PHOTOREDUCTION OF ZINC PORPHIN BY ASCORBIC ACID*

Abstract— Zinc porphin is photoreduced to zinc chlorin through an intermediate dihydroporphin (PH₂) by ascorbic acid in ethanol containing 1% to 10% (v/v) piperidine. Under the same conditions zinc chlorin is more slowly photoreduced to zinc tetrahydroporphin. The reactions leading to chlorin are photosensitized by the product chlorin and so are autocatalytic in red light. Quantum yields for these reactions range up to 0.05.Other aliphatic amines catalyze these reactions, but at rates peculiar to the amine. The immediate product of reduction of zinc porphin, PH₂, is distinguished by an intense band at 437 nm; it reverts to porphin in the dark in the presence of oxygen or dehydroascorbic acid. Its conversion to chlorin is effected by light absorbed by porphin or chlorin, but not by light absorbed by PH₂ itself. A suggested structure for PH₂, compatible with the observed reactions, has added hydrogens on one bridge carbon and one β-pyrrole carbon. The possibility of an analogy between these reactions and the biochemical conversion of protochlorophyll to chlorophyll is discussed.     

Optimization of oxidation of glycoproteins: an assay for predicting coupling to hydrazide chromatographic supports.

A rapid, simple assay for aldehydes generated by oxidation of saccharide units in glycoproteins, using dyes containing hydrazide functionalities, is described. The assay is used, in conjunction with tests of biological activity, to predict oxidation conditions that will result in a maximum of active protein coupled to a hydrazide chromatographic support. Glycoproteins are labeled with Lucifer Yellow CH or Texas Red Hydrazide, and the extent of labeling is determined. Using the assay, it is shown that the efficiency of coupling to Affi-Prep Hydrazide is proportional to oxidation.     

Testing coherent reflection in chinchilla: Auditory-nerve responses predict stimulus-frequency emissions

Coherent-reflection theory explains the generation of stimulus-frequency and transient-evoked otoacoustic emissions by showing how they emerge from the coherent "backscattering" of forward-traveling waves by mechanical irregularities in the cochlear partition. Recent published measurements of stimulus-frequency otoacoustic emissions (SFOAEs) and estimates of near-threshold basilar-membrane (BM) responses derived from Wiener-kernel analysis of auditory-nerve responses allow for comprehensive tests of the theory in chinchilla. Model predictions are based on (1) an approximate analytic expression for the SFOAE signal in terms of the BM traveling wave and its complex wave number, (2) an inversion procedure that derives the wave number from BM traveling waves, and (3) estimates of BM traveling waves obtained from the Wiener-kernel data and local scaling assumptions. At frequencies above 4 kHz, predicted median SFOAE phase-gradient delays and the general shapes of SFOAE magnitude-versus-frequency curves are in excellent agreement with the measurements. At frequencies below 4 kHz, both the magnitude and the phase of chinchilla SFOAEs show strong evidence of interference between short- and long-latency components. Approximate unmixing of these components, and association of the long-latency component with the predicted SFOAE, yields close agreement throughout the cochlea. Possible candidates for the short-latency SFOAE component, including wave-fixed distortion, are considered. Both empirical and predicted delay ratios (long-latency SFOAE delay/BM delay) are significantly less than 2 but greater than 1. Although these delay ratios contradict models in which SFOAE generators couple primarily into cochlear compression waves, they are consistent with the notion that forward and reverse energy propagation in the cochlea occurs predominantly by means of traveling pressure-difference waves. The compelling overall agreement between measured and predicted delays suggests that the coherent-reflection model captures the dominant mechanisms responsible for the generation of reflection-source otoacoustic emissions.     

Cumulant functions in optical coherence theory

Cumulant functions are introduced to describe the statistical state of a radiation field. These functions are simply related to the optical coherence functions but have some interesting features. It is shown that if the cumulant functions of all orders greater than some numberN ₀ vanish then they also vanish for all orders greater than 2. Thermal field is the only field having this property. This property holds whether the field is described by a classical stochastic process or by a quantum density operator. Further the particular operator ordering used in defining these cumulant functions for the quantized field affects only the second order cumulant function. To describe the statistical state of a vector field such as partially polarized or unpolarized radiation, one would need to introduce cumulant tensors.     

Coherent reflection in a two-dimensional cochlea: Short-wave versus long-wave scattering in the generation of reflection-source otoacoustic emissions

The theory of coherent reflection filtering explains the empirical form of the cochlear reflectance by showing how it emerges from the coherent "backscattering" of forward-traveling waves by impedance perturbations in the mechanics of the cochlear partition. Since the theory was developed using the one-dimensional (1-D) transmission-line model of the cochlea, an obvious logical shortcoming is the failure of the long-wavelength approximation near the peak of the traveling wave, where coherent backscattering is purported to occur. Indeed, existing theory suggests that wave reflection may be strongly suppressed in the short-wave regime. To understand how short-wave behavior near the peak modifies the predictions of the long-wave theory, this paper solves the scattering problem in the 2-D cochlear model. The 2-D problem is reduced to a 1-D wave equation and the solution expressed as an infinite series in which successive terms arise via multiple scattering within the cochlea. The cochlear reflectance is computed in response-matched models constructed by solving the inverse problem to control for variations in mechanical tuning among models of different heights and dimensionality. Reflection from the peak region is significantly enhanced by the short-wave hydrodynamics, but other conclusions of the 1-D analysis--such as the predicted relation between emission group delay and the wavelength of the traveling wave--carry over with only minor modifications. The results illustrate the important role of passive hydromechanical effects in shaping otoacoustic emissions and cochlear tuning.     

Modeling the temporal behavior of distortion product otoacoustic emissions

The temporal behavior of the 2f1-f2 distortion product otoacoustic emission is theoretically investigated for the case in which the lower frequency (f1) primary tone is on continuously, and the higher frequency (f2) one is pulsed on and off [e.g., Talmadge et al., J. Acoust. Soc. Am. 105, 275-292 (1999)]. On physical grounds, this behavior is expected to be characterized by various group delays associated with the propagation of (1) the f2 cochlear primary wave between the cochlear base and the primary distortion product generation region around x2 (the f2 tonotopic place), and (2) the 2f1-f2 cochlear distortion product (DP) waves between the cochlear base, the primary generation region of the distortion product, and the region around the 2f1-f2 tonotopic place where the generated apical moving DP wave is reflected toward the cochlear base [e.g., Talmadge et al., J. Acoust. Soc. Am. 104, 1517-1543 (1998)]. An approximate analytic expression is obtained for this behavior from the analysis of the Fourier integral representation of the auditory peripheral response to the primary stimuli. This expression also approximately describes the transient build-up of the components of different latencies in terms of the damping properties of the cochlear partition. It is shown that considerable caution must be applied in attempting to relate phase derivatives of the distortion product otoacoustic emissions for steady state stimuli and the physical time delays which are associated with the temporal behavior of a distortion product emission in the case of a pulsed primary.     

Experimental demonstration of improved neoclassical transport with quasihelical symmetry

Differences in the electron particle and thermal transport are reported between plasmas produced in a quasihelically symmetric (QHS) magnetic field and a configuration with the symmetry broken. The thermal diffusivity is reduced in the QHS configuration, resulting in higher electron temperatures than in the nonsymmetric configuration for a fixed power input. The density profile in QHS plasmas is centrally peaked, and in the nonsymmetric configuration the core density profile is hollow. The hollow profile is due to neoclassical thermodiffusion, which is reduced in the QHS configuration.     

Gas phase activation energy for unimolecular dissociation of biomolecular ions determined by focused RAdiation for gaseous multiphoton ENergy transfer (FRAGMENT)

We present a novel approach for the determination of activation energy for the unimolecular dissociation of a large (>50 atoms) ion, based on measurement of the unimolecular dissociation rate constant as a function of continuous-wave CO(2) laser intensity. Following a short ( approximately 1 s) induction period, CO(2) laser irradiation produces an essentially blackbody internal energy distribution, whose 'temperature' varies inversely with laser intensity. The only currently available method for measuring such activation energies is blackbody infrared radiative dissociation (BIRD). Compared with BIRD, FRAGMENT: (a) eliminates the need to heat the surrounding ion trap and vacuum chamber to each of several temperatures (each requiring hours for temperature equilibration); (b) offers a three-fold wider range of effective blackbody temperature; and (c) extends the range of applications to include initially cold ions (e.g., gas-phase H/D exchange). Our FRAGMENT-determined activation energy for dissociation of protonated bradykinin, 1.2 +/- 0.1 eV, agrees within experimental error to the value, 1.3 +/- 0.1 eV, previously reported by Williams et al. from BIRD experiments. Copyright 1999 John Wiley & Sons, Ltd.