Guest-Host Raman under Liquid Nitrogen Spectroscopy for the Acquisition of Improved Vibrational Spectra of Solids.

Guest-host Raman under liquid nitrogen spectroscopy (GHRUNS) is introduced whereby solid-state guest molecules are isolated inside cage-like host environments for the facile acquisition of their Raman spectra. This convenient method features reduced fluorescence, the analysis of populations in their ground states, and increased signal to noise ratios. Samples are also preserved through the reduction of thermal degradation and oxidation.

Inconsistent reproductive isolation revealed by interactions between fish species.

Interactions between species are central to evolution and ecology, but we do not know enough about how outcomes of interactions between species vary across geographic locations, in heterogeneous environments, or over time. Ecological dimensions of interactions between species are known to vary, but evolutionary interactions such as the establishment and maintenance of reproductive isolation are often assumed to be consistent across instances of an interaction between species. Hybridization among fish species occurs over a large and heterogeneous geographic area and across taxa with distinct evolutionary histories, which allows us to assess consistency in species interactions.

Postexercise hypotension in central aortic pressures following walking and its relation to cardiorespiratory fitness.

Background: Central aortic blood pressure (BP) is reduced after exercise. The aim of this study was to determine whether cardiorespiratory fitness relates to postexercise reductions in aortic BP.

Methods: Sixteen young adults completed maximal exercise testing for peak oxygen uptake (VO2).

Children's Access to Dental Care Affected by Reimbursement Rates, Dentist Density, and Dentist Participation in Medicaid.

Objectives: To assess the relation between Medicaid reimbursement rates and access to dental care services in the context of dentist density and dentist participation in Medicaid in each state.

Methods: Data were from Early and Periodic Screening, Diagnostic, and Treatment reports for 2014, Medicaid reimbursement rate in 2013, dentist density in 2014, and dentist participation in Medicaid in 2014. We assessed patterns of mediation or moderation.

Risk assessment and periodontal prevention in primary care.

The role of risk factors and risk assessment in the prediction of clinical periodontal outcomes, and thus in patient management, continues to be a subject of high professional interest and clinical relevance globally. Advances in our understanding of periodontal disease causality and the role of risk factors as predictors of future disease risk have led to the development of various quantitative tools to calculate risk and inform clinical decision-making. We review the conceptual basis for periodontal risk calculation and frame its potential, as well as its limitations, in the context of similar advances in medical care.

Negative ion properties of trans 2,2',6,6'-tetrafluoroazobenzene: Experiment and theory.

Chemical bonding and the electronic structure of the trans 2,2',6,6'-tetrafluoroazobenzene negative ion have been studied using collision-induced dissociation as well as photodetachment-photoelectron spectroscopy and the experimental results for different properties were compared with the corresponding values calculated using ab initio quantum chemistry methods. The trans 2,2',6,6'-tetrafluoroazobenzene anion was prepared by atmospheric pressure chemical ionization for the collision induced dissociation (CID) experiment and through thermal electron attachment in the photodetachment-photoelectron spectroscopy experiments. The adiabatic electron affinity of trans 2,2',6,6'-tetrafluoroazobenzene was measured to be 1.

Business Barriers and Opportunities for Transforming to Preventive Care to Treat Early Childhood Caries.

Primary, secondary, and tertiary preventive dental services have the potential for achieving the triple aim of better health outcomes for populations, better patient experience of care, and lower per capita costs. Yet, maximization of preventive services has not occurred in dental practice nor been promoted by dental plans. While the lack of such things as diagnostic codes, caries classification systems, and validated risk assessment tools are barriers to increasing preventive care, they may not be the primary barriers that need to be addressed.

Structure and stability of phenoxide and fluorophenoxide anions investigated with infrared multiple-photon dissociation and detachment spectroscopy and tandem mass spectrometry.

The gas-phase infrared multiple-photon dissociation and detachment (IRMPD) vibrational action spectra of the unsubstituted phenoxide anion and a series of fluorine- and trifluoromethyl-substituted phenoxide anions in the spectral region between 600 and 1800 cm(-1) are presented along with density functional theory (DFT) harmonic vibrational frequency calculations to establish the characteristic vibrations of the phenoxide functionality. The fluorophenoxide anions studied include the conjugate bases of o-, m-, and p-fluorophenol (C6H4FO(-)) as well as o-, m-, and p-α,α,α-trifluorocresol (CF3C6H4O(-)). The influence of the substituent on the characteristic vibrational frequencies is interpreted in terms of inductive and resonance shifts.

Laser multiphoton ionization of tetrakis(dimethylamino)ethylene.

The tetrakis(dimethylamino)ethylene (TDAE) molecule possesses the lowest known molecular ionization potential (<5.4 eV) and exhibits an intense Rydberg series between the first and second ionization limit (∼14 eV). The ionization of TDAE using multiphoton ionization photoelectron spectroscopy was carried out using laser light at a variety of wavelengths with a hemispherical energy analyzer.

Synthesis, characterization, and reversible hydrogen sorption study of sodium-doped fullerene.

Herein is presented a novel, straightforward route to the synthesis of an alkali metal-doped fullerene as well as a detailed account of its reversible and enhanced hydrogen sorption properties in comparison to pure C60. This work demonstrates that a reaction of sodium hydride with fullerene (C60) results in the formation of a sodium-doped fullerene capable of reversible hydrogen sorption via a chemisorption mechanism. This material not only demonstrated reversible hydrogen storage over several cycles, it also showed the ability to reabsorb over three times the amount of hydrogen (relative to the hydrogen content of NaH) under optimized conditions.

Negative ions of p-nitroaniline: photodetachment, collisions, and ab initio calculations.

The structures of parent anion, M(-), and deprotonated molecule, [M-H](-), anions of the highly polar p-nitroaniline (pNA) molecule are studied experimentally and theoretically. Photoelectron spectroscopy (PES) of the parent anion is employed to estimate the adiabatic electron affinity (EAa = 0.75 ± 0.

Stability of gas-phase tartaric acid anions investigated by quantum chemistry, mass spectrometry, and infrared spectroscopy.

In an effort to understand the chemical factors that stabilize dianions, experimental and theoretical studies on the stability of the tartrate dianion were performed. Quantum chemical calculations at the coupled cluster level reveal only a metastable state with a possible decomposition pathway (O(2)C-CH(OH)-CH(OH)-CO(2))(2-) → (O(2)C-CH(OH)-CH(OH))(•-) + CO(2) + e(-) explaining the observed gas-phase instability of this dianion. Further theoretical data were collected for the bare dianion, this molecule complexed to water, sodium, and a proton, in both the meso and l forms as well as for the uncomplexed radical anion and neutral diradical.

Synthesis and characterization of a lithium-doped fullerane (Li(x)-C60-H(y)) for reversible hydrogen storage.

Herein, we present a lithium-doped fullerane (Li(x)-C(60)-H(y)) that is capable of reversibly storing hydrogen through chemisorption at elevated temperatures and pressures. This system is unique in that hydrogen is closely associated with lithium and carbon upon rehydrogenation of the material and that the weight percent of H(2) stored in the material is intimately linked to the stoichiometric ratio of Li:C(60) in the material. Characterization of the material (IR, Raman, UV-vis, XRD, LDI-TOF-MS, and NMR) indicates that a lithium-doped fullerane is formed upon rehydrogenation in which the active hydrogen storage material is similar to a hydrogenated fullerene.

Aqueous fullerene aggregates (nC60) generate minimal reactive oxygen species and are of low toxicity in fish: a revision of previous reports.

This review aims to clarify inconsistencies in previous reports regarding the potential for aqueous aggregates of fullerenes (nC60) to generate reactive oxygen species (ROS) and cause toxicity in fish. Methods for evaluation of ROS production and toxicity of aqueous nC60 have evolved over time and limitations in initial studies have led to unintentional erroneous reports of nC60 ROS generation and toxicity. Some of these reports continue to lead to misconceptions of the environmental effects of C60.

The association between nC60 and 17α-ethinylestradiol (EE2) decreases EE2 bioavailability in zebrafish and alters nanoaggregate characteristics.

Manufactured nanoparticles (NPs) released into surface waters will associate with other substances and these interactions may affect environmental fate and bioavailability of NPs and the associated substances. We investigated the association between aqueous aggregates of C(60) (nC(60)) and synthetic estrogen, 17α-ethinylestradiol (EE2), and considered nC(60) physicochemistry and EE2 bioavailability (by measuring vitellogenin (vtg1A/B) gene expression) in zebrafish. Bioavailability of EE2 was reduced with increasing concentration of nC(60) (P < 0.

No bioavailability of 17α-ethinylestradiol when associated with nC60 aggregates during dietary exposure in adult male zebrafish (Danio rerio).

The C(60) fullerene is a manufactured carbon nanoparticle (CNP) that could pose a risk to humans and other organisms after release into the environment. In surface waters, C(60) is likely to be present as aggregates of nC(60) and these aggregates can associate with other substances that are toxic. Our goal was to evaluate the association of a model contaminant [17α-ethinylestradiol (EE2)] with nC(60) and determine bioavailability of EE2 after accumulation by a filter feeding organism [Brine shrimp (BS) Artemia sp.

Anti-inflammatory properties of a novel N-phenyl pyridinone inhibitor of p38 mitogen-activated protein kinase: preclinical-to-clinical translation.

Signal transduction through the p38 mitogen-activated protein (MAP) kinase pathway is central to the transcriptional and translational control of cytokine and inflammatory mediator production. p38 MAP kinase inhibition hence constitutes a promising therapeutic strategy for treatment of chronic inflammatory diseases, based upon its potential to inhibit key pathways driving the inflammatory and destructive processes in these debilitating diseases. The present study describes the pharmacological properties of the N-phenyl pyridinone p38 MAP kinase inhibitor benzamide [3- [3-bromo-4-[(2,4-difluorophenyl)methoxy]-6-methyl-2- oxo-1(2H)-pyridinyl]-N,4-dimethyl-, (-)-(9CI); PH-797804].

SD0006: a potent, selective and orally available inhibitor of p38 kinase.

SD0006 is a diarylpyrazole that was prepared as an inhibitor of p38 kinase-alpha (p38alpha). In vitro, SD0006 was selective for p38alpha kinase over 50 other kinases screened (including p38gamma and p38delta with modest selectivity over p38beta). Crystal structures with p38alpha show binding at the ATP site with additional residue interactions outside the ATP pocket unique to p38alpha that can confer advantages over other ATP competitive inhibitors.

Structural bioinformatics-based prediction of exceptional selectivity of p38 MAP kinase inhibitor PH-797804.

PH-797804 is a diarylpyridinone inhibitor of p38alpha mitogen-activated protein (MAP) kinase derived from a racemic mixture as the more potent atropisomer (aS), first proposed by molecular modeling and subsequently confirmed by experiments. On the basis of structural comparison with a different biaryl pyrazole template and supported by dozens of high-resolution crystal structures of p38alpha inhibitor complexes, PH-797804 is predicted to possess a high level of specificity across the broad human kinase genome. We used a structural bioinformatics approach to identify two selectivity elements encoded by the TXXXG sequence motif on the p38alpha kinase hinge: (i) Thr106 that serves as the gatekeeper to the buried hydrophobic pocket occupied by 2,4-difluorophenyl of PH-797804 and (ii) the bidentate hydrogen bonds formed by the pyridinone moiety with the kinase hinge requiring an induced 180 degrees rotation of the Met109-Gly110 peptide bond.

Gas-phase infrared multiple photon dissociation spectroscopy of isolated SF6- and SF5- anions.

Resonantly enhanced multiple photon dissociation of gas-phase SF(6) (-) and SF(5) (-) is studied using tunable infrared light from the FELIX free electron laser. The photodissociation spectrum of the sulfur hexafluoride anion, producing SF(5) (-), is recorded over the spectral range of 250-1650 cm(-1). The infrared multiple photon dissociation cross section exhibits a strong, broad resonance enhancement at 675 cm(-1) in agreement with the calculated value of nu(3), one of the two IR-active fundamental vibrational modes predicted for the O(h)-symmetry ion.

2-(6-Phenyl-1H-indazol-3-yl)-1H-benzo[d]imidazoles: design and synthesis of a potent and isoform selective PKC-zeta inhibitor.

The inhibition of PKC-zeta has been proposed to be a potential drug target for immune and inflammatory diseases. A series of 2-(6-phenyl-1H indazol-3-yl)-1H-benzo[d]imidazoles with initial high crossover to CDK-2 has been optimized to afford potent and selective inhibitors of protein kinase c-zeta (PKC-zeta). The determination of the crystal structures of key inhibitor:CDK-2 complexes informed the design and analysis of the series.

Electron ionization time-of-flight mass spectrometry: historical review and current applications.

This review presents an overview of electron ionization time-of-flight mass spectroscopy (EITOFMS), beginning with its early development to the employment of modern high-resolution electron ionization sources. The EITOFMS is demonstrated to be ideally suited for analytical and basic chemical physics studies. Studies of the formation of positive ions by electron ionization time-of-flight mass spectroscopy have been responsible for many of the known ionization potentials of molecules and radicals, as well as accepted bond dissociation energies for ions and neutral molecules.

Synthesis, crystal structure, and activity of pyrazole-based inhibitors of p38 kinase.

A series of pyrazole inhibitors of p38 mitogen-activated protein (MAP) kinase were designed using a binding model based on the crystal structure of 1 (SC-102) bound to p38 enzyme. New chemistry using dithietanes was developed to assemble nitrogen-linked substituents at the 5-position of pyrazoles. Calculated log D was used in tandem with structure-based design to guide medicinal chemistry strategy and improve the in vivo activity of a series of molecules.