4-Aminophthalimide Derivatives as Environment-Sensitive Probes

The potential of 4-aminophthalimide (AP) and its derivatives as fluorescence probes for organized media is highlighted. The fluorescence response of AP, as measured from the position of the fluorescence maximum, fluorescence intensity and lifetime, is highly sensitive to the polarity of the medium. The sensitivity of the fluorescence parameters is further enhanced due to the involvement of the emitting intramolecular charge transfer state in hydrogen bonding interaction with the solvent molecules containing hydroxyl groups. It is shown that the microheterogeneous environments of organized media such as cyclodextrins and micelles can be very conveniently monitored using this probe. The results of the investigations carried out employing AP and its derivatives as fluorescence probe molecules in these media clearly suggest that a combination of the hydrophobic interaction with the host media and hydrogen bonding interaction with the solvent molecules determine the location of the fluorophore, which in all cases is found to be the interfacial region separating the nonpolar core of the micelle or the cyclodextrin cavity and the polar aqueous environment. Guidelines for the design of probes of this class of systems for the nonpolar core region of the micelles are provided and possible ways to increase the sensitivity of the fluorescence response of the systems are suggested.     

Going Off the Grid: Iterative Model Selection for Biclustered Matrix Completion

We consider the problem of performing matrix completion with side information on row-by-row and column-by-column similarities. We build upon recent proposals for matrix estimation with smoothness constraints with respect to row and column graphs. We present a novel iterative procedure for directly minimizing an information criterion to select an appropriate amount of row and column smoothing, namely, to perform model selection. We also discuss how to exploit the special structure of the problem to scale up the estimation and model selection procedure via the Hutchinson estimator, combined with a stochastic Quasi-Newton approach. Supplementary material for this article is available online.     

Efficient Krylov subspace methods for uncertainty quantification in large Bayesian linear inverse problems

Uncertainty quantification for linear inverse problems remains a challenging task, especially for problems with a very large number of unknown parameters (e.g., dynamic inverse problems) and for problems where computation of the square root and inverse of the prior covariance matrix are not feasible. This work exploits Krylov subspace methods to develop and analyze new techniques for large‐scale uncertainty quantification in inverse problems. In this work, we assume that generalized Golub‐Kahan‐based methods have been used to compute an estimate of the solution, and we describe efficient methods to explore the posterior distribution. In particular, we use the generalized Golub‐Kahan bidiagonalization to derive an approximation of the posterior covariance matrix, and we provide theoretical results that quantify the accuracy of the approximate posterior covariance matrix and of the resulting posterior distribution. Then, we describe efficient methods that use the approximation to compute measures of uncertainty, including the Kullback‐Liebler divergence. We present two methods that use the preconditioned Lanczos algorithm to efficiently generate samples from the posterior distribution. Numerical examples from dynamic photoacoustic tomography demonstrate the effectiveness of the described approaches.     

Vapor phase acylation of phenol over Hβ, CeHβ and SO42-/ZrO2a

Phenol acylation on Hβ, CeHβ and SO₄ ^2-/ZrO₂ using acetic acid and acetic anhydride as acylating agents is compared in the temperature range 250-400°C. Acetic acid formed phenyl acetate (PA) and o-hydroxy acetophenone (o-HAP) and acetic anhydride formed p-hydroxyacetophenone (p-HAP ) along with PA and o-HAP. The formation of o-HAP and p-HAP, the products of C-acylation of phenol using acetic acid is proposed by studying phenyl acetate conversion on Hb, CeHβ and SO₄ ^2-/ZrO₂. Our studies show that for phenol acylation the most suitable acid site is available on CeHβ. This revised version was published online in June 2006 with corrections to the Cover Date.     

Kinetics and mechanism of electron transfer reactions involving pyridinium chlorochromate and α-hydroxy acids in acid medium catalysed by ruthenium(III)

Summary The oxidation of -hydroxy acids (HA), viz. glycolic acid (GA), mandelic acid (MA) and lactic acid (LA), by pyridinium chlorochromate (PCC) in aqueous ethanoic acid solution was investigated in the presence and absence of Ru^IIICl₃. The order in [HA] and [PCC] was found to be unity, with or without ruthenium(III) catalyst, and the order in [Ru^III] was found also to be unity. The reaction was acid catalysed also in the presence and absence of ruthenium(III) catalyst, and hence the protonated form of PCC, was assumed to be the active species of oxidant. Added salts, and the change in dielectric constant of the medium, did not affect the oxidation rate. No induced polymerization occurred when acrylamide monomer was added to the reaction mixture. The pseudo-first order rate constants (k the formation constants (K _f) of the substrate-catalyst complexes, activation and thermodynamic parameters have been evaluated. Suitable mechanisms in conformity with the experimental observations have been proposed for the uncatalysed and catalysed reactions.     

Photophysical behaviour of some pyrenylethylene derivatives and its implication on trans → cis photoisomerisation reactions

The fluorescence properties of some pyrenylethylene derivatives capable of exhibiting twisted intramolecular charge transfer phenomenon havebeen studied as a function of solvent polarity. The solvent polarity dependent change in the fluorescence quantum yield has been interpreted in terms of intramolecular retational relaxations. The trans → cis photoisomerization data of the compounds indicate that the twist around the ethylenic double bond is accelerated in polar solvents.     

Ruthenium(III), osmium(VIII) and ruthenium(III) + osmium(VIII) catalysed oxidations ofi-propanol by N-bromosuccinimide in basic solution

Summary The oxidation ofi-propanol (IPA) by N-bromosuccinimide (NBS) in basic solution was investigated separately in the presence of Ru^III, Os^VIII and Ru^III + Os^VIII ions. The order in [IPA] was found to be 0.7, 0.5 and 0.3 respectively in the above three cases in the concentration range studied. The order in [NBS] was unity in the presence of Ru^III chloride but was found to be zero in the case of Os^VIII and Ru^III+Os^VIII catalysis. The order in [metalion] was found to be nearly unity in all the three catalysed reactions. Increase in [^–OH] increased the rate of reaction while addition of succinimide retarded the rate of reaction. Decrease in dielectric constantsof the medium decreased the rate of oxidation. The pseudo first order rate constants (k), zero order rate constants (k₀) and the formation constants (k_f) of the substrate-catalyst complexes and the thermodynamic parameters have been evaluated. Suitable mechanisms in conformity with the experimental observations have been proposed for the three catalysed reactions.     

In vivo metabolic investigation of silodosin using UHPLC–QTOF–MS/MS and in silico toxicological screening of its metabolites

Silodosin (SLD) is a novel α1‐adrenoceptor antagonist which has shown promising clinical efficacy and safety in patients with benign prostatic hyperplasia (BPH). However, lack of information about metabolism of SLD prompted us to investigate metabolic fate of SLD in rats. To identify in vivo metabolites of SLD, urine, feces and plasma were collected from Sprague–Dawley rats after its oral administration. The samples were prepared using an optimized sample preparation approach involving protein precipitation followed by solid‐phase extraction and then subjected to LC/HR‐MS/MS analysis. A total of 13 phase I and six phase II metabolites of SLD have been identified in rat urine which includes hydroxylated, N‐dealkylated, dehydrogenated, oxidative, glucosylated, glucuronide and N‐sulphated metabolites, which are also observed in feces. In plasma, only dehydrogenated, N‐dealkylated and unchanged SLD are observed. The structure elucidation of metabolites was done by fragmentation in MS/MS in combination with HRMS data. The potential toxicity profile of SLD and its metabolites were predicted using TOPKAT software and most of the metabolites were proposed to show a certain degree of skin sensitization and occular irritancy. Copyright © 2016 John Wiley & Sons, Ltd.     

A Convenient Method of Esterification of Fatty Acids. Preparation of Alkyl Esters,Sterol Esters,Wax Esters and Triacylglycerols

A quick and mild, one-pot method of esterification of fatty acids with primary, secondary and tertiary alcohols as well as with fatty alcohols, sterols and glycerol is proposed via the acyl bromides formed in situ.