Bipolar pulse conductometric monitoring of ion-selective electrodes: Part 1. Method development with a calcium-selective electrode and elucidation of the basic principles involved

The potential generated by a plastic-membrane calcium ion-selective electrode (i.s.e.) is shown to be indirectly measurable by a non-zero current method based on bipolar pulse conductance. Linear current—voltage curves are obtained using 0–5-V pulses; the current axis intercept is related to the i.s.e. potential. A simple electrical contact (e.g., platinum or stainless steel) can be used instead of a poised reference electrode as the counter electrode in this two-electrode system. Long-term exposure of the i.s.e. to calcium solutions causes an upward drift in the measured current. This drift is minimized by avoiding long exposure times to solution, rinsing the electrode between measurements, and constructing current—voltage curves for determination of the current axis intercepts. Voltage pulses lasting 100 μs are optimum for this method. Shorter pulses are subject to error from capacitive charging currents, and longer pulses yield poorer precision, and degrade the electrode through faradaic reactions. The measured signal is dependent upon Ca²⁺ concentration (rather than activity), making ionic strength adjustment unnecessary. The concentration dependence is induced by application of voltage pulses greater than ~ 15 mV in amplitude. Selectivities of the potentiometric and conductometric methods are shown to be comparable for a variety of interfering monovalent and divalent cations. The conductometric method yields a fast i.s.e. response because of induced migration of Ca²⁺ into the membrane. Response time decreases as the pulse height increases. Pulses greater than 2 V in magnitude yield response times limited by the solution mixing time rather than by the electrode.     

Determination of perfluorooctanoic acid (PFOA) extractable from the surface of commercial cookware under simulated cooking conditions by LC/MS/MS

Salts of pentadecafluorooctanoic acid (PFOA) are polymerization aids used in the manufacture of fluoropolymers; one of the applications of fluoropolymers is the coating of metal cookware products. A method was developed to determine if PFOA might be present in and extracted from the surface of commercial frying pans coated with a DuPont fluoropolymer under simulated cooking conditions. Commercial grade cookware was obtained, then extracted with water and ethanol/water mixtures at 100 and 125 degrees C, and the resulting extracts were analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS). Detection and quantification limits as low as 100 pg cm(-2) were demonstrated. None of the fluoropolymer treated cookware samples analyzed showed detectable levels of PFOA when extracted under simulated cooking conditions.     

Differential inhibition of postnatal brain,spinal cord and body growth by a growth hormone antagonist

Background  

Growth hormone (GH) plays an incompletely understood role in the development of the central nervous system (CNS). In this study, we use transgenic mice expressing a growth hormone antagonist (GHA) to explore the role of GH in regulating postnatal brain, spinal cord and body growth into adulthood. The GHA transgene encodes a protein that inhibits the binding of GH to its receptor, specifically antagonizing the trophic effects of endogenous GH.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

NHC‐Stabilised Silyliumylidene Ions

Donor‐stabilised silyliumylidene ions, from the parent [R?Si:]⁺, are a class of low‐valent silicon species which have received increasing research interest in the last several years. This interest began in the fundamental synthesis and characterisation of these compounds, but has since started to include more investigation into their further reactivity after several stable NHC‐stabilised silyliumylidene ions were reported. This personal account briefly discusses the history of the still‐young field of silyliumylidene ions followed by a more detailed discussion of published work from our group on the further development of silyliumylidene chemistry over the last four years.     

Detection of human and rodent 5-HT3B receptor subunits by anti-peptide polyclonal antibodies

Background  

The 5-HT₃ receptor is a member of a neurotransmitter-gated ion channel family which includes nicotinic acetylcholine, GABA_A, and glycine receptors. While antibodies specific for the 5-HT_3A receptor subunit are plentiful, and have revealed a wealth of structural and functional information, few antisera exist for the detection of 5-HT_3B receptor subunits. Here we describe the generation and characterisation of a rabbit polyclonal antiserum that specifically recognises 5-HT_3B receptor subunits     

Dibenzyl Structuresin a Macromolecular Chain. III. Dibenzyldiisocyanates Reactivity

The reactivity of the 2,2′-, 2,4′-, 4,4′-dibenzyldiisocyanate (2,2′-, 2,4′-, 4,4′-DBDI) with n-butanol in benzene has been studied. The concentrations of all species were monitored by using high performance liquid chromatography (HPLC). The reactivity of 4,4′-DBDI is similar to that of 4,4′-diphenylmethanediisocyanate (4,4′-MDI). Very strong intramolecular catalytic effects were noticed in the case of 2,2′-DBDI, probably due to the variable molecular geometry. These effects are responsible for the whole reaction pattern. The 2,4′-DBDI NCO ortho and para groups reactivities are different and comparable to that of 2,4-toluylenediisocyanate (2,4-TDI).     

Fractal-time stochastic processes and dynamic functions of polymeric systems

Dynamic material functions of polymeric systems are calculated via a defect-diffusion model. The random motion of defects is modelled by a fractaltime stochastic process. It is shown that the dynamic functions of polymeric solutions can be approximated by the defect-diffusion process of the mixed type. The relaxation modulus of Kohlrausch type is obtained for a fractal-time defect-diffusion process, and it is shown that this modulus is capable of portraying the dynamic behavior of typical viscoelastic solutions.The Fourier transforms of the Kohlrausch function are calculated to obtain and. A three-parameter model for and is compared with the previous calculations. Experimental measurements for five polymer solutions are compared with model predictions. D rate of deformation tensor - G(t) mechanical relaxation modulus - H relaxation spectrum - I(t) flux of defects - P _n (s) probability of finding a walker ats aftern-steps - P generating function ofP _n (s) - s(t) fraction of surviving defects - , () gamma function (incomplete) - ₀ zero shear viscosity - ^* () complex viscosity - frequency - t _n n-th moment - F[] Fourier transform - f ^* (u) Laplace transform off(t) - , components of ^* - G _f, _f ^* fractional model - G ₃, ₃ ^* three parameter model - complex conjugate ofz - material time derivative ofD     

Bipolar pulse conductometric monitoring of ion-selective electrodes: Part 2. Studies with the fluoride-selective electrode

Bipolar pulse conductometric monitoring of the fluoride ion-selective electrode (i.s.e.) is evaluated. It is shown that fluoride ion, in addition to affecting the electrode potential, also can have two effects upon the total resistance of the electrode. Fluoride ion can enter a gel layer on the surface of the doped lanthanum fluoride crystal; solution concentrations as low as 10^-9 M fluoride can significantly decrease the gel resistance. Fluoride concentrations in the potentiometric working range of the i.s.e. can also increase the electrode resistance. The conductometric detection limit is 2–4 decades lower than the potentiometric detection limit. However, because of the resistance factors, the conductometric curve is not monotonic, and shows a maximum at a fluoride concentration in the vicinity of the potentiometric detection limit. The two resistive changes possible have different time dependences; the decrease of the gel layer resistance becomes predominant at long measurement times, while the increase of the crystal resistance predominates within the first minute of exposure to solution. Hydroxide is shown to affect the i.s.e. potential and lower the gel layer resistance. Response time to changes in fluoride concentration are less than 15 s and do not show the strong concentration dependence observed potentiometrically. The i.s.e. is shown to have a slightly lower resistance to fluoride entering the crystal than to fluoride leaving it. The small resistive dependence on direction of ion migration may indicate a directional dependence of activation energy for ion transport across the membrane solution interfaces.