A New Synthesis of Quinoline-5,8-Quinone

Sensitised photo-oxidations of 8-hydroxy quinoline (l)or5-hydroxy quinoline (2) gives quinoline-5,8-quinone (3) in 64-70% yield.     

Localization of Fatty Acyl and Double Bond Positions in Phosphatidylcholines Using a Dual Stage CID Fragmentation Coupled with Ion Mobility Mass Spectrometry

A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M?+?Li]⁺ was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C₁₅H₃₁CO⁺, m/z 239) or 18:1 (9Z) (C₁₇H₃₃CO⁺, m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H₂C-HC?=?CH-CH?=?CH₂). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of ¹³C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC.     

Synthesis, characterization and structures of 2-(3,5-dimethylpyrazol-1-yl)ethylseleno derivatives and their probable glutathione peroxidase (GPx) like activity

A series of 2-(3,5-dimethylpyrazol-1-yl)ethylseleno derivatives has been synthesized. The glutathione peroxidase like catalytic activity of these compounds has been studied in a model system, in which reduction of hydrogen peroxide with dithiothreitol (DTT(red)), in the presence of an organoselenium compound was investigated by (1)H NMR spectroscopy. All these compounds exhibit GPx like catalytic activities and the catalytic reaction proceeds through a selenoxide intermediate, identified by (77)Se{(1)H} NMR spectroscopy.     

Microbial metabolism. Part 12. Isolation, characterization and bioactivity evaluation of eighteen microbial metabolites of 4'-hydroxyflavanone

Fermentation of 4'-hydroxyflavanone (1) with fungal cultures, Beauveria bassiana (ATCC 13144 and ATCC 7159) yielded 6,3',4'-trihydroxyflavanone (2), 3',4'-dihydroxyflavanone 6-O-β-D-4-methoxyglucopyranoside (3), 4'-hydroxyflavanone 3'-sulfate (4), 6,4'-dihydroxyflavanone 3'-sulfate (5) and 4'-hydroxyflavanone 6-O-β-D-4-methoxyglucopyranoside (7). B. bassiana (ATCC 13144) and B. bassiana (ATCC 7159) in addition, gave one more metabolite each, namely, flavanone 4'-O-β-D-4-methoxyglucopyranoside (6) and 6,4'-dihydroxyflavanone (8) respectively. Cunninghamella echinulata (ATCC 9244) transformed 1 to 6,4'-dihydroxyflavanone (8), flavanone-4'-O-β-D-glucopyranoside (9), 3'-hydroxyflavanone 4'-sulfate (10), 3',4'-dihydroxyflavanone (11) and 4'-hydroxyflavanone-3'-O-β-D-glucopyranoside (12). Mucor ramannianus (ATCC 9628) metabolized 1 to 2,4-trans-4'-hydroxyflavan-4-ol (13), 2,4-cis-4'-hydroxyflavan-4-ol (14), 2,4-trans-3',4'-dihydroxyflavan-4-ol (15), 2,4-cis-3',4'-dihydroxyflavan-4-ol (16), 2,4-trans-3'-hydroxy-4'-methoxyflavan-4-ol (17), flavanone 4'-O-α-D-6-deoxyallopyranoside (18) and 2,4-cis-4-hydroxyflavanone 4'-O-α-D-6-deoxyallopyranoside (19). Metabolites 13 and 14 were also produced by Ramichloridium anceps (ATCC 15672). The former was also produced by C. echinulata. Structures of the metabolic products were elucidated by means of spectroscopic data. None of the metabolites tested showed antibacterial, antifungal and antiprotozoal activities against selected organisms.     

Orbital alignment in photodissociation probed using strong field ionization

The photodissociation of molecules often produces atomic fragments with polarized electronic angular momentum, and the atomic alignment, for example, can provide valuable information on the dynamical pathways of chemical reactions unavailable by other means. In this work, we demonstrate for the first time that orbital polarization in chemical reactions can be measured with great sensitivity using strong field ionization by exploiting its extreme nonlinearity.     

Non-standard asymptotics in an inhomogeneous gamma process

Nonhomogeneous Poisson process (NHPP) is a commonly used stochastic model that is utilized to describe the pattern of repeated occurrence of certain events or conditions. Aninhomogeneous gamma process evolves as a generalization to NHPP, where the observed failure epochs correspond to every successive κ-th event of the underlying Poisson process, κ being an unknown parameter to be estimated from the data. This article focuses on a special class of inhomogeneous gamma process, calledmodulated power law process (MPLP) that assumes the Weibull form of the intensity function. The traditional power law process is a popular stochastic formulation of certain empirical relationships between the time to failure and the cumulative number of failures, often observed in industrial experiments. The MPLP retains this underlying physical basis and provides a more flexible modeling environment potentially leading to a better fit to the failure data at hand. In this paper, we investigate inference issues related to MPLP. The maximum likelihood estimators (MLE’s) of the model parameters are not in closed form and enjoy the curious property that they are asymptotically normal with a singular variance-covariance matrix. Consequently, the derivation of the large-sample results requires non-standard modifications of the usual arguments. We also propose a set of simple closed-form estimators that are asymptotically equivalent to the MLE’s. Extensive simulation results are carried out to supplement the theoretical findings. Finally, we implement our inference results to a failure dataset arising from a repairable system.     

A new methodology for realizing magnification of holographic images

The article describes a new method for obtaining a holographic image of desired magnification, consistent with the stipulated criteria for its resolution and aberrations.     

Optimal buffer size and dynamic rate control for a queueing system with impatient customers in heavy traffic

We address a rate control problem associated with a single server Markovian queueing system with customer abandonment in heavy traffic. The controller can choose a buffer size for the queueing system and also can dynamically control the service rate (equivalently the arrival rate) depending on the current state of the system. An infinite horizon cost minimization problem is considered here. The cost function includes a penalty for each rejected customer, a control cost related to the adjustment of the service rate and a penalty for each abandoning customer. We obtain an explicit optimal strategy for the limiting diffusion control problem (the Brownian control problem or BCP) which consists of a threshold-type optimal rejection process and a feedback-type optimal drift control. This solution is then used to construct an asymptotically optimal control policy, i.e. an optimal buffer size and an optimal service rate for the queueing system in heavy traffic. The properties of generalized regulator maps and weak convergence techniques are employed to prove the asymptotic optimality of this policy. In addition, we identify the parameter regimes where the infinite buffer size is optimal.