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Background: To meet the World Health Organization goal of reducing physical inactivity by 15% by 2030, a multisectoral system approach is urgently needed to promote physical activity (PA). We report the process of and findings from a codesigned systems mapping project to present determinants of PA in the context of urban New South Wales, Australia., Methods: A participatory conceptual mapping workshop was held in May 2023 with 19 participants working in education, transportation, urban planning, community, health, and sport and recreation. Initial maps were developed and refined using online feedback from the participants. Interviews were conducted with 10 additional policymakers from relevant sectors to further refine the maps., Results: Two systems maps were cocreated, identifying over 100 variables influencing PA and their interconnections. Five settings emerged from the adults' map-social and community, policy, built environment and transportation, health care, and workplace-and 4 for the young people's map-family, school, transportation, and community and environment. The maps share similarities, such as regarding potential drivers within the transportation, community, and built environment sectors; however, the young people's map has a specific focus on the school setting and the adults' map on workplace and health care settings. Interviews with policymakers provided further unique insights into understanding and intervening in the PA system., Conclusions: This codesigned participatory systems mapping process, supplemented by stakeholder interviews, provided a unique opportunity to bring together stakeholders across sectors to understand the complexity within the PA system and begin to identify leverage points for tackling physical inactivity in New South Wales.

Food consumption play a crucial role in human life, yet conventional food production and consumption patterns can be detrimental to the environment. Thus, research and development has been directed towards alternative proteins, with edible insects being promising sources. Edible insects have been recognised for their sustainable benefits providing protein, with less emission of greenhouse gas, land and water usage compared to sources, such as beef, chicken, and dairy products. Among the over 2000 known edible insect species, only four, namely yellow mealworm (Tenebrio molitor), migratory locust/grasshopper (Locusta migratoria), grain mould beetle, also known as lesser mealworm which is a larval form of Alphitobius diaperinus (from the family of Tenebrionidae of darkling beetles) and house cricket (Acheta domesticus), are currently authorised in specific products through specific producers in the EU. The expansion of such foods into Western diets face challenges such as consumer barriers, gaps in microbiological and chemical safety hazard data during production and processing, and the potential for fraudulent supply chain activity. The main aim of this study was to map the supply chain, through interviews with personnel along the supply chain, coupled with searches for relevant publications and governmental documents. Thus, the main potential points of food safety and fraud along the edible insect supply chain were identified. Feed substrate was identified as the main area of concern regarding microbiological and chemical food safety and novel processing techniques were forecast to be of most concern for future fraudulent activity. Despite the on-going authorisation of insect species in many countries there are substantial food safety and authenticity information gaps in this industry that need to be addressed before edible insects can be viewed as a safe and sustainable protein sources by Western consumers., (© 2024. The Author(s).)

Food allergy remains a public health, business, and regulatory challenge. Risk analysis (RA) and risk management (RM) of food allergens are of great importance and analysis for food allergens is necessary for both. The current workhorse techniques for allergen analysis (enzyme linked immunosorbent assay [ELISA] and real-time polymerase chain reaction) exhibit recognized challenges including variable and antibody specific responses and detection of species DNA rather than allergen protein, respectively. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) enables protein identification, with potential for multiplex analysis and traceability to the System of International units (SI), aiding global measurement standardization. In this review, recent literature has been systematically reviewed to assess progress in LC-MS/MS and define the potential and benefits of matrix-assisted laser desorption/ionization-time-of-flight MS (MALDI-ToF-MS) technology for allergen analysis. MALDI-ToF-MS of initially intact protein is already applied to verify in silico-derived peptide sequences for LC-MS/MS analysis. We describe the origins of MALDI and its future perspectives, including affinity bead-assisted assays coupled to MALDI. Based on the proliferation of reliable and reproducible MALDI-based clinical applications, the technique should emulate the detection capability (sensitivity) of established allergen detection techniques, whilst reducing technical support and having equivalent multiplexing potential to competing techniques, for example, LC-MS/MS and ELISA. Although unlikely to offer inherent SI traceability, MALDI-based allergen analysis will complement existing MS approaches for allergens. Affinity bead-MALDI appears capable of higher throughput at lower cost per sample than almost any existing technique, enabling repeated sub-sampling as a way to reduce representative sampling issues., (© 2023 The Authors. Comprehensive Reviews in Food Science and Food Safety published by Wiley Periodicals LLC on behalf of Institute of Food Technologists.)

Spinal cord injury (SCI) is a devastating disorder, which impacts the lives of millions of people worldwide with no clinically standardized treatment. Both pro-recovery and anti-recovery factors contribute to the overall outcome after the initial SCI. Sex is emerging as an important variable, which can affect recovery post-SCI. Contusion SCI at T10 was generated in male and female rats. Open-field Basso, Beattie, Bresnahan (BBB) behavioral test, Von Frey test, and CatWalk gate analysis were performed. Histological analysis was performed at the 45-day post-SCI end point. Male/female differences in sensorimotor function recovery, lesion size, and the recruitment of immune cells to the lesion area were measured. A group of males with less severe injuries was included to compare the outcomes for severity. Our results show that both sexes with the same injury level plateaued at a similar final score for locomotor function. Males in the less severe injury group recovered faster and plateaued at a higher BBB score compared to the more severe injury group. Von Frey tests show faster recovery of sensory function in females compared to both male groups. All three groups exhibited reduced mechanical response thresholds after SCI. The lesion area was significantly larger in the male group with severe injury than in females, as well as in males of less severe injury. No significant differences in immune cell recruitment were identified when comparing the three groups. The faster sensorimotor recovery and significantly smaller lesion area in females potentially indicate that neuroprotection against the secondary injury is a likely reason for sex-dependent differences in functional outcomes after SCI., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Osimanjiang, Allgood, Van Sandt, Burns and Bushman.)

The analytical techniques applied to verify honey authenticity are multifaceted and often result in complex data rich certificates of analysis that are open to interpretation and may be opaque to stakeholders without specialist knowledge. In these cases, the drawing of an independent overarching opinion is challenging. Two questions arise: (Q1) Is it acceptable to report interpretation, particularly if it is adverse, without exhibiting the supporting data? (Q2) How may a valid overarching opinion on authenticity be derived from a large, partially conflicting, dataset? To Q1, it is demonstrated that full disclosure of the data used in interpretation is mandatory. To Q2 it is proposed, with worked examples, to adopt 'evaluative reporting'; a formalised likelihood ratio thought process used in forensic science for evaluation of findings and their strength assessment. In the absence of consensus on techniques for honey authenticity adoption of reporting conventions will allow objective assessments of reports, with equity to all and provide a better basis to identify and address fraud., (© 2022. The Author(s).)

The composition of honey, a complex natural product, challenges analytical methods attempting to determine its authenticity particularly in the face of sophisticated adulteration. Of the advanced analytical techniques available, only isotope ratio mass spectrometry (IRMS) is generally accepted for its reproducibility and ability to detect certain added sugars, with nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HRMS) being subject to stakeholder differences of opinion. Herein, recent reviews of honey adulteration and the techniques to detect it are summarised in the light of which analytical reports are examined that underpinned a media article in late 2020 alleging foreign sugars in UK retailers' own brand honeys. The requirement for multiple analytical techniques leads to complex reports from which it is difficult to draw an overarching and unequivocal authenticity opinion. Thus arose two questions. (1) Is it acceptable to report an adverse interpretation without exhibiting all the supporting data? (2) How may a valid overarching authenticity opinion be derived from a large partially conflicting dataset?, (© 2022. The Author(s).)

Pesticides are a safety issue globally and cause serious concerns for the environment, wildlife and human health. The handheld detection of four pesticide residues widely used in Basmati rice production using surface-enhanced Raman spectroscopy (SERS) is reported. Different SERS substrates were synthesised and their plasmonic and Raman scattering properties evaluated. Using this approach, detection limits for pesticide residues were achieved within the range of 5 ppb-75 ppb, in solvent. Various extraction techniques were assessed to recover pesticide residues from spiked Basmati rice. Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERs) acetate extraction was applied and characteristic spectral data for each pesticide was obtained from the spiked matrix and analysed using handheld-SERS. This approach allowed detection limits within the matrix conditions to be markedly improved, due to the rapid aggregation of nanogold caused by the extraction medium. Thus, detection limits for three out of four pesticides were detectable below the Maximum Residue Limits (MRLs) of 10 ppb in Basmati rice. Furthermore, the multiplexing performance of handheld-SERS was assessed in solvent and matrix conditions. This study highlights the great potential of handheld-SERS for the rapid on-site detection of pesticide residues in rice and other commodities., (© 2022. Crown.)

Peripheral nerves (PNs) are frequently injured as a result of trauma or disease. Development of therapies to regenerate PNs requires the use of animal models, typically beginning in rodents and progressing to larger species. There are several large animal models of PN regeneration that each has their benefits and drawbacks. Sheep have been used in PN studies due to their similarities in body weight to humans and the ease and lesser expense in their care and housing relative to other species. We have investigated the use of sheep for studies of PN regeneration and have developed and tested an injury model in the peroneal branch of the sciatic nerve. Three experimental groups were tested on mature sheep: a bisection; a 5-cm reverse autograft; and sham surgery. Protocols were developed for the post-operative care for animals with this injury, and regeneration was tracked for extended time points via compound muscle action potentials (CMAPs) and endpoint assessments of nerve morphometry, muscle mass and muscle fibrosis. Results indicate the practical viability of this PN injury model and show distinctions in the degree and rate of regeneration between bisection and reverse autograft that persisted 14 months. This long-term study shows bisections lead to significantly improved CMAPS and muscle mass and lesser muscle fibrosis as compared to reverse autograft. The persistence of these discernable changes between two relatively similar experimental groups out to extended time points is an indication of the sensitivity of this nerve section and its potential applicability for comparative studies., (© 2020 Federation of European Neuroscience Societies and John Wiley & Sons Ltd.)

The RNA exosome is a ubiquitously expressed complex of nine core proteins (EXOSC1-9) and associated nucleases responsible for RNA processing and degradation. Mutations in EXOSC3 , EXOSC8 , EXOSC9 , and the exosome cofactor RBM7 cause pontocerebellar hypoplasia and motor neuronopathy. We investigated the consequences of exosome mutations on RNA metabolism and cellular survival in zebrafish and human cell models. We observed that levels of mRNAs encoding p53 and ribosome biogenesis factors are increased in zebrafish lines with homozygous mutations of exosc8 or exosc9 , respectively. Consistent with higher p53 levels, mutant zebrafish have a reduced head size, smaller brain, and cerebellum caused by an increased number of apoptotic cells during development. Down-regulation of EXOSC8 and EXOSC9 in human cells leads to p53 protein stabilisation and G2/M cell cycle arrest. Increased p53 transcript levels were also observed in muscle samples from patients with EXOSC9 mutations. Our work provides explanation for the pathogenesis of exosome-related disorders and highlights the link between exosome function, ribosome biogenesis, and p53-dependent signalling. We suggest that exosome-related disorders could be classified as ribosomopathies., (© 2020 Müller et al.)

Background: The content of the endosperm of the coconut (Cocos nucifera L.) contains "coconut water". This practically sterile liquid which is prized for its delicate, albeit labile, flavor when fresh, has had a recent dramatic increase in global demand. The organoleptic superiority of water from young coconuts means that degree of maturity at harvesting is the most influential factor in yield and composition., Objective: To provide a guide to establishing the authenticity and the potability of samples of coconut water., Method: Review and evaluate the literature on the factors that determine the composition and stability of coconut water., Results: Data is presented on the variances in natural composition, maturity, processing-induced compositional changes, adulterations, product recalls, classical and instrumental methods of analysis and on the available composition standards of coconut water., Conclusions: Advice is provided for official food analysts, and others, on prudent approaches as how to ascertain the authenticity and potability, or otherwise, of coconut water samples., (© Crown copyright 2020.)

The IAEA is currently coordinating a multi-year project to update the TRS-398 Code of Practice for the dosimetry of external beam radiotherapy based on standards of absorbed dose to water. One major aspect of the project is the determination of new beam quality correction factors, k Q , for megavoltage photon beams consistent with developments in radiotherapy dosimetry and technology since the publication of TRS-398 in 2000. Specifically, all values must be based on, or consistent with, the key data of ICRU Report 90. Data sets obtained from Monte Carlo (MC) calculations by advanced users and measurements at primary standards laboratories have been compiled for 23 cylindrical ionization chamber types, consisting of 725 MC-calculated and 179 experimental data points. These have been used to derive consensus k Q values as a function of the beam quality index TPR 20,10 with a combined standard uncertainty of 0.6%. Mean values of MC-derived chamber-specific [Formula: see text] factors for cylindrical and plane-parallel chamber types in 60 Co beams have also been obtained with an estimated uncertainty of 0.4%.

Background: The driving factors for the commercial adulteration of coffee are reviewed., Objective: Methods have been assessed for the identification of the most common materials used to adulterate coffee by dilution, to establish the geographic origins, the genotypes of beans, and to assess the authenticity of Kopi Luwak coffee., Method: The literature was surveyed manually and electronically from 1820 to 2018., Results: A flow diagram has been developed to summarize the best approaches to deal with the authentication of coffee., Conclusions: Encouragement is given to the interlaboratory validation of spectroscopic approaches, the exploration of civet cat deoxyribonucleic acid for the identification of Kopi Luwak, and the development of appropriately large and well-curated datasets of authenticity information across multiple techniques., Highlights: The current analytical difficulties in the authentication of coffee are highlighted and suggestions made to improve the situation., (Copyright ©2019 by AOAC International, Inc. All rights reserved.)

More than a quarter of a million individuals in the US live with spinal cord injury (SCI). SCI disrupts neural circuitry to vital organs in the body. Despite severe incidences of long-term peripheral complications from SCI, the cardio-metabolic consequences and divergences in sex-related responses are not well described. We examined the effects of SCI on functional recovery, cardiac structure and function, body composition, and glucose metabolism on adult female and male Sprague Dawley (SD) rats. SCI was induced at T10 via contusion. Measured outcomes include behavioral assessment, body weight, dual-energy X-ray absorptiometry (DEXA) for body composition, echocardiography for cardiac structure and function, intraperitoneal glucose tolerance test (IPGTT) for glucose metabolism, insulin tolerance test (ITT), and histology of cardiac structure at the endpoint. There was a decrease in body fat percentage in both sexes, with SCI females disproportionately affected in percent body fat change. Left ventricular internal diameter during systole (LVIDs) was decreased in SCI females more than in SCI males. No significant differences in glucose metabolism were observed up to 20 weeks post-injury (PI). These data show significant cardio-metabolic differences as a consequence of SCI and, furthermore, that sex is an underlying factor in these differences.

The origin of the method of standard additions (SAM) and of the use of internal standard (IS) in instrumental chemical analysis and their spread into other areas has been reviewed. Recorded applications of IS range from flame spectroscopy in 1877 through multiple techniques to current use in NMR and standard additions with isotopically labelled internal standards in hyphenated techniques. For SAM, applications stemmed from polarography in 1937 and spread to most instrumental methods. Some misconceptions on priorities are corrected.

The exosome is a conserved multi-protein complex that is essential for correct RNA processing. Recessive variants in exosome components EXOSC3, EXOSC8, and RBM7 cause various constellations of pontocerebellar hypoplasia (PCH), spinal muscular atrophy (SMA), and central nervous system demyelination. Here, we report on four unrelated affected individuals with recessive variants in EXOSC9 and the effect of the variants on the function of the RNA exosome in vitro in affected individuals' fibroblasts and skeletal muscle and in vivo in zebrafish. The clinical presentation was severe, early-onset, progressive SMA-like motor neuronopathy, cerebellar atrophy, and in one affected individual, congenital fractures of the long bones. Three affected individuals of different ethnicity carried the homozygous c.41T>C (p.Leu14Pro) variant, whereas one affected individual was compound heterozygous for c.41T>C (p.Leu14Pro) and c.481C>T (p.Arg161 ∗ ). We detected reduced EXOSC9 in fibroblasts and skeletal muscle and observed a reduction of the whole multi-subunit exosome complex on blue-native polyacrylamide gel electrophoresis. RNA sequencing of fibroblasts and skeletal muscle detected significant >2-fold changes in genes involved in neuronal development and cerebellar and motor neuron degeneration, demonstrating the widespread effect of the variants. Morpholino oligonucleotide knockdown and CRISPR/Cas9-mediated mutagenesis of exosc9 in zebrafish recapitulated aspects of the human phenotype, as they have in other zebrafish models of exosomal disease. Specifically, portions of the cerebellum and hindbrain were absent, and motor neurons failed to develop and migrate properly. In summary, we show that variants in EXOSC9 result in a neurological syndrome combining cerebellar atrophy and spinal motoneuronopathy, thus expanding the list of human exosomopathies., (Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.)

This review discusses the criteria for the selection of appropriate reference samples of chondroitin sulfate (CS) and the properties and specific problems of analytical methods for CS, namely titration with cetylpyridinium chloride; various separations; and UV-Vis, NMR, MS, and IR spectroscopies. Suggestions are put forward with regard to acceptable protocols for manufactures' and for official/referee analysts for the analysis of CS in products.

Food allergy is an increasing problem for those affected, their families or carers, the food industry and for regulators. The food supply chain is highly vulnerable to fraud involving food allergens, risking fatalities and severe reputational damage to the food industry. Many facets are being pursued to ameliorate the difficulties including better food labelling and the concept of thresholds of elicitation of allergy symptoms as risk management tools. These efforts depend to a high degree on the ability reliably to detect and quantify food allergens; yet all current analytical approaches exhibit severe deficiencies that jeopardise accurate results being produced particularly in terms of the risks of false positive and false negative reporting. If we fail to realise the promise of current risk assessment and risk management of food allergens through lack of the ability to measure food allergens reproducibly and with traceability to an international unit of measurement, the analytical community will have failed a significant societal challenge. Three distinct but interrelated areas of analytical work are urgently needed to address the substantial gaps identified: (a) a coordinated international programme for the production of properly characterised clinically relevant reference materials and calibrants for food allergen analysis; (b) an international programme to widen the scope of proteomics and genomics bioinformatics for the genera containing the major allergens to address problems in ELISA, MS and DNA methods; (c) the initiation of a coordinated international programme leading to reference methods for allergen proteins that provide results traceable to the SI. This article describes in more detail food allergy, the risks of inapplicable or flawed allergen analyses with examples and a proposed framework, including clinically relevant incurred allergen concentrations, to address the currently unmet and urgently required analytical requirements. Support for the above recommendations from food authorities, business organisations and National Measurement Institutes is important; however transparent international coordination is essential. Thus our recommendations are primarily addressed to the European Commission, the Health and Food Safety Directorate, DG Santé. A global multidisciplinary consortium is required to provide a curated suite of data including genomic and proteomic data on key allergenic food sources, made publically available on line.

New Findings: What is the topic of this review? This review highlights recent progress in genetically based therapies targeting the primary defect of Duchenne muscular dystrophy. What advances does it highlight? Over the last two decades, considerable progress has been made in understanding the mechanisms underlying Duchenne muscular dystrophy, leading to the development of genetic therapies. These include manipulation of the expression of the gene or related genes, the splicing of the gene and its translation, and replacement of the gene using viral approaches. Duchenne muscular dystrophy is a lethal X-linked disorder caused by mutations in the dystrophin gene. In the absence of the dystrophin protein, the link between the cytoskeleton and extracellular matrix is destroyed, and this severely compromises the strength, flexibility and stability of muscle fibres. The devastating consequence is progressive muscle wasting and premature death in Duchenne muscular dystrophy patients. There is currently no cure, and despite exhaustive palliative care, patients are restricted to a wheelchair by the age of 12 years and usually succumb to cardiac or respiratory complications in their late 20s. This review provides an update on the current genetically based therapies and clinical trials that target or compensate for the primary defect of this disease. These include dystrophin gene-replacement strategies, genetic modification techniques to restore dystrophin expression, and modulation of the dystrophin homologue, utrophin, as a surrogate to re-establish muscle function., (© 2015 The Authors. Experimental Physiology published by John Wiley & Sons Ltd on behalf of The Physiological Society.)

Duchenne muscular dystrophy (DMD) is a lethal, X-linked muscle-wasting disease caused by lack of the cytoskeletal protein dystrophin. There is currently no cure for DMD although various promising approaches are progressing through human clinical trials. By pharmacologically modulating the expression of the dystrophin-related protein utrophin, we have previously demonstrated in dystrophin-deficient mdx studies, daily SMT C1100 treatment significantly reduced muscle degeneration leading to improved muscle function. This manuscript describes the significant disease modifying benefits associated with daily dosing of SMT022357, a second-generation compound in this drug series with improved physicochemical properties and a more robust metabolism profile. These studies in the mdx mouse demonstrate that oral administration of SMT022357 leads to increased utrophin expression in skeletal, respiratory and cardiac muscles. Significantly, utrophin expression is localized along the length of the muscle fibre, not just at the synapse, and is fibre-type independent, suggesting that drug treatment is modulating utrophin transcription in extra-synaptic myonuclei. This results in improved sarcolemmal stability and prevents dystrophic pathology through a significant reduction of regeneration, necrosis and fibrosis. All these improvements combine to protect the mdx muscle from contraction induced damage and enhance physiological function. This detailed evaluation of the SMT C1100 drug series strongly endorses the therapeutic potential of utrophin modulation as a disease modifying therapeutic strategy for all DMD patients irrespective of their dystrophin mutation., (© The Author 2015. Published by Oxford University Press.)

The BIPM graphite calorimeter standard for absorbed dose to water has been used in conjunction with an ionization chamber of known volume and with Monte Carlo simulations of these arrangements to determine the value for Wair in (60)Co radiation and in accelerator photon beams up to 25 MV. The results show no evidence for a variation in Wair at the 0.2% level over this energy range. Taking the constancy of Wair as established, the best estimate is Wair = 34.03 eV with a standard uncertainty of 0.21%. Consistent with this analysis, and assuming the use of the grain density in evaluating the stopping power of graphite, is the value Ic = 81.1 eV for the mean excitation energy for graphite, with standard uncertainty 1.8 eV.

Current routine food allergen quantification methods, which are based on immunochemistry, offer high sensitivity but can suffer from issues of specificity and significant variability of results. MS approaches have been developed, but currently lack metrological traceability. A feasibility study on the application of metrologically traceable MS-based reference procedures was undertaken. A proof of concept involving proteolytic digestion and isotope dilution MS for quantification of protein allergens in a food matrix was undertaken using lysozyme in wine as a model system. A concentration of lysozyme in wine of 0.95 +/- 0.03 microg/g was calculated based on the concentrations of two peptides, confirming that this type of analysis is viable at allergenically meaningful concentrations. The challenges associated with this promising method were explored; these included peptide stability, chemical modification, enzymatic digestion, and sample cleanup. The method is suitable for the production of allergen in food certified reference materials, which together with the achieved understanding of the effects of sample preparation and of the matrix on the final results, will assist in addressing the bias of the techniques routinely used and improve measurement confidence. Confirmation of the feasibility of MS methods for absolute quantification of an allergenic protein in a food matrix with results traceable to the International System of Units is a step towards meaningful comparison of results for allergen proteins among laboratories. This approach will also underpin risk assessment and risk management of allergens in the food industry, and regulatory compliance of the use of thresholds or action levels when adopted.

Substantial changes in ion chamber perturbation correction factors in (60)Co γ-rays, suggested by recent Monte Carlo (MC) calculations, would cause a decrease of about 1.5% in the reference dosimetry of all types of charged particles (electrons, protons and heavier ions) based on calculated kQ values. It has gone largely unnoticed that the ratio of calibration coefficients ND, w, Co60 and NK, air, Co60 yields an experimental value of Fch, Co60 = (sw-air pch)Co60 through ND, air, Co60. Coefficients provided by the IAEA and traceable to the BIPM for 91 NE-2571 chambers result in an average Fch, Co60 which is compared with published (and new) MC simulations and with the value in IAEA TRS-398. It is shown that TRS-398 agrees within 0.12% with the experimental Fch, Co60. The 1.5% difference resulting from MC calculations (1.1% for the new simulations) cannot be justified using current fundamental data and BIPM standards if consistency in the entire dosimetry chain is sought. For photons, MC kQ factors are compared with TRS-398. Using the same uncertainty for Wair, the two sets of data overlap considerably. Experimental kQ values from standards laboratories lie between the two sets of calculated values, showing no preference for one set over the other. Observed chamber-to-chamber differences, that include the effect of waterproof sleeves (also seen for (60)Co), justify the recommendation in TRS-398 for kQ values specifically measured for the user chamber. Current developments on I-values for the stopping powers of water and graphite are presented. A weighted average Iwater = 78 ± 2 eV is obtained from published experimental and DRF-based values; this would decrease sw-air for all types of radiotherapy beams between 0.3% and 0.6%, and would consequently decrease the MC derived Fch, Co60. The implications of a recent proposal for Igraphite = 81 eV are analysed, resulting in a potential decrease of 0.7% in NK, air, Co60 which would raise the experimental Fch, Co60; this would result in an increase of about 0.8% in the current TRS-398 value when referred to the BIPM standards. MC derived Fch, Co60 using new stopping powers would then agree at a level of 0.1% with the experimental value, confirming the need for consistency in the dosimetry chain data. Should world average standards be used as reference, the figures would become +0.4% for TRS-398 and -0.3% for the MC calculation. Fch, Q calculated for megavoltage photons using new stopping powers would decrease by between 0.2% and 0.5%. When they enter as a ratios in kQ, differences with MC values based on current key data would be within 0.2% but their discrepancy with kQ experimental photon values remains unresolved. For protons the new data would require an increase in Wair, Q of about 0.6%, as this is inferred from a combination of calorimetry and ionometry. This consistent scenario would leave unchanged the current TRS-398 kQ (NE-2571) data for protons, as well as for ions heavier than protons unless new independent Wair, Q values become available. Also in these advanced radiotherapy modalities, the need for maintaining data consistency in an analysis that unavoidably must include the complete dosimetry chain is demonstrated.

A systematic analysis of the available data has been carried out for mass energy-absorption coefficients and their ratios for air, graphite and water for photon energies between 1 keV and 2 MeV, using representative kilovoltage x-ray spectra for mammography and diagnostic radiology below 100 kV, and for ¹⁹²Ir and ⁶⁰Co gamma-ray spectra. The aim of this work was to establish 'an envelope of uncertainty' based on the spread of the available data. Type A uncertainties were determined from the results of Monte Carlo (MC) calculations with the PENELOPE and EGSnrc systems, yielding mean values for µ(en)/ρ with a given statistical standard uncertainty. Type B estimates were based on two groupings. The first grouping consisted of MC calculations based on a similar implementation but using different data and/or approximations. The second grouping was formed by various datasets, obtained by different authors or methods using the same or different basic data, and with different implementations (analytical, MC-based, or a combination of the two); these datasets were the compilations of NIST, Hubbell, Johns-Cunningham, Attix and Higgins, plus MC calculations with PENELOPE and EGSnrc. The combined standard uncertainty, u(c), for the µ(en)/ρ values for the mammography x-ray spectra is 2.5%, decreasing gradually to 1.6% for kilovoltage x-ray spectra up to 100 kV. For ⁶⁰Co and ¹⁹²Ir, u(c) is approximately 0.1%. The Type B uncertainty analysis for the ratios of µ(en)/ρ values includes four methods of analysis and concludes that for the present data the assumption that the data interval represents 95% confidence limits is a good compromise. For the mammography x-ray spectra, the combined standard uncertainties of (µ(en)/ρ)(graphite,air) and (µ(en)/ρ)(graphite,water) are 1.5%, and 0.5% for (µ(en)/ρ)(water,air), decreasing gradually down to u(c) = 0.1% for the three µ(en)/ρ ratios for the gamma-ray spectra. The present estimates are shown to coincide well with those of Hubbell (1977 Rad. Res. 70 58-81), except for the lowest energy range (radiodiagnostic) where it is concluded that current databases and their systematic analysis represent an improvement over the older Hubbell estimations. The results for (µ(en)/ρ)(graphite,air) for the gamma-ray dosimetry range are moderately higher than those of Seltzer and Bergstrom (2005 private communication).

A key comparison has been made between the air-kerma standards of the NIST, USA and the BIPM in the medium-energy x-ray range. The results show the standards to be in agreement at the level of the standard uncertainty of the comparison of 3.8 parts in 10 3 , except at 250 kV where the difference is 1.5 times the standard uncertainty. The results are analysed and presented in terms of degrees of equivalence, suitable for entry in the BIPM key comparison database.

At present, only a correction factor for photon transmission, k(l), is systematically applied for the entrance diaphragm of free-air chamber standards for air kerma. In the present work, the Monte Carlo code PENELOPE is used to re-evaluate k(l) for the BIPM standards and new correction factors are calculated for photon scatter and for fluorescence production in the diaphragm. An additional effect arising from electrons emitted from the diaphragm is shown to be significant at the highest photon energies. The results for the radiation qualities used for international comparisons give a combined diaphragm correction factor k(dia) = 0.9980(3) for the BIPM medium-energy standard at 250 kV. This is significantly different from the factor k(l) = 0.9996(1) in use at present and it might be concluded that differences are likely to exist for all free-air chamber standards. The effect of using a conical taper at the downstream edge of the diaphragm is shown to be negligible for these radiation qualities.

A graphite-walled cavity ionization chamber of modular design and variable volume has been used to determine the air-kerma rate in the reference 60Co field at the BIPM. The chamber can be configured in five sizes. High-accuracy mechanical measurements of the volume of the air cavity were made for each configuration using a co-ordinate measuring machine. Ionization current measurements were made for each configuration and corrected for the effects of ion recombination and diffusion, stem scatter and chamber orientation. Monte Carlo calculations of cavity dose were made to evaluate the correction factors kwall and kan. A reproducibility of the ionization current per mass of 1.5 parts in 10(4) was achieved on the repeated assembly of each configuration. The results show an air-kerma rate determination that increases with volume, the total change being around 8 parts in 10(4). When analysed differentially, the air-kerma rate relative to the BIPM standard is Kdiff/KBIPM = 1.0026(6). A detailed uncertainty budget is presented. Possible reasons for the observed behaviour are discussed that might have consequences for all existing standards for air-kerma.

A comparison has been made of the air-kerma standards for medium-energy x-rays of the National Institute of Standards and Technology (NIST) and the Bureau International des Poids et Mesures (BIPM). The comparison involved a series of measurements at the BIPM and the NIST using the air-kerma standards and three NIST reference-class transfer ionization chamber standards. Reference beam qualities in the range from 100 kV to 250 kV were used. The results show the standards to be in reasonable agreement within the combined standard uncertainty of the comparison of 0.37 %, although a significant trend with radiation quality is observed and the possible sources discussed.

The evaluation is described of an automated pyrolysis-gas chromatography-mass spectrometry system combined with a software package to convert total ion current chromatograms into forms that resemble a conventional mass spectra called "spectragrams". The spectragram for a single paint sample can be "closest fit" matched to a previously created paint pyrogram library via pre-determined target compounds in a handling list. Up to 45 paint samples can be dealt with in an overnight unattended run.

A consistent formalism is presented using Monte Carlo calculations to determine the reference air kerma from the measured energy deposition in a primary-standard cavity ionization chamber. A global approach avoiding the use of cavity ionization theory is discussed and its limitations shown in relation to the use of the recommended value for W. The role of charged-particle equilibrium is outlined and the consequent requirements placed on the calculations are detailed. Values for correction factors are presented for the BIPM air-kerma standard for 60Co, making use of the Monte Carlo code PENELOPE, a detailed geometrical model of the BIPM 60Co source and event-by-event electron transport. While the wall correction factor k(wall) = 1.0012(2) is somewhat lower than the existing value, the axial non-uniformity correction k(an) = 1.0027(3) is significantly higher. The use of a point source in the evaluation of k(an) is discussed. A comparison is made of the calculated dose ratio with the Bragg-Gray and Spencer-Attix stopping-power ratios, the results indicating a preference for the Bragg-Gray approach in this particular case. A change to the recommended value for W of up to 2 parts in 10(3) is discussed. The uncertainties arising from the geometrical models, the use of phase-space files, the radiation transport algorithms and the underlying radiation interaction coefficients are estimated.

Here we report the results of the largest study yet carried out on composition profiling of seized "ecstasy" tablets by Raman spectroscopy. Approximately 1500 tablets from different seizures in N. Ireland were analysed and even though practically all the tablets contained MDMA as active constituent, there were very significant differences in their Raman spectra, which were due to variations in both the nature and concentration of the excipients used and/or the degree of hydration of the MDMA. The ratios of the peak heights of the prominent drug bands at 810 cm(-1) and 716 cm(-1) (which vary with hydration state of the drug), and the drug band at 810 cm(-1) against the largest clearly discernible excipient band in the spectrum were measured for all the samples. It was found that there was sufficient variation in composition in the general sample population to make any matches between batches of tablets taken from different seizures significant, rather than the result of random chance. Despite the large number of different batches of tablets examined in this study, only two examples of indistinguishable sets of tablets were found and in only one of these had the two batches of tablets been seized at different times. Finally, the fact that there are many examples of batches of tablets (particularly in different batches taken from single seizures) in which the differences between each set are sufficiently small that they appear to arise only from random variations within a standard manufacturing method implies that, with more extensive data, it may be possible to recognize the "signature" of tablets prepared by major manufacturers.

The air-kerma standards used for the measurement of medium-energy x rays were compared at the National Institute of Standards and Technology (NIST) and at the Bureau International des Poids et Mesures (BIPM). The comparison involved a series of measurements at the BIPM and the NIST using the air-kerma standards and two NIST reference-class transfer ionization standards. Reference beam qualities in the range from 60 kV to 300 kV were used. The results show the standards to be in agreement within the combined standard uncertainty of the comparison of 0.35 %.

Chemistry has been used for the detection of adulteration since the earliest times of recorded history going back at least 3 1/2 millennia. Since the invention of printing the subject is easier to follow. Aspects of law and its application via chemistry in regard to precious metals, food, drink and medicinal materials are reviewed over the last half millennium with particular reference to the U.K.

Raman spectroscopy with far-red excitation has been investigated as a simple and rapid technique for composition profiling of seized ecstasy (MDMA, N-methyl-3,4-methylenedioxyamphetamine) tablets. The spectra obtained are rich in vibrational bands and allow the active drug and excipient used to bulk the tablets to be identified. Relative band heights can be used to determine drug/excipient ratios and the degree of hydration of the drug while the fact that 50 tablets per hour can be analysed allows large numbers of spectra to be recorded. The ability of Raman spectroscopy to distinguish between ecstasy tablets on the basis of their chemical composition is illustrated here by a sample set of 400 tablets taken from a large seizure of > 50,000 tablets that were found in eight large bags. The tablets are all similar in appearance and carry the same logo. Conventional analysis by GC-MS showed they contained MDMA. Initial Raman studies of samples from each of the eight bags showed that despite some tablet-to-tablet variation within each bag the contents could be classified on the basis of the excipients used. The tablets in five of the bags were sorbitol-based, two were cellulose-based and one bag contained tablets with a glucose excipient. More extensive analysis of 50 tablets from each of a representative series of sample bags have distribution profiles that showed the contents of each bag were approximately normally distributed about a mean value, rather than being mixtures of several discrete types. Two of the sorbitol-containing sample sets were indistinguishable while a third was similar but not identical to these, in that it contained the same excipient and MDMA with the same degree of hydration but had a slightly different MDMA/sorbitol ratio. The cellulose-based samples were badly manufactured and showed considerable tablet-to-tablet variation in their drug/excipient ratio while the glucose-based tablets had a tight distribution in their drug/excipient ratios. The degree of hydration in the MDMA feedstocks used to manufacture the cellulose-, glucose- and sorbitol-based tablets were all different from each other. This study, because it centres on a single seizure of physically similar tablets with the same active drug, highlights the fact that simple physical descriptions coupled with active drug content do not in themselves fully characterize the nature of the seized materials. There is considerable variation in the composition of the tablets within this single seizure and the fact that this variation can be detected from Raman spectra demonstrates that the potential benefits of obtaining highly detailed spectra can indeed translate into information that is not readily available from other methods but would be useful for tracing of drug distribution networks.

Raman spectroscopy with far-red excitation has been used to study seized, tableted samples of MDMA (N-methyl-3,4-methylenedioxyamphetamine) and related compounds (MDA, MDEA, MBDB, 2C-B and amphetamine sulfate), as well as pure standards of these drugs. We have found that by using far-red (785 nm) excitation the level of fluorescence background even in untreated seized samples is sufficiently low that there is little difficulty in obtaining good quality data with moderate 2 min data accumulation times. The spectra can be used to distinguish between even chemically-similar substances, such as the geometrical isomers MDEA and MBDB, and between different polymorphic/hydrated forms of the same drug. Moreover, these differences can be found even in directly recorded spectra of seized samples which have been bulked with other materials, giving a rapid and non-destructive method for drug identification. The spectra can be processed to give unambiguous identification of both drug and excipients (even when more than one compound has been used as the bulking agent) and the relative intensities of drug and excipient bands can be used for quantitative or at least semi-quantitative analysis. Finally, the simple nature of the measurements lends itself to automatic sample handling so that sample throughputs of 20 samples per hour can be achieved with no real difficulty.

The NACP electron chamber is one of three parallel-plate chambers recommended for use in the UK. Measurements with this chamber type have indicated a problem in determining the recombination correction. This is due to a variation of the ionization current I with polarizing voltage V which deviates from the accepted Boag theory. It is shown that there is a chamber-dependent threshold voltage below which the NACP chamber follows the Boag theory. Above this voltage the chamber should be used with caution, although it is still possible to correct for the dependence of the chamber response on the dose per pulse. The existence of such deviations from theory demonstrates the usefulness of the 1/I against 1/V plot and the limitations of the Boag two-voltage analysis. Values for the initial recombination and the coefficient of general recombination are measured for several NACP chambers. It is shown that from these one can derive a value for the effective plate separation and the collector radius of each chamber. Differences in the behaviour of NACP chambers manufactured by Scanditronix and Dosetek are discussed and the implications of free-electron collection are considered.

For electron beam reference dosimetry in radiotherapy, it is shown that by choosing the reference depth as dref = 0.6R(50)-0.1 cm, where R50 is the half-value depth in centimeters, the Spencer-Attix water-to-air stopping-power ratio at dref is given by (Llp)airw = 1.2534 - 0.1487 (R50)0.2144. This is derived from data for (Llp)airw obtained from realistic Monte Carlo simulations for 24 clinical beams. The rms deviation of this expression from the Monte Carlo calculations is 0.16%, with a maximum deviation of 0.26%. This approach fully takes into account the spectral differences between real electron beams of the same R50 and allows an absorbed-dose calibration at a standards laboratory to be easily and accurately transferred to a reference clinical beam. Using a single parameter to specify (Llp)airw, rather than the two parameters (R50 and depth) needed when the reference depth is chosen as the depth of dose maximum, has the potential to greatly simplify electron beam dosimetry protocols and allows the use of a similar formalism for photon and electron beam dosimetry. For use in converting a depth-ionization curve into a depth-dose curve, a somewhat less accurate but general expression for (Llp)w(air) as a function of R50 and depth is presented.

A new method is presented to determine the ratio of electron stopping powers which is effective in the transfer of absorbed dose from one medium to another. The method involves an accurate measurement of the electron range in each of the media combined with a full Monte Carlo simulation of each experimental geometry. For the specific case of graphite and water, the uncertainty attainable is estimated to be around +/- 0.5% at the 95% confidence level, which is approximately a factor of three better than the best methods currently in use.

A short overview is presented covering the actual and potential use of cyclodextrins and some of their derivatives in analytical chemistry. The contributions in separation science, including HPLC, GC, CE and MEKC are noted, together with applications in circular dichroism and luminescence techniques, including fluorescence and phosphorescence.

Various azines and substituted phenylene diamines are oxidized by the nitrite ion to give stable radicals in an autocatalytic reaction. This finding has now been developed into highly sensitive methods for nitrite determination by EPR spectrometry. Thus, when the reagent is phenothiazine, the detection limit for nitrite is 0.012 ppm, the relative standard deviation at 0.05 ppm is 1.9%, and the analytical range is 0-1.5 ppm. With N,N,N',N'-tetramethyl-p-phenylenediamine as the reagent, the corresponding values are 0.025 ppm, 2.6%, and 0-1.3 ppm. Nitrate can be determined after prior reduction to nitrite. A mixture of nitrite and nitrate ions can also be quantitatively analysed. The EPR methods were applied to the determination of the nitrite and nitrate contents of prepacked cooked ham and of soft-spreading cheese. The results agreed well with those obtained by ISO and AOAC standard methods for these samples. ca*|Author for correspondence.

Amplification reactions provide a chemical means of enhancing the sensitivity of an analytical measurement. This review describes the various types of amplification reactions currently available, proposes a systematic classification scheme for them and also provides a comprehensive account of amplification reactions for a wide variety of analytes.

Twenty anti-inflammatory and antipyretic drugs have been examined for their fluorescence and phosphorescence characteristics, and conditions established for detection of fourteen of them at trace levels.