Deciphering the work function induced local charge regulation towards activating an octamolybdate cluster-based solid for acidic water oxidation.

The advancement of highly robust and efficient electrocatalysts for the oxygen evolution reaction (OER) under acidic conditions is imperative for the sustainable production of green hydrogen. In accomplishing sustainable and sturdy electrocatalysts for oxygen evolution at low pH, the challenge is tough for non-iridium/ruthenium-based electrocatalysts. This study elaborates on the intrinsic alterations in electronic arrangements and structural disorder upon the precise activation of an octamolybdate cluster-based solid [{Cu(pz)4}2Mo8O26]·2H2O through room temperature grinding with rGO (reduced graphene oxide), resulting in enhanced conductivity, stability, and activity of the electrocatalyst towards the acidic OER without employing any benchmark metal ion (Ru or Ir). Additionally, the work function of the composites was found to be low compared to that of pristine polyoxometalates (POMs), indicative of the improved conducive behavior, which is lacking in the POM structure. The catalyst displays a notably reduced overpotential of 185 mV to achieve a current density of 10 mA cm-2, coupled with significant stability lasting 24 hours at a higher current density of 100 mA cm-2. These findings propose the manipulation of crystalline POMs with highly conductive non-metallic elements to facilitate superior water oxidation at lower pH levels which can help in the production of green hydrogen.

Large Local Internal Stress in an Elastically Bent Molecular Crystal Revealed by Raman Shifts.

The structural dynamics involved in the mechanical flexibility of molecular crystals and the internal stress in such flexible materials remain obscure. Here, the study reports an elastically bending lipidated molecular crystal that shows systematic shifts in characteristic vibrational frequencies across the bent crystal region - revealing the nature of structural changes during bending and the local internal stress distribution. The blueshifts in the bond stretching modes (such as C═O and C-H modes) in the inner arc region and redshifts in the outer arc region of the bent crystals observed via micro-Raman mapping are counterintuitive to the bending models based on intermolecular hydrogen bonds. Correlating these shifts with the trends observed from high-pressure Raman studies on the crystal reveals the local stress difference between the inner arc and outer arc regions of the bent crystal to be ≈2 GPa, more than an order of magnitude higher than the previously proposed value in elastically bending crystals. High local internal stress can have direct ramifications on the properties of molecular piezoelectric energy harvesters, actuators, semiconductors, and flexible optoelectronic materials.

Dynamic Covalent Bonds in the Ebselen Class of Antioxidants Probed by X-ray Quantum Crystallography.

Dynamic bonds are essential structural ingredients of dynamic covalent chemistry that involve reversible cleavage and formation of bonds. Herein, we explore the electronic characteristics of Se-N bonds in the organo-selenium antioxidant ebselen and its derivatives for their propensity to function as dynamic covalent bonds by employing high-resolution X-ray quantum crystallography and complementary computational studies. An analysis of the experimentally reconstructed X-ray wavefunctions reveals the salient electronic features of the Se-N bonds with very low electron density localized at the bonding region and a positive Laplacian value at the bond critical point. Bond orders and percentage covalency and ionicity estimated from the X-ray wavefunctions, along with localized orbital locator (LOL) and electron localization function (ELF) analyses show that the Se-N bond is unique in its closed shell-like features, despite being a covalent bond. Time-dependent DFT calculations simulate the cleavage of Se-N bonds in ebselen in the excited state, further substantiating their nature as dynamic bonds.

Bicyclic (alkyl)(amino)carbene (BICAAC)-supported phosphinidenes.

Herein, the synthesis and characterization of bicyclic (alkyl)(amino)carbene (BICAAC)-stabilized phosphinidenes (1-4) are reported. Compounds 1-3 were obtained by reacting trihalophosphine [PX3, X = Cl (1), Br (2), I (3)] with BICAAC in THF. A BICAAC-stabilized bis-phosphinidene (4) was obtained from the reduction of compound 2. All four compounds were characterized by X-ray crystallography and heteronuclear NMR spectroscopy. Theoretical calculations indicated the predominant C(carbene)P double bond characteristic in compounds 1-4.

The Ambiguous Origin of Thermochromism in Molecular Crystals of Dichalcogenides: Chalcogen Bonds versus Dynamic Se-Se/Te-Te Bonds.

We report thermochromism in crystals of diphenyl diselenide (dpdSe) and diphenyl ditelluride (dpdTe), which is at variance with the commonly known mechanisms of thermochromism in molecular crystals. Variable temperature neutron diffraction studies indicated no conformational change, tautomerization or phase transition between 100 K and 295 K. High-pressure crystallography studies indicated no associated piezochromism in dpdSe and dpdTe crystals. The evolution of the crystal structures and their electronic band structure with pressure and temperature reveal the contributions of intramolecular and intermolecular factors towards the origin of thermochromism-especially the intermolecular Se⋅⋅⋅Se and Te⋅⋅⋅Te chalcogen bonds and torsional modes of vibrations around the dynamic Se-Se and Te-Te bonds. Further, a co-crystal of dpdSe with iodine (dpdSe-I2 ) and an alloy crystal of dpdSe and dpdTe implied a predominantly intramolecular origin of the observed thermochromism associated with vibronic coupling.

The impact of cone beam computer tomography field of view on the precision of digital intra-oral scan registration for static computer-assisted implant surgery: A CBCT analysis.

OBJECTIVES: Registration of intra-oral surface scans to cone beam computer tomography (CBCT) is critical in the digital workflow for static computer-aided implant surgery (sCAIS). This study aimed to assess the impact of CBCT field of view (FoV) on the precision of digital intra-oral scan registration. MATERIALS AND METHODS: Cone beam computer tomography data and intra-oral scans from 20 patients were included. Small FoV CBCT's were created by digitally segmenting a large FoV into three sextants. Virtual implant planning was performed. Digital intra-oral scans were repeatedly registered onto their corresponding large and small FoV CBCT datasets. The distances and angulations between the matching implant positions of each repeated registration were used to determine the precision of the registration process. Wilcoxon Signed Rank Paired Tests were used to compare the differences between large FoV and small FoV. The threshold for statistical significance was set at p = .05. RESULTS: Differences in 3D implant position based on the registration precision between small FoV and large FoV present at both the implant entry point (0.37 ± 0.25 mm vs 0.35 ± 0.23 mm, p = .482) and implant tip (0.49 ± 0.34 mm vs 0.37 ± 0.24 mm, p < .001). Differences in overall angular precision were observed between small FOV and large FoV (1.43 ± 1.36° vs 0.51 ± 0.38°, p < .001). CONCLUSION: CBCT with a small FoV is accompanied by greater precision errors in intra-oral scan registration. However, when sufficient well-distributed teeth are visible in small FoV CBCT, the precision of digital intra-oral scan registration appears to be within clinically acceptable limits for sCAIS.

Case report on cherubism: non-familial variant / Relato de caso de querubismo: uma variante não familiar

Introduction: Cherubism is a rare, non-neoplastic, self-limiting, fibro-osseous disease, characterized by painless expansion of the maxilla, mandible or both. It usually develops in the first and second year of life. The radiographic appearance presentation is ordinarily bilateral, multilocular appearance in the mandible. To the best of our knowledge, very few cases (less than ten) of non-familial cherubism have been reported in the English literature. Objective: To describe non-familial case of cherubism in a 10-year-old child. Materials and methods: The current case was clinically, radiographically and histopathologically analysed for confirmatory diagnosis. Results: H & E stained section showed vascular and cellular stroma containing numerous multinucleated giant cells. Conclusion: Correlating radiographically and histopathologically the case was finally diagnosed as non-familial variant of cherubism.

Introdução: Querubismo é uma doença rara, não neoplásica, autolimitada, fibro-óssea, caracterizada pela expansão indolor da maxila, mandíbula ou ambas. Ela geralmente se desenvolve no primeiro e no segundo ano de vida. A aparência radiográfica é normalmente bilateral, multilocular e localizada na mandíbula. Para melhor conhecimento, poucos casos (menos de dez) de querubismo não familiar foram relatados na literatura. Objetivo: Descrever um caso de querubismo não familiar em uma criança de 10 anos. Materiais e métodos: Para confirmação do diagnóstico, foram realizadas avaliações clínicas, radiográficas e histológicas deste caso. Resultados: Seção corada de H & E mostrou estroma vascular e celular contendo numerosas células gigantes multinucleadas. Conclusão: Na correlação radiográfica e histológica, ficou confirmado diagnóstico de variante não familiar de querubismo.