INTERACTION OF ENZYME-GENERATED SPECIES WITH CHLOROPHYLL-a AND PROBES BOUND TO SERUM ALBUMINS

Abstract— The interaction of serum albumin-bound acceptors with enzyme-generated and protected triplet species was studied in two types of systems. Chlorophyll-a bound to bovine and human serum albumins is efficiently excited by enzymatically generated triplet acetone and acetaldehyde. When the Chl-a concentration is much lower than that of the albumin the interaction occurs with chlorophyll in an aggregate in which one Chl-a is surrounded by several protein molecules. When the Chl-a concentration is higher than that of the protein, the aggregate contains the proteins and fluorescent chlorophylls in a 1:1 ratio. The excess chlorophylls, although able to interact with the donors, are not fluorescent.
In another study, probes bound to various specific sites of serum albumins were used as quenchers of the enzymatically generated triplet acetone. The efficiency of quenching by all the bound probes is equal and in one case even stronger than for the free probes.
A model for the interaction of the excited species contained in the enzyme with the acceptor(s) located in the protein is proposed.
The present results provide further evidence that enzyme-generated and protected triplet carbonyl species can interact through a collisional process with acceptors bound to or constituents of macromolecules.     

Mechanistic insights into the photochromism of trans-10b,10c-dimethyl-10b,10c-dihydropyrene derivatives

A series of dimethyldihydropyrene derivatives was studied to elucidate the photochemical mechanism associated with the switching between the dimethyldihydropyrene (DHP, closed) and metacyclophanediene (CPD, open) forms of the molecule. Quantum yields of ring opening and closure, fluorescence quantum yields and lifetimes, as well as laser flash photolysis studies were performed to establish the effect of substituents on the switching efficiency. Ring opening of the DHPs occurs from the first singlet excited state. The low quantum yields for the ring opening reaction observed (< or =0.042) are a consequence of the low rate constant (< or =1.7 x 10(7) s(-1)) for this process. The quantum yields for ring closure of the CPD were determined for select compounds and were of the order of 0.1-0.4. These results show that the efficiency for ring opening of this class of compounds is intrinsically low, but can be modulated to some extent by the introduction of substituents. These properties should be taken into account when considering what type of photoswitching devices DHPs might be useful for.     

Two-proton correlations in the target fragmentation region of nuclear collisions at 200A GeV

Correlations between protons are studied in the target fragmentation region of reactions of protons and¹⁶O with C, Cu, Ag, Au and of³²S with Al and Au at 200A GeV. The emitted protons were measured with the Plastic Ball detector in the WA80 experiment at the CERN SPS. The comparison of the correlation function with calculations, assuming a spherical, gaussian shaped source with a lifetime τ=0 fm/c, allows the extraction of radius parameters. The values are very close to those expected from the geometry of the target nuclei and increase with the target mass as αA _Target ^1/3 . Even in proton induced reactions the whole target nucleus is involved. The dependence of the radii on centrality, polar angleθ _lab, and energy, and their relation to measured proton yields are presented.     

Synthesis of copper,nickel and cobalt complexes containing a new N2S2 ligand: benzyl-N,N′-alkylbis(2-amino-1-cyclopentencarbodithioate)

The synthesis of [benzyl-N,N-alkylbis(2-amino-1-cyclopentencarbodithioate)]M^II [alkyl = ethene (L₂) and propene, (L₃) and M = Cu, Ni and Co] complexes and their characterization (u.v.–vis., FT-IR, ¹H-n.m.r., mass spectra and cyclic voltametry) are reported.     

A matricial extension of the Helson-Sarason theorem and a characterization of some multivariate linearly completely regular processes

We generalize the theorems of Helson-Szegö and Helson-Sarason for matricial measures. We study two-weighted inequalities for the Hilbert transform in [0, 2π] and in R and give a characterization for the positivity of the angle between past and future of multivariate weakly stationary stochastic processes, in the discrete and the continuous case. We also characterize the multivariate weakly stationary stochastic processes that are linearly completely regular and study the rate of convergence of the maximal correlation coefficient.     

Effect of periodic rest on hearing loss and cochlear damage following exposure to noise

Changes in hearing sensitivity and cochlear damage were determined in two groups of chinchillas exposed to an octave band of noise (OBN) centered at 0.5 kHz, 95 dB SPL on two different schedules: 6 h per day for 36 days, or 15 min/h for 144 days. Hearing sensitivity was measured behaviorally at 1/4-oct frequency intervals from 0.125 to 16.0 kHz before, during, and for a period of 1 to 2 months after the exposure, at which time the animals' cochleas were fixed and prepared for microscopic examination. Cochlear damage was determined by counts of missing sensory cells. Both exposures produced an initial shift of thresholds of 35-45 dB; however, after a few days of exposure, thresholds began to decline and eventually recovered to within 10-15 dB of original baseline values even though the exposure continued. Measures of recovery made after completion of the exposures indicated minimal permanent threshold shifts in all animals. The behavioral and anatomical data indicated that these intermittent exposures produced less temporary and permanent hearing loss and less cochlear damage than continuous exposures of equal energy.     

Dilation of generalized Toeplitz kernels on ordered groups

We introduce the concept of Toeplitz-Kre?n-Cotlar triplet on ordered groups and we prove a general dilation result and a general representation result for the positive definite case.This general result includes and extends previous generalizations of the Kre?n extension theorem, the Sz.-Nagy and Foias commutant lifting theorem and the generalized Herglotz-Bochner-Weil theorem.     

Morphometric analysis of hair cells in the chinchilla cochlea

Ten chinchilla cochleas which ranged in length from 16.00 to 19.71 m were used for this study. The cross-sectional area and perimeter of the inner and outer hair cells and their nuclei were determined at two locations per cochlear turn and at the junction between each of the turns (11 locations from apex to base). Some interanimal variation in hair cell dimensions was noted. However, none of these size variations could be attributed to any known differences among the animals. It was concluded that the data reported here represent the natural variation in hair cell size in chinchillas. The data establish a baseline to which the dimensions of cells from abnormal cochleas can be compared, regardless of the length of the cochlea or the base-to-apex location of the cells.