On the spin coating of viscoplastic fluids

The spin coating of a viscoplastic material is studied using a continuous viscosity function. Thus, the transient model requires the calculation of only velocity, pressure and the moving-free surface of the liquid film, but not the calculation of the yield surface within the liquid. A Finite Element/Newton-Raphson method is presented for solving this moving boundary problem after mapping the deforming domain onto a fixed one. Assuming axial symmetry, the effect of the Bingham, Reynolds, Capillary and gravitational Bond numbers is examined. The magnitude of the first two parameters affects significantly the flow field and the shape of the film as well as the required spinning time in order to produce a film of uniform thickness. Depending on their values, large departures from the corresponding Newtonian solution may be obtained. In these cases the film does not thin out uniformly, but a maximum in its profile is created at the center of the disk. Then, the magnitude of the Capillary number also affects the size of this maximum. The gravitational Bond number affects the film thickness and its profile to a lesser extent.Dedicated to the memory of Professor Tasos C. Papanastasiou     

Risk-Sensitive Control with Near Monotone Cost

The infinite horizon risk-sensitive control problem for non-degenerate controlled diffusions is analyzed under a ‘near monotonicity’ condition on the running cost that penalizes large excursions of the process.     

The effect of arsenic exposure on the biochemical and mineral contents of Labeo rohita bones: An FT-IR study

Arsenic compounds are ubiquitous and widespread in the environment as a result of natural or anthropogenic occurrence. Fish are the major source of protein for human consumption. They are also a source of contamination, because of the amounts of heavy elements they can contain, some of which are highly toxic. Fish bones are high in calcium, which is an essential mineral for normal body function. It consists of water, organic material, and mineral matter. Chelating agents have been used clinically as antidotes for acute and chronic metal intoxications. In the present study, an attempt is made to investigate the bio-accumulation of arsenic and its effect on the biochemical and mineral contents of Labeo rohita bones using, Fourier transform infrared (FT-IR) spectroscopy. The results of the present study indicate that arsenic exposure induces significant reduction on the biochemical and mineral contents of the L. rohita bones. Further, the DMSA treatment significantly improves these levels. This shows that DMSA is an effective chelator for arsenic toxicity. Quantitative curve-fitting analyses of amide I band have proved useful in studying the nature and the extent of protein conformational changes. A decrease in α-helical and random coil structures and an increase in β-sheet structures have been observed due to arsenic exposure. In conclusion, the present study shows that the FT-IR spectroscopy coupled with second derivative and curve-fitting analysis gives useful information about the biochemical and mineral contents of the L. rohita bones.     

FTIR study of zinc-induced biochemical changes in the liver of Indian carp <Emphasis Type="Italic">Labeo rohita</Emphasis>

Zinc is an essential metal for different physiological functions and becomes toxic when elevated concentrations are introduced into the environment. In the present study, an attempt is made to analyze zinc-induced biochemical changes in the liver tissues of freshwater fingerlings of Labeo rohita using Fourier Transformation Infrared Spectroscopy. Several important features have been observed in the FTIR spectra of zinc-intoxicated liver tissues, namely, altered membrane lipid, altered protein profile, and increased glycogen content, indicating an alteration in the lipid and protein profiles leading to modification in membrane composition. Further, it is observed that acute exposure to zinc causes some alteration in protein profile with a decrease in α-helix and an increase in random coil structure. Treatment with the chelating agent D-penicillamine reduces the biochemical contents in the liver tissues. This shows that D-penicillamine is a good antidote for zinc toxicity. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 746–752, September–October, 2008.     

Denumerable state stochastic games with limiting average payoff

We study stochastic games with countable state space, compact action spaces, and limiting average payoff. ForN-person games, the existence of an equilibrium in stationary strategies is established under a certain Liapunov stability condition. For two-person zero-sum games, the existence of a value and optimal strategies for both players are established under the same stability condition.The authors wish to thank Prof. T. Parthasarathy for pointing out an error in an earlier version of this paper. M. K. Ghosh wishes to thank Prof. A. Arapostathis and Prof. S. I. Marcus for their hospitality and support.     

Identification and characterization of stressed degradation products of metoprolol using LC/Q-TOF-ESI-MS/MS and MS(n) experiments

A rapid, specific and reliable isocratic high-performance liquid chromatography combined with quadrupole time-of-flight electrospray ionization tandem mass spectrometry (LC/Q-TOF-ESI-MS/MS) method has been developed and validated for the identification and characterization of stressed degradation products of metoprolol. Metoprolol, an anti-hypertensive drug, was subjected to hydrolysis (acidic, alkaline and neutral), oxidation, photolysis and thermal stress, as per ICH-specified conditions. The drug showed extensive degradation under oxidative and hydrolysis (acid and base) stress conditions. However, it was stable to thermal, neutral and photolysis stress conditions. A total of 14 degradation products were observed and the chromatographic separation of the drug and its degradation products was achieved on a C(18) column (4.6 × 250 mm, 5 μm). To characterize degradation products, initially the mass spectral fragmentation pathway of the drug was established with the help of MS/MS, MS(n) and accurate mass measurements. Similarly, fragmentation pattern and accurate masses of the degradation products were established by subjecting them to LC-MS/QTOF analysis. Structure elucidation of degradation products was achieved by comparing their fragmentation pattern with that of the drug. The degradation products DP(2) (m/z 153) and DP(14) (m/z 236) were matched with impurity B, listed in European Pharmacopoeia and British Pharmacopoeia, and impurity I, respectively. The LC-MS method was validated with respect to specificity, linearity, accuracy and precision.     

Identification and structural characterization of in vivo metabolites of ketorolac using liquid chromatography electrospray ionization tandem mass spectrometry (LC/ESI‐MS/MS)

In vivo metabolites of ketorolac (KTC) have been identified and characterized by using liquid chromatography positive ion electrospray ionization high resolution tandem mass spectrometry (LC/ESI‐HR‐MS/MS) in combination with online hydrogen/deuterium exchange (HDX) experiments. To identify in vivo metabolites, blood urine and feces samples were collected after oral administration of KTC to Sprague–Dawley rats. The samples were prepared using an optimized sample preparation approach involving protein precipitation and freeze liquid separation followed by solid‐phase extraction and then subjected to LC/HR‐MS/MS analysis. A total of 12 metabolites have been identified in urine samples including hydroxy and glucuronide metabolites, which are also observed in plasma samples. In feces, only O‐sulfate metabolite and unchanged KTC are observed. The structures of metabolites were elucidated using LC‐MS/MS and MSⁿ experiments combined with accurate mass measurements. Online HDX experiments have been used to support the structural characterization of drug metabolites. The main phase I metabolites of KTC are hydroxylated and decarbonylated metabolites, which undergo subsequent phase II glucuronidation pathways. Copyright © 2012 John Wiley & Sons, Ltd.     

Unprecedented synergistic effects between weak Lewis and Brønsted acids in Prins cyclization

Novel synergistic effects between Lewis and Br?nsted acids in Prins cyclization are reported. Non-reactive Lewis acids and non-reactive Br?nsted acids, which failed to perform Prins cyclization when used alone, have shown remarkable synergistic effects when used in combination to perform the reaction successfully.     

Identification and structural characterization of in vivo metabolites of ketorolac using liquid chromatography electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS)

In vivo metabolites of ketorolac (KTC) have been identified and characterized by using liquid chromatography positive ion electrospray ionization high resolution tandem mass spectrometry (LC/ESI-HR-MS/MS) in combination with online hydrogen/deuterium exchange (HDX) experiments. To identify in vivo metabolites, blood urine and feces samples were collected after oral administration of KTC to Sprague-Dawley rats. The samples were prepared using an optimized sample preparation approach involving protein precipitation and freeze liquid separation followed by solid-phase extraction and then subjected to LC/HR-MS/MS analysis. A total of 12 metabolites have been identified in urine samples including hydroxy and glucuronide metabolites, which are also observed in plasma samples. In feces, only O-sulfate metabolite and unchanged KTC are observed. The structures of metabolites were elucidated using LC-MS/MS and MS(n) experiments combined with accurate mass measurements. Online HDX experiments have been used to support the structural characterization of drug metabolites. The main phase I metabolites of KTC are hydroxylated and decarbonylated metabolites, which undergo subsequent phase II glucuronidation pathways.