Spectroscopic Determination of Cholinesterase Activity and Inhibition in Sol-Gel Media

Biological activity of cholinesterases can be determined by optically monitoring the enzymatic reaction with indophenyl acetate, (N-4′-acetoxyphenyl)-4-quinone imine. At pH 8.0 cholinesterases hydrolyze this yellow dye to yield a blue reaction product. Cholinesterase inhibitors reduce the rate of this hydrolysis. Thus, by monitoring absorbance of the hydrolysis product at its maximum (630 nm) as a function of time, reaction rates of both cholinesterase activity and cholinesterase inhibition may be quantified spectroscopically. Using this technique, we measured the enzymatic activity of butyrylcholinesterase (BuChE) molecules encapsulated in tetramethyl orthosilicate (TMOS) silicate gel-glass prepared by hydrolysis and condensation. This activity is reduced, in a concentration-dependent manner, by the reversible cholinesterase inhibitors 1,5-bis(4-allyldimethyl-ammoniumphenyl) pentan 3-one dibromide (BADAPP) and 9-amino-1,2,3,4-tetrahydroacridine (THA; tacrine, Cognex). The gel-glasses are rigid, and compact, transparent and porous enough to allow reagents to diffuse in and out.     

Eine mafsanalytische Methode zur Bestimmung des Baryums

Ohne ZusammenfassungAus dem Englischen übersetzt von der Redaktion.(Mitteilung aus dem Havemeyer Chemischen Laboratorium der Universität New York.)     

The intensity of triboluminescence

The first values of the absolute triboluminescence intensity, in units of photons/mol, are reported for molecular crystals and salts. The values range from 5 × 10¹⁶ photons/mol for cholesteryl salicylate to 6.2 × 10¹⁰ photons/mol for magnesium sulfate. The mechanical yield of triboluminescence is defined and the lower limit is determined.     

Analysen von Pferdefett

Ohne Zusammenfassung     

Optical spectra of delocalized dinitroaromatic radical anions revisited

The optical spectra of nine dinitroaromatic radical anions (1,2- and 1,4-dinitrobenzene, 1,5- and 2,6-dinitro naphthalene, 4,4'-dinitrobiphenyl, 2,7-dinitro-9,9-dimethylfluorene, 2,6-dinitroanthracene, and 2,7- and 1,8-dinitrobiphenylene) in dimethylformamide are reported and analyzed. All have delocalized charge distribution, as demonstrated by the vibrational fine structure that is observed in their optical spectra: All show lowest energy absorption bands that correspond to an alpha-homo (highest occupied molecular orbital) to alpha-lumo (lowest unoccupied) transition, as shown by Koopmans-based UB3LYP calculation of the orbital separation of the neutral at the geometry of the radical anion. These single-point calculations are shown to be significantly more accurate for five of these compounds than the much more complex and expensive TD-DFT method. The two-state model should not be used to estimate the electronic coupling in delocalized intervalence compounds such as these. Neighboring orbital estimation of the electronic couplings show that using the two-state model greatly underestimates electronic coupling here.     

Optically-Pumped Far-Infrared Laser Lines of Methanol Isotopomers: 12CH3OH, 12CH3OD, and 12CH2DOH

Twenty-seven new far-infrared laser lines from the isotopomers of methanol: ¹²CD₃OH, ¹²CH₃OD, and ¹²CH₂DOH, were obtained by optically-pumping the molecules with an efficient cw CO₂ laser. The CO₂ laser provided pumping from regular, sequence, and hot-band CO₂ laser transitions. The 2-m long far-infrared cavity was a metal-dielectric waveguide closed by two, flat end mirrors. Several short-wavelength (below 100 m) lines were observed. The frequencies of 28 laser lines observed in this cavity (including new lines and already known lines) were measured with a fractional uncertainty limited by the fractional resetability of the far-infrared laser cavity, of 2 parts in 10⁷.     

Analytical derivation of interference dips in molecular absorption spectra: molecular properties and relationships to Fano's antiresonance

An analytical expression is derived for the decrease in the absorption cross section that occurs when two molecular electronic states are coupled by spin-orbit coupling. The loss of intensity, or interference dip, is common in the spectra of metal compounds. The derivation is based on a coupling of a single forbidden donor state to a broadened harmonic acceptor potential, and leads to simple analytical expressions. The new expressions give line shape functions different from those in the commonly used Fano antiresonance interpretation and are based on interpretable molecular properties.     

Optically-Pumped Far-Infrared Laser Lines in Hydrazine, Methanol, Heavy Water, and Ammonia: New Laser Lines and Frequency Measurements

A far-infrared laser cavity designed to favor short-wavelength laser lines was used to generate optically-pumped far-infrared laser radiation. New far-infrared laser lines were discovered in hydrazine, heavy water, ammonia, and several short-wavelength lines previously discovered in methanol were observed. Wavelength, frequency, and relative intensity measurements were performed on laser lines in the wavelength range 42.4 to 253.7 m. Each far-infrared frequency measurement was obtained by mixing the far-infrared radiation with radiation from two reference CO₂ lasers and from a microwave synthesizer in a metal-insulator-metal diode. The pump laser was a high-Q Fabry Perot resonator oscillating on 275 grating-selected laser lines including regular, sequence, and hot band lines.