Electronic and Magnetic Interactions in 6-Oxoverdazyl Diradicals: Connection through N(1) vs C(3) Revisited.

Four isomeric di-6-oxoverdazyl diradicals connected at their N(1) or C(3) positions with either 1,3- or 1,4-phenylene linkers were obtained and characterized by spectroscopic, electrochemical, magnetic, and structural methods. These results were compared to those for the corresponding 6-oxoverdazyl monoradicals. UV-vis spectroscopy demonstrated that only the N(1)-connected para-through-benzene diradical has a distinct spectrum with significant bathochromic and hypsochromic shifts relative to the remaining species. Electrochemical analysis revealed two one-electron reduction processes in all diradiacals, while only the N(1)-connected para-through-benzene diradical exhibits two one-electron oxidation processes separated by 0.10 V. Variable temperature EPR measurements in polystyrene solid solutions gave negative mean exchange interaction energies J for all diradicals, suggesting the dominance of conformers with significant intramolecular antiferromagnetic interactions for the meta-through-benzene isomers. DFT calculations predict a small preference for the triplet state with the ΔES-T of about 0.25 kcal mol-1 for both meta-through-benzene connected diradicals.

Use of Antimicrobial Silver Coatings on Fixed Orthodontic Appliances, Including Archwires, Brackets, and Microimplants: A Systematic Review.

Orthodontic treatments, while essential for achieving optimal oral health, present challenges in infection control due to the propensity for bacterial adhesion and biofilm formation on orthodontic appliances. Silver-coated orthodontic materials have emerged as a promising solution, leveraging the potent antimicrobial properties of silver nanoparticles (AgNPs). Antibacterial coatings are used in orthodontics to prevent the formation of bacterial biofilms. This systematic review evaluated the literature on antimicrobial silver coatings on fixed orthodontic appliances, including archwires, brackets, and microimplants. Two evaluators, working independently, rigorously conducted a comprehensive search of various databases, including PubMed, PubMed Central, Embase, Scopus and Web of Science. This systematic review comprehensively examined in vitro studies investigating the antimicrobial efficacy of silver-coated orthodontic archwires, brackets, and microimplants. The review registered in PROSPERO CRD42024509189 synthesized findings from 18 diverse studies, revealing consistent and significant reductions in bacterial adhesion, biofilm formation, and colony counts with the incorporation of AgNPs. Key studies demonstrated the effectiveness of silver-coated archwires and brackets against common oral bacteria, such as Streptococcus mutans and Staphylococcus aureus. Microimplants coated with AgNPs also exhibited notable antimicrobial activity against a range of microorganisms. The systematic review revealed potential mechanisms underlying these antimicrobial effects, highlighted implications for infection prevention in orthodontic practice, and suggested future research avenues. Despite some study heterogeneity and limitations, the collective evidence supports the potential of silver-coated orthodontic materials in mitigating bacterial complications, emphasizing their relevance in advancing infection control measures in orthodontics.

Thermal insulation does not hamper assessment of injuries in trauma CT scans.

PURPOSE: The use of thermal insulations reduces the risk of hypothermia, therefore decreases the risk of death in trauma victims. The aim of the study was to assess whether thermal insulations cause artifacts, which may hinder the diagnosis of injuries, and how the used thermo-systems alter the radiation dose in polytrauma computed tomography. METHODS: Computed tomography scans were made using the road accident victim body wrapped consecutively with 7 different covers. 14 injury areas were listed and evaluated by 22 radiologists. The radiation dose was measured using a dosimeter placed on the victim in the abdominal area. RESULTS: No significant artifacts in any of the tested covers were observed. The presence of few minor artifacts did not hinder the assessment of injuries. Certain materials increased (up to 19,1%) and some decreased (up to -30,3%) the absorbed radiation dose. CONCLUSIONS: Thermal insulation systems tested in this study do not cause significant artifacts hindering assessment of injuries in CT scans. Concern for artifacts and increased radiation dose should not be a reason to remove patients' thermal insulation during performing trauma CT-scanning.

Investigating Single Nucleotide Polymorphisms in the Etiology of Cleft Lip and Cleft Palate in the Polish Population.

Cleft lip and/or palate (CL/P) are the most common congenital anomalies in the craniofacial region, leading to morphological and functional disruptions in the facial region. Their etiology involves genetic and environmental factors, with genetics playing a crucial role. This study aimed to investigate the association of four single nucleotide polymorphisms (SNPs)-rs987525, rs590223, rs522616, and rs4714384-with CL/P in the Polish population. We analyzed DNA samples from 209 individuals with CL/P and 418 healthy controls. The impact of SNPs on the presence of CL/P was assessed using multivariate logistic regression. Significant associations were found with rs987525. Specifically, the AC genotype was linked to an increased CL/P risk (odds ratio [OR] = 1.95, 95% confidence interval [CI]: 1.34-2.83, p < 0.001), while the CC genotype was associated with a decreased risk (OR = 0.46, 95% CI: 0.32-0.67, p < 0.001). Rs4714384 was also significant, with the CT genotype correlated with a reduced risk of CL/P (OR = 0.66, 95% CI: 0.46-0.94, p = 0.011). SNPs rs590223 and rs522616 did not show statistically significant associations. These results underscore the role of rs987525 and rs4714384 in influencing CL/P risk and suggest the utility of genetic screening in understanding CL/P etiology.

MicroED: Unveiling the Structural Chemistry of Plant Biomineralisation.

Plants are able to produce various types of crystals through metabolic processes, serving functions ranging from herbivore deterrence to photosynthetic efficiency. However, the structural analysis of these crystals has remained challenging due to their small and often imperfect nature, which renders traditional X-ray diffraction techniques unsuitable. This study explores the use of Microcrystal Electron Diffraction (microED) as a novel method for the structural analysis of plant-derived microcrystals, focusing on Armeria maritima (Milld.), a halophytic plant known for its biomineralisation capabilities. In this study, A. maritima plants were cultivated under controlled laboratory conditions with exposure to cadmium and thallium to induce the formation of crystalline deposits on their leaf surfaces. These deposits were analysed using microED, revealing the presence of sodium chloride (halite), sodium sulphate (thénardite), and calcium sulphate dihydrate (gypsum). Our findings highlight the potential of microED as a versatile tool in plant science, capable of providing detailed structural insights into biomineralisation processes, even from minimal and imperfect crystalline samples. The application of microED in this context not only advances the present understanding of A. maritima's adaptation to saline environments but also opens new avenues for exploring the structural chemistry of biomineralisation in other plant species. Our study advocates for the broader adoption of microED in botanical research, especially when dealing with challenging crystallographic problems.

Bis[1]benzothieno[1,4]thiaborins as a Platform for BODIPY Singlet Oxygen Photosensitizers.

A synthetic approach to two regioisomeric π-electron extended [1,4]thiaborins annulated with two benzothiophene units has been developed. The central thiaborin rings of the boracycles obtained exhibit different electronic properties; this is reflected in their different aromatic characters, boron Lewis acidity and UV-vis spectroscopic behavior. Thiaborins were converted to boron dipyrromethene (BODIPY) complexes. Their emission spectra exhibit two distinct bands resulting from 1 LE and 1 CT transitions. Strong near-infrared phosphorescence in Zeonex thin films at 77 K indicates efficient intersystem crossing and the formation of triplet states. Separation of HOMO and LUMO orbitals between boracyclic and BODIPY moieties facilitates electron transfer to a 1 CT state followed by a transition to the 3 LE triplet state located on the ligand. These unique properties of spiro thiaborin-BODIPY complexes were explored for their application as singlet-oxygen photosensitizers. They show excellent photocatalytic performance with singlet oxygen quantum yields reaching 77 % and full conversion of the model organic substrate achieved after 1.5 h with only 0.05 % mol catalyst load.

Bis[1]benzothieno[1,4]thiaborins as a Platform for BODIPY Singlet Oxygen Photosensitizers.

Invited for the cover of this issue are Krzysztof Durka and co-workers at Warsaw University of Technology, University of Warsaw, Silesian University of Technology and Heinrich-Heine-Universität. The image depicts the generation of singlet oxygen by the BODIPY photosensitizer. Read the full text of the article at 10.1002/chem.202300680.

Skeletal and dental age estimation via postmortem computed tomography in Polish subadults group.

This article is a retrospective analysis of postmortem computed tomography scans of ossification stages of the anterior and posterior intra-occipital sutures, the anterior arch of the atlas, and the neurocentral junction of the axis. We also analyzed the development of secondary ossification centers in the proximal humeral, femoral, and tibial epiphyses, and the distal femoral and tibial epiphyses. Additionally, the development of primary ossification centers in the wrist and metacarpals, and maxillary and mandibular deciduous tooth maturation. A total of 58 cadavers (35 males, 23 females), whose age ranged from 3rd month of pregnancy to 14 years, were analyzed. The results of this study show that analysis of synchondrosis closure, primary, and secondary ossification center development and deciduous tooth changes are a good tool for age estimation in subadults group (fetuses, newborns, infants, and children). The results of the study in a Polish population are consistent with those reported by other authors.

DFT stimulation and experimental insights of chiral Cu(II)-salen scaffold within the pocket of MWW-zeolite and its catalytic study.

A Cu(II)-salen complex encapsulated in MWW-framework as an efficient chiral organocatalyst was developed for the synthesis of 3,4-dihydropyrimidin-2-(1H)-one (DHPMs) derivatives via an asymmetric pathway. In order to confirm its structural properties, single-crystal X-ray diffraction, powder XRD, BET, XPS, FE-SEM, EDX, UV-Vis, and FTIR spectra were used. Using computer-assisted DFT calculations, the Cu(II)-salen complex has been fine-tuned to fit into the pocket of the porous MWW support while keeping its chirality. This organocatalyst was shown to be a potent catalyst for the formation of the desired DHPMs product under short reaction times. Furthermore, this green protocol allows rapid and simple isolation of active MWW-trapped Cu(II)-salen scaffolds and its reusability in at least five consecutive runs without losing much of its activity.

Hirshfeld Atom Refinement of Metal-Organic Complexes: Treatment of Hydrogen Atoms Bonded to Transition Metals.

Hydrogen positions in hydrides play a key role in hydrogen storage materials and high-temperature superconductors. Our recently published study of five crystal structures of transition-metal-bound hydride complexes showed that using aspherical atomic scattering factors for Hirshfeld atom refinement (HAR) resulted in a systematic elongation of metal-hydrogen bonds compared to using spherical scattering factors with the Independent Atom Model (IAM). Even though only standard-resolution X-ray data was used, for the highest-quality data, we obtained excellent agreement between the X-ray and the neutron-derived bond lengths. We present an extended version of this study including 10 crystal structures of metal-organic complexes containing hydrogen atoms bonded to transition-metal atoms for which both X-ray and neutron data are available. The neutron structures were used as a benchmark, and the X-ray structures were refined by applying Hirshfeld atom refinement using various basis sets and DFT functionals in order to investigate the influence of the technical aspects on the length of metal-hydrogen bonds. The result of including relativistic effects in the Hamiltonian and using a cluster of multipoles simulating interactions with a crystal environment during wave function calculations was examined. The effect of the data quality on the final result was also evaluated. The study confirms that a high quality of experimental data is the key factor allowing us to obtain significant improvement in transition metal (TM)-hydrogen bond lengths from HAR in comparison with the IAM. Individual adjustments and better choices of the basis set can improve hydrogen positions. Average differences between TM-H bond lengths obtained with various DFT functionals upon including relativistic effects or between double-ζ and triple-ζ basis sets were not statistically significant. However, if all bonds formed by H atoms were considered, significant differences caused by different refinement strategies were observed. Finally, we examined the refinement of atomic thermal motions. Anisotropic refinement of hydrogen thermal motions with HAR was feasible only in some cases, and isotropically refined hydrogen thermal motions were in similar agreement with neutron values whether obtained with HAR or with the IAM.

Micro-Evolutionary Processes in Armeria maritima at Metalliferous Sites.

Tolerance to heavy metals in plants is a model process used to study adaptations to extremely unfavorable environments. One species capable of colonizing areas with high contents of heavy metals is Armeria maritima (Mill.) Wild. A. maritima plants growing in metalliferous areas differ in their morphological features and tolerance levels to heavy metals compared to individuals of the same species growing in non-metalliferous areas. The A. maritima adaptations to heavy metals occur at the organismal, tissue, and cellular levels (e.g., the retention of metals in roots, enrichment of the oldest leaves with metals, accumulation of metals in trichomes, and excretion of metals by salt glands of leaf epidermis). This species also undergoes physiological and biochemical adaptations (e.g., the accumulation of metals in vacuoles of the root's tannic cells and secretion of such compounds as glutathione, organic acids, or HSP17). This work reviews the current knowledge on A. maritima adaptations to heavy metals occurring in zinc-lead waste heaps and the species' genetic variation from exposure to such habitats. A. maritima is an excellent example of microevolution processes in plants inhabiting anthropogenically changed areas.

The Structural Characterisation and DFT-Aided Interpretation of Vibrational Spectra for Cyclo(l-Cys-d-Cys) Cyclic Dipeptide in a Solid State.

Cyclic dipeptides with two intramolecular peptide bonds forming a six-membered 2,5-diketopiperazine ring are gaining significant attention due to their biological and chemical properties. Small changes in the local geometry of such molecules (from cis to trans) can lead to significant structural differences. This work presents the results of a study of cyclo(l-Cys-d-Cys), a dipeptide comprising two cysteine molecules in opposite chiral configurations, with the functional groups situated at both sides of the diketopiperazine ring. X-ray diffraction (XRD) experiment revealed that the molecule crystallises in the P-1 space group, which includes the centre of inversion. The IR and Raman vibrational spectra of the molecule were acquired and interpreted in terms of the potential energy distribution (PED) according to the results of density functional theory (DFT) calculations. The DFT-assisted analysis of energy frameworks for the hydrogen bond network within molecular crystals was performed to support the interpretation of X-ray structural data. The optimisation of the computational model based on three-molecule geometry sections from the crystallographic structure, selected to appropriately reflect the intermolecular interactions responsible for the formation of 1D molecular tapes in cyclo(l-Cys-d-Cys) crystal, allowed for better correspondence between theoretical and experimental vibrational spectra. This work can be considered the first complete structural characterisation of cyclo(l-Cys-d-Cys), complemented via vibrational spectroscopy results with full band assignment aided with the use of the DFT method.

Postmortem computed tomography assessment of skeletal and dental age in Polish children, adolescents, and young adults.

This paper presents a retrospective analysis of postmortem computed tomography (PMCT) scans of secondary ossification centers in the medial clavicular epiphysis, iliac crest apophysis, proximal humeral epiphysis, distal femoral epiphysis, proximal tibial epiphysis, and distal tibial epiphysis. At the same time, we analyzed PMCT scans of the maxillary and mandibular incisors, canines, premolars, and molars. We assessed 203 corpses, whose age ranged from 2 to 30 years, including 156 males and 47 females. The purpose of our study was to compare the processes of secondary ossification center fusion and permanent tooth maturation. Our research hypothesis was that certain stages of skeletal and dental maturation occur along consistent timelines that can be related to the chronological age. Secondary ossification center fusion was evaluated based on Kreitner and also McKern and Steward's classifications. The process of permanent tooth maturation was evaluated with Demirjian's method. Spearman's correlation coefficients (Rho) were positive in all analyses, which indicates that epiphyseal fusion progresses with age. The strongest relationship between the age and the stages of ossification was observed in the proximal tibial epiphysis (p < 0.001; Rho = 0.93) in females and in the medial clavicular epiphysis (p < 0.001; Rho = 0.77) in males. Studies show the importance of concomitant analysis of skeletal and dental maturation with a subsequent comparison of the results to achieve a greater precision in age estimation. A comparison of the results obtained in the study population of Polish children, adolescents, and young adults with the results of other studies in populations of similar ages showed a number of similarities in the time windows of dental and skeletal maturation. These similarities may help in age estimation.

Investigation of electrocatalytic activity of a new mononuclear Mn(II) complex for water oxidation in alkaline media.

Water splitting is a promising way to alleviate the energy crisis. In nature, water oxidation is done by a tetranuclear manganese cluster in photosystem II. Therefore, the study of water oxidation by Mn complexes is attractive in water splitting systems. In this report, a new mononuclear Mn(II) complex, MnL2 (HL = (E)-3-hydroxy-N'-(pyridin-2-ylmethylene)-2-naphthohydrazide) was prepared and characterized by spectroscopic techniques and single-crystal X-ray diffraction. Crystallographic analysis indicated that the geometry around the Mn(II) ion is distorted octahedral. The MnN4O2 coordination moiety is achieved by bounding of oxygen and two nitrogen donor atoms of two hydrazone ligands. The synthesized complex was also investigated for electrochemical water oxidation using electrochemical techniques, scanning electron microscopy, energy dispersive spectrometry, and PXRD analysis. Linear sweep voltammetry experiment showed that the modified carbon paste electrode by the complex displays high activity for water oxidation reaction with an overpotential of 565 mV at a current density of 10 mA cm-2 and Tafel slope of 105 mV dec-1 in an alkaline solution. It was found that the complex structure finally changes during the reaction and converts to Mn oxide nanoparticles which act as active catalytic species and oxidize the water.

Expedient Synthesis of Oxaboracyclic Compounds Based on Naphthalene and Biphenyl Backbone and Phase-Dependent Luminescence of their Chelate Complexes.

The approach to a series of six- and seven-membered oxaboraheterocycles based on naphthalene or biphenyl backbones was developed. The key synthetic step involved Br/Li exchange in respective potassium (bromoaryl)trifluoroborates followed by quenching with selected electrophiles (CO2 , DMF, Me2 Si(H)Cl) and hydrolytic workup. Two ring-expanded benzoxaborole congeners were obtained by an additional reduction step with LiAlH4 or NaBH4 . The obtained boracyclic compounds were characterized in detail by NMR spectroscopy and single-crystal X-ray diffraction. Specifically, biphenyl-based systems show dynamic behaviour interpreted in terms of inversion of non-planar seven-membered boraheterocycles. The acidity of the obtained compounds varies very strongly (pKa ranges from 3.1-9.6) depending on their structure. Due to the enhanced boron Lewis acidity, selected compounds were used as a basis for luminescent complexes with 8-hydroxyquinoline. A strong phase-dependent variation of emission-band maximum (480-527 nm) and photoluminescence quantum yield (10-95 %) was observed, which was rationalized in terms of specific aggregation effects.

Aurophilic Interactions Studied by Quantum Crystallography.

This is the first use of a wave-function-based crystallographic method to characterize aurophilic interactions from X-ray diffraction data. Theoretical calculations previously suggested the importance of electron correlation and dispersion forces, but no influence of relativistic corrections to the Au...Au interaction energy was found. In this study, we confirm the importance of relativistic corrections in the characterization of aurophilic interactions in addition to electron correlation and dispersion.

Electronic Coupling in 1,2,3-Triazole Bridged Ferrocenes and Its Impact on Reactive Oxygen Species Generation and Deleterious Activity in Cancer Cells.

Mixed-valence (MV) binuclear ferrocenyl compounds have long been studied as models for testing theories of electron transfer and in attempts to design molecular-scale electronic devices (e.g., molecular wires). In contrary to that, far less attention has been paid to MV binuclear ferrocenes as anticancer agents. Herein, we discuss the synthesis of six 1,2,3-triazole ferrocenyl compounds for combined (spectro)electrochemical, electron paramagnetic resonance (EPR), computational, and anticancer activity studies. Our synthetic approach was based on the copper-catalyzed 1,3-dipolar azide-alkyne cycloaddition reaction and enabled us to obtain in one step compounds bearing either one, two, or three ferrocenyl entities linked to the common 1,2,3-triazole core. Thus, two series of complexes were obtained, which pertain to derivatives of 3'-azido-3'-deoxythymidine (AZT) and 3-azidopropionylferrocene, respectively. Based on the experimental and theoretical data, the two mono-oxidized species corresponding to binuclear AZT and trinuclear 3-azidopropionylferrocene complexes have been categorized as class II mixed-valence according to the classification proposed by Robin and Day. Of importance is the observation that these two compounds are more active against human A549 and H1975 non-small-cell lung cancer cells than their congeners, which do not show MV characteristics. Moreover, the anticancer activity of MV species competes or surpasses, dependent on the cell line, the activity of reference anticancer drugs such as cisplatin, tamoxifen, and 5-fluorouracil. The most active from the entire series of compounds was the binuclear thymidine derivative with the lowest IC50 value of 5 ± 2 µM against lung H1975 cancer cells. The major mechanism of antiproliferative activity for the investigated MV compounds is based on reactive oxygen species generation in cancer cells. This hypothesis was substantiated by EPR spin-trapping experiments and the observation of decreased anticancer activity in the presence of N-acetyl cysteine (NAC) free-radical scavenger.

Chemistry of glycol nucleic acid (GNA): Synthesis, photophysical characterization and insight into the biological activity of phenanthrenyl GNA constituents.

The knowledge pertaining to the chemistry and biological activity of glycol nucleic acid (GNA) components, like nucleosides and nucleotides, is still very limited. Herein we report on the preparation of the uracil nucleoside (1) and nucleotide ester GNA (2). The compounds are functionalised with a luminescent phenanthrenyl group. In DMSO, 1 and 2 are brightly fluorescent, with emission maxima at 390 nm, nanosecond decay times (0.6 and 0.75 ns, respectively), and quantum yields of ca. 0.2. In the solid phase, they show excimeric emission, with maxima at 495 nm (1) and 432 nm (2), and decay times of 3.7 ns (1) and 2.9 ns (2). The anticancer activity of the GNA components, as well as gemcitabine hydrochloride, used as a reference drug, were examined in vitro against human cancer HeLa and Ishikawa cells, as well as against normal L929 cells, using a battery of biochemical assays. Furthermore, biodistribution imaging studies were carried out in HeLa cells, with luminescence confocal microscopy, which showed that the compounds localized mainly in the lipophilic cellular compartments. Nucleoside (1) and nucleotide ester (2) features two different anticancer activity profiles. At 24 h of treatment, the nucleoside acts mainly as a toxin and induces necrosis in HeLa cells, whereas the nucleotide ester exhibits pro-apoptotic activity. At longer treatment times (72 h), the nucleoside and the reference, gemcitabine hydrochloride, featured almost identical signs of anticancer activity, such as S-phase cell cycle arrest, proliferation inhibition, and apoptosis induction. In view of this data, one can hypothesize that despite the structural differences, the newly obtained phenanthrenyl GNA nucleoside (1) and gemcitabine may share a common mechanism of anticancer activity in HeLa cancer cells. The GNA components were also examined as antiplasmodial agents against Plasmodium falciparum, in vitro. Nucleoside (1) was found to be more potent than nucleotide (2), displaying activity in the low micromolar range. Furthermore, both phenanthrene derivatives were found to display resistance indices at least 9-fold lower than chloroquine diphosphate (CQDP).

Rotamers in Crystal Structures of Xylitol, D-Arabitol and L-Arabitol.

Rotamers are stereoisomers produced by rotation (twisting) about σ bonds and are often rapidly interconverting at room temperature. Xylitol-massively produced sweetener-(2R,3r,4S)-pentane-1,2,3,4,5-pentol) forms rotamers from the linear conformer by rotation of a xylitol fragment around the C2-C3 bond (rotamer 1) or the C3-C4 bond (rotamer 2). The rotamers form two distinguishable structures. Small differences in geometry of rotamers of the main carbon chain were confirmed by theoretical calculations; however, they were beyond the capabilities of the X-ray powder diffraction technique due to the almost identical unit cell parameters. In the case of rotamers of similar compounds, the rotations occurred mostly within hydroxyl groups likewise rotations in L-arabitol and D-arabitol, which are discussed in this work. Our results, supported by theoretical calculations, showed that energetic differences are slightly higher for rotamers with rotations within hydroxyl groups instead of a carbon chain.

First Experimental Quantitative Charge Density Studies of Advanced Intermediate of Vitamin D Analogues.

Vitamins D are a group of fat-soluble secosteroids which play a regulatory role in the functioning of most cells. Rational design of new vitamin D analogs, of increased therapeutic potency and lowered calcemic side effects, requires high-resolution initial structures and a deep understanding of interactions with the molecular targets. In this paper, using quantum crystallography, we present the first determination of the experimental quantitative charge density of an advanced intermediate of vitamin D analogues as well as a reconstruction of the theoretical electron density of final vitamin D analogues. Application of these methods allows for topological and electrostatic interaction energy analysis. We showed that the A-ring chair conformation has a significant influence on the topological properties of vitamin D compounds. Moreover, the interactions between the CD-ring and side-chain additionally stabilize the crystal structure. These results are supported by our theoretical calculations and previous biological studies.