Theoretical and Experimental Determination of the Proton Affinity of (CF3CH2)2O

We report the experimental determination of the proton affinity of the molecule (CF3CH2)2O using chemical ionization mass spectrometry, and we compare it to the theoretical value obtained for protonation at the oxygen atom using the calculational methodology (MP2/6-31G**//MP2/3-21G). The proton affinity for this molecule as measured by bracketing experiments was between 724 kJ/mole and 741 kJ/mole. Ab initio (MP2/6-31G**//MP2/3-21G) calculations yield a value of about 729 kJ/mole, in agreement with the chemical ionization experiments. The results of these and related calculations suggest that the (MP2/6-31G**//MP2/3-21G) methodology is acceptable for estimating the proton affinities of partially-and fully-fluorinated methyl and ethyl ethers. We submit that any conclusions about the chemistry of fluoroether polymer lubricants based on their basicity can also be predicted reliably with such calculations

Experimental and Calculational Studies of the Interactions of BF3 with Fluoroethers

BF3 was co-condensed with (C2H5)2O, (CF3CH2)2O and (C2F5)2O in excess argon at 15 K. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis(2,2,2,-trifluorodiethyl)ether, and no observable interaction with perfluorodiethyl ether. Molecular orbital (MO) calculations complemented the experimental observations by revealing that fluorine atoms on the ethers decreased electron localization about the oxygen atom. Thus, the experimental data and MO calculations indicated a clear trend between strength of interaction with BF3 and the degree of ether F substitution. The implications of the results for commercial perfluoro ether lubricant/metal oxide surface interactions are discussed

Optimized Structures and Proton Affinities of Fluorinated Dimethyl Ethers: An Ab Initio Study

Ab initio methods have been used to investigate the proton affinity and the geometry changes upon protonation for the molecules (CH3)2O, (CH2F)2O, (CHF2)2O, and (CF3)2O. Geometry optimizations were performed at the MP2/3-2 I G level, and the resulting geometries were used for single-point energy MP2/6-31G calculations. The proton affinity calculated for (CH3)2O was 7 Kjoule/mole from the experimental value, within the desired variance of +/- 8Kjoule/mole for G2 theory, suggesting that the methodology used in this study is adequate for energy difference considerations. For (CF3)20, the calculated proton affinity of 602 Kjoule/mole suggests that perfluorinated ether molecules do not act as Lewis bases under normal circumstances; e.g. degradation of commercial lubricants in tribological applications

Electron Affinity Calculations for Thioethers

Previous work indicated that polyphenyl thioethers possessed chemical properties, related to their electron affinities, which could allow them to function as vapor phase lubricants (VPL). Indeed, preliminary tribological tests revealed that the thioethers could function as vapor phase lubricants but not over a wide temperature and hertzian pressure range. Increasing the electron affinity of the thioethers may improve their VPL properties over this range. Adding a substituent group to the thioether will alter its electron affinity in many cases. Molecular orbital calculations were undertaken to determine the effect of five different substituent groups on the electron affinity of polyphenyl thioethers. It was found that the NO2, F, and I groups increased the thioethers electron affinity by the greatest amount. Future work will involve the addition of these groups to the thioethers followed by tribological testing to assess their VPL properties

On selection criteria for problems with moving inhomogeneities

We study mechanical problems with multiple solutions and introduce a thermodynamic framework to formulate two different selection criteria in terms of macroscopic energy productions and fluxes. Studying simple examples for lattice motion we then compare the implications for both resting and moving inhomogeneities.Comment: revised version contains new introduction, numerical simulations of Riemann problems, and a more detailed discussion of the causality principle; 18 pages, several figure

Andrew Melville, sacred chronology and world history: the Carmina Danielis 9 and the Antichristus

The accepted view of the ecclesiastical reformer Andrew Melville (1545–1622) as the dynamic leader of the Presbyterian movement in Jacobean Scotland has been severely eroded in recent years, with particular criticism of the actual importance of his contribution to the Kirk and to Scottish higher education. While this reductionism has been necessary, it has resulted in an inversion of the overwhelmingly positive traditional image of Melville, and does not give us a rounded assessment of his life and works. This article attempts to partially redress this balance by looking at a neglected aspect of Melville's Latin writings, which showcase his talents as a humanist intellectual and biblical commentator. It focuses on two long poems that are both commentaries and paraphrases of Daniel and Revelation: the Carmina Danielis and the Antichristus. Through these poems, we see how Melville engaged with two problems exercising reformed theologians across Europe: the dating of key biblical events and the historicised meaning of prophecies within these texts. We also find evidence that Melville read widely among both contemporary and ancient commentators on both these issues

ArborZ: Photometric Redshifts Using Boosted Decision Trees

Precision photometric redshifts will be essential for extracting cosmological parameters from the next generation of wide-area imaging surveys. In this paper we introduce a photometric redshift algorithm, ArborZ, based on the machine-learning technique of Boosted Decision Trees. We study the algorithm using galaxies from the Sloan Digital Sky Survey and from mock catalogs intended to simulate both the SDSS and the upcoming Dark Energy Survey. We show that it improves upon the performance of existing algorithms. Moreover, the method naturally leads to the reconstruction of a full probability density function (PDF) for the photometric redshift of each galaxy, not merely a single "best estimate" and error, and also provides a photo-z quality figure-of-merit for each galaxy that can be used to reject outliers. We show that the stacked PDFs yield a more accurate reconstruction of the redshift distribution N(z). We discuss limitations of the current algorithm and ideas for future work.Comment: 10 pages, 13 figures, submitted to Ap

MRI radiomic features are independently associated with overall survival in soft tissue sarcoma

Purpose: Soft tissue sarcomas (STS) represent a heterogeneous group of diseases, and selection of individualized treatments remains a challenge. The goal of this study was to determine whether radiomic features extracted from magnetic resonance (MR) images are independently associated with overall survival (OS) in STS. Methods and Materials: This study analyzed 2 independent cohorts of adult patients with stage II-III STS treated at center 1 (N = 165) and center 2 (N = 61). Thirty radiomic features were extracted from pretreatment T1-weighted contrast-enhanced MR images. Prognostic models for OS were derived on the center 1 cohort and validated on the center 2 cohort. Clinical-only (C), radiomics-only (R), and clinical and radiomics (C+R) penalized Cox models were constructed. Model performance was assessed using Harrell\u27s concordance index. Results: In the R model, tumor volume (hazard ratio [HR], 1.5) and 4 texture features (HR, 1.1-1.5) were selected. In the C+R model, both age (HR, 1.4) and grade (HR, 1.7) were selected along with 5 radiomic features. The adjusted c-indices of the 3 models ranged from 0.68 (C) to 0.74 (C+R) in the derivation cohort and 0.68 (R) to 0.78 (C+R) in the validation cohort. The radiomic features were independently associated with OS in the validation cohort after accounting for age and grade (HR, 2.4; Conclusions: This study found that radiomic features extracted from MR images are independently associated with OS when accounting for age and tumor grade. The overall predictive performance of 3-year OS using a model based on clinical and radiomic features was replicated in an independent cohort. Optimal models using clinical and radiomic features could improve personalized selection of therapy in patients with STS