2,6-Di-tert-butylphenols and phenoxyl radicals with metal—metal bonds

3350v12/xxlarge963.gif" alt="sgr" align="BASELINE" BORDER="0">-Aryl trans-bistriphenylphosphine complexes based on 2,6-di-tert-butylphenol containing Pt—SnCl₃, Pt—GeCl₃ groups were synthesized. Oxidation of these compounds gives the corresponding phenoxyl radicals, which were studied by ESR spectroscopy. The transformation of the diamagnetic complexes to the paramagnetic state is accompanied by cleavage of the Pt—Sn, Pt—Ge bonds and by elimination of SnCl₂, GeCl₂.     

Size Exclusion Chromatographic Determination of PEG 3350 in Human Plasma and Urine

Abstract

A size exclusion chromatographic method is reported that quantitated PEG 3350 in human plasma and urine to a concentration of 10 μg/ml in plasma, or urine. The chromatographic system consisted of a 500 A gel permeation analytical column, a differential refractometer detector, and chloroform as the eluting solvent. Organic extraction was used as an initial separation technique. PEG 400 was used as the internal standard for PEG 3350, and showed similar extraction properties. Spiked plasma standards yielded standard calibration curves with correlation coefficients of greater than 0.99, and relative standard deviations (n=3) of 2.19% (500 μg/ml) and 6.97% (20 μg/ml). The analytical technique was used to estimate the elimination rate constant of PEG 3350 from 5 normal human subjects after oral administration of 240 grams of PEG 3350. K_E was found to be 0.1079 hr^?1 0.03781^?1 hr (mean s.d.) using the Sigma-minus data analysis method on total urines collected from the 5 subjects at varying intervals.     

Identification of cholesterol gallstones using in vitro low-fluence laser-induced fluorescence spectroscopic analysis

Identifying the chemical composition of gallstones may be important in certain cases of calculus biliary disease when planning a dissolution therapy or a fragmentation of the calculi using pulsed lasers. The present study was conducted in vitro to evaluate the feasibility of distinguishing cholesterol gallstones from pigment stones. We propose an identification method in which the stone fluorescence spectrum, induced by a low fluence laser, is recorded using an optical multichannel analyser. Fluorescence spectra of twenty-two stones were recorded together with the fluorescence spectra of various pure compounds likely to compose the gallstones, using successively four different pump lasers (_p=308 nm, 337 nm, 423 nm, 469 nm). The fluorescence spectra of cholesterol gallstones are quite different from the pigment ones. Ratios of fluorescence intensities taken at three different wavelengths enable one to distinguish easily between cholesterol and pigment stones.     

Calculation of Quantum‐Chemical Characteristics of the Ground and Excited Electronic States of Porphin and Its Tetrapyrrole Isomers

Using the CNDO/S method, we have performed quantum3350/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">chemical calculations of the ground and excited electronic states of porphin molecules (symmetry D _2h ) and a number of porphin isomers: porphycene (C_2h ), hemiporphycene, corphycene (C_2v ), isoporphycene, and three nonsynthesized structural isomers of the porphin skeleton by its bridge groups —(CH) _meso —. The results of the calculations are compared with the corresponding data for the free3350/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">base porphin molecule (H₂P). Near the boundary between the occupied and vacant orbitals the isomers form rows of single3350/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">electron levels with similar energy characteristics. For the MOs of these isomers, the H₂P MOs closest in distribution on the 3350/xxlarge8220.gif" alt="ldquo" align="MIDDLE" BORDER="0">comparable3350/xxlarge8221.gif" alt="rdquo" align="MIDDLE" BORDER="0"> atomic centers are given. The weak (Q) and strong (B) transitions in the visible and near UV regions point to the porphyrin type of spectra of all the isomers. The calculation data on the excited electronic states of N3350/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">, g3350/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">, and n3350/xxlarge960.gif" alt="pgr" align="BASELINE" BORDER="0">3350/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">type H₂P near and above the B states are given; the presence of such states in other isomers is shown. The calculation does not point to a difference in the position of the first singlet transitions in the first five isomers. The calculation data on the lower singlet3350/xxlarge8208.gif" alt="dash" align="MIDDLE" BORDER="0">triplet transitions are also reported.     

Spectroscopic and Laser Studies of Mixed Rhodamine 6G and 10-Phenyl-9-acetoxyanthracene Solutions

The spectroscopic and laser parameters of a mixed donor (10-phenyl-9-acetoxyanthracene derivations)-acceptor (rhodamine 6G) solutions have been determined. The studies performed show that rhodamine 6G is responsible for the lasting of the mixed solution. The 10-phenyl-9-acetoxyanthracene added to the R6G lasing solution decreases the spectral range of lasing and the gain value, G(), of the solution. These changes in the lasing parameters are caused by electron energy transfer processes of different types. The results of fluorescence studies of the mixed donor-acceptor solutions point out that the long-range dipole-dipole interaction mechanism of the static quenching accompanied by the formation of nonemitting complexes in the dye mixture is responsible for the noted lasing and fluorescence changes.     

Saturable absorption dynamics of mode-locking dye DODCI

0 –S₁–S_m–S_n multilevel system. An S_m→S₁ absorption recovery time of τ^S1 _A=(600±100) fs is determined. The picosecond and femtosecond pulse excitation leads to S₀→S₁ ground-state absorption bleaching and S₁→S_m first excited-state absorption bleaching. The excited-state absorption cross-sections σ^S1 _ex(S₁→S_m) and σ^Sm _ex(S_m→S_n) are determined. Received: 3 June 1996