Gas-phase structures and mass spectra of binary pentafluorides

Most known non-radioactive pentafluorides have been examined by molecular-beam mass spectrometry and by the deflection of molecular beams in inhomogeneous electric fields. Extensive association of the vapors occurs for all but the lighter pentafluorides and the interhalogens. The interhalogen pentafluorides are strongly polar, consistent with the accepted C_4v symmetry. The transition-metal and Group V pentafluorides are all non-polar, except VF₅ and CrF₅ for which temperature-dependent polarity is observed. However, uncertainty exists as to whether these observations are applicable to monomeric pentafluorides in all cases. Mass-spectral cracking patterns are presented for all species.     

Infrared vibration-rotation spectrum and structure of OCS dimer

Direct observations of infrared absorption in the weakly bound dimer of carbonyl sulphide, produced in pulsed molecular beams, have been made. Diode laser spectra in the 5 micron, carbonyl stretching, wavelength region were recorded with FWHM linewidths of approximately 100 MHz. All of the observations are consistent with OCS dimer having a C _2h , centrosymmetric geometry, with the centres of mass of the monomers nearly opposite one another. This essentially perpendicular structure places the S atoms close to the centre of the complex. The perpendicular distance between the monomer axes is 3·64 Å. Intermolecular potential functions containing dispersion and electrostatic contributions are discussed.     

Integral equation formulation for buoyancy-driven convection problems

An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.     

Permanently oriented antibody immobilization for digoxin determination with a flow-through fluoroimmunosensor

This paper reports a new flow-through fluoroimmunosensor, the function of which is based on antibodies immobilized on an inmunoreactor of controlled-pore glass (CPG), for determination of digoxin, used in the treatment of congestive heart failure and artery disease. The immunosensor has a detection limit of 1.20 microg L(-1) and provides high reproducibility (RSD=4.5% for a concentration of 0.0025 mg L(-1), and RSD=6.7% for 0.01 mg L(-1)). The optimum working concentration range was found to be 1.2 x 10(-3)-4.0 x 10(-2) mg L(-1). The lifetime of the immunosensor was about 50 immunoassays; if stored unused its lifetime can be extended to three months. A sample speed of about 10-12 samples per hour can be attained. Possible interference from substances with structures similar to digoxin (morphine, heroin, tebaine, codeine, pentazocine and narcotine) was investigated. No cross-reactivity was seen at the highest digoxin: interferent ratio studied (1:100). The proposed fluoroimmunosensor was successfully used to determine digoxin concentrations in human serum samples.     

Collisions of DCl with pure and salty glycerol: enhancement of interfacial D --> H exchange by dissolved NaI

The fate of DCl molecules striking pure glycerol and a 2.6 M NaI-glycerol solution is investigated using scattering, uptake, and residence time measurements. We find that dissolved Na+ and I- ions alter every gas-liquid pathway from the moment of contact of DCl with the surface to its eventual emergence as HCl. In particular, the salt enhances both trapping-desorption of DCl and interfacial DCl --> HCl exchange at the expense of DCl entry into the bulk solution. The reduced entry and enhanced desorption of thermalized DCl molecules are interpreted by assuming that Na+ and I- ions bind to interfacial OH groups and tie up surface sites that would otherwise capture incoming DCl molecules. These ion-glycerol interactions may also be responsible for enhancing interfacial D --> H exchange by disrupting the interfacial hydrogen bond network that carries the newly formed H+ ion away from its Cl- pair. This disruption may increase the fraction of interfacial Cl- and H+ that recombine and desorb immediately as HCl before the ions separate and diffuse deeply into the bulk.     

l-type doubling transitions in Δ states of OCS

Molecular beam electric resonance spectroscopy has been used to measure the l-type doubling transitions in carbonyl sulfide. Transitions in J = 4 to J = 20 have been observed for the (02²0) vibrational state and for J = 1 and J = 2 for the (03¹0) state. The data has been analyzed to give the v = 2 energy separation $\text{E}{}_{\mathrm{<mtext>\Delta </mtext>}}{}^0\text{- E}{}_{\mathrm{<mtext>\Sigma </mtext>}}{}^0\text{= ?5.7861(2) + 8.36(1) × 10}{}^{\mathrm{?5}}\text{J(J + 1)}\text{cm}{}^{\mathrm{?1}}$, and the vibrational dependence of q to be 86.52(9)(v₂ + 1) KHz. The dipole moment of the (02²0) vibrational state is 0.6936(3) D.