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Benchmark-quality rovibrational data are reported for the methane dimer from variational nuclear motion computations using an ab initio intermolecular potential energy surface reported by [M. P. Metz et al., Phys. Chem. Chem. Phys., 2019, 21, 13504–13525]. A simple polarizability model is used to compute Raman transition moments that may be relevant for future direct observation of the intermolecular dynamics. Non-negligible ΔK ≠ 0 transition moments arise in this symmetric top system due to strong rovibrational couplings. [ABSTRACT FROM AUTHOR]

The present work intends to join and respond to the excellent and thoroughly documented rovibrational study of X. G. Wang and T. Carrington, Jr. [J. Chem. Phys. 154, 124112 (2021)] that used an approach tailored for floppy dimers with an analytic dimer Hamiltonian and a non-product basis set including Wigner D functions. It is shown in the present work that the GENIUSH black-box-type rovibrational method can approach the performance of the tailor-made computation for the example of the floppy methane–water dimer. Rovibrational transition energies and intensities are obtained in the black-box-type computation with a twice as large basis set and in excellent numerical agreement in comparison with the more efficient tailor-made approach. [ABSTRACT FROM AUTHOR]

All vibrational energies of the formic acid molecule in different forms (trans-, cis-, delocalized-) were converged up to 4500 cm−1 beyond the zero-point vibrational energy with the GENIUSH-Smolyak variational approach and using an ab initio potential energy surface [D. P. Tew and W. Mizukami, J. Phys. Chem. A, 120, 9815–9828 (2016)]. The full-dimensional dipole and polarizability surfaces were fitted to points computed at the CCSD/aug-cc-pVTZ level of theory. Then, body-fixed vibrational dipole and polarizability transition moments were evaluated and used to simulate jet-cooled infrared and Raman spectra of HCOOH. The benchmark-quality vibrational energy, transition moment, and wave function data will be used in further work for comparison with vibrational experiments, and in further rovibrational computations. [ABSTRACT FROM AUTHOR]

The automated development of a new ab initio full-dimensional potential energy surface (PES) is reported for the CH4·F− complex using the Robosurfer program package. The new potential provides a near-spectroscopic quality description over a broad configuration range including the methane-ion dissociation, as well as isolated methane vibrations. In particular, it improves upon the earlier [Czakó, Braams, Bowman (2008)] PES over intermediate methane-fluoride distances. Full-dimensional (12D) variational vibrational computations using the new PES and the GENIUSH-Smolyak algorithm show that tunnelling splittings larger than 0.1 cm−1 appear below the top of the interconversion barrier of the four equivalent minima of the complex. [ABSTRACT FROM AUTHOR]

The complex of a methane molecule and a fluoride anion represents a 12-dimensional (12D), four-well vibrational problem with multiple large-amplitude motions, which has challenged the quantum dynamics community for years. The present work reports vibrational band origins and tunneling splittings obtained in a full-dimensional variational vibrational computation using the GENIUSH program and the Smolyak quadrature scheme. The converged 12D vibrational band origins and tunneling splittings confirm complementary aspects of the earlier full- and reduced-dimensionality studies: (1) the tunneling splittings are smaller than 0.02 cm−1; (2) a single-well treatment is not sufficient (except perhaps the zero-point vibration) due to a significant anharmonicity over the wells; and thus, (3) a full-dimensional treatment appears to be necessary. The present computations extend to a higher energy range than earlier work, show that the tunneling splittings increase upon vibrational excitation of the complex, and indicate non-negligible "heavy-atom" tunneling. [ABSTRACT FROM AUTHOR]

Methodological progress is reported in the challenging direction of a black-box-type variational solution of the (ro)vibrational Schrödinger equation applicable to floppy, polyatomic systems with multiple large-amplitude motions. This progress is achieved through the combination of (i) the numerical kinetic-energy operator (KEO) approach of Mátyus et al. [J. Chem. Phys. 130, 134112 (2009)] and (ii) the Smolyak nonproduct grid method of Avila and Carrington, Jr. [J. Chem. Phys. 131, 174103 (2009)]. The numerical representation of the KEO makes it possible to choose internal coordinates and a body-fixed frame best suited for the molecular system. The Smolyak scheme reduces the size of the direct-product grid representation by orders of magnitude, while retaining some of the useful features of it. As a result, multidimensional (ro)vibrational states are computed with system-adapted coordinates, a compact basis- and grid-representation, and an iterative eigensolver. Details of the methodological developments and the first numerical applications are presented for the CH4·Ar complex treated in full (12D) vibrational dimensionality. [ABSTRACT FROM AUTHOR]

Molecular rotation, vibration, internal rotation, isomerization, tunneling, intermolecular dynamics of weakly and strongly interacting systems, intra-to-inter-molecular energy transfer, hindered rotation and hindered translation over surfaces are important types of molecular motions. Their fundamentally correct and detailed description can be obtained by solving the nuclear Schrödinger equation on a potential energy surface. Many of the chemically interesting processes involve quantum nuclear motions which are 'delocalized' over multiple potential energy wells. These 'large-amplitude' motions in addition to the high dimensionality of the vibrational problem represent challenges to the current (ro)vibrational methodology. A review of the quantum nuclear motion methodology is provided, current bottlenecks of solving the nuclear Schrödinger equation are identified, and solution strategies are reviewed. Technical details, computational results, and analysis of these results in terms of limiting models and spectroscopically relevant concepts are highlighted for selected numerical examples. [ABSTRACT FROM AUTHOR]

In this paper, we demonstrate that it is possible to apply collocation to compute vibrational energy levels of a five-atom molecule using an exact kinetic energy operator (with cross terms and coordinatedependent coefficients). This is made possible by using (1) a pruned basis of products of univariate functions; (2) a Smolyak grid made from nested sequences of grids for each coordinate; (3) a collocation method that obviates the need to solve a generalized eigenvalue problem; (4) an efficient sequential transformation between the (nondirect product) grid and the (nondirect product) basis representations; and (5) hierarchical univariate functions that make it possible to avoid storing large intermediate vectors. The accuracy of the method is confirmed by computing 500 vibrational energy levels of methane. [ABSTRACT FROM AUTHOR]

In this paper, we improve the collocation method for computing vibrational spectra that was presented in the work of Avila and Carrington, Jr. [J. Chem. Phys. 143, 214108 (2015)]. Known quadrature and collocation methods using a Smolyak grid require storing intermediate vectors with more elements than points on the Smolyak grid. This is due to the fact that grid labels are constrained among themselves and basis labels are constrained among themselves. We show that by using the so-called hierarchical basis functions, one can significantly reduce the memory required. In this paper, the intermediate vectors have only as many elements as the Smolyak grid. The ideas are tested by computing energy levels of CH2NH. [ABSTRACT FROM AUTHOR]

In the 1960s, when Dr. Belding Scribner discovered how to accomplish the process of dialysis in a repeated way, he could not imagine that in solving such a problem others as or more difficult would appear. Given the technological progress and the impossibility of assisting all patients through the most modern methods, the medical doctor often finds himself faced with the moral dilemma of choosing which patient in the waiting list will receive the treatment. This same dilemma is amplified in the case of organ transplants. Professionals, students, professors of the juridical and health fields, and the population in general, were interviewed as a means of documenting the moral concepts and opinions surrounding this problem. In the reality in which we find ourselves, it seems to us that deciding who lives, and the responsibility for all the events that culminate in such decisions, is still a subject left open to discussion.

In this paper, we improve the collocation method for computing vibrational spectra that was presented in Avila and Carrington, Jr. [J. Chem. Phys. 139, 134114 (2013)]. Using an iterative eigensolver, energy levels and wavefunctions are determined from values of the potential on a Smolyak grid. The kinetic energy matrix-vector product is evaluated by transforming a vector labelled with (nondirect product) grid indices to a vector labelled by (nondirect product) basis indices. Both the transformation and application of the kinetic energy operator (KEO) scale favorably. Collocation facilitates dealing with complicated KEOs because it obviates the need to calculate integrals of coordinate dependent coefficients of differential operators. The ideas are tested by computing energy levels of HONO using a KEO in bond coordinates. [ABSTRACT FROM AUTHOR]

Curvilinear kinetic energy models are developed for variational nuclear motion computations including the inter- and the low-frequency intra-molecular degrees of freedom of the formic acid dimer. The coupling of the inter- and intra-molecular modes is studied by solving the vibrational Schrödinger equation for a series of vibrational models, from two up to ten active vibrational degrees of freedom by selecting various combinations of active modes and constrained coordinate values. Vibrational states, nodal assignment, and infrared vibrational intensity information is computed using the full-dimensional potential energy surface (PES) and electric dipole moment surface developed by Qu and Bowman [Phys. Chem. Chem. Phys., 2016, 18, 24835; J. Chem. Phys., 2018, 148, 241713]. Good results are obtained for several fundamental and combination bands in comparison with jet-cooled vibrational spectroscopy experiments, but the description of the ν8 and ν9 fundamental vibrations, which are close in energy and have the same symmetry, appears to be problematic. For further progress in comparison with experiment, the potential energy surface, and in particular, its multi-dimensional couplings representation, requires further improvement. [ABSTRACT FROM AUTHOR]

A full-dimensional ab initio potential energy surface of spectroscopic quality is developed for the van-der-Waals complex of a methane molecule and an argon atom. Variational vibrational states are computed on this surface including all twelve (12) vibrational degrees of freedom of the methane–argon complex using the GENIUSH computer program and the Smolyak sparse grid method. The full-dimensional computations make it possible to study the fine details of the interaction and distortion effects and to make a direct assessment of the reduced-dimensionality models often used in the quantum dynamics study of weakly-bound complexes. A 12-dimensional (12D) vibrational computation including only a single harmonic oscillator basis function (9D) to describe the methane fragment (for which we use the ground-state effective structure as the reference structure) has a 0.40 cm−1 root-mean-square error (rms) with respect to the converged 12D bound-state excitation energies, which is less than half of the rms of the 3D model set up with the 〈r〉0 methane structure. Allowing 10 basis functions for the methane fragment in a 12D computation performs much better than the 3D models by reducing the rms of the bound state vibrational energies to 0.07 cm−1. The full-dimensional potential energy surface correctly describes the dissociation of the system, which together with further development of the variational (ro)vibrational methodology opens a route to the study of the role of dispersion forces in the excited methane vibrations and the energy transfer from the intra- to the intermolecular vibrational modes. [ABSTRACT FROM AUTHOR]

In this paper we propose and test a method for computing numerically exact vibrational energy levels of a molecule with six atoms. We use a pruned product basis, a non-product quadrature, the Lanczos algorithm, and the exact normal-coordinate kinetic energy operator (KEO) with the πtμπ term. The Lanczos algorithm is applied to a Hamiltonian with a KEO for which μ is evaluated at equilibrium. Eigenvalues and eigenvectors obtained from this calculation are used as a basis to obtain the final energy levels. The quadrature scheme is designed, so that integrals for the most important terms in the potential will be exact. The procedure is tested on C2H4. All 12 coordinates are treated explicitly. We need only ∼1.52 × 108 quadrature points. A product Gauss grid with which one could calculate the same energy levels has at least 5.67 × 1013 points. [ABSTRACT FROM AUTHOR]

In this paper we propose a new quadrature scheme for computing vibrational spectra and apply it, using a Lanczos algorithm, to CH3CN. All 12 coordinates are treated explicitly. We need only 157'419'523 quadrature points. It would not be possible to use a product Gauss grid because 33 853 318 889 472 product Gauss points would be required. The nonproduct quadrature we use is based on ideas of Smolyak, but they are extended so that they can be applied when one retains basis functions θn1(r1)...θnD(rD) that satisfy the condition α1n1 + ··· + αDnD <= b, where the αk are integers. We demonstrate that it is possible to exploit the structure of the grid to efficiently evaluate the matrix-vector products required to use the Lanczos algorithm. [ABSTRACT FROM AUTHOR]

The size of the quadrature grid required to compute potential matrix elements impedes solution of the vibrational Schrödinger equation if the potential does not have a simple form. This quadrature grid-size problem can make computing (ro)vibrational spectra impossible even if the size of the basis used to construct the Hamiltonian matrix is itself manageable. Potential matrix elements are typically computed with a direct product Gauss quadrature whose grid size scales as ND, where N is the number of points per coordinate and D is the number of dimensions. In this article we demonstrate that this problem can be mitigated by using a pruned basis set and a nonproduct Smolyak grid. The constituent 1D quadratures are designed for the weight functions important for vibrational calculations. For the SF6 stretch problem (D=6) we obtain accurate results with a grid that is more than two orders of magnitude smaller than the direct product Gauss grid. If D>6 we expect an even bigger reduction. [ABSTRACT FROM AUTHOR]

Objective: To evaluate, in vitro, the antimicrobial effect of ozone gas on strains of reference mutans streptococci and strains isolated from children at a high risk of developing caries. Method and Materials: A series of dilutions was obtained from a total of 41 strains, and the effect of ozone was determined for applications of 10, 20, and 40 seconds, as well as a control, in terms of the reduction of viable bacteria. Results: Ozone application for 10 and 20 seconds produced a significant reduction in the number of bacteria, inversely proportional to the bacterial concentration. When exposure lasted 40 seconds, no viable bacteria were obtained. Conclusions: Both time of application and initial bacterial concentration bear an influence on the antimicrobial effect of ozone on mutans streptococci. [ABSTRACT FROM AUTHOR]

Invasion of the maxillary sinus is a relatively frequent complication in dental implant treatment of patients with inadequate bone height in the posterior maxilla. This event usually occurs during surgery and sometimes produces sinusitis. There is a paucity of reports in the literature of implants migrating into the sinus cavity after a period of function. In the 2 clinical cases presented, an intraosseous apical movement of the implants was produced several years after placement of the implants. Hypotheses and possible mechanisms by which an implant may migrate into the maxillary sinus are described. [ABSTRACT FROM AUTHOR]

Copyright of Revista Brasileira de Políticas Públicas is the property of Revista Brasileira de Politicas Publicas and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

A new, highly accurate ab initio ground-state intermolecular potential-energy surface (IPES) for the CO–N2 complex is presented. Thousands of interaction energies calculated with the CCSD(T) method and Dunning's aug-cc-pVQZ basis set extended with midbond functions were fitted to an analytical function. The global minimum of the potential is characterized by an almost T-shaped structure and has an energy of −118.2 cm−1. The symmetry-adapted Lanczos algorithm was used to compute rovibrational energies (up to J = 20) on the new IPES. The RMSE with respect to experiment was found to be on the order of 0.038 cm−1 which confirms the very high accuracy of the potential. This level of agreement is among the best reported in the literature for weakly bound systems and considerably improves on those of previously published potentials. [ABSTRACT FROM AUTHOR]

Phosgene (Cl2C=O) is extremely poisonous, underscoring the importance of accurate infrared detection. Here, the computed vibrational energy levels of phosgene are reported for the first time from a six-dimensional potential energy surface (PES) that was constructed from 25,000 single-point energy computations at the CCSD(T)/cc-pVTZ level of theory. The computed points were fit using a neural network method, and the resulting PES was employed in the determination of vibrational energies and wavefunctions. Bond coordinates were utilised in conjunction with a collocation method to minimise problems that arise from the complicated nature of the kinetic energy operator. The collocation method makes possible the computation of energy levels without integral evaluation, and without the need to solve a generalised eigenvalue problem. Moreover, it is built on a nondirect product-pruned basis that is much smaller than the direct product basis that would be required to obtain the same accuracy. [ABSTRACT FROM AUTHOR]

Anthrax toxin receptors act as molecular clamps or switches that control anthrax toxin entry, pH-dependent pore formation, and translocation of enzymatic moieties across the endosomal membranes. We previously reported that reduction of the disulfide bonds in the immunoglobulin-like (Ig) domain of the anthrax toxin receptor 2 (ANTXR2) inhibited the function of the protective antigen (PA) pore. In the present study, the disulfide linkage in the Ig domain was identified as Cys255-Cys279 and Cys230-Cys315. Specific disulfide bond deletion mutants were achieved by replacing Cys residues with Ala residues. Deletion of the disulfide bond C255-C279, but not C230-C315, inhibited the PA pore-induced release of the fluorescence dyes from the liposomes, suggesting that C255-C279 is essential for PA pore function. Furthermore, we found that deletion of C255-C279 did not affect PA prepore-to-pore conversion, but inhibited PA pore membrane insertion by trapping the PA membrane-inserting loops in proteinaceous hydrophobic pockets. Fluorescence spectra of Trp59, a residue adjacent to the PA-binding motif in von Willebrand factor A (VWA) domain of ANTXR2, showed that deletion of C255-C279 resulted in a significant conformational change on the receptor ectodomain. The disulfide deletion-induced conformational change on the VWA domain was further confirmed by single-particle 3D reconstruction of the negatively stained PA-receptor heptameric complexes. Together, the biochemical and structural data obtained in this study provides a mechanistic insight into the role of the receptor disulfide bond C255-C279 in anthrax toxin action. Manipulation of the redox states of the receptor, specifically targeting to C255-C279, may become a novel strategy to treat anthrax. [ABSTRACT FROM AUTHOR]

Gam1, an early gene product of an avian adenovirus, is essential for viral replication. Gam1 is the first viral protein found to globally inhibit cellular SUMOylation, a critical posttranslational modification that alters the function and cellular localization of proteins. The interaction details at the interface between Gam1 and its cellular targets remain unclear due to the lack of structural information. Although Gam1 has been previously characterized, the purity of the protein was not suitable for structural investigations. In the present study, the gene of Gam1 was cloned and expressed in various bacterial expression systems to obtain pure and soluble recombinant Gam1 protein for in vitro functional and structural studies. While Gam1 was insoluble in most expression systems tested, it became soluble when it was expressed as a fusion protein with trigger factor (TF), a ribosome associated bacterial chaperone, under the control of a cold shock promoter. Careful optimization indicates that both low temperature induction and the chaperone function of TF play critical roles in increasing Gam1 solubility. Soluble Gam1 was purified to homogeneity through sequential chromatography techniques. Monomeric Gam1 was obtained via size exclusion chromatography and analyzed by dynamic light scattering. The SUMOylation inhibitory function of the purified Gam1 was confirmed in an in vitro assay. These results have built the foundation for further structural investigations that will broaden our understanding of Gam1’s roles in viral replication. [ABSTRACT FROM AUTHOR]

Copyright of Implant Dentistry is the property of Lippincott Williams & Wilkins and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Background: Maxillary sinus augmentation is one of the most reliable implant site development options to increase vertical bone height. However, graft consolidation requires adequate angiogenesis and migration of cells involved in osteogenesis and bone remodeling, It is speculated that these biologic events are greatly determined by the dimensions of the maxillary sinus cavity. Hence, the purpose of this study is to assess the influence of the distance from the lateral to the medial wall of the maxillary sinus on the outcomes of sinus augmentation procedures. Methods: A total of 25 patients in need of sinus augmentation were recruited for the study. After initial examination, customized radiographic and surgical guides were fabricated and a cone-beam computerized tomography scan was obtained per patient. The bucco-palatal distance (BPD) was measured at 8, 10, and 12 mm from the alveolar crest. Sinus grafting was performed by a lateral window approach using a particulated allograft material. Patients were followed-up for 6 months. At the time of implant placement, bone core biopsies were harvested using the radio- graphic-surgical guide. Sections of the bone cores at 8, 10, and 12 mm from the alveolar crest were histomorphometrically analyzed. The proportion of vital bone (%VB) was correlated with the BPD using a statistical model. Results: Twenty-one patients underwent sinus augmentation for a total of 24 sinuses; however, the data analyzed contained only one sinus per patient. One sinus developed an infection after grafting, resulting in a 96% success rate for the sinus grafting procedure. Twenty sinuses were used in the final statistical analysis. Histomorphometric analysis revealed that mean %VB was 22.71 ± 19.08, mean percent of remaining allograft was 23.39 ± 20.85, and average percent of non-mineralized connective tissue was 53.90 ± 13.23. Analysis of the correlation between %VB and BPD by linear regression, using the actual values of BPD showed a strong negative association (R²=0.141; P<0.001). Conclusion: The findings suggest that the %VB formation after maxillary sinus augmentation is inversely proportional to the sinus BPD. [ABSTRACT FROM AUTHOR]

Copyright of Implant Dentistry is the property of Lippincott Williams & Wilkins and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Background; Implant-supported restorations have become the most popular therapeutic option for professionals and patients for the treatment of total and partial edentulism. When implants are placed in an ideal position, with adequate prosthetic loading and proper maintenance, they can have success rates >90% over 15 years of function. Implants may be considered a better therapeutic alternative than performing more extensive conservative procedures in an attempt to save or maintain a compromised tooth. Inadequate indication for tooth extraction has resulted in the sacrifice of many sound savable teeth. This article presents a chart that can assist clinicians in making the right decision when they are deciding which route to take. Methods: Articles published in peer-reviewed English journals were selected using several scientific databases and subsequently reviewed. Book sources were also searched, individual tooth- and patient-related features were thoroughly analyzed, particularly when determining if a tooth should be indicated for extraction. Results: A color-based decision-making chart with six different levels, including several factors, was developed based upon available scientific literature. The rationale for including these factors is provided, and its interpretation is justified with literature support. Conclusion: The decision-making chart provided may serve as a reference guide for dentists when making the decision to save or extract a compromised tooth. [ABSTRACT FROM AUTHOR]

Copyright of Implant Dentistry is the property of Lippincott Williams & Wilkins and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)