Electron capture dissociation mass spectrometry of tyrosine nitrated peptides

In vivo protein nitration is associated with many disease conditions that involve oxidative stress and inflammatory response. The modification involves addition of a nitro group at the position ortho to the phenol group of tyrosine to give 3-nitrotyrosine. To understand the mechanisms and consequences of protein nitration, it is necessary to develop methods for identification of nitrotyrosine-containing proteins and localization of the sites of modification. Here, we have investigated the electron capture dissociation (ECD) and collision-induced dissociation (CID) behavior of 3-nitrotyrosine-containing peptides. The presence of nitration did not affect the CID behavior of the peptides. For the doubly-charged peptides, addition of nitration severely inhibited the production of ECD sequence fragments. However, ECD of the triply-charged nitrated peptides resulted in some singly-charged sequence fragments. ECD of the nitrated peptides is characterized by multiple losses of small neutral species including hydroxyl radicals, water and ammonia. The origin of the neutral losses has been investigated by use of activated ion (AI) ECD. Loss of ammonia appears to be the result of non-covalent interactions between the nitro group and protonated lysine side-chains.     

Chemical composition and antimicrobial activity of essential oils from Centaurea pannonica and C. jacea

The chemical composition and antimicrobial activity of the essential oils obtained by hydrodistillation from Centaurea pannonica (Heufel) Simonkai and C. jacea L. (Asteraceae), were investigated. The essential oils were analyzed by GC and GC-MS. Forty five and twenty nine compounds were identified in the two oils, respectively. C. pannonica oil was rich in fatty acids (43.7%), with 9-octadecanoic acid (34.0%) and (Z,Z)-9,12-octadecadienoic acid (8.6%) as the major compounds. In contrast, the essential oil of C. jacea was dominated by oxygenated sesquiterpenes (43.2%), among which caryophyllene oxide (23.5%) and spathulenol (8.9%) were the major constituents. However, the oil was also characterized by an important fatty acid fraction (15.5%), with 9-octadecanoic acid (8.9%) and hexadecanoic acid (6.6%) being the main components. The antimicrobial activities of the essential oils were evaluated by the microdilution method against three Gram-positive and three Gram-negative bacteria, and one yeast. Both oils exhibited significant antimicrobial activity, especially against Gram-positive bacteria.     

Rapid synthesis of carbohydrate derivatives, including mimetics of C-linked disaccharides and C-linked aza disaccharides, using the hetero-Diels-Alder reaction

In this work we demonstrate the value of performing a hetero-Diels-Alder reaction (HDAR) between Danishefsky's diene and a range of aldehydes or imines, under microwave irradiation. By using a range of aldehydes and imines, including those derived from carbohydrates, access to functionalized 2,3-dihydro-4H-pyran-4-ones or 2,3-dihydro-4-pyridinones in good to excellent synthetic yields is possible. A particular strength of the methodology is its ability to access mimetics of C-linked disaccharides and C-linked aza disaccharides, targets of current therapeutic interest, in a rapid, convenient, and diastereoselective manner. The effect of high pressure on the HDARs involving carbohydrate-derived aldehydes and imines is also explored, with enhancement in yields occurring for the aldehyde substrates. Finally, HDARs using carbohydrate derived ketones, enones, and enals are described under a range of conditions. Optimum results were obtained under high-pressure conditions, with highly functionalized carbohydrate derivatives being afforded, in good yields, in this way.     

Qualities of examples in learning and teaching

In this paper, we theorise about the different kinds of relationship between examples and the classes of mathematical objects that they exemplify as they arise in mathematical activity and teaching. We ground our theorising in direct experience of creating a polynomial that fits certain constraints to develop our understanding of engagement with examples. We then relate insights about exemplification arising from this experience to a sequence of lessons. Through these cases, we indicate the variety of fluent uses of examples made by mathematicians and experienced teachers. Following Thompson’s concept of “didactic object” (Symbolizing, modeling, and tool use in mathematics education. Kluwer, Dordrecht, The Netherlands, pp 191–212, 2002), we talk about “didacticising” an example and observe that the nature of students’ engagement is important, as well as the teacher’s intentions and actions (Thompson avoids using a verb with the root “didact”. We use the verb “didacticise” but without implying any connection to particular theoretical approaches which use the same verb.). The qualities of examples depend as much on human agency, such as pedagogical intent or mathematical curiosity or what is noticed, as on their mathematical relation to generalities.     

The hydrological response of heavy clay grassland soils to rainfall in south‐west England using δ2H

Stable isotopes of water have been previously used in catchment studies to separate rain‐event water from pre‐event groundwater. However, there are a lack of studies at the smaller scale looking at the separation of event water from pre‐event water. This is particularly relevant for heavy clay soil systems through which the movement of water is uncertain but is thought to be rainwater‐dominated. The data presented here were collected at a rural site in the south‐west of England. The historic rainfall at the site was isotopically varied but similar to the global meteoric water line, with annual weighted means of ?37‰ for δ²H and ?5.7‰ for δ¹⁸O and with no seasonal variation. Drainage was sampled from the inter‐flow (surface runoff + lateral through‐flow) and drain‐flow (55 cm deep mole drains) pathways of two 1 ha lysimeters during two rainfall events, which had δ²H values of ?68‰ and ?92‰, respectively. The δ²H values of the lysimeter drainage water suggest that there was no contribution of event water during the first, small discharge (Q) event; however, the second larger event did show isotopic variation in δ²H values negatively related to Q indicating that rainwater was contributing to Q. A hydrograph separation indicated that only 49–58% of the inter‐flow and 18–25% of the drain‐flow consisted of event water. This was surprising given that these soil types are considered retentive of soil water. More work is needed on heavy clay soils to understand better the nature of water movement from these systems. Copyright © 2010 John Wiley & Sons, Ltd.     

Evaluating the effectiveness and efficiency of voice therapy using transnasal flexible laryngoscopy: a randomized controlled trial

Transnasal flexible laryngoscopy (TFL) is an examination of laryngeal anatomy and physiology using continuous light. TFL is being used increasingly by voice pathologists in treatment but with little scientific evidence to support it. The purpose of this study was to evaluate the effectiveness and efficiency of TFL as a therapeutic tool. The study used a prospective randomized controlled trial. Fifty dysphonic subjects were recruited and randomly assigned to either a traditional treatment group or a TFL-assisted treatment group. The effectiveness of voice therapy in both treatment groups was measured with a package of voice outcome measures. Subjects in both treatment groups demonstrated statistically significant improvements after voice therapy (perceptual auditory rating of voice quality measurement p < 0.01; instrumental electroglottographic measurement p < 0.01; patient questionnaire measurement p < 0.01). The time taken to complete treatment in both groups was recorded. The average (median) time taken to complete voice therapy in the TFL-assisted treatment group was 2 hours less than in the traditional treatment group (p < 0.01). Voice therapy with TFL as a therapy tool was effective and more efficient than traditional voice therapy.     

Novel Antifungal Tetracyclic Compounds from Bauhinia rufescens LAM.

As the root bark CH₂Cl₂ extract of Bauhinia rufescens showed antifungal activity in a bioassay with the plant pathogenic fungus Cladosporium cucumerinum, a phytochemical investigation was undertaken on material collected in Niger. Activity-guided fractionation of this extract, using different preparative chromatographic methods, allowed the isolation of the four new antifungal tetracyclic compounds 1 – 4 . Their structures were established by ¹H- and ¹³C-NMR data, and single-crystal X-ray analyses were used to confirm the structures of 1 and 3 . The isolated compounds seem to be biogenetically related to a stilbene.