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Abstract Background In many countries, nitrous oxide is used in a gas mixture (EMONO) for short-term analgesia. Cases of addiction, with significant misuse, have been reported in hospitalized patients. Patients suffering from sickle cell disease (SCD) could represent a high-risk population for substance use disorder (SUD) due to their significant pain crisis and repeated use of EMONO. The objective of the PHEDRE study was to assess the prevalence of SUD for EMONO in French SCD patients. Results A total of 993 patients were included. Among 339 EMONO consumers, only 38 (11%) had a SUD, with very few criteria, corresponding mainly to a mild SUD due to a use higher than expected (in quantity or duration) and relational tensions with the care teams. Almost all patients (99.7%) were looking for an analgesic effect, but 68% of patients were also looking for other effects. The independent risks factors associated with at least one SUD criterion were: the feeling of effects different from the expected therapeutic effects of EMONO, at least one hospitalization for vaso occlusive crisis in the past 12 months and the presence of a SUD for at least one other analgesic drug. Conclusions The use of EMONO was not problematic for the majority of patients. Manifestations of SUD that led to tensions with healthcare teams should alert and lead to an evaluation, to distinguish a true addiction from a pseudoaddiction which may be linked to an insufficient analgesic treatment related to an underestimation of pain in SCD patients. Trial registration : Clinical Trials, NCT02580565. Registered 16 October 2015, https://clinicaltrials.gov/

Abstract Cannabis is the main illicit psychoactive substance used by pregnant women in France. The aim of the present national survey was to describe adverse events (AEs) of recreational cannabis use during pregnancy reported to the French Addictovigilance Network (FAN). Spontaneous reports (SRs) of AEs related to recreational cannabis use during pregnancy were collected by the FAN between 01/01/2011 and 31/01/2021 (excluding cannabidiol and synthetic cannabinoids). Over the study period, 160 SRs involved cannabis use alone or in association with tobacco (59% of all SRs) which increased. Among the 175 maternal AEs, the most commons were psychiatric AEs experienced by 96 (64.9%) women, in particular cannabis use disorders (n = 89, 60.1%), dependence (n = 54, 36.5%) and abuse (n = 21, 14.2%). Among the 57 fetal AEs, the most common were heart rhythm disorders that affected 25 (16.9%) fetuses and intrauterine growth restriction (IUGR) (n = 20, 13.5%). Among the 140 neonatal AEs, the most common were IUGR experienced by 39 (26.3%) newborns and prematurity (n = 32, 21.6%). Twelve cases of congenital malformations were observed and 4 intrauterine/neonatal deaths. Furthermore, some of these AEs (n = 13) were unexpected. Cannabis use during pregnancy has problematic consequences for both mothers and infants who need close monitoring.

BackgroundSickle cell disease (SCD) induces chronic haemolytic anaemia and intermittent vaso-occlusion that results in tissue ischaemia causing acute, severe pain episodes that can lead to frequent hospitalizations. These consequences can have repercussions on family, social, school and/or professional life. Here, we present some of the results of the PHEDRE study (Pharmacodépendance Et DREpanocytose-drug dependence and sickle-cell disease), which is the largest study of patients with SCD in France. This paper intends to describe characteristics of the French SCD population. We also aimed to assess the impact of the disease on the lives of patients using objective and subjective variables.MethodsThe PHEDRE study was a national multicentric observational study. Adults, adolescents and children with a confirmed SCD diagnosis were included in the study by their referring doctor. Then, they were interviewed by phone about their socioeconomic status, about the impact of the disease on their lives and about their analgesic and psychoactive drug use.ResultsThe study population consisted of 872 patients (28% were minors). Seventy-two percent of adults were active, and all minors were in school. Many patients presented criteria of severe SCD. Seventy-five percent were homozygous SS, 15% were double heterozygotes SC and 8% were heterozygotes Sβthal, 87% received specific treatment, 58% were hospitalized at least once for vaso-occlusive crisis in the past 12 months, and the number of analgesic drugs taken averaged 3.8. Seventy-five percent of patients reported academic or professional consequences related to their SCD, and 52% reported social consequences.ConclusionsThe impact of SCD on patients' lives can be significant, nevertheless their social integration seems to be maintained. We highlighted respect of recommendations regarding analgesic treatments and only a few patients used tobacco, alcohol or cannabis.Trial registrationClinical Trials, NCT02580565; https://clinicaltrials.gov/ Registered 16 October 2015.

Inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) is an emerging technique for measuring actinide isotopes when assessing pre- and post-detonation nuclear material. In this study, ICP-MS/MS was investigated for direct Np and Pu quantitation in unseparated, dissolved bulk soil matrices. To achieve this, purified nitric oxide (NO) was investigated for the reactivity of Th, Np, U, Pu, Am, and Cm. Purifying NO prior to the collision reaction cell (CRC) results in increased sensitivity and allows for higher gas flows to be utilized for the removal of interferences. The interference from uranium hydrides was mitigated to less than 3.85 x 10 -11 . This method was demonstrated on standard reference materials which were measured for 237 Np and 238,239,240 Pu in dilute sample digestions. The 238 Pu measurement was validated by spiking into a standard reference material and was accurately measured with an excess of 85000 of 238 U., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025. Published by Elsevier B.V.)

Interference removal in inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) is strongly dependent on the gas selected for use within the collision/reaction cell. There has been little investigation on the effects that reaction gas impurities may have on the resulting spectra. The reactivity of 60 elements was evaluated using nitric oxide (NO 99.5%) with and without a gas purifier to reduce H 2 O impurities to <100 pptV. Experiments were performed using V, Ce, Tl and Th to investigate the effects of purified NO at various flowrates (0.22-1.49 mL min -1 ). Purified NO was shown to significantly mitigate oxy-hydride interferences, improve total ion sensitivity (notable at high gas flows), and shift product distributions advantageously. The reduction in oxy-hydride species results in a product distribution favoring the major expected products, where signals were shown to increase by an order of magnitude. Reduced background and increased signal for the major expected products provides avenues for improving various analytical applications of ICP-MS/MS.

A comprehensive understanding of when and how 5f orbitals participate in complex chemical bonding is important for a variety of applications. The actinides are unique in that they possess 5f orbitals and can access high oxidation states, which make them attractive for use in catalysis. Fundamental studies of actinide-ligand interactions offer a mechanism to examine the activation of the 5f orbitals so that the selectivity of 5f orbitals can be assessed. A previous study examined the reaction of Pu + + CO 2 and determined that the reaction efficiency is restricted by a barrier, namely, promotion from the Pu + ground-state configuration, 5f 6 7s, to a reactive-state configuration, 5f 5 6d 2 . The present study illustrates the benefit of activation of Pu's 5f orbitals when studying the reaction of Pu + + NO. In this reaction, PuO + forms in an exothermic, barrierless process. The 5f orbitals can and do participate in forming a linear intermediate, [N-Pu-O] + , and this drives the exothermic reaction. Understanding the conditions under which 5f orbitals are active in chemical bonding is the key to exploiting the actinides' selective catalytic capabilities.

The effect of ion kinetic energy on gas phase ion reactivity with ICP-MS/MS was investigated in order to explore tuning strategies for interference removal. The collision/reaction gases CO 2 , N 2 O and O 2 were used to observe the ion product distribution for 48 elements using an Agilent tandem ICP-MS (ICP-MS/MS) as a function of reaction gas flow rate (pressure) and ion kinetic energy. The kinetic energy of the incident ion was varied by adjusting the octopole bias (V oct ). The three gases all form oxides (MO + ) as the primary product with differing reaction enthalpies that result in distinct differences in the ion energies required for reaction with product ion distributions that vary with Voct. Consequently, by varying the ion kinetic energy (i.e., V oct ), differences in interference reactivity can be used to achieve maximum separation. Three practical application examples were reported to demonstrate how the ion kinetic energy can be varied to achieve the ideal ion product distribution for interference resolution: CO 2 for the removal of 238 U in Pu analyses, CO 2 for the removal of 40 Ar 16 O vs. 56 Fe, and O 2 for the removal of Sm in Eu analyses, analogous to Pu/Am. The results demonstrate how the starting ion energy defined by V oct is an important factor to fully leverage the utility of any given reaction gas to remove interferences in the mass spectrum using ICP-MS/MS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Understanding the reactivity of metal cations with various reaction gases in inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) is important to determine the best gas to use for a given analyte/interference pair. In this study, nitric oxide (NO) was investigated as the reaction gas following previous experimental designs. The reactions with 50 elements were investigated to examine periodic trends in reactivity, validate theoretical modeling of reaction enthalpies as a method to screen reactant gases, and provide a baseline data set for potential in-line gas separation methods. ICP-MS/MS studies involving actinides are typically limited to Th, U, and Pu, with analyses of Np and Am rarely reported in the literature. To date, only two previous methods have investigated the use of NO in ICP-MS/MS analyses. To showcase the utility of NO, a method was developed to measure 239 Pu in the presence of environmental matrix constituent and other actinides, like what could be expected from postdetonation debris, with no chemical separation prior to analysis. 239 Pu + was reacted to form 239 Pu 16 O + , eliminating interferences derived from the sample matrix by measuring the 239 Pu + intensity at m / z = 255 ( 239 Pu 16 O + ). To validate NO for 238 U 1 H + interference removal in environmental matrices, standard reference materials were diluted to 1 mg/g of solution and spiked to 0.05 pg/g of 239 Pu and 1 μg/g 238 U (Pu/U = 5 × 10 -8 ). Measured 239 Pu concentrations were within 6% of the spiked value. These results demonstrate that reliable 239 Pu measurements can be made at levels relevant to nuclear forensics without the need for extensive chemical matrix separation prior to analysis.

This study investigated the potential of utilising the elemental fingerprinting of honey to differentiate New Zealand (NZ) honey from that of international origin. Twenty elements were analysed by ICP-MS in 352 honeys from 34 various countries. Of these, 323 honeys (245 New Zealand honeys, 78 international) and two subsets of data (NZ and European origin, n = 306, and, NZ and Denmark/Germany, n = 280) were visualised using principal component analysis (PCA). For the NZ/Europe subset, 42.2% of data was explained in the first two principal components. Statistical classification rules were also derived using linear discriminant analysis (LDA) and decision tree analysis. Various combinations of elements were explored for classification, considering the effect of soil-derived elements and those from anthropogenic sources. A high degree of accuracy (at least 90%) for the characterisation of New Zealand honey was observed for all statistical models, showing the robustness of these analyses. When using decision tree analysis to distinguish New Zealand samples from international samples, a tree with five terminal nodes (using Cs, Ba and Rb) was created with 92.4% accuracy. This work has demonstrated that elemental fingerprints of honey are a promising tool for categorising New Zealand honey from other geographical locations., (© 2023. The Author(s).)

f-Block chemistry offers an opportunity to test current knowledge of chemical reactivity. The energy dependence of lanthanide cation (Ln + = Ce + , Pr + , Nd + -Eu + ) and actinide cation (An + = Th + , U + -Am + ) oxidation reactions by CO 2 , was observed by inductively coupled plasma tandem mass spectrometry. This reaction is commonly spin-unallowed because the neutral reactant (CO 2 , 1 Σ+g) and product (CO, 1 Σ + ) require the metal and metal oxide cations to have the same spin state. Correlation of the promotion energy ( E p ) to the first state with two free d-electrons with the reaction efficiency indicates that spin conservation is not a primary factor in the reaction rate. The E p likely influences the reaction rate by partially setting the crossing between the ground and reactive states. Comparison of Ln + and An + congener reactivity indicates that the 5f-orbitals play a small role in the An + reactions.

The British Association for the Study of Community Dentistry (BASCD) is marking its 50th anniversary in 2023. The author of this article has been a member of BASCD for those 50 years, including a number as a member of the Council, and offers his personal reflections on some of the range of activities of the Association., (Copyright© 2023 Dennis Barber Ltd.)

The degree of crystallinity in cellulose significantly affects the physical, mechanical, and chemical properties of cellulosic materials, their processing, and their final application. Measuring the crystalline structures of cellulose is a challenging task due to inadequate consistency among the variety of analytical techniques available and the lack of absolute crystalline and amorphous standards. Our article reviews the primary methods for estimating the crystallinity of cellulose, namely, X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Raman and Fourier-transform infrared (FTIR) spectroscopy, sum-frequency generation vibrational spectroscopy (SFG), as well as differential scanning calorimetry (DSC), and evolving biochemical methods using cellulose binding molecules (CBMs). The techniques are compared to better interrogate not only the requirements of each method, but also their differences, synergies, and limitations. The article highlights fundamental principles to guide the general community to initiate studies of the crystallinity of cellulosic materials.

The winter and summer monsoons in Southeast Asia are important but highly variable sources of rainfall. Current understanding of the winter monsoon is limited by conflicting proxy observations, resulting from the decoupling of regional atmospheric circulation patterns and local rainfall dynamics. These signals are difficult to decipher in paleoclimate reconstructions. Here, we present a winter monsoon speleothem record from Southeast Asia covering the Holocene and find that winter and summer rainfall changed synchronously, forced by changes in the Pacific and Indian Oceans. In contrast, regional atmospheric circulation shows an inverse relation between winter and summer controlled by seasonal insolation over the Northern Hemisphere. We show that disentangling the local and regional signal in paleoclimate reconstructions is crucial in understanding and projecting winter and summer monsoon variability in Southeast Asia., (© 2023. Springer Nature Limited.)

Online spectroscopic measurements can be used to provide unique insight into complex chemical systems, enabling new understanding and optimization of chemical processes. A key example of this is discussed here with the monitoring of pH of various acid systems in real-time. In this work the acids used in multiple chemical separations processes, such as TALSPEAK (Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes) and oxalate precipitation, were characterized. Raman spectroscopy, a robust optical approach that can be integrated in corrosive processes, was used to follow the unique fingerprints of the various protonated and deprotonated acid species. This data was analyzed using a hierarchical modeling approach to build a consolidated model scheme using optical fingerprints from all weak acids to measure pH associated with any of the weak acid systems studied here. Validation of system performance included utilizing Raman spectroscopy under dynamic flow conditions to monitor solution pH under changing process conditions in-line. Overall, the Raman based approach provided accurate analysis of weak acid solution pH.

The global burden of the SARS-CoV-2 pandemic is thought to result from a high viral transmission rate. Here, we consider mechanisms that influence host cell-virus binding between the SARS-CoV-2 spike glycoprotein (SPG) and the human angiotensin-converting enzyme 2 (ACE2) with a series of peptides designed to mimic key ACE2 hot spots through adopting a helical conformation analogous to the N-terminal α1 helix of ACE2, the region experimentally shown to bind to the SARS-CoV-2 receptor-binding domain (RBD). The approach examines putative structure/function relations by assessing SPG binding affinity with surface plasmon resonance (SPR). A cyclic peptide (c[KFNHEAEDLFEKLM]) was characterized in an α-helical conformation with micromolar affinity (KD = 500 µM) to the SPG. Thus, stabilizing the helical structure of the 14-mer through cyclization improves binding to SPG by an order of magnitude. In addition, end-group peptide analog modifications and residue substitutions mediate SPG binding, with net charge playing an apparent role. Therefore, we surveyed reported viral variants, and a correlation of increased positive charge with increased virulence lends support to the hypothesis that charge is relevant to enhanced viral fusion. Overall, the structure/function relationship informs the importance of conformation and charge for virus-binding analog design.

Peptide-cellulose conjugates designed for use as optical protease sensors have gained interest for point-of-care (POC) detection. Elevated serine protease levels are often found in patients with chronic illnesses, necessitating optimal biosensor design for POC assessment. Nanocellulose provides a platform for protease sensors as a transducer surface, and the employment of nanocellulose in this capacity combines its biocompatibility and high specific surface area properties to confer sensitive detection of dilute biomarkers. However, a basic understanding of the spatiotemporal relationships of the transducer surface and sensor disposition is needed to improve protease sensor design and development. Here, we examine a tripeptide, fluorogenic elastase biosensor attached to TEMPO-oxidized nanofibrillated cellulose via a polyethylene glycol linker. The synthetic conjugate was found to be active in the presence of human neutrophil elastase at levels comparable to other cellulose-based biosensors. Computational models examined the relationship of the sensor molecule to the transducer surface. The results illustrate differences in two crystallite transducer surfaces ((110) vs. (1-10)) and reveal preferred orientations of the sensor. Finally, a determination of the relative (110) vs. (1-10) orientations of crystals extracted from cotton demonstrates a preference for the (1-10) conformer. This model study potentiates the HNE sensor results for enhanced sensor activity design.

Gene co-expression networks (GCNs) provide multiple benefits to molecular research including hypothesis generation and biomarker discovery. Transcriptome profiles serve as input for GCN construction and are derived from increasingly larger studies with samples across multiple experimental conditions, treatments, time points, genotypes, etc. Such experiments with larger numbers of variables confound discovery of true network edges, exclude edges and inhibit discovery of context (or condition) specific network edges. To demonstrate this problem, a 475-sample dataset is used to show that up to 97% of GCN edges can be misleading because correlations are false or incorrect. False and incorrect correlations can occur when tests are applied without ensuring assumptions are met, and pairwise gene expression may not meet test assumptions if the expression of at least one gene in the pairwise comparison is a function of multiple confounding variables. The 'one-size-fits-all' approach to GCN construction is therefore problematic for large, multivariable datasets. Recently, the Knowledge Independent Network Construction toolkit has been used in multiple studies to provide a dynamic approach to GCN construction that ensures statistical tests meet assumptions and confounding variables are addressed. Additionally, it can associate experimental context for each edge of the network resulting in context-specific GCNs (csGCNs). To help researchers recognize such challenges in GCN construction, and the creation of csGCNs, we provide a review of the workflow., (© The Author(s) 2021. Published by Oxford University Press.)

Determination of geographical origin of honey is important to consumers to confirm authenticity. This study investigated the elemental fingerprint of 181 honey samples collected from apiary sites in six regions of North Island, New Zealand to determine if differences were observed due to region of collection or land use surrounding the hive (e.g. agricultural, rural, urban). Using principal component analysis, soil related elements (Ca, K, Mg, Mn, Na) provided 75.2% discrimination of samples in the first two principal components. Overall, low concentrations of heavy metals were observed; lead was present in close proximity to highly trafficked roads (28.1% of samples; 9.50-76.5 µg kg -1 ) and cadmium was primarily present in honey collected from agricultural land in the Waikato (<51.6 µg kg -1 ). The use of an elemental fingerprint of New Zealand honey may be advantageous to determine the geographical origin compared to honey produced from other countries., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Shapes (conformations) of cellulose molecules are described by their glycosidic linkage torsion angles ϕ and ψ. Although the torsions are known for cellulose in crystals, amorphous shapes are also interesting for understanding reactivity and physical properties. ϕ and ψ determination for unorganized matter is difficult; one approach is to study their range in many related molecules. For example, linkage torsions of cellulose should be similar to those in cellobiose. Herein, torsions were measured for cellooligosaccharides and lactose moieties complexed with proteins in the Protein Data Bank (PDB). These torsions were compared with ϕ/ψ maps based on quantum mechanics energies for solvated cellobiose and analogs lacking hydroxyl groups. Most PDB conformations corresponded to low map energies. Amorphous cellulose should be generally extended with individual linkages that would give 2- to 3-fold helices. The map for an analog lacking hydrogen bonding ability was more predictive for PDB linkages than the cellobiose map., (Published by Elsevier Ltd.)

Background: Gene expression is potentially an important heritable quantitative trait that mediates between genetic variation and higher-level complex phenotypes through time and condition-dependent regulatory interactions. Therefore, we sought to explore both the genomic and condition-specific characteristics of gene expression heritability within the context of chromosomal structure., Results: Heritability was estimated for biological gene expression using a diverse, 84-line, Oryza sativa (rice) population under optimal and salt-stressed conditions. Overall, 5936 genes were found to have heritable expression regardless of condition and 1377 genes were found to have heritable expression only during salt stress. These genes with salt-specific heritable expression are enriched for functional terms associated with response to stimulus and transcription factor activity. Additionally, we discovered that highly and lowly expressed genes, and genes with heritable expression are distributed differently along the chromosomes in patterns that follow previously identified high-throughput chromosomal conformation capture (Hi-C) A/B chromatin compartments. Furthermore, multiple genomic hot-spots enriched for genes with salt-specific heritability were identified on chromosomes 1, 4, 6, and 8. These hotspots were found to contain genes functionally enriched for transcriptional regulation and overlaps with a previously identified major QTL for salt-tolerance in rice., Conclusions: Investigating the heritability of traits, and in-particular gene expression traits, is important towards developing a basic understanding of how regulatory networks behave across a population. This work provides insights into spatial patterns of heritable gene expression at the chromosomal level.

The use of ethylenediaminetetraacetic acid (EDTA) during bivalve hatchery production is thought to improve larval yields due to the reduced exposure to toxic metals (such as Cu); however, few studies have focused on the bioavailability of metals during the rearing process. Greenshell™ mussels (Perna canaliculus) were reared for 48 h with and without EDTA (12 µM) exposure and larvae were subsequently raised to 21 days post-fertilisation with and without EDTA exposure. Survival, shell length, algal ingestion rate, swimming activity, total metal concentration in water, bioavailable metal concentrations and larval metal accumulation were monitored for the 21 day period. Larval fitness (specifically D-yields) was improved on day 2 in the EDTA treatment, whereas an overall negative effect of EDTA treatment on fitness was observed on day 10 and 21. During the first 48 h, increased survival in the EDTA treatment is believed to be due to the reduction of bioavailable Zn concentrations in the rearing seawater. No other metal (essential or non-essential) displayed a consistent trend when comparing metal bioavailability to any of the fitness parameters measured throughout the experiment. Though the measured metal bioavailability was not clearly linked to fitness, the uptake of Al, P, Cr, Fe, Co, Ni, Zn, As, Cd, and Hg by P. canaliculus was reduced during the first 48 h, suggesting that the biological regulation of these elements is just as important as the bioavailability. Overall, treatment of the rearing seawater with 12 µM EDTA is effective for improving Greenshell™ mussel larval yields by decreasing metal bioavailability during the first two days of development but has minimal benefit between day 2 and 21., (Copyright © 2021. Published by Elsevier Inc.)

Professor Dexter French (1918-1981) was an American chemist and biochemist at Iowa State College (University in 1959). He devoted his career to advance knowledge of polysaccharides and oligosaccharides, in particular starch, cyclodextrins, and enzymes. Cyclodextrins are oligosaccharides obtained from starch and are typically cage molecules with a hydrophobic cavity that can encapsulate other compounds nowadays the basis for many industrial applications. Since the 1960s, he has been recognized as an outstanding authority in the field of starches and cyclodextrins and has inspired researchers in laboratories around the world. This review, on the fortieth anniversary of his death, commemorates his remarkable contribution to starch and cyclodextrin chemistry. Firstly, we give an overview of his personal life and career. Secondly, we highlight some of the results on starch and cyclodextrins from Professor French and his group. A third part discusses his impact on the modern chemistry of cyclodextrins and starch., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The approaches in this article seek to enhance understanding of cellulose at the molecular level, independent of the source and the particular crystalline form of cellulose. Four main areas of structure research are reviewed. Initially, the molecular shape is inferred from the crystal structures of many small molecules that have β-(1→4) linkages. Then, conformational analyses with potential energy calculations of cellobiose are covered, followed by the use of Atoms-In-Molecules theory to learn about interactions in experimental and theoretical structures. The last section covers models of cellulose nanoparticles. Controversies addressed include the stability of twofold screw-axis conformations, the influence of different computational methods, the predictability of crystalline conformations by studies of isolated molecules, and the twisting of model cellulose crystals., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Sea turtles are exposed to trace elements through water, sediment, and food. Exposure to these elements has been shown to decrease immune function, impair growth, and decrease reproductive output in wildlife. The present study compares trace element concentrations in green turtles in captivity at Sea Life Park Hawaii (n = 6) to wild green turtles in Kapoho Bay, Hawaii, USA (n = 5-7). Blood and scute samples were collected and analyzed for 11 elements via inductively coupled plasma-mass spectrometry (ICP-MS). Selenium was significantly greater (p < 0.05) in the blood of captive turtles compared with wild turtles, whereas V, Ni, and Pb were significantly greater in the blood of wild turtles. In scute, V, Cu, Se, and Cr were significantly greater in captive turtles, whereas As was significantly greater in wild turtles. Pelleted food fed to the captive turtles and representative samples of the wild turtle diet were analyzed via ICP-MS to calculate trophic transfer factors and daily intake values. Wild turtles had greater estimated daily intake than captive turtles for all elements except Cu and Se. Because captive turtles are fed a diet very different from that of their wild counterparts, captive turtles do not represent control or reference samples for chemical exposure studies in wild turtles. No toxic thresholds are known for sea turtles, but rehabilitation and managed care facilities should monitor sea turtle elemental concentrations to ensure the animals' health. Environ Toxicol Chem 2021;40:208-218. © 2020 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA., (© 2020 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.)

The elemental fingerprint of honey, pollen and bees are useful biomonitors of anthropogenic activities across the world. Elements in honey and pollen may also be analysed for their nutritional value and potential toxicity. There are currently limited studies that address the use of small sample masses while retaining good reproducibility and detection limits during elemental analysis. The aim of this study was to develop a simple analytical method to quantify 39 major, minor, trace and rare earth elements in small mass samples of bees, honey and pollen by inductively coupled plasma mass spectrometry. The final method was validated for 20-200 mg bee, 20-100 mg pollen or 50-200 mg of honey with 0.2 mL nitric acid followed by 0.1 mL hydrogen peroxide in a digestion block (80 °C, 2 h total); samples were made up to a final volume of approximately 6 mL. The method reduces the volume of chemicals used, limits sample manipulation and improves detection limits over traditional digestion methods. The sample preparation and analysis method were deemed to be satisfactory for the three matrices examined, with spike recoveries ranging from 96 (B) to 129% (As) for trace elements and 91 (Pr) to 112% (La) for rare earth elements, and acceptable detection limits (down to 5.07 μg kg -1 for Co using 30 mg sample mass, pollen). Precision was acceptable with the relative percent standard deviation of fully homogenised samples ranging from 0.53 (K, bee, 20 mg) to 24% (As, 30 mg, bee) across the three matrices and all masses analysed. This small mass digestion method enables the analysis of a single bee allowing a more distinctive elemental signature to be determined. Similarly, pollen from fewer flowers of the same species can be pooled together which is advantageous for analysis of flowers that produce little pollen., Competing Interests: Declaration of competing interest None, (Copyright © 2020 Elsevier B.V. All rights reserved.)

Many studies have used grit (in the form of lead (Pb) pellets) presence in avian gizzards as an indicator of Pb shot exposure. However, due to nearly complete pellet absorption in gizzards or rapid passage of pellets, the absence of Pb shot presence in a gizzard does not confirm lack of Pb shot exposure. This study provides the basis for an additional technique to identify if elevated tissue Pb concentration is due to Pb shot exposure. Bioaccessibility of Pb and trace elements (Sb, As, and Sn) present in Pb shot were quantified to determine if any of these elements would be useful as a secondary marker of Pb shot exposure. An avian physiologically based extraction test (PBET) was used to determine pellet dissolution rate and bioaccessible concentrations of Pb, Sb, As, and Sn in a simulated gizzard environment. Of the three trace elements, only Sb concentrations (44-302 μg/mL) extracted into the gizzard solution were greater than environmental background levels (US soil average 0.48 μg/g); thus, no natural source likely provides this amount of Sb. Therefore, there is evidence that Sb can be extracted from Pb shot in bird gizzards at detectable concentrations (above natural background). While further studies are needed to delineate the mechanisms of absorption and distribution, this study lends credence to the hypothesis that Sb may be a useful marker of Pb shot exposure in biological tissues, particularly when Pb pellets are not present nor observed in avian tissues., Competing Interests: The authors have declared that no competing interests exist.

Computerized molecular modeling continues to increase in capability and applicability to carbohydrates. This chapter covers nomenclature and conformational aspects of carbohydrates, perhaps of greater use to computational chemists who do not have a strong background in carbohydrates, and its comments on various methods and studies might be of more use to carbohydrate chemists who are inexperienced with computation. Work on the intrinsic variability of glucose, an overall theme, is described. Other areas of the authors' emphasis, including evaluation of hydrogen bonding by the atoms-in-molecules approach, and validation of modeling methods with crystallographic results are also presented.

Nanocellulose has functionalities suitable for efficient sensor transducer surface design including crystallinity, biocompatible and high specific surface area. Here we explore two forms of nanocellulose as transducer surfaces to enable colorimetric detection of human neutrophil elastase (HNE), and a wide range of inflammatory diseases. A deep eutectic solvent (DES) was utilized to mediate formation of cotton cellulose nanocrystals (DCNCs) employed to prepare a peptide-cellulose conjugate as a protease sensor of HNE. The tetrapeptide-cellulose analog on DCNC is contrasted with an analogous derivative of TEMPO-oxidized wood cellulose nanofibrils (WCNFs). DCNCs showed greater degree of substitution of HNE tetrapeptide and sensitivity to the elastase than WCNFs, despite the smaller surface area and pore sizes. XRD models revealed the higher crystallinity and larger crystallite sizes of DCNCs, indicating the well-arranged cellulose chains for immobilization of the tetrapeptide on (110) lattice reflections of cellulose crystals. The sensitivity of DCNCs-based colorimetric sensor was less than 0.005 U/mL, which would provide a convenient, sensitive sensor applicable for improved colorimetric point of care protease biomarker detection., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The insufficient resolution of conventional methods has long limited the structural elucidation of cellulose and its derivatives, especially for those with relatively low crystallinities or in native cell walls. Recent 2D/3D solid-state NMR studies of 13 C uniformly labeled plant biomaterials have initiated a re-investigation of our existing knowledge in cellulose structure and its interactions with matrix polymers but for unlabeled materials, this spectroscopic method becomes impractical due to limitations in sensitivity. Here, we investigate the molecular structure of unlabeled cotton cellulose by combining natural abundance 13 C- 13 C 2D correlation solid-state NMR spectroscopy, as enabled by the sensitivity-enhancing technique of dynamic nuclear polarization (DNP), with statistical analysis of the observed and literature-reported chemical shifts. The atomic resolution allows us to monitor the loss of Iα and Iβ allomorphs and the generation of a novel structure during ball-milling, which reveals the importance of large crystallite size for maintaining the Iα and Iβ model structures. Partial order has been identified in the "disordered" domains, as evidenced by a discrete distribution of well-resolved peaks. This study not only provides heretofore unavailable high-resolution insights into cotton cellulose but also presents a widely applicable strategy for analyzing the structure of cellulose-rich materials without isotope-labeling. This work was part of a multi-technique study of ball-milled cotton described in the previous article in the same issue.

Interior snowy plover (Charadrius nivosus) population declines and deteriorating conditions throughout the Southern Great Plains (SGP) of Texas, New Mexico, and Oklahoma may be linked to environmental contaminants. Concentrations of V, As, Cd, Pb, and Se were quantified in breeding snowy plover blood, feathers (5th primary; P5), and potential prey (tiger beetles [Cicindela circumpicta and C. togata]). Se was (a) most commonly detected relative to other quantified elements and (b) frequently quantified at levels exceeding background or toxicity thresholds. Of samples greater than instrumentation detection limits, 98% of snowy plover blood and 22% of feather samples were greater than Se toxicity thresholds of 1 ppm ww for blood and 5 ppm dw for feathers (blood quantifiable range: 0.83-15.12 ppm; feathers quantifiable range: 1.90-27.47 ppm). Almost all tiger beetle Se concentrations were below reported invertebrate thresholds of 30 ppm dw (quantifiable range: 0.54-45.84 ppm). Snowy plover blood Se concentrations were related to sex, individual body condition, and local tiger beetle Se concentrations, while plover P5 Se concentrations were related to state, sex, and presence of body molt. Tiger beetle Se concentrations were related to individual study sites in Texas. These results provide some of the first evidence of Se exposure risk for interior snowy plovers nesting in saline lake and alkali flat environments of the SGP. Future efforts should focus upon specific Se uptake pathways during breeding and nonbreeding seasons, as snowy plovers breeding in the SGP appear to be exposed to Se throughout their annual cycle.

The quantitative conversion of nonpertechnetate [Tc(CO) 3 ] + species in nuclear waste storage tank 241-AN-102 at the Hanford Site is demonstrated. A waste sample containing the [Tc(CO) 3 ] + species is added to a developer solution that rapidly converts the nonemissive species into a luminescent complex, which is detected spectroscopically. This method was first demonstrated using a [Tc(CO) 3 ] + sample of nonwaste containing matrix to determine a detection limit (LOD), resulting in a [Tc(CO) 3 ] + LOD of 2.20 × 10 -7 M, very near the LOD of the independently synthesized standard (2.10 × 10 -7 M). The method was then used to detect [Tc(CO) 3 ] + in a simulated waste using the standard addition method, resulting in a [Tc(CO) 3 ] + concentration of 1.89 × 10 -5 M (within 27.7% of the concentration determined by β liquid scintillation counting). Three samples from 241-AN-102 were tested by the standard addition method: (1) a 5 M Na adjusted fraction, (2) a fraction depleted of 137 Cs, and (3) an acid-stripped eluate. The concentrations of [Tc(CO) 3 ] + in these fractions were determined to be 9.90 × 10 -6 M (1), 0 M (2), and 2.46 × 10 -6 M (3), respectively. The concentration of [Tc(CO) 3 ] + in the as-received AN-102 tank waste supernatant was determined to be 1.84 × 10 -5 M.

Catalytic Meerwein-Ponndorf-Verley reductions of ketones and aldehydes in the presence of isopropyl alcohol were performed at aluminum alkoxide sites that were postsynthetically introduced into robust metal-organic frameworks (MOFs). The aluminum was anchored at the bridging hydroxyl sites inherent in some MOFs. MOFs in the UiO-66/67 family as well as DUT-5 were successfully adapted to this strategy. Incorporation of catalytically active aluminum species greatly enhanced the reactivity of the native MOF at 80 °C in the case of both UiO-66, and was almost solely responsible for catalytic activity in the case of metalated UiO-66 and DUT-5. The site isolation of the catalyst prevented aggregation and complete deactivation of the molecular aluminum catalyst, allowing it to be recovered and recycled in the case of UiO-67. This catalyst also proved to be moderately tolerant to wet isopropyl alcohol.

Nanocellulose has high specific surface area, hydration properties, and ease of derivatization to prepare protease sensors. A Human Neutrophil Elastase sensor designed with a nanocellulose aerogel transducer surface derived from cotton is compared with cotton filter paper, and nanocrystalline cellulose versions of the sensor. X-ray crystallography was employed along with Michaelis-Menten enzyme kinetics, and circular dichroism to contrast the structure/function relations of the peptide-cellulose conjugate conformation to enzyme/substrate binding and turnover rates. The nanocellulosic aerogel was found to have a cellulose II structure. The spatiotemporal relation of crystallite surface to peptide-cellulose conformation is discussed in light of observed enzyme kinetics. A higher substrate binding affinity ( K m ) of elastase was observed with the nanocellulose aerogel and nanocrystalline peptide-cellulose conjugates than with the solution-based elastase substrate. An increased K m observed for the nanocellulosic aerogel sensor yields a higher enzyme efficiency ( k cat / K m ), attributable to binding of the serine protease to the negatively charged cellulose surface. The effect of crystallite size and β-turn peptide conformation are related to the peptide-cellulose kinetics. Models demonstrating the orientation of cellulose to peptide O6-hydroxymethyl rotamers of the conjugates at the surface of the cellulose crystal suggest the relative accessibility of the peptide-cellulose conjugates for enzyme active site binding., Competing Interests: The authors declare no conflict of interest.

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent in situ spectroscopic analysis of [Re(CO) 3 ] + species in simulated Hanford tank waste. In this test case, the nonradioactive metal rhenium is substituted for technetium (Tc-99), a weak beta emitter, to demonstrate proof of concept for a method to measure a nonpertechnetate form of technetium in Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the nonemissive [Re(CO) 3 ] + species to a developer solution that enables the rapid, quantitative conversion of the nonemissive species to a luminescent species which can then be detected spectroscopically. The [Re(CO) 3 ] + species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re(CO) 3 ] + species was measured to be at a concentration of 38.9 μM, which was a difference of 2.01% from the actual concentration of 39.7 μM.

The increase in use of nanomaterials such as multiwalled carbon nanotubes (MWCNTs) presents a need to study their interactions with the environment. Trophic transfer was measured between Daphnia magna and Pimephales promelas (fathead minnow, FHM) exposed to MWCNTs with different outer diameter (OD) sizes (MWCNT1 = 8-15 nm OD and MWCNT2 = 20-30 nm OD) in the presence and absence of copper. Pristine FHM were fed D. magna, previously exposed for 3 d to MWCNT1 or MWCNT2 (0.1 mg/L) and copper (0.01 mg/L), for 7 d. D. magna bioaccumulated less MWCNT1 (0.02 μg/g) than MWCNT2 (0.06 μg/g), whereas FHM accumulated more MWCNT1 (0.81 μg/g) than MWCNT2 (0.04 μg/g). In the presence of copper, MWCNT bioaccumulation showed an opposite trend. Mostly MWCNT1 (0.03 μg/g) bioaccumulated in D. magna, however less MWCNT1 (0.21 μg/g) than MWCNT2 (0.32 μg/g) bioaccumulated in FHM. Bioaccumulation factors were higher for MWCNT1s than MWCNT2. However, an opposite trend was observed when copper was added. Plasma metallothionein-2 was measured among treatments; however concentrations were not statistically different from the control. This study demonstrates that trophic transfer of MWCNTs is possible in the aquatic environment and further exploration with mixtures can strengthen the understanding of MWCNT environmental behavior.

Due to long term declines of American Woodcock (Scolopax minor) and widespread distribution of environmentally available lead (Pb) throughout their geographic range, it is important to assess if Pb exposure is a potential contributor to these declines. Woodcock are exposed to Pb through various environmental sources and are known to exhibit relatively high bone-Pb concentrations. Absorption of Pb by birds, and woodcock specifically, is not well understood. Some studies show that interactions among calcium, phosphorus, iron, zinc, and vitamin D levels may play an important role in Pb absorption. Therefore, when future Pb studies are performed for woodcock, and other birds, interactions among these elements should be considered. For example, these interactions are relevant in the acquisition and mobilization of calcium in female birds during egg development and shell calcification. These factors should be considered to understand potential mechanisms of Pb exposure, Pb absorption, and subsequent Pb toxicity to birds in general, and woodcock specifically. This review discusses Pb exposure routes, effects of Pb toxicity, and the distribution of Pb in American woodcock and identifies areas for future research in woodcock and other avian species.

In ecotoxicology, analytical compartmentalization analysis can be used to better understand metal sequestration and detoxification. Metals are typically found in two main compartments, biologically detoxified metal (BDM) and metal sensitive fractions (MSF). The purpose of this study was to analyze the subcellular distribution of cadmium (Cd) in Lymnaea stagnalis. Adult snails were exposed to three concentrations of Cd for 56 days as part of a global ring test for L. stagnalis. At the end of the 56-day exposure, organisms were separated in two sections (viscera and foot). Each section was subsequently divided by differential centrifugation into five total fractions including (metal rich granules, debris, Organelles, heat denatured proteins, and heat stable proteins) followed by Cd analysis. The concentration in each compartment, BDM, MSF, and bioconcentration factors were estimated as well. There was significantly higher bioconcentration of Cd in the viscera section compared with the foot. Cadmium accumulation in all five fractions also increased with increasing exposure concentrations. Cadmium accumulated the most in the heat denatured protein fraction (enzymes) and accumulated the least in the heat stable protein fraction (metallothionein-like proteins). The MSF compartment (~65%) was in higher proportion than the BDM (~30%), but only in the lowest Cd exposure concentration was there a significant difference between these compartments. The results indicated that, in general, there was more Cd accumulated in the metal sensitive fractions, and that the detoxification mechanisms were not efficient enough to avoid toxicity at the two highest concentrations. This study provides evidence that improves our understanding of Cd tissue distribution in freshwater gastropods.

The interaction of two methanol molecules, simplified models of carbohydrates and cellulose, was examined using a variety of quantum mechanics (QM) levels of theory. Energy plots for hydrogen bonding distance (H⋯O) and angle (OH⋯O) were constructed. All but two experimental structures were located in stabilized areas on the vacuum phase energy plots. Each of the 399 models was analyzed with Bader's atoms-in-molecules (AIM) theory, which showed a widespread ability by the dimer models to form OH⋯O hydrogen bonds that have bond paths and Bond Critical Points. Continuum solvation calculations suggest that a portion of the energy-stabilized structures could occur in the presence of water. A survey of the Cambridge Structural Database (CSD) for all donor-acceptor interactions in β-D-glucose moieties examined the similarities and differences among the hydroxyl groups and acetal oxygen atoms that participate in hydrogen bonds. Comparable behavior was observed for the O2H, O3H, O4H, and O6H hydroxyls, acting either as acceptors or donors. Ring O atoms showed distinct hydrogen bonding behavior that favored mid-length hydrogen bonds., (Published by Elsevier Ltd.)

Arsenic is a carcinogenic element that occurs naturally in the environment. High levels of arsenic are found in water in some parts of the world, including Texas. The aims of this study were to determine the distribution of arsenic in muskmelon (Cucumis melo) plants accumulated from arsenic spiked water and to observe effects on plant biomass. Plants were grown and irrigated using water spiked with variable concentrations of arsenic. Inductively coupled plasma mass spectrometry was used to quantify arsenic in different parts of the plant and fruit. Under all conditions tested in this study, the highest concentrations of arsenic were found in the leaves, soil, and roots. Arsenic in the water had no significant effect on plant biomass. Fruits analyzed in this study had arsenic concentrations of 101 μg/kg or less. Consuming these fruits would result in less arsenic exposure than drinking water at recommended levels.

Core-shell structured hydrogels consisting of a flexible interpenetrating polymer network (IPN) core and a rigid semi-IPN shell were prepared through chemical crosslinking of polyvinyl alcohol (PVA) and sodium alginate (SA) with Ca(2+) and glutaraldehyde. Short cellulose nanofibers (CNFs) extracted from energycane bagasse were incorporated in the hydrogel. The shell was micro-porous and the core was macro-porous. The hydrogels could be used in multiple adsorption-desorption cycles for dyes, and the maximum methyl blue adsorption capacity had a 10% increase after incorporating CNFs. The homogeneous distribution of CNFs in PVA-SA matrix generated additional hydrogen bonds among the polymer molecular chains, resulting in enhanced density, viscoelasticity, and mechanical strength for the hydrogel. Specifically, the compressive strength of the hydrogel reached 79.5kPa, 3.2 times higher than that of the neat hydrogel., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The Segal method estimates the amorphous fraction of cellulose Iβ materials simply based on intensity at 18° 2θ in an X-ray diffraction pattern and was extended to cellulose II using 16° 2θ intensity. To address the dependency of Segal amorphous intensity on crystal size, cellulose polymorph, and the degree of polymorphic conversion, we simulated the diffraction patterns of cotton celluloses (Iβ and II) and compared the simulated amorphous fractions with the Segal values. The diffraction patterns of control and mercerized cottons, respectively, were simulated with perfect crystals of cellulose Iβ (1.54° FWHM) and cellulose II (2.30° FWHM) as well as 10% and 35% amorphous celluloses. Their Segal amorphous fractions were 15% and 31%, respectively. The higher Segal amorphous fraction for control cotton was attributed to the peak overlap. Although the amorphous fraction was set in the simulation, the peak overlap induced by the increase of FWHM further enhanced the Segal amorphous intensity of cellulose Iβ. For cellulose II, the effect of peak overlap was smaller; however the lower reflection of the amorphous cellulose scattering in its Segal amorphous location resulted in smaller Segal amorphous fractions. Despite this underestimation, the relatively good agreement of the Segal method with the simulation for mercerized cotton was attributed to the incomplete conversion to cellulose II. The (1-10) and (110) peaks of cellulose Iβ remained near the Segal amorphous location of cellulose II for blends of control and mercerized cotton fibers., (Published by Elsevier Ltd.)

Cellulose I, cellulose II and cellulose I/II hybrid fibers were prepared from energycane bagasse using NaOH and NaClO2 treatments. The definitive defibrillation effect with an average width of 12±5μm was observed for the fibers treated with 20wt% NaOH for 10h and NaClO2 for 2h. The ribbon shaped cellulose I fibers were converted to a swollen state with a rougher surface by 20wt% NaOH treatment for 10h. The percentage of cellulose I decreased from 100% to 5%, and the corresponding CI values increased from 58.2% to 68.8% during the conversion from cellulose I to II. After further NaClO2 treatment, the CI values were decreased because of partial destruction of hydrogen bond network. XRD, NMR and FTIR results present the same trend in the degree of crystallization for all the samples., (Copyright © 2015 Elsevier Ltd. All rights reserved.)