Synchronous excitation method for increasing sensitivity in fluorimetry: The Limitations caused by Raman and Rayleigh Scatter

In cases where the fluorescence of a compound is perturbed by Rayleigh scatter and by stray reflections at the exciting wavelength, the method of synchronous excitation, where the wavelengths of excitation (λ_e) and of analysis (λ_a) are scanned simultaneously with a constant step, c = λ_a - λ_e, between them, gives a distinct improvement in the measurement. When the measurement is hampered by this type of stray light and by Raman scatter simultaneously, it is shown that the technique of synchronous excitation again allows an improvement of the measurement compared to conventional techniques, if appropriate values of c are selected. The use of this technique is illustrated for the measurement of the concentration of phenol in aqueous solution; a lower limit of determination of the order of 5 ppb can be obtained.     

Alternans and higher-order rhythms in an ionic model of a sheet of ischemic ventricular muscle

Life-threatening arrhythmias such as ventricular tachycardia and fibrillation often occur during acute myocardial ischemia. During the first few minutes following coronary occlusion, there is a gradual rise in the extracellular concentration of potassium ions ([K(+)](0)) within ischemic tissue. This elevation of [K(+)](0) is one of the main causes of the electrophysiological changes produced by ischemia, and has been implicated in inducing arrhythmias. We investigate an ionic model of a 3 cmx3 cm sheet of normal ventricular myocardium containing an ischemic zone, simulated by elevating [K(+)](0) within a centrally-placed 1 cmx1 cm area of the sheet. As [K(+)](0) is gradually raised within the ischemic zone from the normal value of 5.4 mM, conduction first slows within the ischemic zone and then, at higher [K(+)](0), an arc of block develops within that area. The area distal to the arc of block is activated in a delayed fashion by a retrogradely moving wavefront originating from the distal edge of the ischemic zone. With a further increase in [K(+)](0), the point eventually comes where a very small increase in [K(+)](0) (0.01 mM) results in the abrupt transition from a global period-1 rhythm to a global period-2 rhythm in the sheet. In the peripheral part of the ischemic zone and in the normal area surrounding it, there is an alternation of action potential duration, producing a 2:2 response. Within the core of the ischemic zone, there is an alternation between an action potential and a maintained small-amplitude response ( approximately 30 mV in height). With a further increase of [K(+)](0), the maintained small-amplitude response turns into a decrementing subthreshold response, so that there is 2:1 block in the central part of the ischemic zone. A still further increase of [K(+)](0) leads to a transition in the sheet from a global period-2 to a period-4 rhythm, and then to period-6 and period-8 rhythms, and finally to a complete block of propagation within the ischemic core. When the size of the sheet is increased to 4 cmx4 cm (with a 2 cmx2 cm ischemic area), one observes essentially the same sequence of rhythms, except that the period-6 rhythm is not seen. Very similar sequences of rhythms are seen as [K(+)](0) is increased in the central region (1 or 2 cm long) of a thin strand of tissue (3 or 4 cm long) in which propagation is essentially one-dimensional and in which retrograde propagation does not occur. While reentrant rhythms resembling tachycardia and fibrillation were not encountered in the above simulations, well-known precursors to such rhythms (e.g., delayed activation, arcs of block, two-component upstrokes, retrograde activation, nascent spiral tips, alternans) were seen. We outline how additional modifications to the ischemic model might result in the emergence of reentrant rhythms following alternans. (c) 2000 American Institute of Physics.     

HPLC Characterization of the Association Mechanism of Organic Compounds with β Cyclodextrin Using a Novel Boron Nitride Nanotube Particulate Stationary Phase

In this paper, a simple homogeneous coating of silica spherical particles with pristine boron nitride nanotubes (BNNTs) was described. BNNTs dissolved in dimethylacetamide (DMAc) were mixed with amino-functionalized silica particles having a 5 μm diameter. Favorable interaction between the amino group and the BNNT surfaces induces the absorption of the BNNTs on the silica. The BNNT-coated silica particles were used as stationary phase for HPLC. For the first time, it was demonstrated that this new particulate BNNT stationary phase can be used for the study of the complexation of solute molecules (terpene molecules used as test drugs in this work) with β cyclodextrin (βCD). The apparent formation constants Kf of terpene derivative/βCD were in the same magnitude as those reported in the literature. The plot of Kf versus the water fraction in the methanol/water mobile phase showed that the BNNT surface played an active role in the complex formation due to terpene/BNNT-specific polar interactions. This work demonstrated that our novel particulate BNNT HPLC stationary phase was an efficient tool to study molecular recognition mechanism and more specifically the association between a drug substance and a target molecule with the aim of reaching biopharmaceutic and clinical applications.     

Liquid methanol Monte Carlo simulations with a refined potential which includes polarizability, nonadditivity, and intramolecular relaxation

Monte Carlo simulations of liquid methanol were performed using a refined ab initio derived potential which includes polarizability, nonadditivity, and intramolecular relaxation. The results present good agreement between the energetic and structural properties predicted by the model and those predicted by ab initio calculations of methanol clusters and experimental values of gas and condensed phases. The molecular level picture of methanol shows the existence of both rings and linear polymers in the methanol liquid phase.     

A comparison of the performance of two chromatographic and three extraction techniques for the analysis of PAHS in sources of drinking water

The aim of this work is to establish a sensitive and reliable method for the analysis of the 16 priority Environmental Protection Agency-defined polycyclic aromatic hydrocarbons (PAHs) found in water samples. Gas chromatography (GC)-mass spectrometry (MS) and high-performance liquid chromatography (HPLC)-fluorescence detection (FLD)-UV techniques are optimized to obtain an adequate resolution of all compounds. Validation of the methods is carried out, and a good performance is observed for both techniques. The HPLC-FLD-UV technique is somewhat more sensitive than the GC-MS technique for the determination of PAHs; thus, the HPLC-FLD-UV method is used to follow up both the solid-phase extraction (SPE) analysis using cartridges and discs and the liquid-liquid extraction (LLE), which are also evaluated for the extraction of the PAHs. Low recoveries between 43% and 79% are obtained using SPE cartridges, and higher values are obtained using SPE discs (56-96%) and LLE (60-105%). Better results are obtained using the LLE technique, and, thus, analysis of real water samples is carried out using this technique. LODs between 0.6 and 21 ng/L and relative standard deviations less than 15% are obtained using a spiked water sample analyzed using the full LLE HPLC-FLD-UV method.     

Sequential reactions promoted by manganese: completely stereoselective synthesis of (E)-alpha,beta-unsaturated amides, ketones, aldehydes, and carboxylic acids

A complete E-selective synthesis of alpha,beta-unsaturated amides through a sequential reaction of a range of dichloroamides with a variety of aldehydes promoted by Rieke manganese (Mn*) is reported. A mechanism based on a sequential aldol-type reaction and a completely stereoselective beta-elimination is proposed to explain these results. The unsaturated amides obtained are readily and efficiently transformed into alpha,beta-unsaturated ketones, aldehydes, or carboxylic acids without loss of the diastereoisomeric purity of the C-C double bond.     

Rashba coupling induced by Lorentz symmetry breaking effects

The arising of a Rashba‐like coupling, a Zeeman‐like term and a Darwin‐like term induced by Lorentz symmetry breaking effects in the non‐relativistic quantum dynamics of a spin‐1/2 neutral particle interacting with external fields is studied. Moreover, the influence of a Rashba‐like coupling induced by a Lorentz symmetry violation background on the Tan–Inkson potential [W.‐C. Tan and J. C. Inkson, Semicond. Sci. Technol. 11 , 1635 (1996)] is discussed.     

Quantum uncertainties of the confined Harmonic Oscillator in position,momentum and phase‐space

Quantum uncertainties in position, momentum and phase‐space are studied in the confined Harmonic Oscillator. Standard deviations and Shannon entropies are used to quantify these uncertainties and their behaviors are compared and contrasted. We observe a minimum in the momentum space Shannon entropy as the box length is increased, a feature that is not present in the momentum space standard deviation. The behaviors of the standard deviation product and the Shannon entropy sum, which form the basis of uncertainty relationships, are also analyzed. Maxima are observed in the product as the box length increases in sharp contrast to the entropy sum. The relationship between these behaviors and that of the Shannon entropy of the phase‐space Wigner function is analyzed and discussed. An analysis of the energetic components is also performed. The results reinforce the idea that the confined Harmonic Oscillator can be considered as an intermediate model which interpolates between the Particle in a Box Model and the Harmonic Oscillator and thus contains characteristics of both models.