Rapid qualitative and quantitative analysis of proanthocyanidin oligomers and polymers by UPLC-MS/MS.

This paper presents the development of a rapid method with ultraperformance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS) for the qualitative and quantitative analyses of plant proanthocyanidins directly from crude plant extracts. The method utilizes a range of cone voltages to achieve the depolymerization step in the ion source of both smaller oligomers and larger polymers. The formed depolymerization products are further fragmented in the collision cell to enable their selective detection. This UPLC-MS/MS method is able to separately quantitate the terminal and extension units of the most common proanthocyanidin subclasses, that is, procyanidins and prodelphinidins. The resulting data enable (1) quantitation of the total proanthocyanidin content, (2) quantitation of total procyanidins and prodelphinidins including the procyanidin/prodelphinidin ratio, (3) estimation of the mean degree of polymerization for the oligomers and polymers, and (4) estimation of how the different procyanidin and prodelphinidin types are distributed along the chromatographic hump typically produced by large proanthocyanidins. All of this is achieved within the 10 min period of analysis, which makes the presented method a significant addition to the chemistry tools currently available for the qualitative and quantitative analyses of complex proanthocyanidin mixtures from plant extracts.

A new rapid detection threshold method for use with older adults: reducing fatigue whilst maintaining accuracy

Taste and smell detection threshold measurements are frequently time consuming especially when the method involves reversing the concentrations presented to replicate and improve accuracy of results. These multiple replications are likely to cause sensory and cognitive fatigue which may be more pronounced in elderly populations. A new rapid detection threshold methodology was developed that quickly located the likely position of each individuals sensory detection threshold then refined this by providing multiple concentrations around this point to determine their threshold. This study evaluates the reliability and validity of this method. Findings indicate that this new rapid detection threshold methodology was appropriate to identify differences in sensory detection thresholds between different populations and has positive benefits in providing a shorter assessment of detection thresholds. The results indicated that this method is appropriate at determining individual as well as group detection thresholds.

A Lab-in-a-briefcase for rapid prostate specific antigen (PSA) screening from whole blood

We present a new concept for rapid and fully portable Prostate Specific Antigen (PSA) measurement, termed “Lab-in-a-Briefcase”, which integrates an affordable microfluidic ELISA platform utilising a melt-extruded fluoropolymer Micro Capillary Film (MCF) containing 10 bore, 200 μm internal diameter capillaries, a disposable multi-syringe aspirator (MSA) plus a sample tray pre-loaded with all required immunoassay reagents, and a portable film scanner for colorimetric signal digital quantitation. Each MSA can perform 10 replicate microfluidic immunoassays on 8 samples, allowing 80measurements to be made in less than 15 minutes based on semi-automated operation and norequirement of additional fluid handling equipment. An assay was optimised for measurement of a clinically relevant range of PSA from 0.9 to 60.0 ng/ml in 15 minutes with CVs in the order of 5% based on intra-assay variability when read using a consumer flatbed film scanner. The PSA assay performance in the MSA remained robust in the presence of undiluted or 1:2 diluted human serum or whole blood, and the matrix effect could simply be overcome by extending sample incubation times. The PSA "Lab-in-a-briefcase" is particularly suited to a low-resource health setting where diagnostic labs and automated immunoassay systems are not accessible, by allowing PSA measurement outside the laboratory using affordable equipment.

Rapid assessment of historic, current and future habitat quality for biodiversity around UK Natura 2000 sites

Changes in landscape composition and structure may impact the conservation and management of protected areas. Species that depend on specific habitats are at risk of extinction when these habitats are degraded or lost. Designing robust methods to evaluate landscape composition will assist decision- and policy-making in emerging landscapes. This paper describes a rapid assessment methodology aimed at evaluating landcover quality for birds, plants, butterflies and bees around seven UK Natura 2000 sites. An expert panel assigned quality values to standard Coordination of Information on the Environment (CORINE) landcover classes for each taxonomic group. Quality was assessed based on historical (1950, 1990), current (2000) and future (2030) land-cover data, the last projected using three alternative scenarios: a growth applied strategy (GRAS), a business-as-might-beusual (BAMBU) scenario, and sustainable European development goal (SEDG) scenario. A quantitative quality index weighted the area of each land-cover parcel with a taxa-specific quality measure. Land parcels with high quality for all taxonomic groups were evaluated for temporal changes in area, size and adjacency. For all sites and taxonomic groups, the rate of deterioration of land-cover quality was greater between 1950 and 1990 than current rates or as modelled using the alternative future scenarios (2000– 2030). Model predictions indicated land-cover quality stabilized over time under the GRAS scenario, and was close to stable for the BAMBU scenario. The SEDG scenario suggested an ongoing loss of quality, though this was lower than the historical rate of c. 1% loss per decade. None of the future scenarios showed accelerated fragmentation, but rather increases in the area, adjacency and diversity of high quality land parcels in the landscape.

Contributions of different cloud types to feedbacks and rapid adjustments in CMIP5

Using five climate model simulations of the response to an abrupt quadrupling of CO2, the authors perform the first simultaneous model intercomparison of cloud feedbacks and rapid radiative adjustments with cloud masking effects removed, partitioned among changes in cloud types and gross cloud properties. Upon CO2 quadrupling, clouds exhibit a rapid reduction in fractional coverage, cloud-top pressure, and optical depth, with each contributing equally to a 1.1 W m−2 net cloud radiative adjustment, primarily from shortwave radiation. Rapid reductions in midlevel clouds and optically thick clouds are important in reducing planetary albedo in every model. As the planet warms, clouds become fewer, higher, and thicker, and global mean net cloud feedback is positive in all but one model and results primarily from increased trapping of longwave radiation. As was true for earlier models, high cloud changes are the largest contributor to intermodel spread in longwave and shortwave cloud feedbacks, but low cloud changes are the largest contributor to the mean and spread in net cloud feedback. The importance of the negative optical depth feedback relative to the amount feedback at high latitudes is even more marked than in earlier models. The authors show that the negative longwave cloud adjustment inferred in previous studies is primarily caused by a 1.3 W m−2 cloud masking of CO2 forcing. Properly accounting for cloud masking increases net cloud feedback by 0.3 W m−2 K−1, whereas accounting for rapid adjustments reduces by 0.14 W m−2 K−1 the ensemble mean net cloud feedback through a combination of smaller positive cloud amount and altitude feedbacks and larger negative optical depth feedbacks.

Rapid changes in LLBL thickness

We employ data from two spacecraft, at the dawn flank of the magnetopause, to investigate fluctuations in the thickness of the low-latitude boundary layer (LLBL). We show the LLBL is considerably thinner shortly after the detection of a flux transfer event than it was during the event. These data are shown to be consistent with the theory of transient increases in the open LLBL thickness caused by a pulse of enhanced reconnection at the magnetopause.

The effect of rapid changes in ionospheric flow on velocity vectors deduced from radar beam-swinging experiments

The effects on the horizontal ionospheric velocity vectors deduced from radar beam-swinging experiments, which occur when changes in the flow take place on short time scales compared with the experiment cycle time, are analysed in detail. The further complications which arise in the interpretation of beam-swinging data, due to longitudinal gradients in the flow and to field-aligned flows, are also considered. It is concluded that these effects are unlikely to seriously compromise statistical determinations of the response time of the flow, e.g. to changes in the north-south component of the IMF, such as have been recently reported by Etemadiet al. (1988, Planet. Space Sci.36, 471), using EISCAT ‘Polar’ data.

EISCAT observations of bursts of rapid flow in the high latitude dayside ionosphere

Observations are presented of short-lived, highly structured bursts of rapid plasma flow observed with the EISCAT radar in the high latitude dayside ionosphere. It is shown that the properties of the bursts are consistent with ionospheric perturbations caused by impulsive, localized reconnection at the Earth's magnetopause, i.e. by flux transfer events.

Rapid preconditioning of data for accelerating convex hull algorithms

Given a dataset of two-dimensional points in the plane with integer coordinates, the method proposed reduces a set of n points down to a set of s points s ≤ n, such that the convex hull on the set of s points is the same as the convex hull of the original set of n points. The method is O(n). It helps any convex hull algorithm run faster. The empirical analysis of a practical case shows a percentage reduction in points of over 98%, that is reflected as a faster computation with a speedup factor of at least 4.

Rapid changes in the redox conditions of the western Tethys Ocean during the early Aptian oceanic anoxic event

The early Aptian (125 to 121 Ma) records an episode of severe environmental change including a major perturbation of the carbon cycle, an oceanic anoxic event (OAE 1a, 122.5 Ma), a platform drowning episode and a biocalcification crisis. We propose to trace changes in the oxygenation state of the ocean during the early Aptian anoxic event using the redox-sensitive trace-element (RSTE) distribution, phosphorus accumulation rates (PARs) and organic-matter characterization in three different basins of the western Tethys. The following sections have been investigated: Gorgo a Cerbara (central Italy) in the Umbria Marche basin, Glaise (SE France) in the Vocontian basin and Cassis/La Bédoule (SE France) located in the Provencal basin. In the Gorgo a Cerbara section, RSTE distributions show a low background level along the main part of the section, contrasted by different maxima in concentrations within the Selli level. In the Glaise section, the Goguel level displays a weak increase in RSTE contents coeval with moderate TOC values. At Cassis/La Bédoule, no significant RSTE enrichments have been observed in sediments equivalent to the Selli level. These differences in the records of the geochemical proxies of the Selli level or its equivalent indicate the deposition under different redox conditions, probably related to the paleogeography. Our data indicate the development of anoxic–euxinic conditions in the deeper part of the Tethys during OAE 1a, whereas in the shallower environments, conditions were less reducing. Moreover, at Gorgo a Cerbara, the Selli level is characterized by rapid changes in the intensity of reducing conditions in the water column. Ocean eutrophication seems to be a major factor in the development and the persistence of anoxia as suggested by the PAR evolution. Higher PAR values at the onset of OAE 1a suggest an increase in nutrient input, whereas the return to lower values through the first part of the OAE 1a interval may be related to the weakened capacity to retain P in the sedimentary reservoir due to bottom-water oxygen depletion. This general pattern is contrasted by the data of Gorgo a Cerbara, where the sediments deposited during the OAE 1a interval show P-enrichments (mainly authigenic P). This is associated with maxima in TOC values and Corg:Ptot ratios, suggesting that a part of the remobilized P was trapped in the sediments and as such prevented from returning to the water column.

Thermoelectric materials: a new rapid synthesis process for non-toxic and high-performance tetrahedrite compounds

The feasibility to synthesize, in large quantity, pure and non-toxic tetrahedrite compounds using high-energy mechanical-alloying from only elemental precursors is reported in the present paper for the first time. Our processing technique allows a better control of the final product composition and leads to high thermoelectric performances (ZT of 0.75 at 700 K), comparable to that reported on sealed tube synthesis samples. Combined with spark plasma sintering, the production of highly pure and dense samples is achieved in a very short time, at least 8 times shorter than in conventional liquid-solid-vapor synthesis process. The process described in this paper is a promising way to produce high performance tetrahedrite materials for cost-effective and large-scale thermoelectric applications.

Asymmetric cyclopropanation of conjugated cyanosulfones using a novel cupreine organocatalyst: rapid access to d3-amino acids

An organocatalytic asymmetric synthesis of a novel, highly functionalised cyclopropane system furnished with versatile substituents and containing a quaternary centre is described. The process utilises a new bifunctional catalyst based on the cinchona alkaloid framework and the products made using this catalyst were obtained as single diastereoisomers, with very high enantioselectivities (up to 96% ee). We have also demonstrated that these resulting cyclopropanes are very useful synthetic intermediates to interesting products, such as the difficult to access d3-amino acids.