Adsorbents for hydrogen-bond accepting hazardous chemicals by post-synthetic modification of UiO-66-NH2.

Adsorbents for hydrogen-bond accepting chemicals such as organophosphates are developed by post-synthetically modifying UiO-66-NH2 through two analogous condensation reactions to incorporate hydrogen-bond donating adsorbent groups. When benzaldehydes are employed as coupling partners, the resulting imine-functionalized MOFs show improvements in uptake capacity with increasingly electron-deficient adsorbent groups. By contrast, when the coupling partners are benzoic acids, the resulting amide-functionalized MOFs exhibit improvements in uptake capacity with increasingly electron-rich adsorbent groups. Both modification approaches also increase binding affinity for organophosphates relative to unmodified UiO-66-NH2, demonstrating successful modification of the MOF scaffold to create adsorbents for hazardous chemicals.

Detection of dimethyl methylphosphonate (DMMP) with an interband cascade laser sensor.

We demonstrate the sensitive detection of dimethyl methylphosphonate (DMMP, a hydrogen-bond (HB) basic phosphonate ester) using additional optical loss induced in an interband cascade laser with top optical cladding layer replaced by an exposed sensing window coated by a HB acidic sorbent layer. Thin coatings of the sorbents HCSFA2 and oapBPAF were deposited on the sensing window to allow reversible capture and concentration of DMMP for optical interrogation. Analyte levels down to 0.1 mg/m3 (∼20 ppb) were tested and successfully detected by monitoring the laser's threshold or its output power at a fixed bias as a function of DMMP delivery concentration.

Variation in blood mercury concentrations in brown skuas (Stercorarius antarcticus) is related to trophic ecology but not breeding success or adult body condition.

Mercury is a pervasive environmental contaminant that can negatively impact seabirds. Here, we measure total mercury (THg) concentrations in red blood cells (RBCs) from breeding brown skuas (Stercorarius antarcticus) (n = 49) at Esperanza/Hope Bay, Antarctic Peninsula. The aims of this study were to: (i) analyse RBCs THg concentrations in relation to sex, year and stable isotope values of carbon (δ13C) and nitrogen (δ15N); and (ii) examine correlations between THg, body condition and breeding success. RBC THg concentrations were positively correlated with δ15N, which is a proxy of trophic position, and hence likely reflects the biomagnification process. Levels of Hg contamination differed between our study years, which is likely related to changes in diet and distribution. RBC THg concentrations were not related to body condition or breeding success, suggesting that Hg contamination is currently not a major conservation concern for this population.

Monocyte CD14 and HLA-DR expression increases with disease duration and severity in amyotrophic lateral sclerosis.

Objective: To investigate changes in immune markers and frequencies throughout disease progression in patients with amyotrophic lateral sclerosis (ALS). Methods: In this longitudinal study, serial blood samples were collected from 21 patients with ALS over a time period of up to 16 months. Flow cytometry was used to quantitate CD14, HLA-DR, and CD16 marker expression on monocyte subpopulations and neutrophils, as well as their cell population frequencies. A Generalized Estimating Equation model was used to assess the association between changes in these immune parameters and disease duration and the Revised Amyotrophic Lateral Sclerosis Functional Rating Scale (ALSFRS-R). Results: CD14 expression on monocyte subpopulations increased with both disease duration and a decrease in ALSFRS-R score in patients with ALS. HLA-DR expression on monocyte subpopulations also increased with disease severity and/or duration. The expression of CD16 did not change relative to disease duration or ALSFRS-R. Finally, patients had a reduction in non-classical monocytes and an increase in the classical to non-classical monocyte ratio throughout disease duration. Conclusion: The progressive immunological changes observed in this study provide further support that monocytes are implicated in ALS pathology. Monocytic CD14 and HLA-DR surface proteins may serve as a therapeutic target or criteria for the recruitment of patients with ALS into clinical trials for immunomodulatory therapies.

Simultaneous real-time spectroscopy using a broadband IR laser source.

In this study, we have developed a simultaneous grating spectroscopy using a broadband IR laser source capable of detecting moving targets in real time. The broadband IR laser source operated in pulsed mode provides a broad spectral range, which covers absorption bands of many chemical analytes. The laser operating conditions were optimized to cover the broadest wavelength range spanning spectral features for the analytes of interest, based on a detailed understanding of the broadband source. This measured the signal from two samples, a 1% acetaminophen KBr pellet sample and toluene in a gas cell. These samples were characterized by illuminating them with the IR broadband source and collecting the transmitted or reflected signal through a grating spectrometer and onto an IR focal plane array (FPA). The results clearly show discrete peaks comparable to the FTIR reference spectra and the spectral features of the samples were successfully discriminated. We believe that the proof of concepts presented here are of broad applicability and will aid advanced real-time standoff detection research.

Figure-of-Merit Characterization of Hydrogen-Bond Acidic Sorbents for Waveguide-Enhanced Raman Spectroscopy.

The optical properties of several hydrogen-bond acidic sorbent materials are evaluated in situ to assess their suitability for waveguide-enhanced Raman spectroscopy (WERS) of vapor-phase organophosphonates. A number of characteristics critical to WERS are evaluated for each sorbent: infrared absorption, Raman spectral background, and the limit of detection for a test hydrogen-bond-basic analyte (dimethyl methylphosphonate, DMMP). We describe the chemical properties of the sorbents that differentiate their optical properties for sensing. Then, we introduce a sorbent figure-of-merit that quantifies these differences and provides a framework to assess the quality of newly developed sorbent materials.

Gas chromatography using a spin-coated stationary phase and a molded elastomer micro-channel.

Many different designs of microfabricated gas chromatography columns have recently been proposed and demonstrated. These designs either incorporate a stationary phase directly into the device which limits the versatility of the column as a separator, or require coating, which presents its own problems with determining the proper conditions for each different stationary phase a user may need. Here, we present a new approach: Uniformly spin coating a flat surface with the stationary phase and creating a column by pressing a lid, with micro-fabricated ridges, down onto the coated substrate. The lids are molded using commercially available epoxies so that when pressed onto a flat surface they create an airtight seal. The epoxy material is rendered inert by a thin layer of gold. We describe the fabrication and initial results from a standard, OV-1, stationary phase as proof of concept.

Time resolved characterization of Fabry-Perot quantum cascade lasers for use in a broadband "white light" source.

We report the time resolved characterization of Fabry-Perot quantum cascade lasers (FP-QCLs). We are developing a custom-built broadband laser source in the Mid-LWIR range by combining several high power FP-QCLs for a single snap shot application. This white light source would enable not only stand-off detection applications in a single snapshot but also new data collection modalities such as live, real-time chemical imaging, requiring extremely rapid measurements. In this study, the two FP-QCLs were operated in CW and pulsed modes with varying applied currents and diode temperatures to optimize the best laser operation condition to cover a broad spectral range including spectral features for the analytes of interest. To understand mode behavior of the FP-QCLs in a short period of time, the spectral output for each test condition was temporally resolved. Under most of the conditions, FP mode hopping was observed during the time evolution through the pulse length (3000 ns). Based on the time-resolved spectra, the ideal spectral characteristics for a single snap shot application are discussed, with respect to a broad spectral bandwidth, a flat-top power profile, and high spectral power density.

Reduction of speckle noise and mitigation of beam wander in tunable external cavity quantum cascade lasers using rotating diamond/KBr pellet coupled with multimode fiber.

We experimentally demonstrate speckle noise reduction and beam wander mitigation by using a rotating diamond/KBr pellet and a multimode fiber (MMF). As the diamond/KBr diffuser is rotated, the reflected speckle images that are captured by an infrared camera are temporally averaged. We demonstrate 78% speckle noise reduction by averaging 25 frames, which is within 80% of the theoretical contrast reduction. Large beam position fluctuations are also significantly suppressed by adding the MMF. This combination of beam wander mitigation and speckle reduction offers significant benefits for emerging optical technologies that use quantum cascade lasers as illumination sources.

Waveguide-enhanced Raman spectroscopy of trace chemical warfare agent simulants.

We report the measurement of waveguide-enhanced Raman spectra from trace concentrations of four vapor-phase chemical warfare agent simulants: dimethyl methylphosphonate, diethyl methylphosphonate, trimethyl phosphate, and triethyl phosphate. The spectra are obtained using highly evanescent nanophotonic silicon nitride waveguides coated with a naturally reversible hyperbranched carbosilane sorbent polymer and exhibit extrapolated one-σ detection limits as low as 5 ppb. We use a finite-element model to explain the polarization and wavelength properties of the differential spectra. In addition, we assign spectral features to both the analyte and the sorbent, and show evidence of changes to both due to hydrogen bonding.

The effects of policy actions to improve population dietary patterns and prevent diet-related non-communicable diseases: scoping review.

Poor diet generates a bigger non-communicable disease (NCD) burden than tobacco, alcohol and physical inactivity combined. We reviewed the potential effectiveness of policy actions to improve healthy food consumption and thus prevent NCDs. This scoping review focused on systematic and non-systematic reviews and categorised data using a seven-part framework: price, promotion, provision, composition, labelling, supply chain, trade/investment and multi-component interventions. We screened 1805 candidate publications and included 58 systematic and non-systematic reviews. Multi-component and price interventions appeared consistently powerful in improving healthy eating. Reformulation to reduce industrial trans fat intake also seemed very effective. Evidence on food supply chain, trade and investment studies was limited and merits further research. Food labelling and restrictions on provision or marketing of unhealthy foods were generally less effective with uncertain sustainability. Increasingly strong evidence is highlighting potentially powerful policies to improve diet and thus prevent NCDs, notably multi-component interventions, taxes, subsidies, elimination and perhaps trade agreements. The implications for policy makers are becoming clearer.

Re-constructing nutritional history of Serengeti wildebeest from stable isotopes in tail hair: seasonal starvation patterns in an obligate grazer.

RATIONALE: Nutritional bottlenecks often limit the abundance of animal populations and alter individual behaviours; however, establishing animal condition over extended periods of time using non-invasive techniques has been a major limitation in population ecology. We test if the sequential measurement of δ(15) N values in a continually growing tissue, such as hair, can be used as a natural bio-logger akin to tree rings or ice cores to provide insights into nutritional stress. METHODS: Nitrogen stable isotope ratios were measured by continuous-flow isotope-ratio mass spectrometry (IRMS) from 20 sequential segments along the tail hairs of 15 migratory wildebeest. Generalized Linear Models were used to test for variation between concurrent segments of hair from the same individual, and to compare the δ(15) N values of starved and non-starved animals. Correlations between δ(15) N values in the hair and periods of above-average energy demand during the annual cycle were tested using Generalized Additive Mixed Models. RESULTS: The time series of nitrogen isotope ratios in the tail hair are comparable between strands from the same individual. The most likely explanation for the pattern of (15) N enrichment between individuals is determined by life phase, and especially the energetic demands associated with reproduction. The mean δ(15) N value of starved animals was greater than that of non-starved animals, suggesting that higher δ(15) N values correlate with periods of nutritional stress. CONCLUSIONS: High δ(15) N values in the tail hair of wildebeest are correlated with periods of negative energy balance, suggesting they may be used as a reliable indicator of the animal's nutritional history. This technique might be applicable to other obligate grazers. Most importantly, the sequential isotopic analysis of hair offers a continuous record of the chronic condition of wildebeest (effectively converting point data into time series) and allows researchers to establish the animal's nutritional diary.

Infrared photothermal imaging spectroscopy for detection of trace explosives on surfaces.

We are developing a technique for the standoff detection of trace explosives on relevant substrate surfaces using photothermal infrared (IR) imaging spectroscopy (PT-IRIS). This approach leverages one or more compact IR quantum cascade lasers, which are tuned to strong absorption bands in the analytes and directed to illuminate an area on a surface of interest. An IR focal plane array is used to image the surface and detect increases in thermal emission upon laser illumination. The PT-IRIS signal is processed as a hyperspectral image cube comprised of spatial, spectral, and temporal dimensions as vectors within a detection algorithm. The ability to detect trace analytes at standoff on relevant substrates is critical for security applications but is complicated by the optical and thermal analyte/substrate interactions. This manuscript describes a series of PT-IRIS experimental results and analysis for traces of RDX, TNT, ammonium nitrate, and sucrose on steel, polyethylene, glass, and painted steel panels. We demonstrate detection at surface mass loadings comparable with fingerprint depositions ( 10µg/cm2 to 100µg/cm2) from an area corresponding to a single pixel within the thermal image.

Trace gas absorption spectroscopy using functionalized microring resonators.

We detect trace gases at parts-per-billion levels using evanescent-field absorption spectroscopy in silicon nitride microring resonators coated with a functionalized sorbent polymer. An analysis of the microring resonance line shapes enables a measurement of the differential absorption spectra for a number of vapor-phase analytes. The spectra are obtained at the near-infrared overtone of OH-stretch resonance, which provides information about the toxicity of the analyte vapor.

Meningitis associated with strongyloidiasis in an area endemic for strongyloidiasis and human T-lymphotropic virus-1: a single-center experience in Japan between 1990 and 2010.

Meningitis caused by enteric flora is a known complication of strongyloidiasis, and human T-lymphotropic virus-1 (HTLV-1) predisposes individuals to severe strongyloidiasis. We reviewed the clinical features of bacterial meningitis associated with strongyloidiasis seen at a single center in subtropical Japan, in an area endemic for both strongyloidiasis and HTLV-1. We found 33 episodes in 21 patients between 1990 and 2010. The results were remarkable for the high incidence of meningitis due to Gram-positive cocci (27.3 %), especially Streptococcus bovis, and culture-negative cases (42.4 %). Given the high incidence of Gram-positive meningitis, a modified approach to corticosteroid use would be advisable in areas where strongyloidiasis is endemic, due to the potentially adverse consequences of glucocorticoid therapy.

Palaeoenvironmental modelling of δ(13) C and δ(15) N values in the North Atlantic Islands: understanding past marine resource use.

RATIONALE: Carbon (δ(13) C) and nitrogen (δ(15) N) analysis has been extensively used to investigate the importance of marine foods in the diet of archaeological populations in the North Atlantic Islands; however, few faunal studies exist to aid the interpretation of results. Palaeoenvironmental modelling of δ(13) C and δ(15) N values is crucial in determining whether changes in the stable isotope values are a result of dietary change, rather than temporal or geographical fluctuations in carbon and nitrogen. Investigating faunal dietary behaviour can provide an insight into past foddering and land management strategies. METHODS: Detailed sampling of wild and domestic species for bulk collagen analysis was undertaken in order to characterise geographical variations in δ(13) C and δ(15) N values in the Outer Hebrides and Orkney. Samples from the Neolithic to the Norse period were analysed to assess temporal and geographical variations in δ(13) C and δ(15) N values, in addition to determining the contribution of marine foods to the diet of local fauna. RESULTS: A δ(15) N shift of 1‰ was observed between the Outer Hebrides and Orkney in the Neolithic and Iron Age. A geographical variation in δ(13) C values was observed in the Norse period between Orkney and the Outer Hebrides. Temporal fluctuations in δ(13) C and δ(15) N values demonstrate variations in foddering practices of sheep in the Outer Hebrides. Pig specimens from the Outer Hebrides demonstrated evidence of marine food consumption in the Iron Age. CONCLUSIONS: Faunal dietary behaviour can act as a vital indicator of the importance of marine resources in the past. Characterisation of faunal δ(13) C and δ(15) N values geographically and temporally is crucial in our interpretation of human dietary behaviour.

Micromechanical photothermal spectroscopy of trace gases using functionalized polymers.

We demonstrate a novel method to spectroscopically detect and identify trace gases. Micromechanical photothermal spectroscopy (MPS) with functionalized sorbent materials provides trace gas spectra in an optical interaction length of only a few micrometers. We use microcavity interferometry to read out displacements as low as 25 fm/√Hz, heating as low as 200 pW/√Hz, and analyte concentrations as low as 65 parts-per-billion for the nerve agent simulant DMMP. MPS integrated with functional materials represents an important new tool in chip-scale optical sensing.

Microscopic and Spectroscopic Studies of Thermally Enhanced Electrospun PMMA Micro- and Nanofibers.

Carbon nanofibers (CNFs) have been incorporated into poly(methyl methacrylate) (PMMA) through electrospinning. The resulting micro- and nanofibers have been characterized by Scanning Electron Microscopy (SEM), which confirmed fiber formation and demonstrated a core-sheath structure of the PMMA fibers. Thermogravimetric Analysis (TGA) was used to obtain the thermal properties of the materials, indicating an enhancement in the thermal properties of the composite fibers. In addition, Fourier Transform Infrared Spectroscopy (FTIR) was utilized to investigate the interactions of PMMA micro- and nanofibers with CNFs, demonstrating the preferred sites of intermolecular interactions between the polymer matrix and the filler.

Waveguide micro-opto-electro-mechanical resonant chemical sensors.

We demonstrate a silicon micro-opto-electro-mechanical sensor based on mass-loading of a chemo-selective polymer coated onto a microbridge. The sensor is probed optically using an on-chip waveguide Fabry-Pérot interferometer for high resolution displacement and resonant frequency measurement. The mechanical resonator is designed with paddles to simplify chemo-selective polymer deposition and to minimize any strain effects from the polymer during analyte sorption. Water vapor sensing experiments indicate mass-loading with minimum humidity detection of DeltaRH = 0.25% corresponding to a measured limit-of-detection of 68 parts-per-million. The sensor response time constant is 30 s with minimum frequency noise of 58 Hz at 149.4 kHz resonance. The measured mass-loading resolution is 4.6 picograms. We extract the chemo-selective polymer's partition coefficient and confirm that strong sorption and mass-loading occurs. Various device improvements are discussed, including scaling up to large single-chip sensor arrays, increasing mass-loading resolution by adjusting the device geometry, and using other chemo-selective polymers with larger partition coefficients. These improvements suggest parts-per-billion limit-of-detection levels for a variety of toxic chemicals.

Element patterns in albatrosses and petrels: influence of trophic position, foraging range, and prey type.

We investigated the concentrations of 22 essential and non-essential elements among a community of Procellariiformes (and their prey) to identify the extent to which trophic position and foraging range governed element accumulation. Stable isotope analysis (SIA) was used to characterise trophic (delta(15)N) and spatial patterns (delta(13)C) among species. Few consistent patterns were observed in element distributions among species and diet appeared to be highly influential in some instances. Arsenic levels in seabird red blood cells correlated with delta(15)N and delta(13)C, demonstrating the importance of trophic position and foraging range for arsenic distribution. Arsenic concentrations in prey varied significantly across taxa, and in the strength of association with delta(15)N values (trophic level). In most instances, element patterns in Procellariiformes showed the clearest separation among species, indicating that a combination of prey selection and other complex species-specific characteristics (e.g. moult patterns) were generally more important determining factors than trophic level per se.