ] ( 2 ) (hmp - = deprotonated 2-hydroxymethylpyridine; (py) 2 CO 2 = deprotonated gem-diol form of di-2-pyridyl ketone). Compound 2- = deprotonated gem-diol form of di-2-pyridyl ketone). Compound 1 features a novel [Mn III 7 Mn II (μ 4 -O) 2 (μ 3 -O) 3 (μ-OR) 5 ] 8+ structural core resembling a supertetrahedron T3, lacking two apexes, while complex 2 has a [Mn III 14 Mn II 2 (μ 4 -O) 4 (μ 3 -O) 6 (μ-N 3 ) 2 core consisting of two [Mn 3 -OR) 2 and thus is a dimeric analogue of 8 . Direct current (dc) magnetic susceptibility studies revealed the presence of dominant antiferromagentic exchange interactions between the Mn ions in complexes 14+ core consisting of two [Mn 8 and small ground state spin values for both compounds. Overall, this work highlights the capability of polyol-like chelates like pypdH 1 and thus is a dimeric analogue of 1 . Direct current (dc) magnetic susceptibility studies revealed the presence of dominant antiferromagentic exchange interactions between the Mn ions in complexes 1 and 2 and small ground state spin values for both compounds. Overall, this work highlights the capability of polyol-like chelates like pypdH 2 to stabilize high nuclearity 3d metal clusters based on polynuclear building blocks., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The combined use of 2-(2-pyridyl)-1,3-propane-diol (pypdH 2 ) and 2-hydroxymethyl-2-(2-pyridyl)-1,3-propane-diol (pyptH 3 ) in Cu 2+ /4f chemistry has afforded a new family of isostructural [Cu 6 M 4 (pypt) 4 (pypdH) 4 (NO 3 ) 8 ] [M = Gd (1), Tb (2), Dy (3), and Y (4)] complexes. These compounds are based on an unprecedented three-layered symmetric [Cu 6 M 4 (μ-OR) 16 ] 8+ structural core, formed from the connection of the metal ions by bridging alkoxide arms of the organic ligands. Direct current magnetic susceptibility studies for complexes 1-3 revealed the presence of dominant ferromagnetic exchange interactions, suggesting the existence of large spin ground state values. Alternating current magnetic studies indicate the presence of slow-magnetic relaxation in 1-3.

The present study investigates the utilization of a supramolecular deep eutectic solvent (SUPRADES), consisting of sulfated-β-cyclodextrin (S-β-CD) and citric acid (CA), as a chiral selector (CS) in capillary electrophoresis for the enantiomeric separation of nefopam (NEF) and five cathinone derivatives (3-methylmethcathinone [3-MMC], 4-methylmethcathinone [4-MMC], 3,4-dimethylmethcathinone [3,4-DMMC], 4-methylethcathinone [4-MEC], and 3,4-methylendioxycathinone [MDMC]). A significant improvement in enantiomeric separation of the target analytes was observed upon the addition of S-β-CD-CA to the background electrolyte (BGE), leading to a baseline separation of all analytes. In particular, the optimum percentage of S-β-CD-CA, added to the BGE, was determined to be 0.075% v/v for NEF (R s  = 1.5) and 0.050% v/v for three out of five cathinone derivatives (R s  = 1.5, 1.6, and 2.4 for 3-MMC, 4-MEC, and 3,4-DMMC, respectively). In the case of 4-MMC and MDMC, a higher percentage of the CS, equal to 0.075% and 0.10% v/v, respectively, was required to achieve baseline separation (R s  = 1.5, 1.9 for MDMC and 4-MMC, respectively). The outcomes of the present study highlight the potential effectiveness of using SUPRADES as a CS in electrophoretic enantioseparations., (© 2024 The Author(s). Electrophoresis published by Wiley‐VCH GmbH.)

Polyethylene terephthalate (PET) plastics find widespread use in various aspects of our daily lives but often end up in the environment as (micro)plastic waste. In this study, the adsorption efficiency of PET microplastics for U-232 has been investigated prior and after surface alteration (e.g. oxidation (PET-ox), MnO 2 -coating (PET/MnO 2 ) and biofilm-formation (PET/Biofilm)) in the laboratory (at pH 4, 7 and 9) and seawater samples under ambient conditions and as a function of temperature. The results revealed a significant increase in the adsorption efficiency upon surface alteration, particularly after biofilm development on the MP's surface. Specifically, the K d values evaluated for the adsorption of U-232 by PET, PET-ox, PET/MnO 2 and PET/Biofilm are 12, 27, 73 and 363, respectively, at pH 7 and under ambient conditions. The significantly higher adsorption efficiency of the altered and particularly biofilm-coated PET, emphasizes the significance of surface alteration, which may occur under environmental conditions. In addition, according to the thermodynamic investigations the adsorption of U-232 by PET-MPs (both non-treated and modified), the adsorption is an endothermic and entropy-driven reaction. A similar behavior has been also observed using seawater solutions and assumes that surface alteration is expected to enhance the radionuclide, stability, mobility and bioavailability in environmental water systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Ambient Ionization Mass Spectrometry (AI-MS) techniques have revolutionized analytical chemistry by enabling rapid analysis of samples under atmospheric conditions with minimal to no preparation. In this study, the optimization of a cold atmospheric plasma for the analysis of food and pharmaceutical samples, liquid and solid, using a Heat-Assisted Dielectric Barrier Discharge Ionization (HA-DBDI) source is described. A significant enhancement in analyte signals was observed when a heating element was introduced into the design, potentially allowing for greater sensitivity. Furthermore, the synergy between the inlet temperature of the mass spectrometer and the heating element allows for precise control over the analytical process, leading to improved detection sensitivity and selectivity. Incorporating computational fluid dynamic (CFD) simulations into the study elucidated how heating modifications can influence gas transport properties, thereby facilitating enhanced analyte detection and increased signal intensity. These findings advance the understanding of HA-DBDI technology and provide valuable insights for optimizing AI-MS methodologies for a wide range of applications in food and pharmaceutical analysis.

Gallic acid (GA), a phenolic acid found in fruits and vegetables, has been consumed by humans for centuries. Its extensive health benefits, such as antimicrobial, antioxidant, anticancer, anti-inflammatory, and antiviral properties, have been well-documented. GA's potent antioxidant capabilities enable it to neutralize free radicals, reduce oxidative stress, and protect cells from damage. Additionally, GA exerts anti-inflammatory effects by inhibiting inflammatory cytokines and enzymes, making it a potential therapeutic agent for inflammatory diseases. It also demonstrates anticancer properties by inhibiting cancer cell growth and promoting apoptosis. Furthermore, GA offers cardiovascular benefits, such as lowering blood pressure, decreasing cholesterol, and enhancing endothelial function, which may aid in the prevention and management of cardiovascular diseases. This review covers the chemical structure, sources, identification and quantification methods, and biological and therapeutic properties of GA, along with its applications in food. As research progresses, the future for GA appears promising, with potential uses in functional foods, pharmaceuticals, and nutraceuticals aimed at improving overall health and preventing disease. However, ongoing research and innovation are necessary to fully understand its functional benefits, address current challenges, and establish GA as a mainstay in therapeutic and nutritional interventions.

In the course of an investigation of the supramolecular behaviour of copper(II) complexes with the 5-phenylimidazole/perchlorate ligand system (`blend') remarkable solvatomorphism has been observed. By employing a variety of crystallization solvents (polar protic, polar/non-polar aprotic), a series of 12 crystalline solvatomorphs with the general formula [Cu(ClO 4 ) 2 (LH) 4 ]·x(solvent) have been obtained [LH = 5-phenylimidazole, x(solvent) = 3.3(H 2 O) (1), 2(methanol) (2), 2(ethanol) (3), 2(1-propanol) (4), 2(2-propanol) (5), 2(2-butanol) (6), 2(dimethylformamide) (7), 2(acetone) (8), 2(tetrahydrofurane) (9), 2(1,4-dioxane) (10), 2(ethyl acetate) (11) and 1(diethyl ether) (12)]. The structures have been solved using single-crystal X-ray diffraction and the complexes were characterized by thermal analysis and infrared spectroscopy. The solvatomorphs are isostructural (triclinic, P1), with the exception of compound 9 (monoclinic, P2 1 /n). The supramolecular structures and the role of the various solvents is discussed. All potential hydrogen-bond functionalities, both of the [Cu(ClO 4 ) 2 (LH) 4 ] units and of the solvents, are utilized in the course of the crystallization process. The supramolecular assembly in all structures is directed by strong recurring N imidazole -H...O perchlorate motifs leading to robust scaffolds composed of the [Cu(ClO 4 ) 2 (LH) 4 ] host complexes. The solvents are located in channels and, with the exception of the disordered waters in 1 and the diethyl ether in 12, participate in hydrogen-bonding formation with the [Cu(ClO 4 ) 2 (LH) 4 ] complexes, serving as both hydrogen-bond acceptors and donors (for the polar protic solvents in 2-6), or solely as hydrogen-bond acceptors (for the polar/non-polar aprotic solvents in 7-11), linking the complexes and contributing to the stability of the crystalline compounds., (open access.)

Methanol is a toxic alcohol contained in alcoholic beverages as a natural byproduct of fermentation or added intentionally to counterfeits to increase profit. To ensure consumer safety, many countries and the EU have established strict legislation limits for methanol content. Methanol concentration is mostly detected by laboratory instrumentation since mobile devices for routine on-site testing of beverages in distilleries, at border stations or even at home are not available. Here, we validated a handheld methanol detector for beverage analysis in an ISO 5725 interlaboratory trial: a total of 119 measurements were performed by 17 independent participants (distilleries, universities, authorities, and competence centers) from six countries on samples with relevant methanol concentrations (0.1, 1.5 vol%). The detector was based on a microporous separation filter and a nanostructured gas sensor allowing on-site measurement of methanol down to 0.01 vol% (in the liquid) within only 2 min by laymen. The detector showed excellent repeatability (<5.4%), reproducibility (<9.5%) and small bias (<0.012 vol%). Additional measurements on various methanol-spiked alcoholic beverages (whisky, rum, gin, vodka, tequila, port, sherry, liqueur) indicated that the detector is not interfered by environmental temperature and spirit composition, featuring excellent linearity ( R > 0.99) down to methanol concentrations of 0.01 vol%. This device has been recently commercialized (Alivion Spark M-20) with comparable accuracy to the gold-standard gas chromatography and can be readily applied for final product inspection, intake control of raw materials or to identify toxic counterfeit products.2 > 0.99) down to methanol concentrations of 0.01 vol%. This device has been recently commercialized (Alivion Spark M-20) with comparable accuracy to the gold-standard gas chromatography and can be readily applied for final product inspection, intake control of raw materials or to identify toxic counterfeit products.

Scandium (Sc) isotopes have recently attracted significant attention in the search for new radionuclides with potential uses in personalized medicine, especially in the treatment of specific cancer patient categories. In particular, Sc-43 and Sc-44, as positron emitters with a satisfactory half-life (3.9 and 4.0 h, respectively), are ideal for cancer diagnosis via Positron Emission Tomography (PET). On the other hand, Sc-47, as an emitter of beta particles and low gamma radiation, may be used as a therapeutic radionuclide, which also allows Single-Photon Emission Computed Tomography (SPECT) imaging. As these scandium isotopes follow the same biological pathway and chemical reactivity, they appear to fit perfectly into the "theranostic pair" concept. A step-by-step description, initiating from the moment of scandium isotope production and leading up to their preclinical and clinical trial applications, is presented. Recent developments related to the nuclear reactions selected and employed to produce the radionuclides Sc-43, Sc-44, and Sc-47, the chemical processing of these isotopes and the main target recovery methods are also included. Furthermore, the radiolabeling of the leading chelator, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA), and its structural analogues with scandium is also discussed and the advantages and disadvantages of scandium complexation are evaluated. Finally, a review of the preclinical studies and clinical trials involving scandium, as well as future challenges for its clinical uses and applications, are presented.

We here report on the observation of upconverted photoluminescence (UC-PL) from the blue-light-emitting 9,10-diphenylanthracene (DPA) mixed with the yellow-light-absorbing bifunctional sensitizer/activator component of (3,3,7,8,12,13,17,18-octaethylporphyrin-22,24-diid-2-one) Pt II (PtOEP-K). Yellow-to-blue UC-PL (0.680 eV spectral upshift) is achieved at room temperature under ultralow power continuous incoherent photoexcitation (220 μW/cm 2 ) despite the absence of triplet energy transfer (TET) between PtOEP-K and DPA. Under selective CW-laser photoexcitation of PtOEP-K in DPA:PtOEP-K, a 2.5% UC-PL quantum yield is obtained; that is an improvement exceeding by more than 3 orders of magnitude the UC-PL quantum yield of TTA-UC material combinations wherein no TET is operative. The PL response of DPA:PtOEP-K to varying laser fluence suggests that bimolecular annihilation reactions between triplet-excited PtOEP-K facilitate the UC-PL activation in DPA. These findings pave the way toward low-complexity strategies for the reduction of transmission losses in solar energy technologies through an innovative wavelength upshifting protocol involving excitonic materials.

Canthin-4-one is synthesized via a six-step procedure starting from commercially available 3-amino-4-bromopyridine in 26% overall yield. 3-Amino-4-bromopyridine is initially converted to 8-bromo-1,5-naphthyridin-4(1 H )-one. O-Methylation, intermolecular Pd-catalyzed C-C coupling, and demethylation afford the key intermediate, 8-(2-chlorophenyl)-1,5-naphthyridin-4(1 H )-one, for which intramolecular C-N coupling completes the synthesis of the canthin-4-one skeleton. Ten canthin-4-one analogues were prepared in addition to the parent compound. With minor modifications, the synthesis also applies to the synthesis of two series of isocanthin-4-ones.

Indoor air quality (IAQ) is critical to the health and wellbeing of people. As the majority of people spend greater amounts of time indoors, either in office spaces or households, the level of air pollutants in such environments is critical. Building materials and furniture are known sources of air pollutants such as Volatile Organic Compounds (VOCs) and may be associated with discomfort, detrimental health of the occupants, etc. In this study, the VOCs found in a brand new office complex were monitored over a period of 6 months, with an emphasis on monitoring and quantifying harmful VOCs and identifying their emission source. Air samples were taken from a closed, unoccupied office space on a weekly basis and analysed using Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC-MS), while continuous monitoring of the air quality was performed using two commercially available IAQ sensors. To identify the source of the emitted VOCs, pieces of all construction material that were used in the office, including flooring, finished wall material, and adhesive glues, were removed, and placed in air-tight glass containers prior to analysis confirming that the source of VOCs is indeed the flooring. Identified compounds included mainly material origin VOCs such as BTEX (benzene, toluene, ethylbenzene, xylene) and styrene, but also common VOCs such as acetone and propan-2-ol. Of significant importance was the concentration of toluene that was found to be the most abundant VOC in both the flooring material and the indoor air., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

We present the development of a platform of well-defined, dynamic covalent amphiphilic polymer conetworks (APCN) based on an α,ω-dibenzaldehyde end-functionalized linear amphiphilic poly(ethylene glycol)- b -poly(propylene glycol)- b -poly(ethylene glycol) (PEG- b -PPG- b -PEG, Pluronic) copolymer end-linked with a triacylhydrazide oligo(ethylene glycol) triarmed star cross-linker. The developed APCNs were characterized in terms of their rheological (increase in the storage modulus by a factor of 2 with increase in temperature from 10 to 50 °C), self-healing, self-assembling, and mechanical properties and evaluated as a matrix for gel polymer electrolytes (GPEs) in both the stretched and unstretched states. Our results show that water-loaded APCNs almost completely self-mend, self-organize at room temperature into a body-centered cubic structure with long-range order exhibiting an aggregation number of around 80, and display an exceptional room temperature stretchability of ∼2400%. Furthermore, ionic liquid-loaded APCNs could serve as gel polymer electrolytes (GPEs), displaying a substantial ion conductivity in the unstretched state, which was gradually reduced upon elongation up to a strain of 4, above which it gradually increased. Finally, it was found that recycled (dissolved and re-formed) ionic liquid-loaded APCNs could be reused as GPEs preserving 50-70% of their original ion conductivity.

N-heterocycles are essential building blocks and scaffolds in medicinal chemistry. A Pd-catalyzed, Ru-photoredox-mediated C-H arylation is applied herein, for converting a series of functionality-inclusive (6-phenylpyridin-2-yl)pyrimidines to single arylated derivatives, using phenyldiazonium tetrafluoroborate as aryl source. This green chemistry-compliant transformation is induced by LED light. The drug-like modular substrates are constructed via combination of Biginelli multi-component condensation and Suzuki C-C cross-coupling, in order to strategically install, adjacent to the Ph-ring intended to undergo C-H arylation, a (6-pyridin-2-yl)pyrimidine that plays the role of a chelating directing moiety for the C-H arylation catalyst. The scope has been demonstrated on a series of 26 substrates, comprising diverse Ph-ring substituents and substitution patterns, as well as with 13 different aryl donors. Substrates in which the Ph-ring (arylation acceptor) was replaced by an electron-rich heteroaryl counterpart (2-/3-thiophene or -benzofuran) have also been examined and found to undergo arylation regioselectively. End-product conformations afford interesting motifs for occupying 3D chemical space, as implied by single-crystal X-ray diffraction, which has allowed the elucidation of six structures of aryl derivatives and one of an unprecedented pyrimidine-pyridine-benzofuran carbopalladated complex, believed to be a C-H activation derivative., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Indoor air quality (IAQ) has attracted a lot of attention due to its complexity and direct effect on human health. Indoor settings in libraries entail various volatile organic compounds (VOCs) linked to the aging and degradation of print material. The effect of the storage environment on paper life expectancy was investigated by targeting the VOC emissions of old and new books using headspace solid phase micro extraction-gas chromatography/mass spectrometry (HS-SPME-GC/MS) analysis. "Sniffing" of book degradation markers showed both ubiquitously and infrequently occurring VOCs. Old book "degradomics" revealed mostly alcohols (57%) and ethers (12%), whereas new books resulted mainly to ketones (40%) and aldehydes (21%). Chemometric processing of the results with principal component analysis (PCA) corroborated our initial observations and was able to discriminate the books by age into three groups: very old books (from the 1600 s to mid-1700), old books (from the 1800s to the early 1900s), and modern books (from the mid-twentieth century onwards) based on their gaseous markers. The measured mean concentrations of selected VOCs (acetic acid, furfural, benzene, and toluene) were below the respective guidelines set for similar places (i.e. museums). The applied non-invasive, green analytical methodology (HS-SPME-GC/MS) can assist librarians, stakeholders, and researchers to evaluate the IAQ, as well as the degree of degradation, and take the appropriate measures for book restoration and monitoring protocols., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The synthesis, characterization, and single-crystal-to-single-crystal (SCSC) exchange reactions of a new 3D Cu 2+ MOF based on 5-aminoisophthalic acid (H 2 AIP), [Cu 6 (μ 3 -ΟΗ) 3 (ΑΙΡ) 4 (HΑΙΡ)] n ·6 n DMF· n H 2 O - UCY-16 ·6 n DMF· n H 2 O, are reported. It exhibits a 3D structure based on two [Cu 4 (μ 3 -OH) 2 ] 6+ butterfly-like secondary building units, differing in their peripheral ligation, bridged through HAIP - /AIP 2- ligands. This compound displays the capability to exchange the coordinating ligand(s) and/or guest solvent molecules through SCSC reactions. Interestingly, heterogeneous reactions of single crystals of UCY-16 ·6 n DMF· n H 2 O with primary alcohols resulted not only in the removal of the lattice DMF molecules but also in an unprecedented structural alteration that involved the complete or partial replacement of the monoatomic bridging μ 3 -OH - anion(s) of the [Cu 4 (μ 3 -OH) 2 ] 6+ butterfly structural core by various alkoxy groups. Similar crystal-to-crystal exchange reactions of UCY-16 ·6 n DMF· n H 2 O with long-chain aliphatic alcohols (C x H 2 x +1 OH, x = 8-10, 12, 14, and 16) led to analogues containing fatty alcohols. Notably, the exchanged products with the bulkier alcohols UCY-16/ n -C x H 2 x +1 OH·S' ( x O being quite stable in this solvent, in contrast to the pristine MOF, and exhibit a hydrophobic/superhydrophobic surface as confirmed from the investigation of their water contact angles and capability to remove hydrophobic pollutants from aqueous media.2 O being quite stable in this solvent, in contrast to the pristine MOF, and exhibit a hydrophobic/superhydrophobic surface as confirmed from the investigation of their water contact angles and capability to remove hydrophobic pollutants from aqueous media.

The two-electron reductive activation of O 2 to O 2 is of particular interest to the scientific community mainly due to the use of peroxides as green oxidants and in powerful fuel cells. Despite of the great importance of vanadium(IV) species to activate the two-electron reductive activation of O 2- , the mechanism is still unclear. Reaction of V 2 , the mechanism is still unclear. Reaction of V IV O 2+ species with the tridentate-planar N,N,N- carboxamide (ΗL) ligands in solution (CH 3 OH:H 2 , at room temperature, resulted in the quick formation of [V 2 , at room temperature, resulted in the quick formation of [V V (═O)(η 2 -O 2 )(κ 3 -L)(H 2 O)] and cis -[V V (═O) 2 -L)] compounds. Oxidation of the V 3 -L)] compounds. Oxidation of the V IV O 2+ complexes with the sterically hindered tridentate-planar N,N,N- carboxamide ligands by atmospheric O 2 gave only cis -[V V (═O) 2 -L)] compounds. The mechanism of formation of [V 3 -L)] compounds. The mechanism of formation of [V V (═O)(η 2 -O 2 )(κ 3 -L)(H 2 O)] (I) and cis -[V V (═O) 2 -L)] (II) complexes vs time, from the interaction of [V 3 -L)] (II) complexes vs time, from the interaction of [V IV (═O)(κ 3 -L)(Η 2 Ο) 2 ] + with atmospheric O 2 , was investigated with 51 V, 1 H NMR, UV-vis, cw-X-band EPR, and 18 labeling IR and resonance Raman spectroscopies revealing the formation of a stable intermediate ( 2 ). EPR, MS, and theoretical calculations of the mechanism of the formation of I and II revealed a pathway, through a binuclear [V Id ). EPR, MS, and theoretical calculations of the mechanism of the formation of I and II revealed a pathway, through a binuclear [V IV (═O)(κ 3 -L)(H 2 O)(η 1 ,η 1 -O 2 )V IV (═O)(κ 3 -L)(H 2 O)] 2+ H NMR spectroscopies, cyclic voltammetry, and the reactivity of the complexes [V 1 H NMR spectroscopies, cyclic voltammetry, and the reactivity of the complexes [V IV (═O)(κ 3 -L)(Η 2 Ο) 2 ] + reduction fit better to an intermediate with a binuclear nature. Dynamic experiments in combination with computational calculations were undertaken to fully elucidate the mechanism of the O 2 reduction fit better to an intermediate with a binuclear nature. Dynamic experiments in combination with computational calculations were undertaken to fully elucidate the mechanism of the O 2 reduction to O 2 2- by [V IV (═O)(κ 3 -L)(Η 2 Ο) 2 ] + . The galvanic cell {Zn|V III ,V II || Id , [V IV O(κ 3 -L)(H 2 O) 2 |C(s)} was manufactured, demonstrating the important applicability of this new chemistry to Zn|H + |O 2 |C(s)} was manufactured, demonstrating the important applicability of this new chemistry to Zn|H 2 O 2 fuel cells technology generating H 2 O 2 in situ from the atmospheric O 2 .

A comprehensive study was performed to determine an optimum enantioseparation method for fluorine-substituted amphetamine and cathinone derivatives (fluor-amphetamine and fluor-cathinone derivatives), using a binary system consisting of carboxymethyl-β-CD (CM-β-CD) and a deep eutectic solvent (DES), namely choline chloride-ethylene glycol (ChCl-EG). Under this framework, the optimization and modeling of the separation conditions in a binary system were performed with the objective of maximizing resolution and minimizing analysis time. This was achieved through the application of response surface methodology. In particular, the effect of chiral selector concentration and percentage of DES on resolution and analysis time were investigated and optimized using a complete experimental design. The optimum enantioseparation conditions were determined to be 13.84 mM CM-β-CD and 0.15% v/v ChCl-EG for fluorine-substituted amphetamine derivatives and 14.36 mM and 0.75% v/v ChCl-EG for fluorine-substituted cathinone derivatives, respectively. This combination resulted in a baseline separation for eight out of the nine analytes studied. Overall, the results demonstrated the synergistic effect of the CM-β-CD/DES dual system and highlighted the significance of DESs as additives in capillary electrophoresis., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Constantina Kapnissi-Christodoulou reports financial support, administrative support, article publishing charges, equipment, drugs, or supplies, and statistical analysis were provided by University of Cyprus., (Copyright © 2023 Elsevier B.V. All rights reserved.)

HiSorb and solid-phase microextraction (SPME), two environmentally friendly micro-extraction techniques based on the same fundamental principles, were evaluated for their extraction efficiency of volatile organic compounds (VOCs) from goat cheese whey wastewater. For this purpose, a sample preparation method based on the headspace-HiSorb technique was developed and evaluated for its efficiency in terms of the amount of extracted compounds and reproducibility of results. Thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) and GC/MS analytical methods were used to perform the wastewater analysis, respectively. The experimental parameters of HiSorb were evaluated in terms of probe coating, extraction time, stirring speed, sample volume, extraction temperature and salt addition. Under optimal extraction conditions, it was observed that the use of the divinylbenzene/carbon wide range/polydimethylsiloxane (DVB/CWR/PDMS) triple coating for HiSorb and DVB/Carboxen (CAR)/PDMS for SPME, was best suited to extract a broader range of VOCs with higher peak intensities. A total of 34 VOCs were extracted and determined with the DVB/CWR/PDMS HiSorb probe, while only 23 VOCs were determined with the conventional DVB/CAR/PDMS SPME fiber. The DVB/CWR/PDMS HiSorb probe has a higher adsorbent capacity which results in a higher sensitivity for VOCs compared to the DVB/CAR/PDMS SPME fiber. Furthermore, the HiSorb technique exhibits better reproducibility, as indicated by the lower relative standard deviation (RSD) of 3.7% compared to 7.1% for SPME. Therefore, the HiSorb technique is an effective method for detecting VOCs in complex matrices, such as wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This study presents a novel treatment system using a submerged anaerobic membrane bioreactor (SAnMBR) followed by adsorption onto thermally treated biowaste, and ending with a final treatment using powdered activated carbon (PAC). Despite limited phosphate and ammonium ion removal during SAnMBR operation, thermally treated eggshell (EGSL) and seagrass (SG) received SAnMBR effluent and enhanced phosphate recovery, achieving removal rates of 71.8-99.9% and 60.5-78.0%, respectively. The SAnMBR achieved an 85% COD removal, which was slightly reduced further by biowaste treatment. However, significant further reductions in COD to 20.2 ± 5.2 mg/L for EGSL effluent and 57.0 ± 13.3 mg/L for SG effluent were achieved with PAC. Phytotoxicity tests showed the SAnMBR effluent after PAC treatment notably improved seed growth compared to untreated wastewater. In addition, volatile organic compounds (VOCs) were significantly reduced in the system, including common wastewater contaminants such as dimethyl disulfide, dimethyl trisulfide, phenol, p-cresol, nonanal, and decanal. Fractionation analysis of the solid fraction, post-adsorption from both synthetic and domestic wastewater, indicated that for SG, 77.3%-94% of the total phosphorus (TP) was inorganically bound, while for EGSL, it ranged from 94% to 95.3%. This study represents the first attempt at a proof-of-concept for simultaneous treatment of domestic wastewater and phosphorus recovery using this integrated system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In this study, an optimized environmentally friendly procedure was employed to enhance the sustainable utilization of phenolic antioxidants derived from aloe vera rind by-products. The procedure involved the application of ultrasound-assisted extraction (UAE) in combination with deep eutectic solvents (DESs). Eleven different DESs and three conventional solvents were employed as extraction media for polyphenolic compounds. Choline chloride-citric acid (ChCl-CA) was selected as the most suitable extractant, considering its extraction efficiency in relation to the total phenolic content. The operating conditions of UAE were optimized and modeled by the use of response surface methodology in order to maximize the yield of total phenolics and antioxidant capacity. The optimal operational parameters for the UAE procedure were determined to be 16.5 min, 74% ( v / v ) DES in water, and a solvent-to-solid ratio equal to 192. HPLC analysis, which was performed on the optimum extract, revealed significant levels of phenolics present in the aloe rind. Efficient recovery of the extracted antioxidants was obtained by the use of solid-phase extraction (SPE) and polyamide cartridges. The ChCl-CA DES exhibited excellent recycling capability with a yield of over 90% through SPE. Finally, the greenness of the method was evaluated using the green AGREE and AGREEprep metrics. The results highlighted the sustainability and the greenness of the proposed extraction procedure for the aloe by-product.

In this study, a novel supramolecular deep eutectic solvent consisting of sulfated-β-CD and citric acid (S-β-CD-CA) is reported for the first time. This innovative system was evaluated as a sole chiral selector in capillary electrophoresis for the enantioseparation of six fluorine-substituted amphetamine analogs, yielding remarkable outcomes. Baseline separations of all amphetamine analogs under study were achieved in less than 21.00 min using the S-β-CD-CA as the chiral selector. It was observed that the addition of 0.050 % v/v S-β-CD-CA into the background electrolyte resulted in the baseline separation of five out of the six fluorine-substituted amphetamine analogs, while in the case of the para-substituted amphetamine analog, 4-fluoramphetamine (4-FA), a higher percentage (0.15 % v/v) was required to achieve baseline enantioseparation. These findings emphasized the potential of this new supramolecular system in providing a class of solvents with promising chiral recognition properties., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Constantina Kapnissi-Christodoulou reports financial support, administrative support, article publishing charges, equipment, drugs, or supplies, and statistical analysis were provided by University of Cyprus., (Copyright © 2024. Published by Elsevier B.V.)

Based on the strong binding and high selectivity properties of 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H 2 bihyat) for [U VI O 2 ] 2+ , novel binucleating ligands (BLs) N , N ', N ″, N‴ -((1,4-phenylenebis(oxy))bis(1,3,5-triazine-6,2,4-triyl))tetrakis( N -methylhydroxylamine) (H 4 qtn), N 1 , N 4 -bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)benzene-1,4-diamine (H 4 pdl), and N enl) were synthesized. Binuclear complexes formed by coordination of hard metal ions with H 1 , N bihyat due to the increase in entropy accompanying the formation of more chelate rings. Reaction of either H 2 -bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)ethane-1,2-diamine (H 4 enl) were synthesized. Binuclear complexes formed by coordination of hard metal ions with H 4 qtn are thermodynamically more stable than their mononuclear analogues with H 2 bihyat due to the increase in entropy accompanying the formation of more chelate rings. Reaction of either H 4 qtn or H 4 pdl or H 4 enl with [U VI O 2 resulted in the isolation of the binuclear complexes [(U 2+ and [V V O 2 ] + resulted in the isolation of the binuclear complexes [(U VI O 2 ) 2 (μ-qtn)(H 2 O) 4 ] ( 1 ), [(V V O 2 ) 2 (μ-qtn)][PPh 4 ] 2 [PPh4] ( 2 ), [(U VI O 2 ) 2 (μ-pdl)(H 2 O) 2 (MeOH) 2 ] ( 3 ), [(V V O 2 ) 2 (μ-pdl)][PPh 4 ] 2 ( 4 ), [(U VI O 2 ) 2 (μ-enl)(H 2 O) 4 ] ( 5 ), and [(V V O 2 ) 2 were characterized by single-crystal X-ray diffraction analysis in solid state and by NMR and ESI-MS in solution. The comparison of the coordination ability of the BLs with either pyridine-2,6-dicarboxylic acid (H 4 ] 2 ( 6 ). The binuclear complexes 1-6 were characterized by single-crystal X-ray diffraction analysis in solid state and by NMR and ESI-MS in solution. The comparison of the coordination ability of the BLs with either pyridine-2,6-dicarboxylic acid (H 2 dipic) or H 2 bihyat or CO 3 2- toward [U VI was investigated by NMR and UV-vis spectroscopies and DFT theoretical calculations, revealing a superior performance of BLs. The selectivity of the BLs for [U 2 ] 2+ and [V V O 2 ] + was investigated by NMR and UV-vis spectroscopies and DFT theoretical calculations, revealing a superior performance of BLs. The selectivity of the BLs for [U VI is decreased compared to that of H 2 bihyat but increases considerably at pH > 9 values. Formation of the mixed-metal binuclear species [U 2+ over [V V O 2 ] + ] influences the selectivity and dynamics of the reaction of H 2 bihyat but increases considerably at pH > 9 values. Formation of the mixed-metal binuclear species [U VI O 2 (μ-O)V V O 2 ] influences the selectivity and dynamics of the reaction of H 4 qtn for [U VI in aqueous solution. The results of this study provide crucial information for the ligand design and the development of stronger and more selective systems.2 ] 2+ and [V V O 2 ] + in aqueous solution. The results of this study provide crucial information for the ligand design and the development of stronger and more selective systems.

The adsorption of actinide ions (Am(III) and U(VI)) from aqueous solutions using pristine and oxidized carbon fabrics was investigated by means of batch experiments at different pH values (pH 4, 7 and 9) and temperatures (25, 35 and 45 °C) under ambient atmospheric conditions. The experimental results indicated that both the pH and the fabric texture affected the adsorption rate and the relative removal efficiency, which was 70% and 100% for Am(III) and U(VI), respectively. The K d (L/kg) values for U(VI) were generally found to be higher (2 < log 10 (K d )< 3) than the corresponding values for Am(III) adsorption (1.5 < log 10 (K d ) < 2). The data obtained from the experiments regarding the temperature effect implied that the relative adsorption for both actinides increases with temperature and that adsorption is an endothermic and entropy-driven reaction. The application of the fabrics to remove the two actinides from contaminated seawater samples showed that both the relative removal efficiency and the K d values decreased significantly due to the presence of competitive cations (e.g., Ca 2+ and Fe 3+ ) and complexing anions (CO 3 ) in the respective waters. Nevertheless, the removal efficiency was still remarkable (50% and 90% for Am(III) and U(VI), respectively), demonstrating that these materials could be attractive candidates for the treatment of radionuclide/actinide-contaminated waters.2- ) in the respective waters. Nevertheless, the removal efficiency was still remarkable (50% and 90% for Am(III) and U(VI), respectively), demonstrating that these materials could be attractive candidates for the treatment of radionuclide/actinide-contaminated waters.

Conformational templating of conjugated polyelectrolytes with single-stranded DNAs (ssDNAs) has the prospect of tailoring excited state dynamics for specific optoelectronic applications. We use ultrafast time-resolved infrared spectroscopy to study the photophysics of a cationic polythiophene assembled with different ssDNAs, inducing distinct conformations (flexible disordered structures vs more rigid complexes with increased backbone planarity). Intrachain polarons are always produced upon selective excitation of the polymer, the extent being dependent on backbone torsional order. Polaron formation and decay were monitored through evolution of IR-active vibrational modes that interfere with mid-IR polaron electronic absorption giving rise to Fano-antiresonances. Selective UV excitation of ssDNAs revealed that stacking interactions between thiophene rings and nucleic acid bases can promote the formation of an intermolecular charge transfer complex. The findings inform designers of functional conjugated polymers by identifying that involvement of the scaffold in the photophysics needs to be considered when developing such structures for optoelectronic applications.

3D naturally derived composites consisting of calcium alginate hydrogels (CA) and oxidized biochar obtained from Luffa cylindrica (ox-LC) were synthesized and further evaluated as adsorbents for the removal of U(VI) from aqueous media. Batch-type experiments were conducted to investigate the effect of various physicochemical parameters on the adsorption performance of materials. The maximum adsorption capacity (q max ) was 1.7 mol kg -1 (404.6 mg·g -1 ) at pH 3.0 for the CA/ox-LC with a 10% wt. ox-LC content. FTIR spectroscopy indicated the formation of inner-sphere complexes between U(VI) and the surface-active moieties existing on both CA and ox-LC, while thermodynamic data revealed that the adsorption process was endothermic and entropy-driven. The experimental data obtained from the adsorption experiments were well-fitted by the Langmuir and Freundlich models. Overall, the produced composites exhibited enhanced adsorption efficiency against U(VI), demonstrating their potential use as effective adsorbents for the recovery of uranium ions from industrial effluents and seawater.

1,2,6-Thiadiazines treated with visible light and 3 O 2 under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental and theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers that produce 1 O 2 and then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide that ring contracts with selective carbon atom excision and complete atom economy. The reaction was optimized under both batch and continuous-flow conditions and is also efficient in green solvents.

InAs-based nanocrystals can enable restriction of hazardous substances (RoHS) compliant optoelectronic devices, but their photoluminescence efficiency needs improvement. We report an optimized synthesis of InAs@ZnSe core@shell nanocrystals allowing to tune the ZnSe shell thickness up to seven mono-layers (ML) and to boost the emission, reaching a quantum yield of ≈70% at ≈900 nm. It is demonstrated that a high quantum yield can be attained when the shell thickness is at least ≈3ML. Notably, the photoluminescence lifetimeshows only a minor variation as a function of shell thickness, whereas the Auger recombination time (a limiting aspect in technological applications when fast) slows down from 11 to 38 ps when increasing the shell thickness from 1.5 to 7MLs. Chemical and structural analyses evidence that InAs@ZnSe nanocrystals do not exhibit any strain at the core-shell interface, likely due to the formation of an InZnSe interlayer. This is supported by atomistic modeling, which indicates the interlayer as being composed of In, Zn, Se and cation vacancies, alike to the In 2 ZnSe 4 crystal structure. The simulations reveal an electronic structure consistent with that of type-I heterostructures, in which localized trap states can be passivated by a thick shell (>3ML) and excitons are confined in the core., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The effect of the combined use of amino acid-based ionic liquids (AAILs) and deep eutectic solvents (DESs) with either cyclodextrin- (CD) or cyclofructan- (CF) based chiral selectors for the chiral separation of amphetamine derivatives was investigated in the present study. A non-significant improvement in enantiomeric separation of target analytes was observed when AAILs were combined with either CF or CD. On the other side, a markedly improved chiral separation of enantiomers was obtained using the dual carboxymethyl-β-cyclodextrin/DES system, highlighting the existence of a synergistic effect. After the addition of 0.5% v/v of choline chloride-ethylene glycol, the resolution of the enantiomers of amphetamine, methamphetamine and 3-fluorethamphetamine, increased from 1.4, 1.1, 1.0 to 1.8, 1.8, and 1.5 min, and the analysis times increased from 19.54, 20.48, 18.71 to 35.71, 35.78 and 32.90 min, respectively. This was not the case for the CF/DES dual system, in which the separation of amphetamines worsened, indicating an antagonistic effect. In conclusion, DESs are a very promising additive in capillary electrophoresis that can improve the separation of chiral molecules in combination with CDs but not CFs., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Constantina Kapnissi-Christodoulou reports financial support was provided by University of Cyprus., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The binding of actinide ions (Am(III) and U(VI)) in aqueous solutions by hybrid silica-hyperbranched poly(ethylene imine) nanoparticles (NPs) and xerogels (XGs) has been studied by means of batch experiments at different pH values (4, 7, and 9) under ambient atmospheric conditions. Both materials present relatively high removal efficiency at pH 4 and pH 7 (>70%) for Am(III) and U(VI). The lower removal efficiency for the nanoparticles is basically associated with the compact structure of the nanoparticles and the lower permeability and access to active amine groups compared to xerogels, and the negative charge of the radionuclide species is formed under alkaline conditions (e.g., UO 2 (CO 3 ) 3 4- and Am(CO 3 ). Generally, the adsorption process is relatively slow due to the very low radionuclide concentrations used in the study and is basically governed by the actinide diffusion from the aqueous phase to the solid surface. On the other hand, adsorption is favored with increasing temperature, assuming that the reaction is endothermic and entropy-driven, which is associated with increasing randomness at the solid-liquid interphase upon actinide adsorption. To the best of our knowledge, this is the first study on hybrid silica-hyperbranched poly(ethylene imine) nanoparticle and xerogel materials used as adsorbents for americium and uranium at ultra-trace levels. Compared to other adsorbent materials used for binding americium and uranium ions, both materials show far higher binding efficiency. Xerogels could remove both actinides even from seawater by almost 90%, whereas nanoparticles could remove uranium by 80% and americium by 70%. The above, along with their simple derivatization to increase the selectivity towards a specific radionuclide and their easy processing to be included in separation technologies, could make these materials attractive candidates for the treatment of radionuclide/actinide-contaminated water.2 - ). Generally, the adsorption process is relatively slow due to the very low radionuclide concentrations used in the study and is basically governed by the actinide diffusion from the aqueous phase to the solid surface. On the other hand, adsorption is favored with increasing temperature, assuming that the reaction is endothermic and entropy-driven, which is associated with increasing randomness at the solid-liquid interphase upon actinide adsorption. To the best of our knowledge, this is the first study on hybrid silica-hyperbranched poly(ethylene imine) nanoparticle and xerogel materials used as adsorbents for americium and uranium at ultra-trace levels. Compared to other adsorbent materials used for binding americium and uranium ions, both materials show far higher binding efficiency. Xerogels could remove both actinides even from seawater by almost 90%, whereas nanoparticles could remove uranium by 80% and americium by 70%. The above, along with their simple derivatization to increase the selectivity towards a specific radionuclide and their easy processing to be included in separation technologies, could make these materials attractive candidates for the treatment of radionuclide/actinide-contaminated water.

Metal-organic frameworks (MOFs) have attracted considerable interest as emerging heterogeneous catalysts for organic transformations of synthetic utility. Herein, a Lewis-acidic MOF, {[Cu 3 (PEIP) 2 (5-NH 2 - m BDC)(DMF)]·7DMF}∞, denoted as Cu(ΙΙ)-PEIP, has been synthesized via a one-pot process and deployed as an efficient heterogeneous catalyst for a Diels-Alder cycloaddition. Specifically, the [4 + 2] cycloaddition of 13 substituted azachalcone dienophiles with cyclopentadiene has been investigated. MOF-catalyzed reaction conditions were optimized, leading to the selection of water as the solvent, in the presence of 10% mol sodium dodecyl sulfate (SDS) to address substrate solubility. The Cu(II)-PEIP catalyst showed excellent activity under these green and mild conditions, exhibiting comparable or, in some cases, superior efficiency to a homogeneous catalyst often employed in Diels-Alder reactions, namely, Cu(OTf) 2 . The nature of the azachalcone substituent played a significant role in the reactivity of the dienophiles, with electron-withdrawing (EW) substituents enhancing conversion and electron-donating (ED) ones exhibiting the opposite effect. Coordinating substituents appeared to enhance the endo selectivity. Importantly, the Cu(II)-PEIP catalyst can be readily isolated from the reaction mixture and recycled up to four times without any significant reduction in conversion or selectivity.

A quantitative analytical procedure was developed and validated by the use of Ultra- Performance Liquid Chromatography tandem Mass Spectrometry (UPLC-MS/MS) for the determination of Cannabidiol (CBD), Cannabinol (CBN), Δ 9 -Tetrahydrocannabinol (Δ 9 -THC), Cannabichromene (CBC), Cannabigerol (CBG) and 11-Nor- 9- Carboxy- Tetrahydrocannabinol (THC-COOH) in an unconventional biological matrix, cerumen. All the investigated calibration curves were characterized by high correlation values (R 2 ≥ 0.9965). The LODs and LOQs ranged from 0.004 to 0.009 μg g -1 and 0.012-0.029 μg g -1 , respectively. Intra-assay and inter-assay precision were found to be 0.6-2.5%, and 0.8-2.2%, respectively. All recovery values of cannabinoids, with the use of the optimum cotton swab, at low (0.008 μg g -1 of cerumen), medium (0.037 μg g -1 of cerumen) and high (0.16 μg g -1 of cerumen) control levels, were estimated to be above 86%. The method developed here permitted the analysis of real cerumen samples obtained from fourteen cannabis users. In twelve out of fourteen cases, Δ 9 -THC was found to be positive, while in six cases, three major cannabinoids, CBN, CBG and Δ 9 -THC were quantified at concentrations 0.02-0.21 μg g -1 , 0.01-0.24 μg g -1 and 0.01-4.86 μg g -1 , respectively. Subject #8 has the highest amount of the detected substances in both left and right ear, with Δ 9 -THC at a concentration of 1.85 and 4.86 μg g -1 , CBG 0.06 and 0.24 μg g -1 , CBN 0.10 and 0.21 μg g -1 , respectively. In addition, a detection window for the substances Δ 9 -Tetrahydrocannabinol, Cannabinol and Cannabigerol, in cerumen, was defined with success. In this case, Δ 9 -THC reached a maximum detection frame of up to fifteen days after smoking 0.5 g of marijuana cigarette. ANOVA-one-way analysis also indicated that the average earwax production of non-cannabis users differs significantly from the one of cannabis users (p = 0.048, <0.05). On the other hand, no significant difference was noticed between male and female users as the p value exceeded 0.05. In addition, no significant effect was observed on earwax production in regard to age, frequency and the last time of use (p > 0.05). These last three factors proved to have a significant impact on cannabinoids concentrations, since p values were less than 0.05., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Microbiota and the metabolites they produce within the large intestine interact with the host epithelia under the influence of a range of host-derived metabolic, immune, and homeostatic factors. This complex host-microbe interaction affects intestinal tumorigenesis, but established microbial or metabolite profiles predicting colorectal cancer (CRC) risk are missing. Here, we aimed to identify fecal bacteria, volatile organic compounds (VOC), and their associations that distinguish healthy (non-adenoma, NA) from CRC prone (high-risk adenoma, HRA) individuals. Analyzing fecal samples obtained from 117 participants ≥15 days past routine colonoscopy, we highlight the higher abundance of Proteobacteria and Parabacteroides distasonis , and the lower abundance of Lachnospiraceae species, Roseburia faecis , Blautia luti , Fusicatenibacter saccharivorans , Eubacterium rectale , and Phascolarctobacterium faecium in the samples of HRA individuals. Volatolomic analysis of samples from 28 participants revealed a higher concentration of five compounds in the feces of HRA individuals, isobutyric acid, methyl butyrate, methyl propionate, 2-hexanone, and 2-pentanone. We used binomial logistic regression modeling, revealing 68 and 96 fecal bacteria-VOC associations at the family and genus level, respectively, that distinguish NA from HRA endpoints. For example, isobutyric acid associations with Lachnospiraceae incertae sedis and Bacteroides genera exhibit positive and negative regression lines for NA and HRA endpoints, respectively. However, the same chemical associates with Coprococcus and Colinsella genera exhibit the reverse regression line trends. Thus, fecal microbiota and VOC profiles and their associations in NA versus HRA individuals indicate the significance of multiple levels of analysis towards the identification of testable CRC risk biomarkers.

This review uses the National Cancer Institute (NCI) COMPARE program to establish an extensive list of heterocyclic iminoquinones and quinones with similarities in differential growth inhibition patterns across the 60-cell line panel of the NCI Developmental Therapeutics Program (DTP). Many natural products and synthetic analogues are revealed as potential NAD(P)H:quinone oxidoreductase 1 (NQO1) substrates, through correlations to dipyridoimidazo[5,4- f ]benzimidazoleiminoquinone (DPIQ), and as potential thioredoxin reductase (TrxR) inhibitors, through correlations to benzo[1,2,4]triazin-7-ones and pleurotin. The strong correlation to NQO1 infers the enzyme has a major influence on the amount of the active compound with benzo[ e ]perimidines, phenoxazinones, benz[ f ]pyrido[1,2- a ]indole-6,11-quinones, seriniquinones, kalasinamide, indolequinones, and furano[2,3- b ]naphthoquinones, hypothesised as prodrugs. Compounds with very strong correlations to known TrxR inhibitors had inverse correlations to the expression of both reductase enzymes, NQO1 and TrxR, including naphtho[2,3- b ][1,4]oxazepane-6,11-diones, benzo[ a ]carbazole-1,4-diones, pyranonaphthoquinones (including kalafungin, nanaomycin A, and analogues of griseusin A), and discorhabdin C. Quinoline-5,8-dione scaffolds based on streptonigrin and lavendamycin can correlate to either reductase. Inhibitors of TrxR are not necessarily (imino)quinones, e.g., parthenolides, while oxidising moieties are essential for correlations to NQO1, as with the mitosenes. Herein, an overview of synthetic methods and biological activity of each family of heterocyclic imino(quinone) is provided.

The initial use of a tetradentate Schiff base (LH 2 ) derived from the 2 : 1 condensation between 2-hydroxyacetophenone and cyclohexane-1,2-diamine in 4f-metal chemistry is described. The 1 : 2 reaction of Ln(NO 3 ) 3 · x H 2 O (Ln = lanthanoid or yttrium) and LH 2 in MeOH/CH 2 Cl 2 has provided access to isostructural complexes [Ln(NO 3 ) 3 (L'H 2 )(MeOH)] in moderate to good yields. Surprisingly, the products contain the corresponding Schiff base ligand L'H 2 possessing six aliphatic -CH 2 - groups instead of the -CH-(CH 2 ) 4 -CH- unit of the cyclohexane ring, i.e. an unusual ring-opening of the latter has occurred. A mechanism for this Ln III -assisted/promoted LH 2 → L'H 2 transformation has been proposed assuming transient Ln II species and a second LH 2 molecule as the H 2 source for the reduction of the cyclohexane moiety. DFT calculations provide strong evidence for the great thermodynamic stability of the products in comparison with analogous complexes containing the original intact ligand. The structures of the Pr III , Sm III , Gd III , Tb III , and Ho III complexes have been determined by single-crystal X-ray crystallography. The 9-coordinate Ln III centre in the molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the bidentate chelating organic ligand, and one oxygen atom from the coordinated MeOH group. In the overall neutral bis(zwitterionic) L'H 2 ligand, the acidic H atoms are clearly located on the imino nitrogen atoms and this results in the formation of an unusual 16-membered chelating ring. The coordination polyhedra defined by the nine donor atoms around the 4f-metal-ion centres can be best described as distorted, spherical capped square antiprisms. The Eu III , Tb III , and Dy III complexes exhibit Ln III -based luminescence in the visible region, with the coordinated L'H 2 molecule acting as the antenna. Ac magnetometry experiments show that the Dy III member of the family behaves as an SIM at zero field and under external dc fields of 0.1 and 0.2 T without the enhancement of the peaks' maxima, suggesting that QTM is not the relaxation path. The Gd III complex behaves, rather unexpectedly, as a SIM with two different magnetic relaxation paths occurring at very close temperatures; this behaviour is tentatively attributed to a very small axial zero-field splitting ( D ∼ 0.1 cm -1 ), which cannot be detected by magnetization or susceptibility experiments. The prospects of the present, first results in the lanthanoid(III)-LH 2 chemistry are discussed.

Two different silica conformations (xerogels and nanoparticles), both formed by the mediation of dendritic poly (ethylene imine), were tested at low pHs for problematic uranyl cation sorption. The effect of crucial factors, i.e., temperature, electrostatic forces, adsorbent composition, accessibility of the pollutant to the dendritic cavities, and MW of the organic matrix, was investigated to determine the optimum formulation for water purification under these conditions. This was attained with the aid of UV-visible and FTIR spectroscopy, dynamic light scattering (DLS), ζ-potential, liquid nitrogen (LN 2 ) porosimetry, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Results highlighted that both adsorbents have extraordinary sorption capacities. Xerogels are cost-effective since they approximate the performance of nanoparticles with much less organic content. Both adsorbents could be used in the form of dispersions. The xerogels, though, are more practicable materials since they may penetrate the pores of a metal or ceramic solid substrate in the form of a precursor gel-forming solution, producing composite purification devices.

The synthesis, crystal structures, Mössbauer spectra and variable temperature dc and ac magnetic susceptibility studies of a new family of trinuclear heterometallic Fe 3+ /Ln 3+ complexes, [Fe 2 Ln(PhCO 2 ) 3 ((py) 2 CO 2 )((py) 2 C(OMe)O) 2 (NO 3 )Cl] (Ln = Gd (1/Gd), Tb (1/Tb), Dy (1/Dy), and Ho (1/Ho)), where (py) 2 CO 2 2- and (py) 2 are the anions of the - -diol and hemiketal derivatives of di-2-pyridyl ketone, are reported. Compounds 1/Ln are based on an asymmetric "V-shaped" [Fe gem -diol and hemiketal derivatives of di-2-pyridyl ketone, are reported. Compounds 1/Ln are based on an asymmetric "V-shaped" [Fe 3+ (μ-OR)Ln(μ-OR) 2 Fe 3+ structural core formed from the connection of the two terminal Fe 6+ structural core formed from the connection of the two terminal Fe 3+ ion either through one or two alkoxide groups originating from the alkoxide-type bridging ligands. Direct current magnetic susceptibility studies reveal the presence of weak antiferromagnetic interactions between the Fe 3+ ions. Alternating current magnetic studies indicate the presence of a slow-magnetic relaxation process in 1/Dy with an energy barrier 3+ ions. Alternating current magnetic studies indicate the presence of a slow-magnetic relaxation process in 1/Dy with an energy barrier U eff s. The electronic, magnetic and relaxation properties of the complexes were further monitored by variable temperature τ 0 > 80 K the spectra from the complexes comprise two quadrupole doublets the hyperfine parameters of which reflect the distinct coordination environment of the two Fe -7 s. The electronic, magnetic and relaxation properties of the complexes were further monitored by variable temperature 57 < 20 K, the Mössbauer spectra for 1/Dy are affected by magnetic relaxation effects. At 1.5 K, the spectrum of 1/Dy comprises well defined magnetic sextets indicating relaxation times slower than the characteristic time of the Mössbauer technique (10 T s) in agreement with the dynamic magnetic measurements. 1/Gd exhibits broad unresolved magnetic sextets at 1.5 K indicating that the spin relaxation time is of the order of the Mössbauer characteristic time at this temperature. For 1/Tb, 1/Ho the Mössbauer spectra exhibit slight broadening even at the lowest available temperature consistent with magnetic relaxation times less than 10 3+ terminal sites. At T < 20 K, the Mössbauer spectra for 1/Dy are affected by magnetic relaxation effects. At 1.5 K, the spectrum of 1/Dy comprises well defined magnetic sextets indicating relaxation times slower than the characteristic time of the Mössbauer technique (10 -7 s) in agreement with the dynamic magnetic measurements. 1/Gd exhibits broad unresolved magnetic sextets at 1.5 K indicating that the spin relaxation time is of the order of the Mössbauer characteristic time at this temperature. For 1/Tb, 1/Ho the Mössbauer spectra exhibit slight broadening even at the lowest available temperature consistent with magnetic relaxation times less than 10 -7 s.

Organic radicals have long been suggested as candidates for organic magnets and components in organic spintronic devices. Herein, we demonstrate spin current emission from an organic radical film via spin pumping at room temperature. We present the synthesis and the thin film preparation of a Blatter-type radical with outstanding stability and low roughness. These features enable the fabrication of a radical/ferromagnet bilayer, in which the spin current emission from the organic radical layer can be reversibly reduced when the ferromagnetic film is brought into simultaneous resonance with the radical. The results provide an experimental demonstration of a metal-free organic radical layer operating as a spin source, opening a new avenue for the development of purely organic spintronic devices and bridging the gap between potential and real applications.

Carob ( Ceratonia siliqua ) is an exceptional source of significant bioactive compounds with great economic importance in the Mediterranean region, where it is widely cultivated. Carob fruit is used for the production of a variety of products and commodities such as powder, syrup, coffee, flour, cakes, and beverages. There is growing evidence of the beneficial effects of carob and the products made from it on a range of health problems. Therefore, metabolomics could be used to explore the nutrient-rich compounds of carob. Sample preparation is a crucial step in metabolomics-based analysis and has a great impact on the quality of the data obtained. Herein, sample preparation of carob syrup and powder was optimized, to enable highly efficient metabolomics-based HILIC-MS/MS analysis. Pooled powder and syrup samples were extracted under different conditions by adjusting pH, solvent type, and sample weight to solvent volume ratio (Wc/Vs). The metabolomics profiles obtained were evaluated using the established criteria of total area and number of maxima. It was observed that the Wc/Vs ratio of 1:2 resulted in the highest number of metabolites, regardless of solvent type or pH. Aqueous acetonitrile with a Wc/Vs ratio of 1:2 satisfied all established criteria for both carob syrup and powder samples. However, when the pH was adjusted, basic aqueous propanol 1:2 Wc/Vs and acidic aqueous acetonitrile 1:2 Wc/Vs provided the best results for syrup and powder, respectively. We strongly believe that the current study could support the standardization of the metabolomics sample preparation process to enable more efficient LC-MS/MS carob analysis.

Tomato pomace was slowly pyrolyzed at 350 and 550 °C (under an N 2 flow of 50 L/h) at a rate of 6 °C/min and a residence time of 1:30 h to produce two biochars named B350 and B550, respectively. In addition, the two biochars were chemically activated with ΚΟΗ (at a ratio of 1:10 w/v) at 800 °C to produce two new materials named BA350 and BA550. The four biochars produced were characterized physically and chemically (pH, yield, calorific value). They were also analyzed by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (B.E.T), elemental analysis (EA), and thermogravimetric analysis (TGA). The results showed that as the pyrolysis temperature increased (350 to 550 °C), the specific surface area (SSA) increased. The latter was also significantly increased by the activation process. EA showed a variation in the mineral content of the produced biochars, resulting in a different content of the biochars after activation. The parameters studied showed that biochars from tomato waste could be used as an organic amendment to improve soil fertility in agricultural. In addition, because of their ability to absorb water, they could be used as a water reservoir in soils in arid areas., Competing Interests: Declaration of competing interest The authors have no competing interests to declare that are relevant to the content of this article., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The bamboo family of plants is one of the fastest-growing species in the world. As such, there is an abundance of bamboo residues available for exploitation, especially in southeast Asian, central African and south American regions. The preparation of efficient adsorbents from bamboo residues is an emerging exploitation pathway. Biochars, activated carbons or raw bamboo fibers embedded with nanoparticles, each class of materials has been shown to be highly efficient in adsorption processes. This review aims to summarize recent findings in the application of bamboo-based adsorbents in the removal of organic, inorganic, or gaseous pollutants. Therefore, this review first discusses the preparation methods and surface modification methodologies and their effects on the adsorbent elemental content and other basic properties. The following sections assess the recent progress in the adsorption of heavy metals, organics, and gaseous substances by bamboo-based adsorbents, focusing on the optimum adsorption capacities, adsorption mechanisms and the optimum-fitting kinetic models and isotherms. Finally, research gaps were identified and directions for future research are proposed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

The Overhauser effect in the dynamic nuclear polarization (DNP) of non-conducting solids has drawn much attention due to the potential for efficient high-field DNP as well as a general interest in the underlying principles that enable the Overhauser effect in small molecules. We recently reported the observation of 1H and 2H Overhauser effects in H3C- or D3C-functionalized Blatter radical analogs, which we presumed to be caused by methyl rotation. In this work, we look at the mechanism for methyl-driven Overhauser DNP in greater detail, considering methyl librations and tunneling in addition to classical rotation. We predict the temperature dependence of these mechanisms using density functional theory and spin dynamics simulations. Comparisons with results from ultralow-temperature magic angle spinning-DNP experiments revealed that cross-relaxation at temperatures above 60 K originates from both libration and rotation, while librations dominate at lower temperatures. Due to the zero-point vibrational nature of these motions, they are not quenched by very low temperatures, and methyl-driven Overhauser DNP is expected to increase in efficiency down to 0 K, predominantly due to increases in nuclear relaxation times., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

3,3',3''-(Benzene-1,3,5-triyl)tris(1-phenyl-1H-benzo[e][1,2,4]triazin-4-yl) (1) is a C 3 -symmetrical triradical comprised of three Blatter radical units connected at the 1, 3, 5 positions of a central trimethylenebenzene core. This triradical has an excellent air, moisture, and thermal stability. Single-crystal XRD indicates that triradical 1 adopts a propeller-like geometry with the benzotriazinyl moieties twisted by 174.1(2)° and packs in 1D chains along the c axis to form an extensive network of weak intermolecular interactions. Frozen solution continuous wave (CW) EPR spectra and variable-temperature field-sweep echo-detected (FSED) spectra revealed an intramolecular ferromagnetic exchange within the spin system, supporting a quartet S = 3/2 ground state. DFT calculations further supported these experimental findings., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Myoglobin has been demonstrated to function as a nitrite reductase to produce nitric oxide during hypoxia. One of the most intriguing aspects of the myoglobin/nitrite interactions revealed so far is the unusual O-binding mode of nitrite to the ferric heme iron, although conflicting data have been reported for the electronic structure of this complex also raising the possibility of linkage isomerism. In this work, we applied resonance Raman spectroscopy in a temperature-dependent approach to investigate the binding of nitrite to ferric myoglobin and the properties of the formed adduct from ambient to low temperatures (293 K to 153 K). At ambient temperature the high spin state of the ferric heme Fe-O-N[double bond, length as m-dash]O species is present and upon decreasing the temperature the low spin state is populated, demonstrating that a thermally-induced spin crossover phenomenon takes place analogous to what has been observed in many transition metal complexes. The observed spin crossover is fully reversible and is not due to linkage isomerism, since the O-binding mode is retained upon the spin transition. The role of the heme pocket environment in controlling the nitrite binding mode and spin transition is discussed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Luffa cylindrica biomass was converted to biochar and the removal of 241 Am by pristine and oxidized biochar fibers was investigated in laboratory and environmental water samples. This species has the added advantage of a unique microsponge structure that is beneficial for the production of porous adsorbents. The main purpose of this study was to valorize this biomass to produce an efficient adsorbent and investigate its performance in radionuclide-contaminated waters. Following the preparation of Am 3+ solutions at a concentration of 10 -12 mol/L, the adsorption efficiency ( K ) was determined as a function of pH, adsorbent mass, ionic strength, temperature, and type of aqueous solution by batch experiments. At the optimum adsorbent dose of 0.1 g and pH value of 4, a log d value of 4.2 was achieved by the oxidized biochar sample. The effect of temperature and ionic strength indicated that adsorption is an endothermic and entropy-driven process (Δ 10 K d value of 4.2 was achieved by the oxidized biochar sample. The effect of temperature and ionic strength indicated that adsorption is an endothermic and entropy-driven process (Δ H ° = -512 kJ mol -1 ) leading to the formation of inner-sphere complexes. The adsorption kinetics were relatively slow (24 h equilibrium time) due to the slow diffusion of the radionuclide to the biochar surface and fitted well to the pseudo-first-order kinetic model. Oxidized biochar performed better compared to the unmodified sample and overall appears to be an efficient adsorbent for the treatment of S ° = -1.2 J K -1 mol -1 ) leading to the formation of inner-sphere complexes. The adsorption kinetics were relatively slow (24 h equilibrium time) due to the slow diffusion of the radionuclide to the biochar surface and fitted well to the pseudo-first-order kinetic model. Oxidized biochar performed better compared to the unmodified sample and overall appears to be an efficient adsorbent for the treatment of 241 Am-contaminated waters, even at ultra-trace concentrations.