Energy Transfer from the Aminophthalate Dianion to Fluorescein

Energy transfer from the excited aminophthalate dianion species to fluorescein at pH 8.32 (Tris-HCl buffer) was studied. The excited aminophthalate dianion species was obtained either by excitation with UV radiation (330 nm), with fluorescence emission, or by the well-known chemical reaction luminol-hydrogen peroxide in an alkaline medium, with chemiluminescent emission, both with _max at 425 nm. The influence of Co²⁺ and Mg²⁺ on fluorescence and chemiluminescence (CL) was studied. It was found that at low concentrations (10^–7–10^–9 M), these ions do not modify the fluorescein fluorescence, however, the CL is strong affected. The effect of the concentration of these elements, which exert an influence on CL even at a high dilution (nanomolar concentration), was determined. In the case of Co²⁺ the prooxidant character is stronger than in the case of Mg²⁺, and therefore the CL enhancer effect is higher. Compared to the system without catalyst, their presence ensures stronger, prolonged, and stable light emission. The emission spectra, in the presence of fluorescein, show two bands with maxima at 425 and 520 nm, the second one being specific to fluorescein emission. The intensity of aminophthalate dianion luminescence is lower and the duration shorter in the presence of fluorescein. The influence of Co²⁺ and Mg²⁺ catalyst and fluorescein concentration on the energy transfer process was studied. The efficiency of the energy transfer process for these two situations (fluorescence and CL) was compared. An attempt was made to replace hydrogen peroxide with superoxide anion (solubilized by means of crown ether) and its effect upon the energy transfer process was observed.     

An interactive program for finite incidence structures

It has been shown (see [3]) that every finite incidence structure can be represented in a suitable way by a polynomial over a convenient finite field. In this paper we present a FORTRAN interactive program which examines the incidence structure associated to a given polynomial over GF(9). Further, a second program is exhibited, which determines a complete system of mutually orthogonal latin squares related to a polynomial associated to a projective plane of order nine.     

Aromatization of aliphatic compounds—III: Abnormal michael addition to diethyl-α-acetyl-α'-methyl succinate

While isobutyl vinyl ketone reacts with α-acetyl-α'-methyl succinate to give a normal Michael adduct, the Mannich base or its quaternary derivative as a source of vinylketonc gives the butenolide derivative 8a. Isobutyl cyclohexenoneacetic acid (1b) previously stated to be the reaction product was present only as a by-product. When α-acetyl-α'-methyl succinate is treated with acrylic acid derivatives only butenolides 8c–8f were obtained.     

Quantitative determination of vitamin b12 by cyan dosage,with infrared absorption spectrophotometry

Microchimica Acta - Vitamin B12 has been determined by measurement of the infrared absorption of the cyano-group band at 2137 cm?1, the samples being pelleted with KBr. The error is within...     

Amplified extended modes in random lasers

We report on a new random laser phenomenon that gives rise to narrow emission modes without requiring optical cavities. Sharp emission peaks are observed experimentally over a broad range of scattering strengths and analyzed in numerical calculations. We find that the introduction of exponential gain in a multiple light scattering process strongly increases the importance of very long light paths. Such long paths are rare and often neglected in passive disordered materials but we show that they can dominate the emission spectrum from an amplifying disordered system.     

On the luminescence of luminol in DMSO in the presence of potassium superoxide-18-crown-6-ether and fluorescein

Luminol solution in DMSO in the presence of [18C6…K]⁺ O₂⁻ supramolecular complex (achieved from KO₂ and 18-Crown-6 (18C6)-ether) is chemiluminescent, and its intensity depends on the complex concentration. Using fluorescein (Fl) as an energy acceptor in this system, the luminescence energy transfer process from chemically excited species, aminophtalate dianion, to Fl could be evidenced. On the basis of Förster theory, the critical energy transfer distance, for both fluorescence and chemiluminescence, has been determined. The values are comparable: 22.41 Å (for chemiluminescence) and 20.88 Å (for fluorescence).     

Surface Adsorption and Photo-Reactivity of Sulfonylurea Herbicides

Photodegradation of two sulfonylurea herbicides, triasulfuron and thifensulfuron-methyl adsorbed on Preveza or Nea Malgara soils (Greece) was studied in outdoor and laboratory experiments. Herbicides on adsorbed phase and kept in the dark were characterised by a high reactivity, giving depletion curves that can be all described by a first order equation. In the irradiation experiments the kinetic behaviour of photodegradation was complex and characterised by a double step photoreaction. After a first period varying from 8 to 24 h the rate of reaction was reduced to 7-31% of the initial rate. The kinetic constant related to the degradation of triasulfuron practically showed the same values of those obtained for thifensulfuron-methyl. The half-lives obtained on Nea Malgara soil were generally higher than those obtained using Preveza soil. The observed behaviour is explained considering the photochemical properties of the herbicides, and the organic matter content of the soils.     

Universal bound on N-point correlations from inflation

Models of inflation in which non-Gaussianity is generated outside the horizon, such as curvaton models, generate distinctive higher-order correlation functions in the cosmic microwave background and other cosmological observables. Testing for violation of the Suyama-Yamaguchi inequality τ(NL) ≥ (6/5f (NL))(2), where f(NL) and f(NL) denote the amplitude of the three-point and four-point functions in certain limits, has been proposed as a way to distinguish qualitative classes of models. This inequality has been proved for a wide range of models, but only weaker versions have been proved in general. In this Letter, we give a proof that the Suyama-Yamaguchi inequality is always satisfied. We discuss scenarios in which the inequality may appear to be violated in an experiment such as Planck and how this apparent violation should be interpreted.     

Ab initio study of exchange coupling for the consistent understanding of the magnetic ordering at room temperature in V[TCNE] x

We report quantum chemical calculations providing the exchange coupling constants of the V[TCNE]₂ model system, describing the amorphous room temperature molecular magnet V[TCNE] _x (TCNE = tetracyanoethylene, x ~ 2). The geometry is optimized for the ideal lattice using density functional theory (DFT) calculations with periodic boundary conditions. Broken-symmetry DFT calculations indicate antiparallel spin alignment resulting in ferrimagnetic ordering, but heavily overestimate the value of the exchange coupling. Better estimates of the exchange coupling parameters between the V(II) ion and the [TCNE]^? anionic radical are obtained by means of multiconfigurational calculations performed on smaller molecular models cut from the optimized crystal lattice. Complete active space self-consistent field and multireference second-order perturbation theory calculations provide the sign and the strength of the nearest-neighbor as well as next-nearest-neighbor interactions along all three crystallographic directions. We are able to explain also intuitively the mechanism for antiferromagnetic spin coupling in terms of the superexchange pathways, discussing the role of the main four types of contributions to superexchange. Moreover, we clarify the influence of the transition metal ion on the strength of the exchange interaction and on the critical temperature for long-range ferrimagnetic ordering.