Thermochemistry of bis-arene- and arenetricarbonyl-chromium compounds containing hexamethylbenzene, 1,3,5-trimethylbenzene and naphthalene.

Microcalorimetric measurements at elevated temperatures of the heats of thermal decomposition and iodination have led to values of the standard enthalpies of formation of the following crystalline compounds (values given in kJ mol^?1) at 298K: [Cr(η⁶-1,3,5-C₆H₃(CH₃)₃)₂] = (63±12); [Cr(η⁶-C₆(CH₃)₆)₂] : -(88±12); [Cr(1,2,3,4,4a,8a-η-C₁₀H₈)₂] = (407±11); [Cr(CO)₃(1,2,3,4,4a,8a-η-C₁₀H₈)] = -(258±8). Separate measurements by the vacuum sublimation microcalorimetric technique gave the following values for the enthalpy of sublimation at 298K (kJ mol^?1) : [Cr(η⁶-1,3,5-C₆H₃(CH₃)₃)₂] = (104±1); [Cr(η⁶-C₆(CH₃)₆)₂] = (119±4); [Cr(CO)₃(1,2,3,4,4a,8a-η-C₁₀H₈)] = (107±3). From these and other data, the bond enthalpy contributions of the metal-ligand bonds in the gaseous metal complexes were evaluated as follows: [(η₆-C₆(CH₃)₆)-Cr] (155±7); [(η⁶-C₆H₃(CH₃)₃)-Cr] (151±6); [(1,2,3,4,4a, 8a-η-C₁₀H₈)-Cr](145±6) kJ mol^?1]The question of the transferability of the enthalpy contributions of chromium—ligand bonds between organochronium complexes is discussed with aid of information from structural and spectroscopic investigation. The limitations of the procedure are defined.The thermodynamic data are used to discuss various substitution, redistribution and exchange reaction of Cr(η-arene)₂ and [Cr(CO)₃(η-arene)] compounds.     

Initial Measurements of Plasma Potential in the Core of the MST Reversed Field Pinch with a Heavy Ion Beam Probe

Measurement of the plasma potential in the core of MST marks both the first interior potential measurements in an RFP, as well as the first measurements by a Heavy Ion Beam Probe (HIBP) in an RFP. The HIBP has operated with (20-110) keV sodium beams in plasmas with toroidal currents of (200-480) kA over a wide range of densities and magnetic equilibrium conditions. A positive plasma potential is measured in the core, consistent with the expectation of rapid electron transport by magnetic fluctuations and the formation of an outwardly directed ambipolar radial electric field. Comparison between the radial electric field and plasma flow is underway to determine the extent to which equilibrium flow is governed by E×B. Measurements of potential and density fluctuations are also in progress.Unlike HIBP applications in tokamak plasmas, the beam trajectories in MST (RFP) are both three-dimensional and temporally dynamic with magnetic equilibrium changes associated with sawteeth. This complication offers new opportunity for magnetic measurements via the Heavy Ion Beam Probe (HIBP). The ion orbit trajectories are included in a Grad-Shafranov toroidal equilibrium reconstruction, helping to measure the internal magnetic field and current profiles. Such reconstructions are essential to identifying the beam sample volume locations, and they are vital in MST's mission to suppress MHD tearing modes using current profile control techniques. Measurement of the electric field may be accomplished by combining single point measurements from multiple discharges, or by varying the injection angle of the beam during single discharges.The application of an HIBP on MST has posed challenges resulting in additional diagnostic advances. The requirement to keep ports small to avoid introducing magnetic field perturbations has led to the design and successful implementation of cross-over sweep systems. High levels of ultraviolet radiation are driving alternative methods of sweep plate operation. While, substantial levels of plasma flux into the HIBP diagnostic chambers has led to the use of magnetic plasma suppression.     

Matrix characterization of oscillation for double sequences

The notion of oscillation for ordinary sequences was presented by Hurwitz in 1930. Using this notion Agnew and Hurwitz presented regular matrix characterization of the resulting sequence space. The primary goal of this article is to extend this definition to double sequences, which grants us the following definition: the double oscillation of a double sequence of real or complex number is given P-lim sup_{(m,n)→∞;(α,β)→∞}|S _m,n -S _α,β |. Using this concept a matrix characterization of double oscillation sequence space is presented. Other implication and variation shall also be presented.      

Associations between Neurocardiovascular Signal Entropy and Physical Frailty

In this cross-sectional study, the relationship between noninvasively measured neurocardiovascular signal entropy and physical frailty was explored in a sample of community-dwelling older adults from The Irish Longitudinal Study on Ageing (TILDA). The hypothesis under investigation was that dysfunction in the neurovascular and cardiovascular systems, as quantified by short-length signal complexity during a lying-to-stand test (active stand), could provide a marker for frailty. Frailty status (i.e., “non-frail”, “pre-frail”, and “frail”) was based on Fried’s criteria (i.e., exhaustion, unexplained weight loss, weakness, slowness, and low physical activity). Approximate entropy (ApEn) and sample entropy (SampEn) were calculated during resting (lying down), active standing, and recovery phases. There was continuously measured blood pressure/heart rate data from 2645 individuals (53.0% female) and frontal lobe tissue oxygenation data from 2225 participants (52.3% female); both samples had a mean (SD) age of 64.3 (7.7) years. Results revealed statistically significant associations between neurocardiovascular signal entropy and frailty status. Entropy differences between non-frail and pre-frail/frail were greater during resting state compared with standing and recovery phases. Compared with ApEn, SampEn seemed to have better discriminating power between non-frail and pre-frail/frail individuals. The quantification of entropy in short length neurocardiovascular signals could provide a clinically useful marker of the multiple physiological dysregulations that underlie physical frailty.     

Electron transfer dissociation with supplemental activation to differentiate aspartic and isoaspartic residues in doubly charged peptide cations

Electron-transfer dissociation (ETD) with supplemental activation of the doubly charged deamidated tryptic digested peptide ions allows differentiation of isoaspartic acid and aspartic acid residues using the c + 57 or z ^• − 57 peaks. The diagnostic peak clearly localizes and characterizes the isoaspartic acid residue. Supplemental activation in ETD of the doubly charged peptide ions involves resonant excitation of the charge reduced precursor radical cations and leads to further dissociation, including extra backbone cleavages and secondary fragmentation. Supplemental activation is essential to obtain a high quality ETD spectrum (especially for doubly charged peptide ions) with sequence information. Unfortunately, the low-resolution of the ion trap mass spectrometer makes detection of the diagnostic peak, [M-60], for the aspartic acid residue difficult due to interference with side-chain loss from arginine and glutamic acid residues.     

A [3+2] annulation procedure for methylenecyclopentanes

A two step sequence converts certain cyclic enones to fused methylenecyclopentanes using the annulation reagent 2-chloromethyl-3-trimethylsilylpropene.