Triplet states of humic acids studied by laser flash photolysis using different excitation wavelengths

The spectra and kinetics of short-lived intermediates formed from aqueous (0.1 N NaOH) solutions of the natural mixture of humic and fulvic acids (HFA) were studied by laser flash photolysis using excitation wavelengths of 337, 390, 470, and 520 nm. Laser photolysis of HFA with light of 520 and 470 nm results in the formation of triplet excited states (T_HFA) characterized by the broad absorption spectrum with a maximum near 630 nm and lifetimes of 0.15 ms in deoxygenated solutions. The formation of two types of T_HFA with lifetimes of 0.1 and 2 ms and absorption spectra with maxima at 570 nm is observed under photolysis with light of 337 and 390 nm. The estimation of quantum yields of T_HFA gives 1 and 0.3% under photolysis with excitation wavelengths of 337 and 520 nm, respectively. The rate constants of T_HFA quenching by molecular oxygen are equal to (7—8)·10⁸ L mol^–1 s^–1.     

Programming package “ESCAPAK” for calculations of electronic structure,adapted for the ES series computers

Branch of the Institute of Chemical Physics, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 3, pp. 132–134, May–June, 1989.     

Molecular gradients: an efficient approach for optimizing the surface properties of biomaterials and biochips

A variety of molecular gradients of alkanethiols with the structure HS-(CH(2))(m)-X (m = 15; X = COOH, CH(2)NH(2), or CH(3)) and oligo(ethylene glycol)-terminated alkanethiols with the structures HS-(CH(2))(15)-CO-NH-Eg(n) (n = 2, 4, or 6), HS-(CH(2))(15)-CO-NH-Eg(2)-(CH(2))(2)-NH-CO-(CH(2))(4)-biotin, and HS-(CH(2))(15)-CO-NH-Eg(6)-CH(2)-COOH were prepared on polycrystalline gold films. These gradients were designed to serve as model surfaces for fundamental studies of protein adsorption and immobilization phenomena. Ellipsometry, infrared spectroscopy, and X-ray photoelectron spectroscopy, operating in scanning mode, were used to monitor the layer composition, gradient profiles, tail group conformation, and overall structural quality of the gradient assemblies. The gradient profiles were found to be 4-10 mm wide, and they increased in width with increasing difference in molecular complexity between the thiols used to form the gradient. The oligo(ethylene glycol) thiols are particularly interesting because they can be used to prepare so-called conformational gradients, that is, gradients that display a variation in oligo(ethylene glycol) chain conformation from all trans on the extreme Eg(2,4) sides, via an amorphous-like phase in the mixing regimes, to helical at the extreme Eg(6) sides. We demonstrate herein a series of experiments where the above gradients are used to evaluate nonspecific binding of the plasma protein fibrinogen, and in agreement with previous studies, the highest amounts of nonspecifically bound fibrinogen were observed on all-trans monolayers, that is, on the extreme Eg(2,4) sides. Moreover, gradients between Eg(2) and a biotinylated analogue have been prepared to optimize the conditions for the immobilization of streptavidin. Ellipsometry and infrared spectroscopy reveal high levels of immobilization over a fairly broad range of compositions in the gradient regime, with a maximum between 50 and 60% of the biotinylated analogue in the monolayer. A pI gradient composed of (NH(3)(+)/COO(-))-terminated thiols was also prepared and evaluated with respect to its ability to separate differently charged proteins, pepsin, and lysozyme, on a solid surface.     

Electronic structure of saturated hydrocarbons in the semi-empirical equivalent orbital method

The problem of obtaining the matrix elements of Hartree-Fock Hamiltonians for alkanes using the EO method is considered. It has been shown that the data on the electronic structure of diamond together witht ₁/e splitting in the neopentane photoelectron spectrum are helpful to produce such EO method parameter scale which involves even “through space” interactions. In terms of the EO method the photoelectron spectra of propane, butane, isobutane, and neopentane are interpreted. The valence band structure of polyethylene in analytical form is obtained.     

One-stage conversion of aromatic carboxylic acids into 2, 5-diaryl-1, 3, 4-oxadiazoles

A method has been developed for the one-stage conversion of aromatic carboxylic acids into symmetrical 2, 5-diaryl-1, 3, 4-oxadiazoles by heating them with hydrazine hydrochloride in polyphosphoric acid.     

C(3)-azido cephem II

The major product from the thermolysis and photolysis of C(3)-azido cephem 2 is the ring expanded 1,4,6-thiadiazepine azetidinone.     

Effect of Peptization on Texture and Physicomechanical Properties of Aluminum Hydroxides

The method of low-temperature adsorption of nitrogen was applied to study structural characteristics of commercial peptized aluminum hydroxides. An increase or decrease in the porometric volume, depending on the nature and concentration of the peptizing agent, was analyzed. The phenomena observed are explained in terms of the mechanism suggested for formation of the pore system in commercial aluminum hydroxides. The dependence of the physicomechanical properties of active aluminum oxide on synthesis conditions and texture characteristics of commercial aluminum hydroxides was studied.     

Structure and dynamic stability of cyclodextrin inclusion complexes with 1,4-disubstituted bicyclo[2.2.2]octanes

The properties of inclusion complexes of 1,4-di-R-bicyclo[2.2.2]octaves (R = H (1), Me (2), Cl (3), Br (4), and OH (5)) with cyclodextrins have been studied by NMR, microcalorimetry, and force-field computations. The compounds2 and3 (but not the other compounds) give dynamically stable 1:2 guest-host complexes with -cyclodextrin. Microcalorimetry of5 in water indicates a moderately strong 1:1 complex with - but weak complexes with - or -cyclodextrin. The behaviour depends on the subtle interplay size, polarity, hydrophobicity and type of solvent.