Identification of common glycosyl groups of flavonoid O‐glycosides by serial mass spectrometry of sodiated species

Flavonoid O‐glycosides are a ubiquitous and important group of plant natural products in which a wide variety of sugars are O‐linked to an aglycone. Determining the identity of the sugars, and the manner in which they are linked, by mass spectrometry alone is challenging. To improve the identification of common O‐linked di‐ and trisaccharides when analysing mixtures of flavonoid O‐glycosides by liquid chromatography/mass spectrometry (LC/MS), the fragmentation of electrosprayed sodium adducts in an ion trap mass spectrometer was investigated. The sodium adducts [M + Na]⁺ of kaempferol 3‐O‐glycosides generated sodiated glycosyl groups by the neutral loss of kaempferol. The product ion spectra of these sodiated glycosyl groups differed between four isomeric kaempferol 3‐O‐rhamnosylhexosides and four isomeric kaempferol 3‐O‐glucosylhexosides in which the primary hexose was either glucose or galactose and bore the terminal glucose or rhamnose at either C‐2 or C‐6. Fragmentation of sodiated glycosyl groups from linear O‐triglucosides and branched O‐glucosyl‐(1 → 2)‐[rhamnosyl‐(1 → 6)]‐hexosides produced sodiated disaccharide residues, and the product ion spectra of these ions assisted the identification of the complete sugar. The product ion spectra of the sodiated glycosyl groups were consistent among flavonoid O‐glycosides differing in the position at which the sugar was O‐linked to the aglycone, and the nature of the aglycone. The abundance of sodiated species was enhanced by application of a pre‐trap collision voltage, without the need to dope with salt, allowing automated LC/MS methods to be used to identify the glycosyl groups of common flavonoid O‐glycosides, such as rutinosides, robinobiosides, neohesperidosides, gentiobiosides and sophorosides. Copyright © 2011 John Wiley & Sons, Ltd.     

Magnesium nitride as a convenient source of ammonia: preparation of primary amides

The use of magnesium nitride (Mg 3N 2) as a convenient source of ammonia has been explored for the direct transformation of esters to primary amides. Methyl, ethyl, isopropyl, and tert-butyl esters are converted to the corresponding carboxamides in good yields (75-99%).     

Synthesis of natural products from the Indian neem tree Azadirachta indica

The synthesis of five natural products (3, 6, 7, 10, and 14), isolated from the Indian neem tree Azadirachta indica, is reported from a common intermediate (2). The judicious choice of transacetalization conditions allows efficient access to both the azadirachtinin (9 and 10) and the azadirachtin (3, 6, 7, and 14) skeletons.     

The Verdet constant of Er-doped crystalline YAG and tellurite glass at 1645 nm

We describe the measurement of the Verdet constant of undoped and Er-doped crystalline YAG and tellurite glass at 1645 nm. The undoped YAG value is compared to those measured using visible light. We show that the paramagnetic nature of Er reduces the Verdet constant but that the decrease is probably not significant for the typical Er doping levels used in Er:YAG or in Er:tellurite-glass mid-IR lasers.     

Inverse problems in queueing theory and Internet probing

Queueing theory is typically concerned with the solution of direct problems, where the trajectory of the queueing system, and laws thereof, are derived based on a complete specification of the system, its inputs and initial conditions. In this paper we point out the importance of inverse problems in queueing theory, which aim to deduce unknown parameters of the system based on partially observed trajectories. We focus on the class of problems stemming from probing based methods for packet switched telecommunications networks, which have become a central tool in the measurement of the structure and performance of the Internet. We provide a general definition of the inverse problems in this class and map out the key variants: the analytical methods, the statistical methods and the design of experiments. We also contribute to the theory in each of these subdomains. Accordingly, a particular inverse problem based on product-form queueing network theory is tackled in detail, and a number of other examples are given. We also show how this inverse problem viewpoint translates to the design of concrete Internet probing applications.     

REMUS100 AUV with an integrated microfluidic system for explosives detection

Quantitating explosive materials at trace concentrations in real-time on-site within the marine environment may prove critical to protecting civilians, waterways, and military personnel during this era of increased threat of widespread terroristic activity. Presented herein are results from recent field trials that demonstrate detection and quantitation of small nitroaromatic molecules using novel high-throughput microfluidic immunosensors (HTMI) to perform displacement-based immunoassays onboard a HYDROID REMUS100 autonomous underwater vehicle. Missions were conducted 2–3 m above the sea floor, and no HTMI failures were observed due to clogging from biomass infiltration. Additionally, no device leaks were observed during the trials. HTMIs maintained immunoassay functionality during 2 h deployments, while continuously sampling seawater absent without any pretreatment at a flow rate of 2 mL/min. This 20-fold increase in the nominal flow rate of the assay resulted in an order of magnitude reduction in both lag and assay times. Contaminated seawater that contained 20–175 ppb trinitrotoluene was analyzed.

Heavy traffic analysis of a storage model with long range dependent On/Off sources

We consider a fluid queueing system with infinite storage capacity and constant output rate offered a superposition ofN identical On/Off sources, where the ratio of input to output rate is small. The On and/or Off periods have heavy tailed distributions with infinite variance, giving rise to Long Range Dependence in the arrival process. In the limit of a large number of sources and high load, it is shown that the tail of the stationary queue content distribution is Weibullian, implying much larger queue contents than in the classical case of exponential tails. Noting that similar results were recently found by I. Norros for a storage system input by a Fractional Brownian Motion, we then show how the two models are related, thus providing a further physical motivation for the Fractional Brownian Motion model.