A di-μ-oxomolybdenum(V) complex of 6-acetonylisoxanthopterin,undergoing oxygen atom transfer with dimethyl sulphoxide

The new compound, Na[(Mo₂ ^VO₄)(pte)(OMe)(MeOH)₂] (pte = anion of 6-acetonylisoxanthopterin), has been prepared using the redox non-innocent title ligand in MeOH–H₂O, and characterized by elemental analysis and physico-chemical methods including e.s.m.s., i.r., u.v.–vis. and ¹H-n.m.r. spectra. Rate constants data (1.4 × 10^–3 s^–1 at 300 K) for its oxygen atom transfer with dimethyl sulphoxide tally with those of synthetic analogue systems reported earlier by different authors. The negative activation entropy (–206.3 J mol^–1 deg^–1) is consistent with an associative mechanism for this reaction.     

Coordination chemistry of f-block elements with imine acids. Part IV. Synthetic and chiroptical studies on lanthanide(III) complexes of imine acids derived from L-alanine,L-valine,L-tyrosine and L-glutamic acid

Summary N-(orthovanillidene)L-alanine (OVAlaH₂), N-(salicylidene)L-valine (SValH₂), N-(orthovanillidene)L-valine (OVValH₂), N-(orthovanillidene)L-tyrosine (OVTyrH₃) and N-(salicylidene)L-glutamic acid (SGluH₃) react with La^III, Pr^III, Nd^III and Sm^III to yield new chiral complexes. Their dominant conformers were determined from c.d. spectra supported by¹H n.m.r. data, except for the L-glutamic acid derived complexes which were insoluble.     

Simple thiazocine-2-acetic acid derivatives via ring-closing metathesis

A new protocol for synthesis of 2-heterocylylacetic acid derivatives involving conjugate addition of allyl mercaptan to an acrylate containing a tethered olefinic site followed by RCM (ring-closing metathesis) is described. In this series, sulfanyl derivatives were unreactive, while sulfoxide and sulfone analogues provided the corresponding thiazocines in fair to excellent yields. Use of the sulfoxide oxidation state as a protecting group for sulfides inert to RCM is demonstrated also. Thus, oxidation of sulfide 9 [N-allyl-N-[2-(allylthio)-4-(1H-indol-1-yl)-4-oxobutyl]-4-methylbenzenesulfonamide] followed by cyclization yielded the corresponding thiazocine sulfoxide 12. Deprotection (deoxygenation) of 12 was accomplished using Lawesson's reagent, producing 1-[[4-[4-(methylphenyl)sulfonyl]-3,4,5,8-tetrahydro-2H-1,4-thiazocin-2-yl]acetyl]-1H-indole (21) in 67% unoptimized yield.     

Development and validation of LC‐MS/MS method for the estimation of β‐hydroxy‐β‐methylbutyrate in rat plasma and its application to pharmacokinetic studies

A simple, sensitive and specific high‐performance liquid chromatography mass spectrometry (LC‐MS/MS) method was developed and validated for the quantification of β‐hydroxy‐β‐methyl butyrate (HMB) in small volumes of rat plasma using warfarin as an internal standard (IS). The API‐4000 LC‐MS/MS was operated under the multiple reaction‐monitoring mode using the electrospray ionization technique. A simple liquid–liquid extraction process was used to extract HMB and IS from rat plasma. The total run time was 3 min and the elution of HMB and IS occurred at 1.48 and 1.75 min respectively; this was achieved with a mobile phase consisting of 0.1% formic acid in a water–acetonitrile mixture (15:85, v/v) at a flow rate of 1.0 mL/min on a Agilent Eclipse XDB C₈ (150 × 4.6, 5 µm) column. The developed method was validated in rat plasma with a lower limit of quantitation of 30.0 ng/mL for HMB. A linear response function was established for the range of concentrations 30–4600 ng/mL (r > 0.998) for HMB. The intra‐ and inter‐day precision values for HMB were acceptable as per Food and Drug Administration guidelines. HMB was stable in the battery of stability studies, viz. bench‐top, autosampler freeze–thaw cycles and long‐term stability for 30 days in plasma. The developed assay method was applied to a bioavailability study in rats. Copyright © 2012 John Wiley & Sons, Ltd.     

Influence of preparation route and slip casting conditions on titania and barium titanate ceramics

Titania (TiO₂) and barium titanate (BaTiO₃) were synthesized using three different dicarboxylates, which included oxalate, malate and tartarate. These powders were characterized by X-ray powder diffraction, scanning electron micrographs, BET specific surface area and particle size distribution. Their properties depended to a great extent on the nature of the precursor. The titania and barium titanate powders obtained from the tartarate precursor were found to be good for slip casting. Slips of these oxides with different solids contents were prepared at different pH values using both distilled water and ethanol as the dispersing agent and also with and without deflocculant. The rheological behaviors of the suspensions were then determined, and the slip, green and sedimentation bulk densities were measured. The minimum viscosities were observed at pH 8.2 for the TiO₂–water and pH 10.2 for the BaTiO₃–water system.     

Cavity cluster approach for quantification of cavitational intensity in sonochemical reactors

The mechanism involved in the spectacular effects from cavitation phenomenon is very complex and there have been several proposed theories to explain the observed results. The experimental as well as the visual observations indicate that a single collapsing cavity is also influenced by the dynamics of the surrounding cavities, which are very near to the collapsing cavity. The observed effects and erosion patterns cannot be explained properly on the basis of a single cavity collapse and hence in this study a cavity cluster (group of cavities) has been considered to understand the mechanism of cavitational effects. The effect of intensity, frequency of ultrasound, initial size of the cluster and the fraction of energy transferred from the collapsing cavities to the surrounding cavities on the cavitational intensity quantified in terms of the pressure pulse generated at the collapse of cavities as well as the active zone of cavitation has been investigated using bubble/cavity dynamics equations, numerically. On the basis of the trends obtained, empirical correlations estimating the collapse pressure and active volume of cavitation, have been developed.     

Tracking an Auto-Regressive Process with Limited Communication per Unit Time

Samples from a high-dimensional first-order auto-regressive process generated by an independently and identically distributed random innovation sequence are observed by a sender which can communicate only finitely many bits per unit time to a receiver. The receiver seeks to form an estimate of the process value at every time instant in real-time. We consider a time-slotted communication model in a slow-sampling regime where multiple communication slots occur between two sampling instants. We propose a successive update scheme which uses communication between sampling instants to refine estimates of the latest sample and study the following question: Is it better to collect communication of multiple slots to send better refined estimates, making the receiver wait more for every refinement, or to be fast but loose and send new information in every communication opportunity? We show that the fast but loose successive update scheme with ideal spherical codes is universally optimal asymptotically for a large dimension. However, most practical quantization codes for fixed dimensions do not meet the ideal performance required for this optimality, and they typically will have a bias in the form of a fixed additive error. Interestingly, our analysis shows that the fast but loose scheme is not an optimal choice in the presence of such errors, and a judiciously chosen frequency of updates outperforms it.     

Ultrasonic degradation of polymers: effect of operating parameters and intensification using additives for carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA)

Use of ultrasound can yield polymer degradation as reflected by a significant reduction in the intrinsic viscosity or the molecular weight. The ultrasonic degradation of two water soluble polymers viz. carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) has been studied in the present work. The effect of different operating parameters such as time of irradiation, immersion depth of horn and solution concentration has been investigated initially using laboratory scale operation followed by intensification studies using different additives such as air, sodium chloride and surfactant. Effect of scale of operation has been investigated with experiments in the available different capacity reactors with an objective of recommending a suitable type of configuration for large scale operation. The experimental results show that the viscosity of polymer solution decreased with an increase in the ultrasonic irradiation time and approached a limiting value. Use of additives such as air, sodium chloride and surfactant helps in increasing the extent of viscosity reduction. At higher frequency operation the viscosity reduction has been found to be negligible possibly attributed to less contribution of the physical effects. The viscosity reduction in the case of ultrasonic horn has been observed to be more as compared to other large capacity reactors. Kinetic analysis of the polymer degradation process has also been performed. The present work has enabled us to understand the role of the different operating parameters in deciding the extent of viscosity reduction in polymer systems and also the controlling effects of low frequency high power ultrasound with experiments on different scales of operation.     

Interactive classification using data envelopment analysis

In this paper, we illustrate how data envelopment analysis (DEA) can be used to aid interactive classification. We assume that the scoring function for the classification problem is known. We use DEA to identify difficult to classify cases from a database and present them to the decision-maker one at a time. The decision-maker assigns a class to the presented case and based on the decision-maker class assignment, a tradeoff cutting plane is drawn using the scoring function and decision-maker’s input. The procedure continues for finite number of iterations and terminates with the final discriminant function. We also show how a hybrid DEA and mathematical programming approach can be used when user interaction is not desired. For non-interactive case, we compare a hybrid DEA and mathematical programming based approach with several statistical and machine learning approaches, and show that the hybrid approach provides competitive performance when compared to the other machine learning approaches.