Introduction of 4-chloro-alpha-cyanocinnamic acid liquid matrices for high sensitivity UV-MALDI MS

Matrix-assisted laser desorption/ionization (MALDI) is a key ionization technique in mass spectrometry (MS) for the analysis of labile macromolecules. An important area of study and improvements in relation to MALDI and its application in high-sensitivity MS is that of matrix design and sample preparation. Recently, 4-chloro-alpha-cyanocinnamic acid (ClCCA) has been introduced as a new rationally designed matrix and reported to provide an improved analytical performance as demonstrated by an increase in sequence coverage of protein digests obtained by peptide mass mapping (PMM) (Jaskolla, T. W.; et al. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 12200-12205). This new matrix shows the potential to be a superior alternative to the commonly used and highly successful alpha-cyano-4-hydroxycinnamic acid (CHCA). We have taken this design one step further by developing and optimizing an ionic liquid matrix (ILM) and liquid support matrix (LSM) using ClCCA as the principle chromophore and MALDI matrix compound. These new liquid matrices possess greater sample homogeneity and a simpler morphology. The data obtained from our studies show improved sequence coverage for BSA digests compared to the traditional CHCA crystalline matrix and for the ClCCA-containing ILM a similar performance to the ClCCA crystalline matrix down to 1 fmol of BSA digest prepared in a single MALDI sample droplet with current sensitivity levels in the attomole range. The LSMs show a high tolerance to contamination such as ammonium bicarbonate, a commonly used buffering agent.

Ensemble yield simulations: crop and climate uncertainties, sensitivity to temperature and genotypic adaptation to climate change

Estimates of the response of crops to climate change rarely quantify the uncertainty inherent in the simulation of both climate and crops. We present a crop simulation ensemble for a location in India, perturbing the response of both crop and climate under both baseline (12 720 simulations) and doubled-CO2 (171720 simulations) climates. Some simulations used parameter values representing genotypic adaptation to mean temperature change. Firstly, observed and simulated yields in the baseline climate were compared. Secondly, the response of yield to changes in mean temperature was examined and compared to that found in the literature. No consistent response to temperature change was found across studies. Thirdly, the relative contribution of uncertainty in crop and climate simulation to the total uncertainty in projected yield changes was examined. In simulations without genotypic adaptation, most of the uncertainty came from the climate model parameters. Comparison with the simulations with genotypic adaptation and with a previous study suggested that the relatively low crop parameter uncertainty derives from the observational constraints on the crop parameters used in this study. Fourthly, the simulations were used, together with an observed dataset and a simple analysis of crop cardinal temperatures and thermal time, to estimate the potential for adaptation using existing cultivars. The results suggest that the germplasm for complete adaptation of groundnut cultivation in western India to a doubled-CO2 environment may not exist. In conjunction with analyses of germplasm and local management

Temperature sensitivity of the low-moisture-content limit to negative seed longevity-moisture content relationships in hermetic storage

Background and Aims The negative logarithmic relationship between orthodox seed longevity and moisture content in hermetic storage is subject to a low-moisture-content limit (m(c)), but is m(c) affected by temperature? Methods Red clover (Trifolium pratense) and alfalfa (Medicago sativa) seeds were stored hermetically at 12 moisture contents (2-15 %) and five temperatures (-20, 30, 40, 50 and 65 degrees C) for up to 14.5 years, and loss in viability was estimated. Key Results Viability did not change during 14.5 years hermetic storage at -20 degrees C with moisture contents from 2.2 to 14.9 % for red clover, or 2.0 to 12.0 % for alfalfa. Negative logarithmic relationships between longevity and moisture contents > m(c) were detected at 30-65 degrees C, with discontinuities at low moisture contents; m(c) varied between 4.0 and 5.4 % (red clover) or 4.2 and 5.5 % (alfalfa), depending upon storage temperature. Within the ranges investigated, a reduction in moisture content below m(c) at any one temperature had no effect on longevity. Estimates of m(c) were greater the cooler the temperature, the relationship (P < 0.01) being curvilinear. Above m(c), the estimates of C-H and C-Q (i.e. the temperature term of the seed viability equation) did not differ (P > 0.10) between species, whereas those of K-E and C-W did (P < 0.001). Conclusions The low-moisture-content limit to negative logarithmic relationships between seed longevity and moisture content in hermetic storage increased the cooler the storage temperature, by approx. 1.5 % over 35 degrees C (4.0-4.2 % at 65 degrees C to 5.4-5.5 % at 30-40 degrees C) in these species. Further reduction in moisture content was not damaging. The variation in m(c) implies greater sensitivity of longevity to temperature above, compared with below, m(c). This was confirmed (P < 0.005).

Influence of vegetation on the local climate and hydrology in the tropics: sensitivity to soil parameters

Land use change with accompanying major modifications to the vegetation cover is widespread in the tropics, due to increasing demands for agricultural land, and may have significant impacts on the climate. This study investigates (1) the influence of vegetation on the local climate in the tropics; (2) how that influence varies from region to region; and (3) how the sensitivity of the local climate to vegetation, and hence land use change, depends on the hydraulic characteristics of the soil. A series of idealised experiments with the Hadley Centre atmospheric model, HadAM3, are described in which the influence of vegetation in the tropics is assessed by comparing the results of integrations with and without tropical vegetation. The sensitivity of the results to the soil characteristics is then explored by repeating the experiments with a differing, but equally valid, description of soil hydraulic parameters. The results have shown that vegetation has a significant moderating effect on the climate throughout the tropics by cooling the surface through enhanced latent heat fluxes. The influence of vegetation is, however, seasonally dependent, with much greater impacts during the dry season when the availability of surface moisture is limited. Furthermore, there are significant regional variations both in terms of the magnitude of the cooling and in the response of the precipitation. Not all regions show a feedback of vegetation on the local precipitation; this result has been related both to vegetation type and to the prevailing meteorological conditions. An important finding has been the sensitivity of the results to the specification of the soil hydraulic parameters. The introduction of more freely draining soils has changed the soil-moisture contents of the control, vegetated system and has reduced, significantly, the climate sensitivity to vegetation and by implication, land use change. Changes to the soil parameters have also had an impact on the soil hydrology and its interaction with vegetation, by altering the partitioning between fast and slow runoff processes. These results raise important questions about the representation of highly heterogeneous soil characteristics in climate models, as well as the potential influence of land use change on the soil characteristics themselves.

Headspace volatile markers for sensitivity of cocoa (Theobroma cacao L.) somatic embryos to cryopreservation

The mechanisms that reduce the viability of plant somatic embryos following cryopreservation are not known. The objective of the present study was to evaluate the sensitivity of cocoa (Theobroma cacao L.) somatic embryos at different stages of an encapsulation-dehydration protocol using stress-related volatile hydrocarbons as markers of injury and recovery. The plant stress hormone ethylene and volatile hydrocarbons derived from hydroxyl radicals (methane) and lipid peroxidation (ethane) were determined using gas chromatography headspace analysis. Ethylene and methane were the only volatiles detected, with both being produced after each step of the cryogenic protocol. Ethylene production was significantly reduced following exposure to liquid nitrogen, but then increased in parallel with embryo recovery. In contrast, the production of methane was cyclic during recovery, with the first cycle occurring earlier for embryos recovered from liquid nitrogen and desiccation than those recovered from earlier steps in the protocol. These results suggest that loss of somatic embryo viability during cryopreservation may be related to the oxidative status of the tissue, and its capacity to produce ethylene. This study has demonstrated that headspace volatile analysis provides a robust non-destructive analytical approach for assessing the survival and recovery of plant somatic embryos following cryopreservation.

Dynamics of QoI sensitivity in Mycosphaerella fijiensis in Costa Rica during 2000 to 2003

From 1997 onward, the strobilurin fungicide azoxystrobin was widely used in the main banana-production zone in Costa Rica against Mycosphaerella fijiensis var. difformis causing black Sigatoka of banana. By 2000, isolates of M. fijiensis with resistance to the quinolene oxidase inhibitor fungicides were common on some farms in the area. The cause was a single point mutation from glycine to alanine in the fungal target protein, cytochrome b gene. An amplification refractory mutation system Scorpion quantitative polymerase chain reaction assay was developed and used to determine the frequency of G 143A allele in samples of M. fijiensis. Two hierarchical surveys of spatial variability, in 2001 and 2002,found no significant variation in frequency on spatial scales <10 in. This allowed the frequency of G143A alleles on a farm to be estimated efficiently by averaging single samples taken at two fixed locations. The frequency of G 143A allele in bulk samples from I I farms throughout Costa Rica was determined at 2-month intervals. There was no direct relationship between the number of spray applications and the frequency of G143A on individual farms. Instead, the frequency converged toward regional averages, presumably due to the large-scale mixing of ascospores dispersed by wind. Using trap plants in an area remote from the main producing area, immigration of resistant ascospores was detected as far as 6 km away both with and against the prevailing wind.

Sensitivity distributions and cross-resistance patterns of Mycosphaerella graminicola to fluquinconazole, prochloraz and azoxystrobin over a period of nine years

The sensitivity of 73 isolates of Mycosphaerella graminicola collected over the period 1993–2002 from wheat fields in South England was tested in vitro against the triazole fluquinconazole, the strobilurin azoxystrobin and to the imidazole prochloraz. Over the sampling period, sensitivity of the population to fluquinconazole and prochloraz decreased by factors of approximately 10 and 2, respectively, but there was no evidence of changes in sensitivity to azoxystrobin. There was no correlation between sensitivity to fluquinconazole and prochloraz, but there was a weak negative cross-resistance between fluquinconazole and azoxystrobin.

Identification of lipophilic flavones and flavonols by comparative HPLC, TLC and UV spectral analysis

The identification of lipophilic flavones and flavonols using a combination of high performance liquid chromatography, thin layer chromatography and UV spectral analysis is discussed. Data are provided for the flavones, apigenin, luteolin and tricetin and twelve of their methyl ethers, 8-hydroxyluteolin, 6-hydroxyluteolin and scutellarein and fourteen of their methyl ethers, and some 6,8-dihydroxyapigenin and 6,8-dihydroxyluteolin derivatives. Data for some forty two flavonols with extra 6- and/or 8-hydroxylation, mostly 6-hydroxykaempferol and quercetagetin derivatives, are also presented. The remaining compounds analysed include fourteen 5-deoxyflavones, four 5-methoxyflavones and five 5-deoxyflavonols plus further 5-hydroxylated flavones and flavonols without B-ring oxidation or with 2-, 5- or 6-hydroxylation. Copyright © 2003 John Wiley & Sons, Ltd.

Oxorhenium(V) complexes with tetradentate NSNO pyridylthioazophenolates: syntheses, spectral and electrochemical studies

A family of oxorhenium (V) complexes of newly designed pyridylthioazophenolate ligands has been synthesized and isolated in pure form. The solid state structure of an organic compound (HL1) has been established by X-ray crystallography. The molecular structure observed in the solid state is that the two molecules of the ligand (HL1) in the asymmetric unit have similar geometries, except for the orientation of the pyridine ring. This series of organic moieties acts as tetradentate monobasic NSNO donor chelators in oxorhenium(V) complexes which has been characterized by elemental analyses, IR, H-1-NMR, UV-Vis. The complexes are 1: 1 electrolytes in nature in MeOH solution, the counter anion being ClO4). The electrochemical studies of the [(ReO)-O-V(L)Cl]ClO4 complexes in MeCN using TBAP as supporting electrolyte exhibit quasi-reversible voltammogram showing one-electron couple for [(ReO)-O-VI(L)Cl](2+)-[(ReO)-O-V(L)Cl](+) in the 1.11-1.29 V vs SCE range.

Ruthenium (III) complexes of tetradentate NSNO pyridylthioazophenolates: Synthesis, spectral studies, crystal structure and redox properties

A family of ruthenium (III) complexes of tetradentate monobasic NSNO donor chelators (HL) have been synthesized and isolated in their pure form. On chromatographic separation, trans-dichloro and cis-dichloro ruthenium (111) complexes of pyridylthioazophenolates are eluted using 19:1 and 7:3 (v/v) DCM-MeOH mixtures, respectively. Both cis and trans isomers of the dark brown colored ruthenium (111) complexes, having the general formula of [Ru(L)Cl-2], have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. The magnetic moments of both the cis- and trans-[Ru(L)Cl-2] complexes are in the range of 1.71-1.79 BM. One of the complexes, trans-[Ru(L1)Cl-2] (2a), has been subjected to single-crystal X-ray analysis which confirms that the chlorines are in mutually trans positions in the molecule. The EPR spectra of the cis-[Ru(L)Cl-2] complexes (1) in DMF are consistent with the fact that the complexes are low-spin octahedral with one unpaired electron having three different g values (g(x) not equal g(y) not equal g(z)) complexes are monomeric with an octahedral coordination sphere. The electrochemical studies of [Ru(L)Cl,] in DMF show a quasi-reversible voltammogram. The reduction potentials for the cis-isomers are comparatively lower than those of the corresponding trans isomers. On reaction with the bidentate bipyridyl ligand in the presence of AgNO3, the cis-[Ru(L)Cl-2] complexes (1) produce a series of complexes with the general formula [Ru(L)(bpy)(2)](PF6)(2) (3). which have also been characterized by elemental analyses, spectroscopic and other physico-chemical tools. (c) 2006 Elsevier Ltd. All rights reserved.

Tris-(1,3-diaryltriazenide) complexes of rhodium: synthesis, structure and, spectral and electrochemical properties

Reaction of 1,3-diaryltriazenes (abbreviated in general as HL-R, where R stands for the para-substituent in the aryl fragment and H stands for the dissociable hydrogen atom, R = OCH3, CH3, H, Cl, NO2) with [Rh(PPh3)(2)(CO)Cl] in ethanol in the presence of NEt3 produces a series of tris-diaryltriazenide complexes of rhodium of type [Rh(L-R)(3)], where the triazenes are coordinated to rhodium as monoanionic, bidentate N,N-donors. Structure of the [Rh(L-OCH3)(3)] complex has been determined by X-ray crystallography. The complexes are diamagnetic, and show characteristic H-1 NMR signals and intense MLCT transitions in the visible region. They also fluoresce in the visible region under ambient condition while excited at around 400 nm. Cyclic voltammetry on these complexes shows a Rh(III)-Rh(IV) oxidation (within 0.84-1.67 V vs SCE), followed by an oxidation of the coordinated tri- and azene ligand (except the R = NO2 complex). An irreversible reduction of the coordinated triazene is also observed for all the complexes below -1.03 V vs SCE.

Palladium and platinum complexes of 2-(2 '-carboxyphenylazo)-4-methylphenol: synthesis, structure and spectral properties

Reaction of 2-(2'-carboxyphenylazo)-4-methylphenol (H2L) with [M(PPh3)(2)Cl-2] (M = Pd, Pt) affords mixed-ligand complexes of type [M(PPh3)(L)]. Structures of both the complexes have been determined by X-ray crystallography. Both the complexes are square planar, where the 2-(2'-carboxyphenylazo)-4-methylphenol is coordinated to the metal center, via dissociation of the two acidic protons, as a dianionic tridentate O,N,O-donor, and the fourth position is occupied by the triphenylphosphine. These complexes show intense MLCT transitions in the visible region.

Comparative and international education: policy transfer, context sensitivity and professional development

This paper examines the intellectual and professional contribution of comparative and international studies to the field of education. It explores the nature of the challenges that are currently being faced, and assesses its potential for the advancement of future teaching, research and professional development. Attention is paid to the place of comparative and international education (CIE)-past and present-in teacher education, in postgraduate studies, and in the realms of policy and practice, theory and research. Consideration is first given to the nature and history of CIE, to its initial contributions to the field of education in the UK, and to its chief mechanisms and sites of production. Influential methodological and theoretical developments are examined, followed by an exploration of emergent questions, controversies and dilemmas that could benefit from sustained comparative analysis in the future. Conclusions consider implications for the place of CIE in the future of educational studies as a whole; for relations between and beyond the 'disciplines of education'; and for the development of sustainable research capacity in this field.