Spin-orbit coupling of electrons on separate lanthanide atoms of Pr2O2 and its singly charged cation.

Although it plays a critical role in the photophysics and catalysis of lanthanides, spin-orbit coupling of electrons on individual lanthanide atoms in small clusters is not well understood. The major objective of this work is to probe such coupling of the praseodymium (Pr) 4f and 6s electrons in Pr2O2 and Pr2O2+. The approach combines mass-analyzed threshold ionization spectroscopy and spin-orbit multiconfiguration second-order quasi-degenerate perturbation theory. The energies of six ionization transitions are precisely measured; the adiabatic ionization energy of the neutral cluster is 38 045 (5) cm-1. Most of the electronic states involved in these transitions are identified as spin-orbit coupled states consisting of two or more electron spins. The electron configurations of these states are 4f46s2 for the neutral cluster and 4f46s for the singly charged cation, both in planar rhombus-type structures. The spin-orbit splitting due to the coupling of the electrons on the separate Pr atoms is on the order of hundreds of wavenumbers.

Stepwise Sulfite Reduction on a Dinuclear Ruthenium Complex Leading to Hydrogen Sulfide.

Sulfite reduction by dissimilatory sulfite reductases is a key process in the global sulfur cycle. Sulfite reductases catalyze the 6e- reduction of SO32- to H2S using eight protons (SO32- + 8H+ + 6e- → H2S + 3H2O). However, detailed research into the reductive conversion of sulfite on transition-metal-based complexes remains unexplored. As part of our ongoing research into reproducing the function of reductases using dinuclear ruthenium complex {(TpRu)2(µ-Cl)(µ-pz)} (Tp = HB(pyrazolyl)3), we have targeted the function of sulfite reductase. The isolation of a key SO-bridged complex, followed by a sulfite-bridged complex, eventually resulted in a stepwise sulfite reduction. The reduction of a sulfite to a sulfur monoxide using 4H+ and 4e-, which was followed by conversion of the sulfur monoxide to a disulfide with concomitant consumption of 2H+ and 2e-, proceeded on the same platform. Finally, the production of H2S from the disulfide-bridged complex was achieved.

Theoretical Study of Si/C Equally Mixed Dodecahedrane Analogues.

To gain insight into the effect of Si/C arrangement on the molecular framework of strained polyhedral compounds, dodecahedrane analogues containing equal numbers of carbon and silicon (Si/C equally mixed dodecahedrane analogues) were investigated using the ab initio molecular orbital method. There are 1648 isomers for which the Si/C arrangement on the molecular framework is different. Based on the geometry optimization of all the isomers as well as the carbon and silicon analogues, the characteristics of the structure, relative energy, and strain energy of the Si/C equally mixed compounds are presented. Then, important factors controlling the relative energy, such as strain energy, are proposed through regression analysis. Also discussed is the correlation between the relative energy and the indices of Si/C dispersion, such as the number of skeletal C-Si single bonds and condensed five-membered rings constituting the polyhedral structure.

Electronic states and transitions of PrO and PrO+ probed by threshold ionization spectroscopy and spin-orbit multiconfiguration perturbation theory.

The precise ionization energy of praseodymium oxide (PrO) seeded in supersonic molecular beams is measured with mass-analyzed threshold ionization (MATI) spectroscopy. A total of 33 spin-orbit (SO) states of PrO and 23 SO states of PrO+ are predicted by second-order multiconfigurational quasi-degenerate perturbation (MCQDPT2) theory. Electronic transitions from four low-energy SO levels of the neutral molecule to the ground state of the singly charged cation are identified by combining the MATI spectroscopic measurements with the MCQDPT2 calculations. The precise ionization energy is used to reassess the ionization energies and the reaction enthalpies of the Pr + O → PrO+ + e- chemi-ionization reaction reported in the literature. An empirical formula that uses atomic electronic parameters is proposed to predict the ionization energies of lanthanide monoxides, and the empirical calculations match well with available precise experimental measurements.

The Alteration of Brain Function by the Improvement of Periodontal Tissues and Occlusal State.

Objective: In this study, we have introduced a case in which the effective blood oxygenation level-dependent signal on functional magnetic resonance imaging (fMRI) was altered by the improvement of periodontal tissue and occlusal function in a patient with periodontitis Stage II Grade B. Material and Methods. A 61-year-old female patient requiring periodontal treatment was diagnosed as having periodontitis Stage II Grade B via clinical and radiographic examinations. Her past medical history included type 2 diabetes, hypertension, and hyperlipidemia. Following the patient's informed written consent, the periodontal initial treatment provided to the patient included tooth brushing instruction and scaling and root planing; however, occlusal adjustment was not performed at this stage. Occlusal force and fMRI results were also evaluated at the initial and reevaluation examinations. Results: After the periodontal initial treatment had been performed, it was noted that the patient's periodontal tissue and occlusal force had improved. It was also evident from fMRI that cerebral blood flow had been activated in the insula, primary motor cortex, and premotor cortex. Conclusion: This result suggested that the periodontal ligament had recovered and the periodontal ligament neuron had been further subjected to clenching in the insula so that the muscle spindle sensation impacted the motor cortex.

The catalytic activity and adsorption in faujasite and ZSM-5 zeolites: the role of differential stabilization and charge delocalization.

Adsorption and chemical reactions occurring on industrially important ZSM-5 and faujasite zeolite catalysts are investigated with the quantum-mechanical fragment molecular orbital method combined with periodic boundary conditions. Suitable fragmentation patterns are devised and tested providing important case studies of computing real materials with fragmentation methods. A good accuracy is demonstrated in comparison to full calculations, and a good agreement with the available experimental data is obtained. The full production cycle of p-xylene on faujasite zeolite is mapped. The catalytic role of the zeolite in the dehydration reaction, analyzed with the partition analysis, is attributed to the delocalization of the negative charge over the zeolite. On the other hand, an increase of the barrier in the Diels-Alder reaction by the zeolite is attributed to the preferential stabilization of the reactants over the transition state as demonstrated by the guest-zeolite interaction energy.

Free Energy Decomposition Analysis Based on the Fragment Molecular Orbital Method.

A decomposition of the free energy is developed in the many-body expansion framework of the fragment molecular orbital (FMO) method combined with umbrella sampling molecular dynamics (MD). In FMO/MD simulations, performed with density-functional tight-binding and periodic boundary conditions, all atoms are treated quantum mechanically. The free energy is computed and decomposed for a series of SN2 Menshutkin reactions in water. The barrier lowering by the solvent is attributed to the competition between the solvent polarization and the solute-solvent interactions including charge transfer.

Analysis of Guest Adsorption on Crystal Surfaces Based on the Fragment Molecular Orbital Method.

For gaining insights into interactions in periodic systems, an analysis is developed based on the fragment molecular orbital method combined with periodic boundary conditions. The adsorption energy is decomposed into guest and surface polarization and deformation energy, guest-surface and guest-guest interactions, and the vibrational free energy. The analysis is applied to the adsorption of guest molecules to Ih (001) ice surface. The cooperativity effects result in a non-linear change in the adsorption energy with coverage due to many-body effects. The role of dispersion is found to be dominant for guests with long hydrophobic tails. A rule is proposed relating the length of the alkyl tail with the formation of the guest layer. The computed binding enthalpies are in good agreement with experimental values. For high coverage, adsorbed molecules can form an ordered layer known as self-assembled monolayer.

Effect of COVID-19 on dental telemedicine in Japan.

BACKGROUND/PURPOSE: In Japan, medical and dental care is provided by the universal health insurance system. The Ministry of Health, Labour, and Welfare (MHLW) in Japan sets the rules for health care services provided by health insurance. The MHLW issued a notice in 2020 permitting telemedicine and dental telemedicine for the first visit and for follow-up visits to prevent the spread of COVID-19 infection. We conducted this study to clarify the status of dental telemedicine during 2020. MATERIALS AND METHODS: We used data from lists obtained on the MHLW website in the analysis. We investigated the number of dental institutions conducing dental telemedicine for the first visit and for follow-up visits by prefecture. RESULTS: In each prefecture, fewer dental institutions conducted telemedicine for the first visit than for follow-up visits. Regions with large metropolitan areas had higher numbers of dental institutions conducting dental telemedicine for the first visit and follow-up visits. Private dental clinics provided the largest proportion of dental telemedicine for the first visit, and general hospitals provided the largest proportion for follow-up visits. CONCLUSION: Our study findings indicated that many dental institutions in Japan made efforts to provide dental services via dental telemedicine using the telephone or online with video to help prevent the spread of COVID-19 infection. Dental telemedicine can help patients to access dental services and dental care, thereby expanding the potential of dental telemedicine in Japan.

Quantum-Mechanical Structure Optimization of Protein Crystals and Analysis of Interactions in Periodic Systems.

A fast quantum-mechanical approach, density-functional tight-binding combined with the fragment molecular orbital method and periodic boundary conditions, is used to optimize atomic coordinates and cell parameters for a set of protein crystals: 1ETL, 5OQZ, 3Q8J, 1CBN, and 2VB1. Good agreement between experimental and calculated structures is obtained for both atomic coordinates and cell parameters. Sterical clashes present in the experimental structures are corrected by simulations. The partition analysis is extended to treat periodic boundary conditions and applied to analyze protein-solvent interactions in crystals.

Comparison of group 14 elements in sp3 and sp2 environment by fragment structure energy analysis.

To explore the characteristics of group 14 elements in sp3 and sp2 hybrid environments systematically, the concept of fragment structure energy (FSE) was proposed through ab initio molecular orbital method. A fragment in this study means a building block of molecular structure and the energy of each kind of fragments (FSE) is obtained from the total electronic energy of different size of model compounds by just a simple algebraic method. The model compounds are the hydrogen-terminated diamond and graphene analogs as the typical compounds in the ideal sp3 - and sp2 -environment, respectively. As a result, the sp3 environment was found to be more stable than the sp2 for all the group 14 elements (C-Pb) in the ideal hybrid environment. Furthermore, a mixing effect of carbon and heavier group 14 elements (E = Si, Ge, Sn, and Pb) was investigated by comparing the E/C-alternately mixed- and the pure FSEs.

Associations of cytokine levels in gingival crevicular fluid of mobile teeth with clinical improvement after initial periodontal treatment.

Studies suggest that analysis of gingival crevicular fluid (GCF) is useful for evaluating periodontal status. In this study, clinical variables related to tooth mobility, and multiple cytokine levels in proximate GCF, were measured at four time points during initial periodontal treatment: before treatment (baseline), after supragingival scaling, after occlusal adjustment, and after scaling and root planing (SRP); 20 teeth from 13 patients with periodontitis were included. Baseline interleukin (IL)-10 level in GCF was significantly higher around teeth that showed substantial improvement in periodontal epithelial surface area (PESA) after SRP than around teeth without PESA improvement. IL-3 and IL-16 levels in GCF at baseline were significantly higher around teeth with a periodontal inflamed surface area (PISA) of 0 mm2 after SRP than around teeth without PISA improvement. In addition, baseline IL-7, IL-11, and IL-12p40 levels in GCF were significantly lower around teeth with decreased mobility after occlusal adjustment than around teeth without decreased mobility. These results suggest that pre-treatment cytokine levels in GCF are useful in predicting the effects of initial periodontal treatment.

The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene.

There are various nonplanar heteroatom analogues of benzene-cyclic 6π electron systems-and among them, hexasilabenzene (Si6 H6 ) is well known as a typical example. To determine the factors that control their planarity, quantum chemical calculations and an energy component analysis were performed. The results show that the energy components mainly controlling the planarity of benzene and hexasilabenzene are different. For hexasilabenzene, electron repulsion energy was found to be significantly important for the planarity. The application of the pseudo Jahn-Teller effect and the Carter-Goddard-Malrieu-Trinquier model for the interpretation of the planarity of the benzene analogues was also investigated. Furthermore, based on the quantitative results, it was revealed that the planarization of hexasilabenzene is realized by introducing substituents with π-accepting ability, such as the boryl group, that bring about a reduction of the π-electron repulsion on the silicon skeleton. © 2018 Wiley Periodicals, Inc.

Central nicotinic stimulation reduces vascular conductance in the gingiva in anesthetized rats.

OBJECTIVE: The central effects of nicotine on gingival blood flow and vascular conductance were investigated. BACKGROUND: Nicotine is absorbed in cigarette smoking, which is a risk factor for periodontal disease. Although studies have shown peripheral effects of nicotine on gingival blood flow and gingival vascular conductance, little is known about its central effects. METHODS: We used laser Doppler flow measurements to investigate the changes of gingival blood flow produced by 5 min intracerebroventricular (i.c.v.) injection of (-)-nicotine ditartrate in rats anesthetized by urethane and alpha-chloralose, along with occasional measurements of the blood pressure from the femoral artery. RESULTS: The i.c.v. injection of nicotine at 15, 50, and 150 microg reduced the gingival blood flow significantly, compared with saline. The maximal reduction was dose-dependent. Next, we measured the blood pressure and gingival blood flow in the i.c.v. injection of nicotine at 50 microg, to calculate the gingival vascular conductance. The blood pressure was reduced, along with the change of gingival blood flow immediately after the injection, whereas the gingival vascular conductance fell with a time-lag. CONCLUSION: These results suggest that the reduction of gingival blood flow by central nicotinic stimulation is accompanied in part by a change of vascular tonus in the gingiva.

Evidence for the presence of nicotinic receptors on rat subfornical organ neurons.

The sensitivity of subfornical organ (SFO) neurons in rat slice preparations to nicotine was studied using whole-cell patch-clamp recordings and immunohistochemistry. In the current-clamp mode, nicotine at 10 microM depolarized the membrane and increased the firing rate. In the voltage-clamp mode, nicotine elicited inward currents in a dose-dependent manner. The net current-voltage relationships of the nicotine-induced currents displayed inward rectification above -40 mV. The relatively alpha4beta2-selective nicotinic acetylcholine (ACh) receptor antagonist, dihydro-beta-erythroidine, reduced the peak amplitudes of the nicotine-induced inward currents. Immunohistochemical experiments with alpha4 antibody showed the existence of immunopositive cells in the subfornical organ. These results suggest that neurons in the subfornical organ are excited via alpha4beta2 nicotinic acetylcholine receptors.