Highly Selective Asymmetric Intramolecular Selenocyclisation

Asymmetric intramolecular selenocyclisation of alkenoic acids, alkenols and alkenyl urethanes using chiral ferrocenylselenenyl cations proceeds smoothly to give the corresponding lactones, cyclic ethers and N-heterocyclic compounds, respectively, in moderate yields with very high diastereoselectivities.     

Surface-Mediated Solid Phase Reaction. IX. A Convenient Procedure for Aldol Reaction of Ketene Silyl Acetals with Aldehydes on the Solid Surface of Alumina

The aldol reaction of ketene silyl acetals with aldehydes proceeds efficiently on the solid surface of alumina impregnated with anhydrous zinc chloride under sonication providing aldol products in high yields and with good stereoselectivity.     

Toward numerical simulations of fluid–structure interactions for investigation of obstructive sleep apnea

Obstructive sleep apnea (OSA) is a medical condition characterized by repetitive partial or complete occlusion of the airway during sleep. The soft tissues in the airway of OSA patients are prone to collapse under the low-pressure loads incurred during breathing. This paper describes efforts toward the development of a numerical tool for simulation of air–tissue interactions in the upper airway of patients with sleep apnea. A procedure by which patient-specific airway geometries are segmented and processed from dental cone-beam CT scans into signed distance fields is presented. A sharp-interface embedded boundary method based on the signed distance field is used on Cartesian grids for resolving the airflow in the airway geometries. For simulation of structure mechanics with large expected displacements, a cut-cell finite element method with nonlinear Green strains is used. The fluid and structure solvers are strongly coupled with a partitioned iterative algorithm. Preliminary results are shown for flow simulation inside the three-dimensional rigid upper airway of patients with obstructive sleep apnea. Two validation cases for the fluid–structure coupling problem are also presented.     

An efficient green protocol for the synthesis of coumarin fused highly decorated indenodihydropyridyl and dihydropyridyl derivatives

A simple, convenient, environmentally benign, and mild synthetic method has been established to afford highly decorated indenodihydropyridine and dihydropyridine derivatives employing a green solvent ethyl-l-lactate and an organo-catalyst (±)lactic acid. A wide range of functional groups were tolerated in the developed protocol. The target molecules were obtained in moderate to good yields applying the current method.     

Viscous flow in a mixed compression intake

Numerical simulation of the flow in a two‐dimensional mixed compression intake is carried out by solving unsteady viscous compressible equations using a stabilized finite element method. The effect of bleed in starting/unstarting of the intake and controlling the buzz instability is investigated in detail. Higher bleed leads to an increase in the ability of the intake to sustain larger back‐pressure for stable operation. The amount of bleed and its location is varied to understand its effect on the performance of the intake. Two kinds of unsteady oscillations are observed: ‘little’ and ‘big’ buzz. The frequency of the both kinds of buzz oscillations is found to be super‐harmonic of the fundamental acoustic frequency of intake modeled as an open‐closed organ pipe. The frequency as well as amplitudes of the big buzz cycles is larger than those of the little buzz. The little‐ and big‐buzz are found to occur for low‐ and high‐subcritical state of the intake and are very similar to Ferri and Dailey criteria, respectively. Buzz is eliminated when relatively high bleed is implemented, both, upstream and downstream of the throat. The effect of rate of change of back‐pressure on the start/unstart of the intake is investigated. Two situations are considered. The first case is that of an intake where the back‐pressure remains below the critical value. It is found that the intake remains started if the change in back‐pressure is gradual. However, it unstarts if the back‐pressure is changed relatively rapidly. The second set of simulations is an attempt to model the situation where the back‐pressure at the exit of the intake exceeds the critical value and a logic is incorporated in the feed back loop of the fuel modulation to start the intake. Low rate of change of pressure is unsuccessful in starting the intake. Relatively high rates result in either a quick starting of the intake or a slow unstart. Copyright © 2010 John Wiley & Sons, Ltd.     

Kinetics of Polymerization of Methyl Methacrylate initiated by AIBN in the Presence of Acetophenone

The present investigation aims at estimating the retarding effect of acetophenone in the polymerization of methyl methacrylate initiated by α,α' -azobisisobutyronitrile in the temperature range of 50 to 80°C. The results are interpreted in terms of Tüdös kinetic parameter (β). The effects of varying concentrations of substrate, monomer, initiator, and salts have been investigated. A suitable reaction scheme and rate expression have been suggested on the basis of the experimental findings, and another kinetic parameter (K) to represent the reactivity of acetophenones toward the polymer radical has been obtained graphically.     

Immobilized Carboxypeptidase A for Sequential Analysis

The use of carboxypeptidase for sequence determination is attractive because of its technical simplicity. In chemical methods all molecules of a peptide are made to go through a degradation cycle before a new cycle is started. In the enzymatic degradation of a protein, the order of the amino acid residues is not necessarily determined in a stepwise fashion but rather from the rate at which the amino acids appear in the digest, i.e., an amino acid appearing faster than another presumably precedes it in the sequence. Under favorable circumstances the rate of appearance of the amino acids released during digestion give sufficient evidence for the C-terminal sequence to be deduced. The present work pertains to a study on the use of immobilized carboxypeptidase A columns for sequential analyses.     

Profiling primaquine metabolites in primary human hepatocytes using UHPLC‐QTOF‐MS with 13C stable isotope labeling

Therapeutic efficiency and hemolytic toxicity of primaquine (PQ), the only drug available for radical cure of relapsing vivax malaria are believed to be mediated by its metabolites. However, identification of these metabolites has remained a major challenge apparently due to low quantities and their reactive nature. Drug candidates labeled with stable isotopes afford convenient tools for tracking drug‐derived metabolites in complex matrices by liquid chromatography‐tandem mass spectrometry (LC‐MS‐MS) and filtering for masses with twin peaks attributable to the label. This study was undertaken to identify metabolites of PQ from an in vitro incubation of a 1:1 w/w mixture of ¹³C₆‐PQ/PQ with primary human hepatocytes. Acquity ultra‐performance LC (UHPLC) was integrated with QTOF‐MS to combine the efficiency of separation with high sensitivity, selectivity of detection and accurate mass determination. UHPLC retention time, twin mass peaks with difference of 6 (originating from ¹³C₆‐PQ/PQ), and MS‐MS fragmentation pattern were used for phenotyping. Besides carboxy‐PQ (cPQ), formed by oxidative deamination of PQ to an aldehyde and subsequent oxidation, several other metabolites were identified: including PQ alcohol, predictably generated by oxidative deamination of PQ to an aldehyde and subsequent reduction, its acetate and the alcohol's glucuronide conjugate. Trace amounts of quinone‐imine metabolites of PQ and cPQ were also detected which may be generated by hydroxylation of the PQ/cPQ quinoline ring at the 5‐position and subsequent oxidation. These findings shed additional light on the human hepatic metabolism of PQ, and the method can be applied for identification of reactive PQ metabolites generated in vivo in preclinical and clinical studies. Copyright © 2013 John Wiley & Sons, Ltd.     

Low-Valent Titanium Mediated Deprotection of N-Allyl/Benzyl Amines: A New Approach

A novel low-valent titanium (LVT) mediated cleavage of N-allyl/benzyl amines is reported. Regio- and chemo-selective cleavages were also observed.