GABA, epigallocatechin gallate, tea, and the gut-brain axis.

Our investigations on GABA-enriched tea and the reduction of stress in a student cohort have shown that more than just GABA may be involved. The effects of other constituents that are changed in the enrichment process are likely to be important. We have concentrated on GABA as well as the major tea flavonoid, epigallocatechin gallate. While this flavonoid is known to get to the brain on oral administration, it is far from clear that GABA does the same. GABA may act primarily on the gut and influence brain function via the gut-brain axis and the gut microbiome. In addition, there may be a microbiome in the brain that has a role. The situation is complex and not clearly understood. Mixtures of bioactive compounds are always difficult to investigate, but even the precise mechanisms of how pure oral GABA acts as a neuro-nutraceutical is unclear.

Conformational variability in the D2 loop of Plasmodium Apical Membrane antigen 1.

Apical Membrane Antigen 1 (AMA1) plays a vital role in the invasion of the host erythrocyte by the malaria parasite, Plasmodium. It is thus an important target for vaccine and anti-malaria therapeutic strategies that block the invasion process. AMA1, present on the surface of the parasite, interacts with RON2, a component of the parasite's rhoptry neck (RON) protein complex, which is transferred to the erythrocyte membrane during invasion. The D2 loop of AMA1 plays an essential role in invasion as it partially covers the RON2-binding site and must therefore be displaced for invasion to proceed. Several structural studies have shown that the D2 loop is very mobile, a property that is probably important for the function of AMA1. Here we present three crystal structures of AMA1 from P. falciparum (strains 3D7 and FVO) and P. vivax (strain Sal1), in which the D2 loop could be largely traced in the electron density maps. The D2 loop of PfAMA1-FVO and PvAMA1 (as a complex with a monoclonal antibody Fab) has a conformation previously noted in the P. knowlesi AMA1 structure. The D2 loop of PfAMA1-3D7, however, reveals a novel conformation. We analyse the conformational variability of the D2 loop in these structures, together with those previously reported. Three different conformations can be distinguished, all of which are highly helical and show some similarity in their secondary structure organisation. We discuss the significance of these observations in the light of the flexible nature of the D2 loop and its role in AMA1 function.

A multiphoton ionisation photoelectron imaging study of thiophene.

Thiophene is a prototype for the excited state photophysics that lies at the heart of many technologies within the field of organic electronics. Here, we report a multiphoton ionisation photoelectron imaging study of gas-phase thiophene using a range of photon energies to excite transitions from the ground electronic state to the first two electronically excited singlet states, from the onset of absorption to the absorption maximum. Analysis of the photoelectron spectra and angular distributions reveal features arising from direct photoionisation from the ground electronic state, and resonance-enhanced photoionisation via the electronically excited singlet states. The first two ionisation energies from the ground electronic state were confirmed to be 8.8 eV (adiabatic) and 9.6 eV (vertical). The ionisation energies from the first two electronically excited singlet states were found to be 3.7 eV (adiabatic) and 4.4 eV (vertical).

An expert consensus on managing dupilumab-related ocular surface disorders in people with atopic dermatitis 2024.

BACKGROUND: Atopic dermatitis (AD) is the most common inflammatory skin condition which affects all ages. New therapies, including the monoclonal antibody therapy dupilumab, offer excellent efficacy. However, in clinical trials, and emphasised in real-world observations, the unexpected increased frequency of ocular adverse effects became apparent. The effectiveness of dupilumab and the unpredictability of ocular adverse effects mean that clinicians need guidance on counselling patients prior to treatment and on managing them if they arise. OBJECTIVES: The British Association of Dermatologists (BAD) and Royal College of Ophthalmologists collaborated on this consensus guidance on managing dupilumab-related ocular surface disorders (DROSD). METHODS: A multidisciplinary group was formed of adult and paediatric dermatologists and ophthalmologists with DROSD expertise, patient representation, and BAD Clinical Standards Unit. A literature search was conducted, and the results reviewed. All recommendations were reviewed, discussed and voted on. RESULTS: The recommendations pertain to dermatology and ophthalmology management, and apply to all ages, unless otherwise stated. Importantly, initiation of dupilumab for AD should not be delayed for most eye disorders except acute new problems, e.g. infections, or potentially severe conditions, e.g. a history of corneal transplant (ophthalmology advice should be sought first). There is insufficient evidence to recommend lubricant drops prophylactically. Dermatologists should assess eye complaints to diagnose DROSD; a severity grading system is provided. DROSD management differs slightly in those aged <7 years as ocular complications may affect neuro-ocular development; therefore, irrespective of DROSD severity, this population should be referred for ophthalmology advice. In those aged ≥7 years, dermatologists should feel confident to trial treatment and reserve ophthalmology advice for severe or non-responding cases. Discussion about dupilumab withdrawal should be prompted by a significant impact on quality of life, threat to sight, or other complications. CONCLUSIONS: Although dupilumab is a highly effective agent for treating AD, the risk of ocular adverse effects should not inhibit clinicians or patients from using it, but clinicians should be aware of them. If a patient develops DROSD, there are clear pathways to assess severity and offer initial management; where ineffective, dermatologists should assess the urgency and seek advice from or initiate referral to ophthalmology. While the evidence reviewed for these guidelines reflects the extensive literature on dupilumab, we believe our advice has relevance for ocular surface disorders in atopic dermatitis (AD) patients treated with tralokinumab and lebrikizumab.

Blood Pressure-Lowering Medications, Sodium Reduction, and Blood Pressure.

BACKGROUND: Both blood pressure-lowering medication and sodium reduction are effective in hypertension control, but whether blood pressure-lowering medication modifies the effect of sodium reduction is unclear. This study aims to evaluate the dose-response effect of sodium intake reduction on blood pressure in treated hypertensive individuals and the impact of different classes of blood pressure-lowering drugs. METHODS: We searched multiple databases and reference lists up to July 9, 2024. Randomized controlled trials with a duration of ≥2 weeks comparing the effect of different levels of sodium intake (measured by 24-hour urinary sodium excretion) on blood pressure in hypertensive individuals treated with constant blood pressure-lowering medications were included. Instrumental variable meta-analyses based on random effects models were conducted to evaluate the dose effect of sodium reduction on blood pressure. Subgroup analyses were performed based on the class of blood pressure-lowering drugs. RESULTS: We included 35 studies (median duration of 28 days) with a total of 2885 participants. For every 100 mmol reduction in 24-hour urinary sodium excretion, systolic blood pressure decreased by 6.81 mm Hg (95% CI, 4.96-8.66), diastolic blood pressure decreased by 3.85 mm Hg (95% CI, 2.26-5.43), and mean arterial pressure decreased by 4.83 mm Hg (95% CI, 3.22-6.44). The dose-response effects varied across classes of blood pressure-lowering medications, with greater effects observed in the ß-blockers, renin-angiotensin-aldosterone system inhibitors, and dual therapy groups. No significant subgroup differences were observed based on age, baseline 24-hour urinary sodium excretion, blood pressure levels, or study duration. CONCLUSIONS: Pooled evidence suggests a dose-response relationship between sodium reduction and blood pressure in treated individuals with hypertension, influenced by the class of blood pressure-lowering medications.

The "simple" photochemistry of thiophene.

The static gas-phase ("simple") ultraviolet absorption spectrum of thiophene is investigated using a combination of a vibronic coupling model Hamiltonian with multi-configuration time-dependent Hartree quantum dynamics simulations. The model includes five states and all 21 vibrations, with potential surfaces calculated at the complete active space with second-order perturbation level of theory. The model includes terms up to eighth-order to describe the diabatic potentials. The resulting spectrum is in excellent agreement with the experimentally measured spectrum of Holland et al. [Phys. Chem. Chem. Phys. 16, 21629 (2014)]. The, until now not understood, spectral features are assigned, with a combination of strongly coupled vibrations and vibronic coupling between the states giving rise to a progression of triplets on the rising edge of the broad spectrum. The analysis of the underlying dynamics indicates that population transfer between all states takes place on a sub-100 fs timescale, with ring-opening occurring at longer times. The model thus provides a starting point for further investigations into the complicated photo-excited dynamics of this key hetero-aromatic molecule.

Finding food: how generalist predators use contact-chemosensory information to guide prey preferences.

Understanding the processes that guide carnivores in finding and selecting prey is a fundamental, unresolved challenge in sensory biology. To our knowledge, no published work has yet revealed the complete structural identities of compounds that cue preferences by generalist predators for different prey species. With this research imperative in mind, we determined the chemistry driving consumer preferences for live, intact, prey. The present study used two generalist predatory species (sea stars, Pisaster ochraceus; whelks, Acanthinucella spirata), along with two foundation prey species (mussels, Mytilus californianus; barnacles, Balanus glandula), inhabiting rocky, wave-swept shores. Each prey species is known to secrete either a 29.6 kDa (named "KEYSTONEin") or a 199.6 kDa (named "MULTIFUNCin") glycoprotein as a contact-chemical cue. Here, experimental manipulations utilized faux prey consisting of cleaned barnacle or mussel shells infused with KEYSTONEin, MULTIFUNCin, or seawater (control) gels. Whelks exhibited a strong penchant for MULTIFUNCin over KEYSTONEin, irrespective of shell type. In contrast, sea stars generally preferred KEYSTONEin over MULTIFUNCin, but this preference shifted depending on the experimental context in which they encountered physical (shell) and chemical (glycoprotein) stimuli. This study ultimately demonstrates clear and contrasting chemical preferences between sea stars and whelks. It highlights the importance of experimental setting in determining chemical preferences. Finally, it shows that prey preferences by these predators hinge only on one or two contact-protein cues, without the need for quality coding via fluid-borne compounds, low-molecular-weight substances, or mixture blends.

Formula-led methods using first morning fasting spot urine to assess usual salt intake: a secondary analysis of PURE study data.

OBJECTIVES: Observational studies that assess the relationship between salt intake and long-term outcomes require a valid estimate of usual salt intake. The gold-standard measure in individuals is sodium excretion in multiple nonconsecutive 24-h urines. Multiple studies have demonstrated that random spot urine samples are not valid for estimating usual salt intake; however, some researchers believe that fasting morning spot urine samples produce a better measure of usual salt intake than random spot samples. METHODS: We have used publicly available data from a PURE China validation study to compare estimates of usual salt intake from morning spot urine samples and four published formulae with mean of two 24-h urine samples (reference). We estimated the mean and 95% confidence interval of absolute and relative error for each formula-led method and the degree to which estimates were able to be classified into the correct quartile of intake. Bland-Altman plots were used to test the level of agreement. RESULTS: The results show that compared with the reference method, all formulae-led estimates from spot urine collections have high error rates: both random and systematic. This is demonstrated for individual estimates, as well as by quartiles of reference salt intake. This study conclusively demonstrates the unsuitability of morning spot urine formula-led estimates of usual salt intake. CONCLUSION: Our findings support international recommendations to not conduct, fund, or publish research studies that use spot urine samples with estimating equations to assess individuals' salt intake in association with health outcomes.

Analysis of ductal carcinoma in situ by self-reported race reveals molecular differences related to outcome.

BACKGROUND: Ductal carcinoma in situ (DCIS) is a non-obligate precursor to invasive breast cancer (IBC). Studies have indicated differences in DCIS outcome based on race or ethnicity, but molecular differences have not been investigated. METHODS: We examined the molecular profile of DCIS by self-reported race (SRR) and outcome groups in Black (n = 99) and White (n = 191) women in a large DCIS case-control cohort study with longitudinal follow up. RESULTS: Gene expression and pathway analyses suggested that different genes and pathways are involved in diagnosis and ipsilateral breast outcome (DCIS or IBC) after DCIS treatment in White versus Black women. We identified differences in ER and HER2 expression, tumor microenvironment composition, and copy number variations by SRR and outcome groups. CONCLUSIONS: Our results suggest that different molecular mechanisms drive initiation and subsequent ipsilateral breast events in Black versus White women.

Dreams interrupted: characteristics of REM sleep-associated seizures and status epilepticus.

STUDY OBJECTIVES: Seizures are rare in rapid eye movement sleep (REM). However; seizures sometimes occur in REM, and a small number of focal epilepsy patients display their maximum rate of interictal epileptiform discharges in REM. We sought to systematically identify and characterize seizures in REM. METHODS: We reviewed all admissions to the Epilepsy Monitoring Unit (EMU) at the Winnipeg Health Sciences Centre over 12-months in 2014-2015. American Academy of Sleep Medicine sleep-stage scoring was initially applied in the standard 30-second epochs. Then, to capture sudden changes in sleep-wake state on shorter timescales that are associated with seizure formation and propagation, we re-scored ictal and peri-ictal EEG epochs every 1 second. Patients found to have seizures in REM were subject to chart review spanning three years pre- and post-admission. RESULTS: REM seizures occurred in 3/63 EMU patients. Notably, one patient exhibited continuous epileptiform activity, consistent with focal nonconvulsive electrographic status epilepticus, throughout REM cycles for each night of her admission. Otherwise, discrete REM seizures constituted a small fraction of the other patients' total seizures (range 5.0-8.3%), occurred shortly after REM onset from non-REM 2, and were manifest as minor epileptic arousals. CONCLUSIONS: Our results confirm that REM seizures are rare, while highlighting outliers who widen the known spectrum of heterogeneous sleep effects on seizures/epilepsy. We also report the first case of paradoxical status epilepticus in REM.

Sensitisation to the acrylate co-polymers glyceryl acrylate/acrylic acid co-polymer, sodium polyacrylate and acrylates/C10-30 alkyl acrylate cross-polymer (Carbopol®) is rare.

BACKGROUND: Acrylate polymers and cross-polymers (ACPs) are frequently used cosmetic ingredients. The British Society for Cutaneous Allergy (BSCA) and the UK Cosmetic, Toiletry and Perfumery Association (CTPA) collaborated to investigate the allergenic potential of three commonly-used ACPs. OBJECTIVES: The objective of this study is to determine the prevalence of allergic contact dermatitis (ACD) to three ACPs: glyceryl acrylate/acrylic acid co-polymer, sodium polyacrylate, and acrylates/C10-30 alkyl acrylate cross-polymer (Carbopol®). MATERIALS AND METHODS: The BSCA prospectively audited data collected from 20 centres in the UK and Ireland between 1st September 2021 and 1st September 2022. Patients with suspected ACD to (meth)acrylates, with facial dermatitis, or consecutive patients, were patch tested to glyceryl acrylate/acrylic acid co-polymer 10% aqueous (aq.) sodium polyacrylate 2% aq., and to acrylates/C10-30 alkyl acrylate cross-polymer 2% aq. (Carbopol®). The frequencies of positive, irritant, and doubtful reactions were recorded. RESULTS: In total, 1302 patients were patch tested. To glyceryl acrylate/acrylic acid co-polymer, there was one doubtful reaction in a patient allergic to multiple (meth)acrylates, and one irritant. To sodium polyacrylate, there were four irritant reactions, one doubtful, and one positive reaction; in all cases, relevance was unknown and there was no demonstrable (meth)acrylate allergy. There were no reactions to Carbopol®. CONCLUSIONS: Sensitisation to these concentrations of the three tested ACPs is rare. Elicitation of dermatitis in (meth)acrylate-sensitised patients by exposure to these three ACPs appears unlikely.

Treatment Access among Younger Medicaid Beneficiaries with Multiple Myeloma.

PURPOSE: Continuous Medicaid coverage prior to a cancer diagnosis has been associated with earlier detection and better outcomes, for patients with solid tumors. In this study, we aimed to determine if this was observed among patients with multiple myeloma, a hematologic cancer where there are no routine screening tests and most are diagnosed through acute medical events. MATERIALS AND METHODS: This is an analysis of the Merative MarketScan Multistate Medicaid Database, a claims-based dataset. In total, 1105 patients < 65 years old were included in the analyses. Among them, 66% had continuous enrollment (at least 6 months enrollment prior to myeloma), and 34% had discontinuous enrollment (2-6 months enrollment prior to myeloma). Multivariable Cox regression was used to estimate the association between continuous enrollment status and receipt of myeloma treatment within 1 year of index date. RESULTS: Only 54% of all Medicaid enrollees received myeloma therapy and only 12% received stem cell transplant within the 1st year. Those with continuous enrollment were less likely to receive any treatment (adjusted hazard ratio [aHR] 0.59; 95% confidence interval [CI] 0.59-0.70; P < .001) and to receive stem cell transplant (aHR 0.51; 95% CI 0.32-0.81; P = .005). CONCLUSION: Patients with continuous Medicaid coverage prior to diagnosis were less likely to receive myeloma therapy. Future studies should examine whether myeloma patients with continuous Medicaid enrollment have more chronic financial instability and/or higher medical needs and, thus, have higher barriers to care.

Sugar and sugar-sweetened beverages in relation to premature aging in adult survivors of childhood cancer.

BACKGROUND: Premature aging is a significant concern in adult survivors of childhood cancer as they develop aging-related conditions at a younger age than their peers with no history of childhood cancer. Although modifiable lifestyle factors, such as diet, are postulated to affect aging process, supporting evidence is sparse. METHODS: We examined if the consumption of sugar and sugar-sweetened beverages was related to premature aging in 3322 adult survivors of childhood cancer in the St. Jude Lifetime Cohort. Premature aging was assessed using the Deficit Accumulation Index (DAI) that was a ratio of the number of age-related chronic health conditions each survivor had out of 44 conditions total. Multinomial logistic regressions adjusting for confounders were used to estimate odds ratios (ORs) and 95% confidence intervals (CIs). RESULTS: There were 46% of childhood cancer survivors consumed SSBs once or more times per day. High intake of sugar, especially sugars added to foods during preparation or processing, and habitual consumption of sugar-sweetened beverage were associated with an increased risk of premature aging. DISCUSSION: Our findings support a need to include strategies to reduce sugar and sugar-sweetened beverages consumption in lifestyle interventions to promote healthy aging in adult survivors of childhood cancer.

Modeling Photodissociation: Quantum Dynamics Simulations of Methanol.

A comprehensive computational study of the gas-phase photodissociation dynamics of methanol is presented. Using a multiconfigurational active space based method (RASSCF) to obtain multidimensional potential energy surfaces (PESs) on-the-fly, direct quantum dynamics simulations were run using the variational multi-configurational Gaussian method (DD-vMCG). Different initial excitation energies were simulated to investigate the dependence of the branching ratios on the electronic state being populated. A detailed mechanistic explanation is provided for the observed differences with respect to the excitation energy. Population of the lowest lying excited state of methanol leads to rapid hydroxyl hydrogen loss as the main dissociation channel. This is rationalized by the strongly dissociative nature of the PES cut along the O-H stretching coordinate, confirmed by the broad feature in the absorption spectrum. In contrast, more energetic excitations lead mainly to C-O bond breaking. Again, analysis of the diabatic surfaces offers a clear explanation in terms of the nature of the electronic states involved and the coupling between them. The type of calculations presented, as well as the subsequent analysis of the results, should be seen as a general workflow for the modeling of photochemical reactions.

Verazine biosynthesis from simple sugars in engineered Saccharomyces cerevisiae.

Steroidal alkaloids are FDA-approved drugs (e.g., Zytiga) and promising drug candidates/leads (e.g., cyclopamine); yet many of the ≥697 known steroidal alkaloid natural products remain underutilized as drugs because it can be challenging to scale their biosynthesis in their producing organisms. Cyclopamine is a steroidal alkaloid produced by corn lily (Veratrum spp.) plants, and it is an inhibitor of the Hedgehog (Hh) signaling pathway. Therefore, cyclopamine is an important drug candidate/lead to treat human diseases that are associated with dysregulated Hh signaling, such as basal cell carcinoma and acute myeloid leukemia. Cyclopamine and its semi-synthetic derivatives have been studied in (pre)clinical trials as Hh inhibitor-based drugs. However, challenges in scaling the production of cyclopamine have slowed efforts to improve its efficacy and safety profile through (bio)synthetic derivatization, often limiting drug development to synthetic analogs of cyclopamine such as the FDA-approved drugs Odomzo, Daurismo, and Erivedge. If a platform for the scalable and sustainable production of cyclopamine were established, then its (bio)synthetic derivatization, clinical development, and, ultimately, widespread distribution could be accelerated. Ongoing efforts to achieve this goal include the biosynthesis of cyclopamine in Veratrum plant cell culture and the semi-/total chemical synthesis of cyclopamine. Herein, this work advances efforts towards a promising future approach: the biosynthesis of cyclopamine in engineered microorganisms. We completed the heterologous microbial production of verazine (biosynthetic precursor to cyclopamine) from simple sugars (i.e., glucose and galactose) in engineered Saccharomyces cerevisiae (S. cerevisiae) through the inducible upregulation of the native yeast mevalonate and lanosterol biosynthetic pathways, diversion of biosynthetic flux from ergosterol (i.e., native sterol in S. cerevisiae) to cholesterol (i.e., biosynthetic precursor to verazine), and expression of a refactored five-step verazine biosynthetic pathway. The engineered S. cerevisiae strain that produced verazine contains eight heterologous enzymes sourced from seven different species. Importantly, S. cerevisiae-produced verazine was indistinguishable via liquid chromatography-mass spectrometry from both a commercial standard (Veratrum spp. plant-produced) and Nicotiana benthamiana-produced verazine. To the best of our knowledge, this is the first report describing the heterologous production of a steroidal alkaloid in an engineered yeast. Verazine production was ultimately increased through design-build-test-learn cycles to a final titer of 83 ± 3 µg/L (4.1 ± 0.1 µg/g DCW). Together, this research lays the groundwork for future microbial biosynthesis of cyclopamine, (bio)synthetic derivatives of cyclopamine, and other steroidal alkaloid natural products.

A prospective observational cohort study comparing the treatment effectiveness and safety of ciclosporin, dupilumab and methotrexate in adult and paediatric patients with atopic dermatitis: results from the UK-Irish A-STAR register.

BACKGROUND: The main conventional systemic atopic dermatitis (AD) treatments are methotrexate (MTX) and ciclosporin (CyA). Dupilumab was the first novel systemic agent to enter routine clinical practice. There are no head-to-head randomised controlled trials or real-world studies comparing these agents directly. Network meta-analyses provide indirect comparative efficacy and safety data and have shown strong evidence for dupilumab and CyA. OBJECTIVES: The aim of this study was to compare the real-world clinical effectiveness and safety of CyA, dupilumab and MTX in AD. METHODS: We compared the effectiveness and safety of these systemic agents in a prospective observational cohort study of adult and paediatric patients recruited into the UK-Irish Atopic eczema Systemic TherApy Register (A-STAR). Treatment effectiveness measures included Eczema Area and Severity Index (EASI), Patient-Oriented Eczema Measure (POEM), Peak Pruritus Numerical Rating Scale (PP-NRS), Dermatology Life Quality Index (DLQI) and children's DLQI (cDLQI). Minimum duration of treatment was 28 days and follow-up was 12 months. Adjusted Cox-regression was used to compare the hazards of achieving EASI-50, EASI-75 and EASI-90 over time, and linear mixed-effects models were used to estimate changes in efficacy scores. Treatment safety was assessed by examining adverse events (AEs) at follow-up visits. RESULTS: 488 patients (n=311 adults and n=177 children/adolescents) on dupilumab (n=282), methotrexate (n=149), or CyA (n=57) were included. CyA and MTX were primarily used first line, while dupilumab was mainly a second line systemic as per UK National Institute of Clinical and Care Excellence (NICE) recommendations. EASI-50, EASI-75 and EASI-90 were achieved more rapidly in the dupilumab and CyA groups compared to MTX. After adjustment for previous severity, the reduction in EASI, POEM, PP-NRS and DLQI was greater for patients treated with dupilumab compared to MTX. In severe patients the reduction in EASI, POEM, and PP-NRS was even greater with CyA. The incidence of AEs was similar across groups (734, 654 and 594 per 10,000 person-month on CyA, dupilumab and MTX respectively). CONCLUSIONS: This real-world comparison of CyA, dupilumab and MTX in AD suggests that dupilumab is consistently more effective than MTX and that CyA is most effective in very severe disease within one follow-up year.

On the Structure and Role of Avian Eggshells: A 31P, 1H, and 13C Solid-State NMR Study.

The eggshell is a composite and highly ordered structure formed by biomineralization. Besides other functions, it has a vital and intricate role in the protection of an embryo from various potentially harsh environmental conditions. Solid-state nuclear magnetic resonance (SSNMR) has been used for detailed structural investigations of the chicken, tinamou, and flamingo eggshell materials. 31P NMR spectra reveal that hydroxyapatite and ß-tricalcium phosphate in the ratio 3:2 represent major constituents of phosphate species in the eggshells. All three eggshells exhibit similar spectra, except for the line widths, which implies different structural order of phosphate species in the chicken, tinamou, and flamingo eggshells. 1H NMR spectra for these materials are comparable, differentiating overlapped peaks in three spectral regions at around 7, 4-5, and 1-2 ppm. These spectral regions have been attributed to protons from NH or CaHCO3, water, and possibly isolated monomeric water molecules or hydroxyl groups in calcium-deficient hydroxyapatite. 1H-13C CP MAS NMR revealed the presence of organic matter in the form of lipids and proteins. Two overlapped resonances in the carbonyl region at around 173 and 169 ppm are assigned to the carbonyls of the peptide bonds and the bicarbonate unit in calcite, respectively. Fourier-transform infrared spectroscopy (FTIR) spectra confirmed the presence of structural units detected in the NMR spectra.

Willingness to adopt green house gas mitigation measures: Agricultural land managers in the United Kingdom.

Rapid uptake of greenhouse gas (GHG) mitigation measures is central to reducing agricultural and land use emissions and meeting the UK Net Zero policy. The socioeconomic challenges and barriers to uptake are poorly understood, with yet unclear structural pathways to the uptake of GHG mitigation measures. Using an online survey of 201 agricultural land managers across the UK, and applying multiple linear regression and stepwise regression analysis, this research established farm and farmers' factors influencing perceptions and willingness to adopt GHG mitigation measures. The results consistently show that farm sector, farmers' business perception, and labour availability influence willingness to adopt GHG mitigation measures. Based on the farmers' qualitative feedback, other barriers to adoption include costs and concerns for profitability, lack of flexibility in land tenancy contracts, poor awareness and knowledge of the application of some GHG mitigation measures, perception about market demand e.g bioenergy crops, and scepticism about the future impacts of adopting varying GHG mitigation measures. In the midst of the ongoing net zero transition, this study identifies existing barriers to the uptake of GHG mitigation measures, and specifically, a substantial gap between farmers and the science of GHG mitigation measures and the need to incentivise a farm and farming community-led policy interventions to promote adoption of GHG mitigation measures.

From capture to detection: A critical review of passive sampling techniques for pathogen surveillance in water and wastewater.

Water quality, critical for human survival and well-being, necessitates rigorous control to mitigate contamination risks, particularly from pathogens amid expanding urbanization. Consequently, the necessity to maintain the microbiological safety of water supplies demands effective surveillance strategies, reliant on the collection of representative samples and precise measurement of contaminants. This review critically examines the advancements of passive sampling techniques for monitoring pathogens in various water systems, including wastewater, freshwater, and seawater. We explore the evolution from conventional materials to innovative adsorbents for pathogen capture and the shift from culture-based to molecular detection methods, underscoring the adaptation of this field to global health challenges. The comparison highlights passive sampling's efficacy over conventional techniques like grab sampling and its potential to overcome existing sampling challenges through the use of innovative materials such as granular activated carbon, thermoplastics, and polymer membranes. By critically evaluating the literature, this work identifies standardization gaps and proposes future research directions to augment passive sampling's efficiency, specificity, and utility in environmental and public health surveillance.

The role of ruminant urine and faeces in the recycling of nutrients by forages.

This study addresses the effect of using animal excreta on the nutritional content of forages, focusing on macro- and micro-element concentrations (nitrogen; N, phosphorus; P, sulphur; S, copper; Cu, zinc; Zn, manganese; Mn, selenium; Se) from animal feed to excreta, soil, and plants. Data were collected from pot and field trials using separate applications of sheep or cattle urine and faeces. Key findings indicate that soil organic carbon (SOC) and the type of excreta significantly influences nutrient uptake by forages, with varied responses among the seven elements defined above. Although urine contributes fewer micronutrients compared to faeces (as applied at a natural volume/mass basis, respectively), it notably improves forage yield and micronutrient accumulation, thus potentially delivering positive consequences at the farm level regarding economic performance and soil fertility when swards upon clayey soil types receive said urine in temperate agro-climatic regions (i.e., South West England in the current context). In contrast, faeces application in isolation hinders Se and Mn uptake, once again potentially delivering unintended consequences such as micronutrient deficiencies in areas of high faeces deposition. As it is unlikely that (b)ovine grazing fields will receive either urine or faeces in isolation, we also explored combined applications of both excreta types which demonstrates synergistic effects on N, Cu, and Zn uptake, with either synergistic or dilution effects being observed for P and S, depending largely on SOC levels. Additionally, interactions between excreta types can result in dilution or antagonistic effects on Mn and Se uptake. Notably, high SOC combined with faeces reduces Mn and Se in forages, raising concerns for grazed ruminant systems under certain biotic situations, e.g., due to insufficient soil Se levels typically observed in UK pastures for livestock growth. These findings underscore the importance of considering SOC and excreta nutritional composition when designing forage management to optimize nutrient uptake. It should be noted that these findings have potential ramifications for broader studies of sustainable agriculture through system-scale analyses, as the granularity of results reported herein elucidate gaps in knowledge which could affect, both positively and negatively, the interpretation of model-based environmental impact assessments of cattle and sheep production (e.g., in the case of increased yields [beneficial] or the requirement of additional synthetic supplementation [detrimental]).