New Material for Surface-Enhanced Raman Spectroscopy

A chemical method of synthesis and application of coating materials that are especially suitable for surface-enhanced Raman spectroscopy (SERS) has been developed. The purpose of this development is to facilitate the utilization of the inherently high sensitivity of SERS to detect chemicals of interest (analytes) in trace amounts, without need for lengthy sample preparation. Up to now, the use of SERS has not become routine because the methods available have not been able to reproduce sampling conditions and provide quantitative measurements. In contrast, the coating materials of the present method enable analysis with minimum preparation of samples, and SERS measurements made using these materials are reproducible and reversible. Moreover, unlike in methods investigated in prior efforts to implement SERS, sampling is not restricted to such specific environments as electrolytes or specific solvents. The coating materials of this method are porous glasses, formed in sol-gel processes, that contain small particles of gold or silver metal. Materials of this type can be applied to the sample-contact surfaces of a variety of sampling and sensing devices, including glass slides, glass vials, fiber-optic probes, and glass tubes. Glass vials with their insides coated according to this method are particularly convenient for SERS to detect trace chemicals in solutions: One simply puts a sample solution containing the analyte(s) into a vial, then puts the vial into a Raman spectrometer for analysis. The chemical ingredients and the physical conditions of the sol-gel process have been selected so that the porous glass formed incorporates particles of the desired metal with size(s) to match the wavelength(s) of the SERS excitation laser in order to optimize the generation of surface plasmons. The ingredients and processing conditions have further been chosen to tailor the porosity and polarity of the glass to optimize the sample flow and the interaction between the analyte(s) and the plasmon field that generates Raman photons. The porous silica network of a sol-gel glass creates a unique environment for stabilizing SERS-active metal particles. Relative to other material structures that could be considered for SERS, the porous silica network offers higher specific surface area and thus greater interaction between analyte molecules and metal particles. Efforts to perform SERS measurements with the help of sampling devices coated by this method have been successful. In tests, numerous organic and inorganic chemicals were analyzed in several solvents, including water. The results of the tests indicate that the SERS measurements were reproducible within 10 percent and linear over five orders of magnitude. One measure of the limits of detectability of chemicals in these tests was found to be a concentration of 300 parts per billion. Further development may eventually make it possible to realize the full potential sensitivity of SERS for detecting some analytes in quantities as small as a single molecule

Material for surface-enhanced Raman spectroscopy, and SER sensors and method for preparing same

Metal-doped sol-gel materials, suitable for use as sensors for surface-enhanced Raman spectroscopic analysis for trace chemical detection, are produced by effecting gelation and solvent removal of a doped sol-gel under mild temperature conditions. At least in certain instances reaction and drying will desirably be effected in an oxygen-starved environment. The metal of the sol-gel material functions, when irradiated, to produce a plasmon field for interaction with molecules of an analyte in contact therewith, increasing by orders of magnitude Raman photons that are generate by excitation radiation, and the method allows matching of the metal and metal particle size to a wavelength of light (or incident radiation, e.g., laser radiation) to generate surface plasmons. The porosity of the sol-gel material dramatically increases the surface area, and thereby the amount of metal exposed for analyte interaction. The sensors provided may be in the form of glass vials, fiber optics, multi-well micro-sample plates, etc., having surface coatings of the doped sol-gel material, to provide sampling systems for use in a Raman instrument

On-Demand Urine Analyzer

A lab-on-a-chip was developed that is capable of extracting biochemical indicators from urine samples and generating their surface-enhanced Raman spectra (SERS) so that the indicators can be quantified and identified. The development was motivated by the need to monitor and assess the effects of extended weightlessness, which include space motion sickness and loss of bone and muscle mass. The results may lead to developments of effective exercise programs and drug regimes that would maintain astronaut health. The analyzer containing the lab-on-a- chip includes materials to extract 3- methylhistidine (a muscle-loss indicator) and Risedronate (a bone-loss indicator) from the urine sample and detect them at the required concentrations using a Raman analyzer. The lab-on- a-chip has both an extractive material and a SERS-active material. The analyzer could be used to monitor the onset of diseases, such as osteoporosis

Reducing patient delay with symptoms of acute coronary syndrome:a research protocol for a systematic review of previous interventions to investigate which behaviour change techniques are associated with effective interventions

Introduction: Delay to presentation with symptoms of acute coronary syndrome (ACS) is common meaning many fail to achieve optimal benefit from treatments. Interventions have had variable success in reducing delay. Evidence suggests inclusion of behaviour change techniques (BCTs) may improve effectiveness of interventions but this has not yet been systematically evaluated. Data from other time-critical conditions may be relevant.Methods and analysis: A systematic review will be undertaken to identify which BCTs are associated with effective interventions to reduce patient delay (or prompt rapid help-seeking) among people with time-critical conditions (eg, chest pain, ACS, lumps, stroke, cancer and meningitis). A systematic search of a wide range of databases (including Cochrane Library, MEDLINE, EMBASE, CINAHL, PsycInfo) and grey literature will be undertaken to identify all relevant intervention studies (randomised controlled trials, controlled clinical trials and cohort studies). Two independent reviewers will screen abstracts to identify relevant studies, apply inclusion criteria to full papers, assess methodological quality and extract data.Primary outcome measure: Change in patient decision time BCTs reported in each of the included studies will be categorised and presented according to the latest reliable taxonomy. Results of included studies will be synthesised, exploring relationships between inclusion of each BCT and effectiveness of the overall intervention. Where possible, means and SDs for differences in delay time will be calculated and combined within meta-analyses to derive a standardised mean difference and 95% CI. Analysis of (1) all time-critical and (2) ACS-only interventions will be undertaken

Proton Pump Inhibitors Inhibit PHOSPHO1 Activity and Matrix Mineralisation In Vitro

Proton pump inhibitors (PPIs) have been associated with an increased risk of fragility fractures in pharmaco-epidemiological studies. The mechanism is unclear, but it has been speculated that by neutralising gastric acid, they may reduce intestinal calcium absorption, causing secondary hyperparathyroidism and bone loss. Here we investigated that hypothesis that the skeletal effects of PPI might be mediated by inhibitory effects on the bone-specific phosphatase PHOSPHO1. We found that the all PPIs tested inhibited the activity of PHOSPHO1 with IC50 ranging between 0.73 µM for esomeprazole to 19.27 µM for pantoprazole. In contrast, these PPIs did not inhibit TNAP activity. We also found that mineralisation of bone matrix in primary osteoblast cultures was inhibited by several PPIs in a concentration dependent manner. In contrast, the histamine-2 receptor antagonists (H2RA) nizatidine, famotidine, cimetidine and ranitidine had no inhibitory effects on PHOSPHO1 activity. Our experiments show for the first time that PPIs inhibit PHOSPHO1 activity and matrix mineralisation in vitro revealing a potential mechanism by which these widely used drugs are associated with the risk of fractures

Inter-individual responses to sprint interval training, a pilot study investigating interactions with the sirtuin system

Acknowledgements We thank the Human Nutrition and Genomics Units, Rowett Institute, University of Aberdeen for technical support. This work was supported by the Scottish Government's Rural and Environment Science and Analytical Services Division and an NHS Grampian Endowment Fund grant.Peer reviewedPostprintPostprin

Diagnosis, extent, impacts, and management of subsoil constraints in the northern grains cropping region of Australia

Productivity of grain crops grown under dryland conditions in north-eastern Australia depends on efficient use of rainfall and available soil moisture accumulated in the period preceding sowing. However, adverse subsoil conditions including high salinity, sodicity, nutrient imbalances, acidity, alkalinity, and high concentrations of chloride (Cl) and sodium (Na) in many soils of the region restrict ability of crop roots to access this stored water and nutrients. Planning for sustainable cropping systems requires identification of the most limiting constraint and understanding its interaction with other biophysical factors. We found that the primary effect of complex and variable combinations of subsoil constraints was to increase the crop lower limit (CLL), thereby reducing plant available water. Among chemical subsoil constraints, subsoil Cl concentration was a more effective indicator of reduced water extraction and reduced grain yields than either salinity or sodicity (ESP). Yield penalty due to high subsoil Cl was seasonally variable, with more in-crop rainfall (ICR) resulting in less negative impact. A conceptual model to determine realistic yield potential in the presence of subsoil Cl was developed from a significant positive linear relationship between CLL and subsoil Cl:Since grid sampling of soil to identify distribution of subsoil Cl, both spatially across landscape and within soil profile, is time-consuming and expensive, we found that electromagnetic induction, coupled with yield mapping and remote sensing of vegetation offers potential to rapidly identify possible subsoil Cl at paddock or farm scale.Plant species and cultivars were evaluated for their adaptations to subsoil Cl. Among winter crops, barley and triticale, followed by bread wheat, were more tolerant of high subsoil Cl concentrations than durum wheat. Chickpea and field pea showed a large decrease in yield with increasing subsoil Cl concentrations and were most sensitive of the crops tested. Cultivars of different winter crops showed minor differences in sensitivity to increasing subsoil Cl concentrations. Water extraction potential of oilseed crops was less affected than cereals with increasing levels of subsoil Cl concentrations. Among summer crops, water extraction potential of millet, mungbean, and sesame appears to be more sensitive to subsoil Cl than that of sorghum and maize; however, the differences were significant only to 0.7 m. Among pasture legumes, lucerne was more tolerant to high subsoil Cl concentrations than the others studied.Surface applied gypsum significantly improved wheat grain yield on soils with ESP >6 in surface soil (0–0.10 m). Subsurface applied gypsum at 0.20–0.30 m depth did not affect grain yield in the first year of application; however, there was a significant increase in grain yield in following years. Better subsoil P and Zn partially alleviated negative impact of high subsoil Cl. Potential savings from improved N fertilisation decisions for paddocks with high subsoil Cl are estimated at ~$AU10 million per annum