The nature of molecular excited states produced by weak light sources

It is shown that upon excitation of a molecule by light from a thermal source, the incident field tends to act as a projection operator for a subspace spanned by eigenstates of the molecular hamiltonian. Furthermore, for chaotic light sources there is an effective upper limit, τ, for the time during which there is coherent excitation. If τ is much greater than the uncertainty minimum, as is normally the case, the reduced density operator for the excited states of the molecule becomes “filtered”, the extent of which determines the pattern of subsequent radiative and radiationless decay processes. The limitation of the “filtering” process to the interval τ provides a new distinction for large- and small-molecule behavior.     

Chain transfer studies of alternating copolymerization

Dimethylaniline (DMA) induces chain transfer in the zinc bromide-complexed donor–acceptor polymerizations of styrene–acrylonitrile to form alternating copolymers. The Mayo plots are linear, but the rates decrease with increase in DMA and degradative chain transfer occurs. Although conventional free-radical transfer agents have negligible effect on the rates or molecular weights, a twentyfold reduction of molecular weight is obtained with DMA. Spectroscopic data indicate the formation of an equimolar complex of DMA and ZnBr₂, but the lowering of molecular weight is not attributable to the reduction of the effective ZnBr₂, concentration. A possible mechanism involving a competition between [ZnBr₂(DMA)₂] and [ZnBr₂,DMA,AN] is suggested.     

High-performance liquid chromatographic determination of peptides in biological fluids by automated pre-column fluorescence derivatization with fluorescamine

Peptides containing a free alpha- or epsilon-amino group react with fluorescamine under mild alkaline conditions to generate a highly fluorescent but unstable reaction product and, consequently, practical high-performance liquid chromatographic (HPLC) approaches to analysis have typically involved the use of postcolumn derivatization. An automated precolumn approach is reported in which peptides are reacted with fluorescamine just prior to HPLC analysis by a commercially available autoinjector with derivatization capabilities. The autoinjector added base and fluorescamine reagent solutions to a sample vial containing peptide analytes, and the derivatization reaction was allowed to proceed for 5 min at room temperature prior to injection into the HPLC system. The derivatized peptides were analyzed by reversed-phase HPLC with fluorescence detection (excitation at 390 nm; emission 470-nm cut-off filter) on an octylsilica column. Optimization of the precolumn reaction conditions and the use of narrower HPLC columns (2 mm I.D.) resulted in a typical on-column detection limit of 30-50 fmol of peptide, which was substantially lower than that in previously reported post-column methods. This approach was applied to the HPLC of several naturally occurring and synthetic peptides containing alpha- and epsilon-amino groups. In combination with solid-phase extraction, prior to automated precolumn fluorescence derivatization and chromatographic analysis, the methodology was used for the determination of a synthetic growth hormone-releasing peptide in plasma samples.     

Vibrotactile identification of vowels

The ability of subjects to identify vowels in vibrotactile transformations of consonant-vowel syllables was measured for two types of displays: a spectral display (frequency by intensity), and a vocal tract area function display (vocal tract location by cross-sectional area). Both displays were presented to the fingertip via the tactile display of the Optacon transducer. In the first experiments the spectral display was effective for identifying vowels in /b/V/ context when as many as 24 or as few as eight spectral channels were presented to the skin. However, performance fell when the 12- and 8-channel displays were reduced in size to occupy 1/2 or 1/3 of the 24-row tactile matrix. The effect of reducing the size of the display was greater when the spectrum was represented as a solid histogram ("filled" patterns) than when it was represented as a simple spectral contour ("unfilled" patterns). Spatial masking within the filled pattern was postulated as the cause for this decline in performance. Another experiment measured the utility of the spectral display when the syllables were produced by multiple speakers. The resulting increase in response confusions was primarily attributable to variations in the tactile patterns caused by differences in vocal tract resonances among the speakers. The final experiment found an area function display to be inferior to the spectral display for identification of vowels. The results demonstrate that a two-dimensional spectral display is worthy of further development as a basic vibrotactile display for speech.     

Comparison of the pharmacokinetics and phototoxicity of protoporphyrin IX metabolized from 5-aminolevulinic acid and two derivatives in human skin in vivo

Our novel approach was to compare the pharmacokinetics of 5-aminolevulinic acid (ALA), ALA-n-butyl and ALA-n-hexylester induced protoporphyrin IX (PpIX), together with the phototoxicity after photodynamic therapy (PDT) in human skin in vivo, using iontophoresis as a dose-control system. A series of four increasing doses of each compound was iontophoresed into healthy skin of 10 volunteers. The kinetics of PpIX metabolism (n = 4) and the response to PDT (n = 6) performed 5 h after iontophoresis, were assessed by surface PpIX fluorescence and post-irradiation erythema. Whilst ALA-induced PpIX peaked at 7.5 h, highest PpIX fluorescence induced by ALA-n-hexylester was observed at 3-6 h and no clear peak was seen with ALA-n-butylester. With ALA-n-hexylester, more PpIX was formed after 3 (P < 0.05) and 4.5 h, than with ALA or ALA-n-butylester. All compounds showed a linear correlation between logarithm of dose and PpIX fluorescence/phototoxicity at 5 h, with R-values ranging from 0.87 to 1. In addition, the ALA-n-hexylester showed the tendency to cause greater erythema than ALA and ALA-n-butylester. Fluorescence microscopy (n = 2) showed similar PpIX distributions and penetration depths for the three drugs, although both ALA esters led to a more homogeneous PpIX localization. Hence, ALA-n-hexylester appears to have slightly more favorable characteristics for PDT than ALA or ALA-n-butylester.     

Interfacial properties of precipitate-based ion-selective electrodes : Rotating disk impedance measurements of the Ag2S/Ag (aqueous) interface

Three-electrode rotating disk impedance measurements were made from 31.6 kHz to 0.0178 Hz on Ag₂S/Ag⁺ (aqueous) and Ag₂S/Ag systems. Membranes were prepared from materials precipitated in excess of silver or sulfide ions, and stoichiometric mixtures. Impedances were analyzed, as a function of rotation rate and bathing activities, to isolate bulk conductivities, internal diffusion, surface kinetic and dissolution/crystallization impedances. High-frequency bulk resistivities, R_∞, varied by four with precipitation and pressing conditions. Resistivities were the same for solution and ohmic configurations for each preparation. For ohmic contacts, R_∞ and R(DC) were identical. Solution contact cells in 10^-1 M and 10^-2 M bathing silver ion solution gave identical frequency-dependent impedances which were independent of rotation rate. Thus, solution diffusional impedances and solution dependent surface kinetics were eliminated, and a finite Warburg, interior-Ag⁺-defect, diffusion impedance was indicated. Summation of bulk membrane and contact resistances, and this Warburg impedance served as a 'background' correction in analyzing dilute bathing solution interfacial impedances for surface effects. Corrected impedances in 10^-3 –10^-5 M AgNO₃ showed solution diffusional behaviour combined with surface kinetic and dissolution impedances. An iterative linear least-squares method resolved these quantities. The surface resistance suggests a potential-dependent rate constant; dissolution time constants were solution-independent and smaller than those for solution diffusion. Thus, dissolution can be a rate-limiting step in establishment of steady-state potentials.     

Pt-catalyzed cyclization/migration of propargylic alcohols for the synthesis of 3(2H)-furanones, pyrrolones, indolizines, and indolizinones

Several heterocycles such as furanones, pyrrolones, and indolizines, which are of pharmacological importance, are easily accessed via the Pt(II)-catalyzed heterocyclization/1,2-migration of propargylic ketols or hydroxy imine derivatives. This method sidesteps the challenges of traditional heteroaromatic oxygenation strategies such as regioselectivity and functional group tolerance in the syntheses of these heterocycles.     

Development of an Electrochemical Technique for the Removal of Ultratrace Levels of Heavy Metals from Water Using Accelerated Electrodeposition

A readily available source of ultrapure water is a basic requirement in most analytical work. The earliest requirement for ultrapure water was in electrochemical research^1. In recent years, nuclear reactors, semiconductor and electronic industries require very pure water^2,3. Ultrapure water is needed to prepare standards whenever the determination of ultratrace (ppb) concentrations of metals is required.