Line Shift Investigations for Different Isotopomers of Carbon Monoxide

Line shift coefficients for five lines of five different isotopomers in the fundamental band of CO in the spectral region near 2058 cm⁻¹were measured using a three channel lead salt diode laser spectrometer. The study includes the linesP(3) of¹³C¹⁷O,R(3) of¹³C¹⁸O,P(9) of¹²C¹⁸O,P(10) of¹³C¹⁶O, andP(21) of¹²C¹⁶O, and covers collisions with N₂, O₂, H₂, D₂, He, Ne, Ar, Kr, and Xe. Line shifts of the isotopomers¹³C¹⁶O,¹²C¹⁸O,¹³C¹⁸O, and¹³C¹⁷O were determined for the first time. Within the experimental uncertainty no significant dependence of the shift effect on the isotopomer was found. TheR-branch line under study shows a smaller line shift coefficient than aP-branch line with a similar rotational quantum number. With increasing mass of the noble gas perturber the absolute size of the shift coefficient increases. Moreover self- and nitrogen-broadening coefficients for the isotopomer lines were determined. Compared to previous measurements no significant deviations between different isotopomers were observed.     

Macroscopic limits for stochastic partial differential equations of McKean–Vlasov type

A class of quasilinear stochastic partial differential equations (SPDEs), driven by spatially correlated Brownian noise, is shown to become macroscopic (i.e., deterministic), as the length of the correlations tends to 0. The limit is the solution of a quasilinear partial differential equation. The quasilinear SPDEs are obtained as a continuum limit from the empirical distribution of a large number of stochastic ordinary differential equations (SODEs), coupled though a mean-field interaction and driven by correlated Brownian noise. The limit theorems are obtained by application of a general result on the convergence of exchangeable systems of processes. We also compare our approach to SODEs with the one introduced by Kunita.     

Characterization of optimized Na+ and Cl− liquid membranes for use with extracellular, self-referencing microelectrodes

Self-referencing with ion-selective microelectrodes (ISMs) is a useful approach for monitoring near-real-time ion flux near single cells and across epithelia. While ISMs for H⁺, Ca²⁺, and K⁺ have been optimized for use with self-referencing, ISMs for two other primary inorganic ions, Na⁺ and Cl⁻, have not. In this study, we have characterized ISMs based on three Na⁺ ionophores (I, VI, and X) and one Cl⁻ ionophore to assess their suitability for use with self-referencing. ISMs constructed with Na⁺ ionophore VI have short response times (≈100 ms) but possess nearly an order of magnitude less selectivity for Na⁺ over K⁺ than ISMs constructed with Na⁺ ionophore X. The Na⁺ ionophore X mixture was enhanced to give it a shorter response time while not compromising its selectivity. A Cl⁻-selective microelectrode was constructed and characterized with superior anionic selectivity compared with previously reported Cl⁻ ISMs used with self-referencing. This Cl⁻-selective microelectrode, however, has a relatively slow response time (≈3 s), thus requiring changes to the self-referencing protocol. Self-referencing with these ISMs will enable near-real-time ion flux measurements for Na⁺ and Cl⁻.     

Bulk and single-molecule characterization of an improved molecular beacon utilizing H-dimer excitonic behavior

Pairs of fluorophores in close proximity often show self-quenching of fluorescence by the well-known H-dimer mechanism. We use a pair of fluorophores in the new dicyanomethylenedihydrofuran (DCDHF) dye family in the design and characterization of a new fluorescent probe for nucleic acid detection, which we refer to as a self-quenched intramolecular dimer (SQuID) molecular beacon (MB). We obtain a quenching efficiency of 97.2%, higher than the only other reported value for a MB employing fluorophore self-quenching by H-dimer formation. Furthermore, the excellent single-molecule (SM) emitter characteristics of the DCDHF dyes allow observation of individual SQuID MB-target complexes immobilized on a surface, where the doubled SM emission intensity of our target-bound beacon ensures a higher signal-to-background ratio than conventional fluorophore-quencher MBs. Additional advantages of the SQuID MB are single-pot labeling, visible colorimetric detection of the target, and intrinsic single-molecule two-step photobleaching behavior, which offers a specific means of discriminating between functional MBs and spurious fluorescence.