Optical detection of NO3 and NO2 in “pure” HNO3 vapor,the liquid-phase decomposition of HNO3

Flowing and static gas-phase samples of HNO₃ in O₂ and N₂ were analyzed by long-path ultraviolet/visible (UV/VIS) spectroscopy to reveal the presence of both NO₂ and NO₃, the concentrations of which were calculated using differential absorption cross sections. NO₂ is produced predominantly by the heterogeneous decomposition of HNO₃, whereas NO₃ is generated in the gas phase by the thermal decomposition of N₂O₅, a product of the self-disproportionation of liquid HNO₃. © 1993 John Wiley & Sons, Inc.     

Anatoxins and degradation products, determined using hybrid quadrupole time-of-flight and quadrupole ion-trap mass spectrometry: forensic investigations of cyanobacterial neurotoxin poisoning

The potent neurotoxins from cyanobacteria, anatoxin-a (AN), its methyl analogue, homoanatoxin-a (HMAN), and their degradation products, have been studied using nano-electrospray hybrid quadrupole time-of-flight mass spectrometry (QqTOF-MS). The anatoxin degradation products, which are readily produced in vivo by either reduction or epoxidation, were also examined in this study. The high mass accuracy QqTOF-MS data was used to confirm formula assignments for major product ions and quadrupole ion-trap (QIT)-MS was used to construct fragmentation pathways for anatoxins. Significant differences between these fragmentation pathways were observed. Comparisons between the spectra of compounds that differ in side-chain length (the AN and HMAN series) were used to identify ions that are characteristic of the homologues. The application to forensic samples in which the principal neurotoxin had undergone rapid biodegradation has been demonstrated and used to confirm anatoxin poisoning of dogs.     

Solid Phase Synthesis. Evidence for and Quantification of Intra res in Reactions

Abstract

Intrareaction occurs between moieties attached to copolystyrene-2% divinylbenzene resin as used in solid phase synthesis even when only 0.5% of the phenyl residues are functionalized. Evidence for this interaction has been obtained from the dimeric products resulting from Dieckmann cyclization of resin bound sebacates and ω-cyanopelargonyl thiol resin esters, from kinetic and product data on radioactivity scrambling during the Dieckmann cyclization of uniquely singly labeled tertiary alkyl pimeloyl resin esters, and from anhydride formation with carboxymethyl resin. The extent to which site-site interactions can occur as a function of the percentage functionalization has been measured quantitatively by radiotracer studies on intraresin anhydride formation from carboxymethyl substituted resin. The synthesis and characterization of the resin bound re-actants is described, and the significance of these observations is discussed.     

Investigating microcrystalline cellulose crystallinity using Raman spectroscopy

Cellulose - Microcrystalline cellulose (MCC) is a semi-crystalline material with inherent variable crystallinity due to raw material source and variable manufacturing conditions. MCC crystallinity...     

Planar 2‐Pyridyl‐1,2,3‐triazole Derived Metallo‐ligands: Self‐assembly with PdCl2 and Photocatalysis

Self‐assembled metallosupramolecular architectures (MSAs) with built‐in functionalities such as light‐harvesting metal centers are a promising approach for developing emergent properties within discrete molecular systems. Herein we describe the synthesis of two new but simple “click” ligands featuring a bidentate 2‐pyridyl‐1,2,3‐triazole chelate pocket linked to a monodentate pyridyl (either 3‐ or 4‐substituted, L1 and L2 ) unit. The ligands and the corresponding four Pd^IIand Pt^IImetallo‐ligands ( Pd1 , Pd2 , Pt1 and Pt2 ) were synthesized and characterized using nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and X‐ray crystallography. Solid‐state characterization of the series of ligands and metallo‐ligands revealed that these compounds display a co‐planar conformation of all the aryl units. The Pt^IIcontaining metallo‐ligands ( Pt1 and Pt2 ) were found to assemble into square ( Sqr ) and triangular ( Tri ) shaped architectures when combined with neutral PdCl₂ linker units. Additionally, the ability of the Pt^IImetallo‐ligands and Tri to photocatalyze the cycloaddition of singlet oxygen to anthracene was investigated.     

A unified semiclassical description of elastic scattering by a central field

The diffraction-integral formulation of the semiclassical limit of the quantal wavefunction, as proposed in an earlier paper, is applied to the treatment of elastic scattering by a general central-field potential. Angular-momentum quantisation is shown to be a natural consequence of the theory and partial-wave series representations of the s-matrix and asymptotic wavefunction are derived. In addition, the method and results establish a connection between refractive, diffractive, dynamical and uniform-approximation theories of semiclassical scattering.     

Molecular recognition. Electrostatic effects in supramolecular self-assembly

A di-positively charged metal-based receptor is shown to form 1:1 or 2:1 association complexes with rigid, linear two-site guests depending on the site separation, suggesting that electrostatic repulsion controls the association nuclearity.     

The Photophysics of Thin Polymer Films of Poly-(meta-phenylene-co-2,5-dioctoxy-para-phenylenevinylene)

Summary.  We have investigated the effect of film preparation procedures on the photoluminescence efficiency of the luminescent co-polymer poly-(m-phenylene-co-2,5-dioctoxy-p-phenylenevinylene) (PmPV). The photoluminescence efficiency of PmPV films improved by up to 50% when the solution was degassed by bubbling argon gas through it prior to spin casting in an inert atmosphere and baking under vacuum. Photoinduced absorption and doping measurements show that this preparation method reduces polaron photogeneration, which reduces the photoluminescence (PL) yield through exciton quenching and excited state absorption. It is proposed that this sample preparation method increases interchain separation, reducing the formation of polarons and non-radiative quenching routes, thus resulting in increased PL efficiency. Received June 23, 2000. Accepted (revised) August 3, 2000     

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.