Photodegradation of butyl acrylate in the troposphere by OH radicals: kinetics and fate of 1,2‐hydroxyalcoxy radicals

The rate constant of the reaction of OH radicals with butyl acrylate was studied for the first time using an atmospheric simulation chamber at 298 K and ～750 Torr of air or nitrogen. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC‐FID), and the rate constant was determined using a relative rate method with different references. The obtained average value of (1.80 ± 0.26) × 10^?11 cm³ molecule^?1 s^?1 is in agreement with previous determinations of the rate constants of OH radicals with acrylates and methacrylates in the literature. Additionally, product identification under atmospheric conditions was performed for the first time by the GC‐MS technique. Butyl glyoxalate was observed as the degradation product in accordance with the addition of OH to the less substituted carbon atom of the double bond, followed by decomposition of the 1,2‐hydroxyalkoxy radicals formed. Room temperature rate coefficient was used to estimate the atmospheric lifetime of the ester studied. Reactivity trends are discussed in terms of the substituent effects and the length of the hydrogenated chain of the ester. The atmospheric persistence of BUAC was calculated taking into account the experimental rate constant obtained. Copyright © 2008 John Wiley & Sons, Ltd.     

Alkaline hydrolysis of cephaloridine: An 1H?NMR study. Temperature dependence of the rate constants

A kinetic study on the basic hydrolysis of cephaloridine at pD= 10.5 was carried out by using the ¹H? NMR technique. Epimerization at H₇, a nucleophilic attack of hydroxyl ion on the β-lactam carbonyl group followed by the release of the pyridine molecule, and isomerization of the double bond at position 3 in the dihydrothiazine ring were the major reactions observed. Based on the results obtained, it should be emphasized that the presence of a pyridine group at 3′ results in a slightly increased formation constant for the exo methylene compound relative to other cephalosporins with different substituents at that position. The activation energy for the epimerization constant and the cleavage of the β-lactam ring at pD 10.5 was 21.2 kcal/mol. © 1993 John Wiley & Sons, Inc.     

Non-aqueous fluorimetric determination of scandium in silicate rocks

A method for the fluorimetric determination of scandium with 1,2,7-trihydroxyanthraquinone in dimethylformamide medium is described. The calibration graphs obtained by the normal, synchronous, and synchronous first and second derivative techniques are linear between 12 and 225 ng/ml, and the detection limit is 2 ng/ml. The method is applied to the determination of Sc(III) in two simulated and two naturally occurring rocks.     

The Blume-Emery-Griffiths neural network with synchronous updating and variable dilution

The thermodynamic and retrieval properties of the Blume-Emery-Griffiths neural network with synchronous updating and variable dilution are studied using replica mean-field theory. Several forms of dilution are allowed by pruning the different types of couplings present in the Hamiltonian. The appearance and properties of two-cycles are discussed. Capacity-temperature phase diagrams are derived for several values of the pattern activity. The results are compared with those for sequential updating. The effect of self-coupling is studied. Furthermore, the optimal combination of dilution parameters giving the largest critical capacity is obtained.     

Micro-Raman investigations of the formaldehyde-ice system

Rapidly frozen aqueous solutions containing variable amounts of dissolved formaldehyde (0.1, 5, 7, 10, 15, and 20 mol %) have been analyzed by micro-Raman spectroscopy at ambient pressure and low temperature. The importance of the formladehyde-ice system has been repeatedly quoted in various contexts, such as atmospheric and snowpack chemistry and interstellar and cometary ices. Understanding and characterizing the effects of freezing and the interactions of formaldehyde with ice are therefore of relevant interest. In this study, the distinct vibrational signatures of the oligomers present in the solution and in the frozen ice mixtures have been identified in the 120-4000 cm(-1) spectral range. From the subtle changes of the bands assigned to the CO and CH group frequencies, at least two distinct crystalline phases (pI and pII) are found to coexist with ice at different temperatures. Depending on the cooling-rewarming protocol, pI is found to crystallize in the 163-213 K temperature range. Above approximately 213 K, pI gets transformed irreversibly into pII which is stable up to approximately 234 K. pII is found to interact more strongly with ice than pI, as revealed, for example, by the drop in frequency of the bands assigned to the O-H stretching as pI transforms into pII. It is suggested that pII consists of a hydrogen-bonded network of oligomers and water molecules. On the other hand, it is suggested that the oligomers mainly present in pI interact through weak forces with the surrounding water molecules.     

Monte carlo estimates of domain-deformation sensitivities

It is shown that, when a Monte Carlo algorithm is used for estimation of any physical quantity A, a simple and fast additional procedure can be implemented that simultaneously estimates the sensitivity of A to any problem parameter. The proposed approach is general and systematic in the sense that: (i) it includes domain-deformation sensitivities, i.e., cases where a change in the parameter modifies the domain over which the sampled random variables are defined and (ii) a simple generic procedure is presented to address all remaining free choices in terms of variance minimization.     

Self-similarities in the frequency-amplitude space of a loss-modulated CO2 laser

We show the standard two-level continuous-time model of loss-modulated CO2 lasers to display the same regular network of self-similar stability islands known so far to be typically present only in discrete-time models based on mappings. Our results suggest that the two-parameter space of class B laser models and that of a certain class of discrete mappings could be isomorphic.     

On the Rubin–Stark Conjecture for a special class of CM extensions of totally real number fields

We use Greithers recent results on Brumers Conjecture to prove Rubins integral version of Starks Conjecture, up to a power of 2, for an infinite class of CM extensions of totally real number fields, called nice extensions under the assumption that a certain Iwasawa –invariant vanishes. As a consequence and under the same assumption, we show that the Brumer–Stark Conjecture is true for nice extensions, up to a power of 2.Mathematical Subject Classification (1991): 11R42, 11R58, 11R27Research on this project was partially supported by NSF grants DMS–9801267 and DMS–0196340.in final form: 16 July 2003     

Structural and spectroscopic study of 5,7-dihydroxy-flavone and its complex with aluminum

The structure, stability and molar absorptivity of the complex formed between AlCl(3) and 5,7-dihydroxy-flavone in methanol were investigated using UV-Vis spectroscopy and the AM1 method. The molar ratio method and Job's method of continuous variation were applied to ascertain the stoichiometric composition of the complex in methanol at constant ionic strength. A 1:2 complex was indicated by both methods. The molar absorptivity and stability constant of the complex were determined using a simple and accurate procedure that requires solutions having the ligand and metal ion in the stoichiometric proportion. The high stability constant demonstrates that the complexation reaction is total. The structure of this complex, obtained by the quantum semi-empirical AM1 method, indicates that two classes of metal-ligand interactions are involved in the formation of the metal complex: (a) two simple covalent bonds between the aluminum atom and the oxygen atoms of o-hydroxyl groups of 5,7-dihydroxy-flavone; (b) two stronger Coulombic interactions between the aluminum atom and the carbonyl oxygen atoms of the ligand.     

On the Norm of Elementary Operators

The norm problem is considered for elementary operators of theform U_a,b: AA,x axb+bxa (a,bA) in the special case when A isa subalgebra of the algebra of bounded operators on a Banachspace. In particular, the lower estimate || is established when the Banach space is a Hilbertspace and A is the algebra of all bounded linear operators.