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Background Genomic technologies such as genetic testing and precision treatments are rapidly becoming routine in oncology care, and nurses play an increasingly important role in supporting the growing demands for genomics-informed healthcare. Policy infrastructure such as competencies, standards, scope of practice statements, and education and curriculum frameworks are urgently needed to guide these practice and education changes.Purpose This study is part of a larger three-phase project to develop recommendations and catalyze action for genomics-informed oncology nursing education and practice for the Canadian Association of Nurses in Oncology and the Canadian Association of Schools of Nursing. This phase aimed to enhance understanding of policy needs and action drivers for genomics-informed oncology nursing education and practice through the perspectives of Canadian oncology nurses and patient partners.Methods Interpretive description methodology guided the study. Twenty semi-structured virtual interviews were conducted; 17 with oncology nurses in various domains of practice, and three with patient partner representatives. Data collection and analysis occurred concurrently.Results Our analysis identified three themes: 1) nurses and patients recognize that it is time for action, 2) nurses and patients see advantages to executing intentional, strategic, and collaborative policy development, and 3) leadership and advocacy are required to drive action.Conclusion Nursing policy infrastructure is required to increase genomic literacy, support nurses in providing safe patient care, and establish clear roles, responsibilities, and accountabilities within the interdisciplinary team. Strong leadership and advocacy at the practice, organizational, and systems levels are vital to accelerating action.

The distribution and state of subsea permafrost is largely unknown. Present maps, which rely heavily on model results, suggest that subsea permafrost is confined to the Beaufort, Siberian and Laptev seas. Here we show that discontinuous subsea permafrost exists along the Labrador coast (56 °N) under the influence of the Labrador Coastal Current. High-resolution bathymetric data reveal the presence of subsea thermokarst environments on the coastal seabed of Nain, Nunatsiavut, where an ice-rich sediment sample was recovered in July 2022 at a water depth of 27 m. Porewater analysis indicates that ground ice can persist in the sediments due to freshened submarine groundwater seepage that freezes at higher temperatures (0 °C) than seawater (−1.8 °C). The formation and preservation of subsea permafrost landforms is due to cold waters of the Labrador Coastal Current entering the coastal areas and remaining less than 0 °C for most of the year. Therefore, evidence of subsea permafrost landforms in coastal Labrador and the distribution of cold bottom water in the Northern Hemisphere suggests that subsea permafrost is likely to be preserved elsewhere in subarctic regions, especially where freshened submarine groundwater seepage elevates the freezing temperature. This highlights the potential underestimation of subsea permafrost in the world’s coastal oceans.

Animals can learn about sources of danger while minimizing their own risk by observing how others respond to threats. However, the distinct neural mechanisms by which threats are learned through social observation (known as observational fear learning1–4(OFL)) to generate behavioural responses specific to such threats remain poorly understood. The dorsomedial prefrontal cortex (dmPFC) performs several key functions that may underlie OFL, including processing of social information and disambiguation of threat cues5–11. Here we show that dmPFC is recruited and required for OFL in mice. Using cellular-resolution microendoscopic calcium imaging, we demonstrate that dmPFC neurons code for observational fear and do so in a manner that is distinct from direct experience. We find that dmPFC neuronal activity predicts upcoming switches between freezing and moving state elicited by threat. By combining neuronal circuit mapping, calcium imaging, electrophysiological recordings and optogenetics, we show that dmPFC projections to the midbrain periaqueductal grey (PAG) constrain observer freezing, and that amygdalar and hippocampal inputs to dmPFC opposingly modulate observer freezing. Together our findings reveal that dmPFC neurons compute a distinct code for observational fear and coordinate long-range neural circuits to select behavioural responses.

Background Genetics and genomics (GG) are transforming approaches to healthcare in Canada and around the globe. Canadian nurses must be prepared to integrate GG in their practice, but modest research in this area suggests that Canadian nurses have limited GG competency. Countries that have integrated GG across nursing provided guidance to nurses about the practice implications of GG through regional nursing policy documents. These documents propelled action to integrate GG across nursing. Little is known about the GG content in the nursing policy document infrastructure in Canada.Purpose This study aimed to examine the guidance for GG-informed nursing practice as provided by Canadian nursing organizations in official professional documents.Methods Qualitative document analysis was used. A hybrid inductive/deductive analysis approach was used to analyze findings within the diffusion of innovation theory framework.Results There is an overall lack of depth and breadth of Canadian nursing documents that include content related to GG. Of the (n  =  37) documents analyzed, four themes were generated including (a) GG guidance in nursing education; (b) regulators’ requirements for foundational GG knowledge, (c) Canadian Nurses Association (CNA) as an early catalyst to GG integration; and (d) early adopters in speciality practice.Conclusion There are opportunities to enhance the guidance available to Canadian nurses for the application of GG, through documents of nursing professional associations, nursing education accreditation organizations, and regulatory bodies. Findings suggest oncology and perinatal nurses are the early adopters which is an important consideration in future strategies to implement GG into Canadian nursing.

Our objective was to characterize T and B cell responses to vaccination with SARS-CoV-2 antigens in immunocompromised rheumatoid arthritis (RA) patients. In 22 RA patients, clinical and biological variables were analyzed before and 4 weeks after each of 3 messenger RNA (mRNA) vaccine doses and compared with unmatched healthy individuals. Sequentially sampled peripheral blood mononuclear cells and sera were collected to determine immune profiles and to analyze the T cell response to a spike peptide pool and B cell specificity to the receptor-binding domain (RBD). Anti-spike antibodies were detectable in 6 of 22 RA patients after 1 dose of vaccine with increasing titers after each booster dose, although the overall response was lower compared with that in healthy control individuals. Responding patients after the first dose were more likely to have RA antibodies and a higher baseline proportion of circulating follicular B cells. In RA patients, the mRNA vaccine elicited a robust CD4+T response to a spike peptide pool following the first and second doses. Consistent with the serologies, RBD-specific B cells exhibited a modest increase after the first dose and the second dose resulted in marked increases only in a fraction of the RA patients to both ancestral and omicron RBD. Our results highlight the importance of multidose COVID-19 vaccination in RA patients to develop a protective humoral response. However, these patients rapidly develop specific T CD4+responses, despite delayed B cell responses.Immunity to SARS-CoV-2 mRNA-based vaccines in RA: B responses are decreased, and booster doses improve humoral response. Spike-specific T CD4+responses are preserved despite immunosuppression.

Composted or heat-treated biological soil amendments of animal origin (BSAAOs) can be added to soils to provide nutrients for fresh produce. These products lower the risk of pathogen contamination of fresh produce compared with the use of untreated BSAAOs; however, meteorological conditions, geographic location, and soil properties can influence the presence of pathogenic bacteria or their indicators (e.g., generic Escherichia coli) and allow potential for produce contamination. Replicated field plots of loamy or sandy soils were tilled and amended with dairy manure compost (DMC), poultry litter compost (PLC), or no compost (NoC) over two field seasons and noncomposted heat-treated poultry pellets (HTPPs) during the second field season. Plots were inoculated with a three-strain cocktail of rifampin-resistant E. coli(rE. coli) at levels of 8.7 log CFU/m2. Direct plating and most-probable-number methods measured the persistence of rE. coliand Listeriaspp. in plots through 104 days postinoculation. Greater survival of rE. coliwas observed in PLC plots in comparison to DMC plots and NoC plots during year 1 (P< 0.05). Similar trends were observed for year 2, when rE. colisurvival was also greater in HTPP-amended plots (P< 0.05). Survival of rE. colidepended on soil type, and water potential and temperature were significant covariables. Listeriaspp. were found in NoC plots, but not in plots amended with HTPPs, PLC, or DMC. Radish data demonstrate that PLC treatment promoted the greatest level of rE. colitranslocation compared with DMC and NoC treatments (P< 0.05). These results are consistent with findings from studies conducted in other regions of the United States, and they inform northeast produce growers that composted and noncomposted poultry-based BSAAOs support greater survival of rE. coliin field soils. This result has the potential to affect the food safety risk of edible produce grown in BSAAO-amended soils as a result of pathogen contamination.

DEMOCRATS FOR LIFE OF America was supposed to change the direction and ideology of the Democratic Party. Its leaders laid claim to a mission that would 'get in there and [...]

Recently, Maclean's published an article about our research exploring the benefits of joint education sessions between college and degree nursing students. Typically, degree and diploma nursing students rarely interact during [...]

IN JANUARY THIS YEAR, A MOTHER of six walked into a Walgreen's pharmacy in Milwaukee, Wis., to get a prescription filled for emergency contraception (EC). The condom she and her [...]

Adaptive behaviour necessitates the formation of memories for fearful events, but also that these memories can be extinguished. Effective extinction prevents excessive and persistent reactions to perceived threat, as can occur in anxiety and ‘trauma- and stressor-related’ disorders1. However, although there is evidence that fear learning and extinction are mediated by distinct neural circuits, the nature of the interaction between these circuits remains poorly understood2–6. Here, through a combination of in vivo calcium imaging, functional manipulations, and slice physiology, we show that distinct inhibitory clusters of intercalated neurons (ITCs) in the mouse amygdala exert diametrically opposed roles during the acquisition and retrieval of fear extinction memory. Furthermore, we find that the ITC clusters antagonize one another through mutual synaptic inhibition and differentially access functionally distinct cortical- and midbrain-projecting amygdala output pathways. Our findings show that the balance of activity between ITC clusters represents a unique regulatory motif that orchestrates a distributed neural circuitry, which in turn regulates the switch between high- and low-fear states. These findings suggest that the ITCs have a broader role in a range of amygdala functions and associated brain states that underpins the capacity to adapt to salient environmental demands.

Crystalline structures and lattice water molecules are believed to strongly influence the ability of metal oxides to reversibly and rapidly insert protons in aqueous batteries. In the present work, we performed a systematic analysis of the electrochemical charge storage properties of nanostructured TiO2electrodes composed of either anatase or amorphous TiO2in a mild buffered aqueous electrolyte. We demonstrate that both materials allow reversible bulk proton insertion up to a maximal reversible gravimetric capacity of ∼150 mA·h·g–1. We also show that the TiO2crystallinity governs the energetics of the charge storage process, with a phase transition for anatase, while having little effect on either the interfacial charge transfer kinetics or the apparent rate of proton diffusivity within the metal oxide. Finally, with both TiO2electrodes, reversible proton insertion leads to gravimetric capacities as high as 95 mA·h·g–1at 75 C. We also reveal two competitive reactions decreasing the Coulombic efficiency at low rates, i.e., hydrogen evolution and a nonfaradaic self-discharge reaction. Overall, this work provides a comprehensive overview of the proton-coupled electrochemical reactivity of TiO2and highlights the key issues to be solved to truly benefit from the unique properties of protons as fast charge carriers in metal oxides.

An adult female Cape porcupine (Hystrix africaeaustralis) was presented because of marked abdominal distension, acute dyspnea, and lethargy. Physical examination and standard radiographs revealed marked and diffuse gaseous dilation of the stomach and intestines of undetermined origin. The porcupine died despite medical therapy and surgical intervention. Postmortem examination revealed chronic fungal (Aspergillus flavus) rhinitis. Given that rodents are obligate nasal breathers, the rhinitis likely resulted in substantial upper airway obstruction leading to aerophagia.

Recent years have seen advances in our understanding of the neural circuits associated with trauma-related disorders, and the development of relevant assays for these behaviors in rodents. Although inherited factors are known to influence individual differences in risk for these disorders, it has been difficult to identify specific genes that moderate circuit functions to affect trauma-related behaviors. Here, we exploited robust inbred mouse strain differences in Pavlovian fear extinction to uncover quantitative trait loci (QTL) associated with this trait. We found these strain differences to be resistant to developmental cross-fostering and associated with anatomical variation in basolateral amygdala (BLA) perineuronal nets, which are developmentally implicated in extinction. Next, by profiling extinction-driven BLA expression of QTL-linked genes, we nominated Ppid(peptidylprolyl isomerase D, a member of the tetratricopeptide repeat (TPR) protein family) as an extinction-related candidate gene. We then showed that Ppidwas enriched in excitatory and inhibitory BLA neuronal populations, but at lower levels in the extinction-impaired mouse strain. Using a virus-based approach to directly regulate Ppidfunction, we demonstrated that downregulating BLA-Ppidimpaired extinction, while upregulating BLA-Ppidfacilitated extinction and altered in vivo neuronal extinction encoding. Next, we showed that Ppidcolocalized with the glucocorticoid receptor (GR) in BLA neurons and found that the extinction-facilitating effects of Ppidupregulation were blocked by a GR antagonist. Collectively, our results identify Ppidas a novel gene involved in regulating extinction via functional actions in the BLA, with possible implications for understanding genetic and pathophysiological mechanisms underlying risk for trauma-related disorders.

Mild aqueous electrolytes containing multivalent metal salts are currently scrutinized for the development of ecosustainable energy-related devices. However, the role of soluble multivalent metal ions in the electrochemical reactivity of transition metal oxides is a matter of debate, especially when they are performed in protic aqueous electrolytes. Here, we have compared, by means of (spectro)electrochemistry, the reversible electrochromic reduction of transparent nanostructured ?-WO3thin films in mild aqueous electrolytes of various chemical composition and pH. This study reveals that reversible proton insertion is the only charge storage mechanism over a large pH range and that it is effective for aqueous electrolytes prepared from either organic (such as acetic acid) or inorganic (such as solvated multivalent cations) Bro?nsted acids. By refuting charge storage mechanisms relying on the reversible insertion of multivalent metal ions, notably in aqueous electrolytes based on Al3+ions or a mixture of Al3+and Zn2+ions, these fundamental results pave the way for the rational development of electrolytes and active materials for a range of aqueous-based devices, such as the emerging concept of an energy-saving smart window, which we also address in this study.

An in situand real-time electrochemical method has been devised for quantitatively monitoring the self-assembly of a ferrocene-labeled cyclic disulfide derivative (i.e., a thioctic acid derivative) on a polycrystalline gold electrode under electrode polarization. Taking advantage of the high sensitivity, specificity, accuracy, and temporal resolution of this method, we were able to demonstrate an unexpectedly facilitated formation of the redox-active SAM when the electrode was held at a moderate cathodic potential (−0.4 V vs SCE in CH3CN), affording a saturated monolayer from only micromolar solutions in less than 10 min, and a totally impeded SAM growth when the electrode was polarized at a slightly anodic potential (+0.5 V vs SCE in CH3CN). This method literally allows for switching on/off the formation of SAMs under “soft” conditions. Moreover the cyclic disulfide-based SAM was completely desorbed at this potential contrary to the facilitated deposition of a ferrocene-labeled alkanethiol. Such a strikingly contrasting behavior could be explained by an energetically favored release of the thioctic-based SAM through homolytic cleavage of the Au–S bond followed by intramolecular cyclization of the generated thiyl diradicals. Moreover, the absence of a discernible transient faradaic current response during the potential-assisted adsorption/desorption of the redox-labeled cyclic disulfide led us to conclude in a potential-dependent reversible surface reaction where no electron is released or consumed. These results provide new insights into the formation of disulfide-based SAMs on gold but also raise some fundamental questions about the intimate mechanism involved in the facilitated adsorption/desorption of SAMs under electrode polarization. Finally, the possibility to easily and selectively address the formation/removal of thioctic-based SAMs on gold by applying a moderate cathodic/anodic potential offers another degree of freedom in tailoring their properties and in controlling their self-assembly, nanostructuration, and/or release.

Due to their eco-sustainability and versatility, organic electrodes are promising candidates for large-scale energy storage in rechargeable aqueous batteries. This is notably the case of aqueous hybrid batteries that pair the low voltage of a zinc anode with the high voltage of a quinone-based (or analogue of quinone-based) organic cathode. However, the mechanisms governing their charge–discharge cycles remain poorly understood and are even a matter of debate and controversy. No consensus exists on the charge carrier in mild aqueous electrolytes, especially when working in an electrolyte containing a multivalent metal cation such as Zn2+. In this study, we comprehensively investigate the electrochemical reactivity of two model quinones, chloranil, and duroquinone, either diluted in solution or incorporated into carbon-based composite electrodes. We demonstrate that a common nine-member square scheme proton-coupled electron transfer mechanism allows us to fully describe and rationalize their electrochemical behavior in relation to the pH and chemical composition of the aqueous electrolyte. Additionally, we highlight the crucial role played by the pKas associated with the reduced states of quinones in determining the nature of the charge carrier that compensates for the negative charges reversibly injected in the active material. Finally, contrary to the widely reported findings for Zn/organic batteries, we unequivocally establish that the predominant solid-state charge carriers in Zn2+-based mild aqueous electrolytes are not multivalent Zn2+cations but rather protons supplied by the weakly acidic hexaaqua metal ions (i.e., [Zn(H2O)6]2+]).

The eastern north coast of Greenland is considered to be highly sensitive to the ongoing Arctic warming, but there is a general lack of data on modern conditions and in particular on the modern distribution of climate and environmental proxies to provide a baseline and context for studies on past variability. Here we present a detailed investigation of 11 biogenic proxies preserved in surface sediments from the remote High Arctic Wandel Sea shelf, the entrance to the Independence, Hagen, and Danmark fjords. The composition of organic matter (organic carbon, C:N ratios, δ13C, δ15N, biogenic silica, and IP25) and microfossil assemblages revealed an overall low primary production dominated by benthic diatoms, especially at the shallow sites. While the benthic and planktic foraminiferal assemblages underline the intrusion of chilled Atlantic waters into the deeper parts of the study area, the distribution of organic‐walled dinoflagellate cysts is controlled by the local bathymetry and sea ice conditions. The distribution of the dinoflagellate cyst Polarella glacialismatches that of seasonal sea ice and the specific biomarker IP25, highlighting the potential of this species for paleo sea ice studies. The information inferred from our multiproxy study has important implications for the interpretation of the biogenic‐proxy signal preserved in sediments from circum‐Arctic fjords and shelf regions and can serve as a baseline for future studies. This is the first study of its kind in this area. A new multiproxy reference baseline is provided for assessing past changes in High Arctic fjord and shelf environmentsCysts of the ice‐dwelling dinoflagellate Polarella glacialisare tightly connected with seasonal sea ice and show promise as new paleo sea‐ice proxyBenthic diatoms and ice algae are the main primary producers in the shallower sites, whereas heterotrophic dinoflagellates and benthic foraminifera are indicative of Atlantic water intrusion and dominate at the deeper sites

'We will repeat and intensify this year all we did in the previous election cycles. The pro-abortion groups, the liberals in the Church, the over-cautious attorneys, and the people who [...]

This paper, with the use of data from the SHRP 2 naturalistic driving study, provides a preliminary evaluation of the effectiveness of high-visibility crosswalks (HVCs) in improving pedestrian safety at un-controlled locations. This evaluation was accomplished by analyzing the driving behavior of SHRP 2 participants at three uncontrolled locations at the Erie County, New York, test site. In this context, crash surrogates (i.e., speed, acceleration, throttle pedal actuation, and brake application) were used to evaluate the participants’ driving behavior, primarily on the basis of data from before and after the HVC installation. The before–after analysis allowed the assessment of HVC effectiveness in driver behavior modification. Mixed logit and random parameters linear regression models were estimated, and panel effects and unobserved heterogeneity were accounted for. Several factors were explored and controlled for (e.g., vehicle and driver characteristics, roadside environment, weather conditions), and the preliminary exploratory results show that HVCs can improve pedestrian safety and positively modify driving behavior.

Semiconductive transparent thin films of periodically organized nanostructured SnO2were prepared on flat conductive ITO substrates by evaporation-induced self-assembly (EISA) under different dip-coating regimes and then functionalized by two redox-active chromophores, i.e., the flavin mononucleotide (FMN) able to reversibly exchange 2 e–and 2 H+and the [OsII(bpy)2(4,4′-CH2PO3H2-bpy)]2+complex (OsP) involving a fast and reversible one-electron transfer. The redox behavior of these two chemisorbed chromophores was investigated by cyclic voltammetry and cyclic voltabsorptometry. On account of the distinct formal potential of the two redox chromophores relative to the position of the lower conduction band edge of SnO2, the heterogeneous electron transfer was observed to be either reversible (FMN) or irreversible (OsP). In the case of the OsP-functionalized SnO2electrode, quantitative analysis of the cyclic voltabsorptograms was achieved within the framework of our previously proposed kinetic model of charge transfer/transport in mesoporous semiconductive films (Renault et al. Phys. Chem. Chem. Phys.2015, 17, 10592), allowing for direct comparison between EISA–TiO2and EISA–SnO2electrodes. It is notably shown that the interfacial electron transfer between the adsorbed redox chromophore and the SnO2interface is the rate-determining process under our experimental conditions. It is additionally demonstrated that the electrons trapped in the low-energy surface states of EISA–SnO2can directly participate in the interfacial electron transfer, a behavior that strongly contrasts that which we had previously found at EISA–TiO2electrodes (i.e., wherein only electrons from the conduction band were involved in the interfacial electron transfer).

Biogeochemical cycling of elements largely occurs in dissolved state, but many elements may also be bound to natural nanoparticles (NNP, 1–100 nm) and fine colloids (100–450 nm). We examined the hypothesis that the size and composition of stream water NNP and colloids vary systematically across Europe. To test this hypothesis, 96 stream water samples were simultaneously collected in 26 forested headwater catchments along two transects across Europe. Three size fractions (~1–20 nm, >20–60 nm, and >60 nm) of NNP and fine colloids were identified with Field Flow Fractionation coupled to inductively coupled plasma mass spectrometry and an organic carbon detector. The results showed that NNP and fine colloids constituted between 2 ± 5% (Si) and 53 ± 21% (Fe; mean ± SD) of total element concentrations, indicating a substantial contribution of particles to element transport in these European streams, especially for P and Fe. The particulate contents of Fe, Al, and organic C were correlated to their total element concentrations, but those of particulate Si, Mn, P, and Ca were not. The fine colloidal fractions >60 nm were dominated by clay minerals across all sites. The resulting element patterns of NNP <60 nm changed from North to South Europe from Fe‐ to Ca‐dominated particles, along with associated changes in acidity, forest type, and dominant lithology. Stream phosphorus is largely bound to natural nanoparticles and colloidsThe chemical composition of colloids varies systematically from Northern to Southern European streams

Ongoing developments of sustainable energy technologies based on high-surface-area semiconductive metal oxide electrodes operating under mild and safe aqueous conditions require deep understanding of proton and electron transfer/transport throughout their porous structure. To address this issue, we investigated the electrochemical reductive protonation of high surface area nanostructured amorphous TiO2electrodes (produced by glancing angle deposition) in both buffered and unbuffered aqueous solutions. Quantitative analysis of the two charge storage mechanisms was achieved, allowing proper deconvolution of the electrical double-layer capacitive charge storage from the reversible faradaic one resulting from the proton-coupled reduction of bulk TiO2. We evidence that this latter process occurs reversibly and extensively (up to an intercalation ratio of 20%) not only under strongly acidic pH conditions but also, more interestingly, under neutral pH with the intercalated proton arising from the buffer rather than water. Moreover, we show that in comparison with reductive Li+intercalation the proton-coupled electron charge storage occurs more rapidly (in a few seconds). This important finding suggests that a high-rate and high-power charge storage device could potentially be achieved with the reversible H+-coupled charge/discharge process in TiO2at neutral pH, opening thus new opportunities to the development of eco-friendly batteries for electrical energy storage.

Anal squamous cell cancer (SCC) is a relatively uncommon cancer in the United States. Anal SCC has long been associated with human immunodeficiency virus (HIV) positivity and/or men who have sex with men. The incidence of anal SCC has been increasing in both genders regardless of HIV status. Few clinicians are aware that white women, when not controlling for gender and sexual preference together, have the highest incidence of anal SCC. Anal intraepithelial neoplasia (AIN), dysplastic cells of the anal canal due to human papilloma virus infection, is believed to be the precursor to anal SCC. A vaccination has been approved by the Federal Drug Administration (FDA) for the prevention of high-risk human papilloma virus infections in presexually active girls and boys. Currently, there are no consensus guidelines for AIN screening, treatment or follow-up. Although anal SCC is treatable when caught early, treatment is often associated with significant morbidity. The purpose of this paper is to raise awareness of anal SCC and its precursor, AIN, in the non-HIV+ and non-MSM populations, and discuss means by which to decrease the incidence of anal SCC in all populations.

This study contributes to the communal effort to improve understanding of sea spray generation and transport. For the first time, laboratory‐derived sea spray generation functions (SSGFs) are parameterized in the Meso‐NH mesoscale atmospheric model and are field tested. Formulated from the MATE19 laboratory experiments (Bruch et al., 2021, https://doi.org/10.1007/s10546-021-00636-y) the two SSGFs are driven by the upwind component of the wave‐slope variance 〈Sx2〉$\langle {S}_{x}^{2}\rangle $(herein B21A), or both 〈Sx2〉$\langle {S}_{x}^{2}\rangle $and the wind friction velocity cubed u∗3${u}_{\ast }^{3}$(herein B21B). In this first attempt to incorporate the SSGFs in Meso‐NH, the simulations are run without a wave model, and the wave‐wind SSGFs are assumed wind‐dependent. Model evaluation is achieved with a new set of sea spray and meteorological measurements acquired over the 0.1–22.75 μm radius range and U101–20 m s−1wind speeds onboard R/V Atalante during the 25 day SUMOS field campaign in the Bay of Biscay. The B21B SSGF offers particularly good sensitivity to a wide range of environmental conditions over the size range, with an average overestimation by a factor 1.5 compared with measurements, well below the deviations reported elsewhere. B21A also performs well for larger droplets at wind speeds above 15 m s−1. Associated with airflow separation and wave breaking, wave‐slope variance allows to represent multiple wave scales and to scale sea spray generation in the laboratory and the field. Using Meso‐NH simulations we find that sea spray may be transported inland and to altitudes well above the marine atmospheric boundary layer. The effects of sea spray on weather and climate remain poorly understood as a result of sparse measurements and large uncertainties in the generation flux. With the aim of improving sea spray transport in atmospheric models, two sea spray generation functions derived from the MATE19 laboratory campaign are parameterized in the Meso‐NH mesoscale atmospheric model. The simulations are run over the Bay of Biscay in February–March 2021, and are compared with super‐micron sea spray concentrations measured during the SUMOS field campaign. Results show that the laboratory‐derived generation functions allow accurate predictions of sea spray concentrations. Furthermore, simulations show that sea spray droplets can be transported far over land, and high into the atmosphere, highlighting their availability to contribute to a wide range of atmospheric processes. With comparable wave‐slope variance behavior in laboratory and field conditions we use laboratory‐derived sea spray generation functions in the fieldParameterized with laboratory generation functions and validated using field measurements, Meso‐NH yields accurate sea spray concentrationsBy populating the atmosphere beyond 2.5 km altitude and 100 km inland, sea spray can intervene in a range of weather and cimate processes With comparable wave‐slope variance behavior in laboratory and field conditions we use laboratory‐derived sea spray generation functions in the field Parameterized with laboratory generation functions and validated using field measurements, Meso‐NH yields accurate sea spray concentrations By populating the atmosphere beyond 2.5 km altitude and 100 km inland, sea spray can intervene in a range of weather and cimate processes

Forest biodiversity is critical for many ecosystem functions and services. Yet, it remains uncertain how plant functional diversity influences ecosystem functioning across environmental gradients and contiguous larger areas. We integrated remote sensing and terrestrial biosphere modeling to explore functional diversity–productivity relationships at multiple spatial scales for a heterogeneous forest ecosystem in Switzerland. We initialized forest structure and composition in the ecosystem demography model (ED2) through a combination of ground‐based surveys, airborne laser scanning and imaging spectroscopy for forest patches at 10 × 10‐m spatial grain. We derived morphological and physiological forest traits and productivity from model simulations at patch‐level to relate morphological and physiological aspects of functional diversity to the average productivity from 2006 to 2015 at 20 × 20 to 100 × 100‐m spatial extent. We did this for model simulations under observed and experimental conditions (mono‐soils, mono‐cultures and mono‐structures). Functional diversity increased productivity significantly (p< 0.001) across all simulations at 20 × 20 to 30 × 30 m scale, but at 100 × 100‐m scale positive relationships disappeared under homogeneous soil conditions potentially due to the low beta diversity of this forest and the saturation of functional richness represented in the model. Although local functional diversity was an important driver of productivity, environmental context underpinned the variation of productivity (and functional diversity) at larger spatial scales. In this study, we could show that the integration of remotely sensed information on forest composition and structure into terrestrial biosphere models is important to fill knowledge gaps about how plant biodiversity affects carbon cycling and biosphere feedbacks onto climate over large contiguous areas. We explored relationships between forest biodiversity and productivity at multiple spatial scales to better understand how plant traits and their diversity influence the functioning of forest ecosystems. To do this across large contiguous areas, we simulated a temperate mixed forest by combining process‐based terrestrial biosphere modeling with remotely sensed information about forest structure and composition. We found that higher functional diversity was associated with higher productivity at local spatial scale (tens of meters), while soil depth and texture were the main drivers of productivity at the hectare scale. At this larger scale, functional diversity tended to be saturated due to the low turnover of species and functional traits of the temperate mixed forest and the limited representation of physiological diversity in the model. We explored forest functional diversity—productivity relationships using a terrestrial biosphere model initialized with remote sensingHigher functional diversity at 20 × 20 to 30 × 30 m scale was associated with higher productivity (p< 0.001) across all simulationsSoil depth and texture were the main drivers of productivity at the hectare scale, while functional diversity saturated at coarser scales We explored forest functional diversity—productivity relationships using a terrestrial biosphere model initialized with remote sensing Higher functional diversity at 20 × 20 to 30 × 30 m scale was associated with higher productivity (p< 0.001) across all simulations Soil depth and texture were the main drivers of productivity at the hectare scale, while functional diversity saturated at coarser scales

Although cardiac resynchronization therapy (CRT) is an established treatment for heart failure with reduced ejection fraction, 30 to 50% patients are non-responders. In this retrospective single-centre study, 19 patients underwent cardiac MRI pre-CRT, and global left ventricular (LV) strain and late gadolinium enhancement (LGE) were measured by a blinded reader. LV reverse remodeling was independently assessed using transthoracic echocardiogram before and after CRT implant. Both LV strain and extent of LGE correlated significantly with measures of reverse LV remodeling (reduction in LV volume and improvement in LV ejection fraction). These findings suggest that CMR derived strain analysis and scar evaluation may be useful preimplant predictors of response to CRT. Larger prospective multi-center studies are needed to confirm these findings and to further evaluate the role of CMR strain imaging in guiding CRT treatment decisions.

Background:Tensions and hierarchies among nurses who have different educational preparations can hinder effective communication and collaborative practices.Method:A 2-year longitudinal cohort study involving 214 participants explored the influences of joint education on Canadian Practical Nursing (PN) and Bachelor of Science in Nursing (BScN) students.Results:Joint education helps students dismantle unhelpful power relations, address myths and misconceptions about the other, and develop respect for each other's contributions to patient care.Conclusion:Joint education enhances collaboration between nursing designations by placing a focus on the actual knowledge, skill, and judgment rather than on the hierarchies established through credentialing. Joint education also assists students to see overlap in scope of practice and points of intersection requiring collaboration. This understanding promotes safe patient-focused care. Contextualizing the findings within broader discourses, such as the professions, institutions, regulating organizations, and sociopolitical relations within nursing, exposes future possibilities within nursing education. [Joint education enhances collaboration between nursing designations by placing a focus on the actual knowledge, skill, and judgment rather than on the hierarchies established through credentialing. Joint education also assists students to see overlap in scope of practice and points of intersection requiring collaboration. This understanding promotes safe patient-focused care. Contextualizing the findings within broader discourses, such as the professions, institutions, regulating organizations, and sociopolitical relations within nursing, exposes future possibilities within nursing education. [J Nurs Educ. 2016;55(11):623–630.]

Les déficits de mémoire prospective (MP) font partie des principales plaintes rapportées par des individus présentant un trouble cognitif léger (Mild cognitive impairment[MCI]). Bien que peu d’études s’y soient intéressées, on reconnaît généralement que les troubles de la MP pourraient constituer un marqueur précoce permettant d’identifier les individus à risque d’évoluer vers une démence. En dépit de leur fréquence élevée et de leurs conséquences fonctionnelles appréciables, les déficits de MP font rarement l’objet d’une évaluation formelle en contexte clinique, car il existe peu de tests standardisés ou d’outils cliniques sensibles et fiables. Dans cet article, nous ferons un survol de la littérature actuelle des études portant sur l’évaluation de la MP dans le MCI, avec une attention particulière portée sur les diverses méthodes d’évaluation actuellement disponibles. Nous rapporterons également des résultats préliminaires d’études qui ont été faites dans notre laboratoire. Ces informations serviront de base pour, nous l’espérons, stimuler les cliniciens à évaluer l’intégrité de la MP chez leurs patients âgés chez qui on soupçonne une détérioration du fonctionnement cognitif.

Chronoabsorptometry response of transparent mesoporous semiconductive metal oxide film loaded with a redox-active dye is established in the framework of fast electron diffusion. It is shown that the effect of uncompensated resistance is to delay the electron accumulation in the semiconductive thin film. Consequently, this effect must be duly taken into account when interfacial charge transfer rates between the adsorbed redox species and the porous semiconductor are extracted from chronoabsorptometry responses. This is illustrated with the quantitative analysis of the chronoabsorptometry responses of a heme-based redox probe strongly adsorbed in highly ordered mesoporous TiO2thin films (prepared from evaporation-induced self-assembly, EISA). It is shown that the reduction of the redox probe originates from the conduction band and not from the localized traps in the bandgap. These results are in quantitative agreement with differential cyclic voltabsorptometry recently reported by us, thus showing full consistency of both methods.

Reducing water losses in agriculture needs a solid understanding of when evaporation (E) losses occur and how much water is used through crop transpiration (T). Partitioning ecosystem T is however challenging, and even more so when it comes to short‐statured crops, where many standard methods lead to inaccurate measurements. In this study, we combined biometeorological measurements with a Soil‐Plant‐Atmosphere Crop (SPA‐Crop) model to estimate T and E at a Swiss cropland over two crop seasons with winter cereals. We compared our results with two data‐driven approaches: The Transpiration Estimation Algorithm (TEA) and the underlying Water Use Efficiency (uWUE). Despite large differences in the productivity of both years, the T to evapotranspiration (ET) ratio had relatively similar seasonal and diurnal dynamics, and averaged to 0.72 and 0.73. Our measurements combined with a SPA‐Crop model provided T estimates similar to the TEA method, while the uWUE method produced systematically lower T even when the soil and leaves were dry. T was strongly related to the leaf area index, but additionally varied due to climatic conditions. The most important climatic drivers controlling T were found to be the photosynthetic photon flux density (R2= 0.84 and 0.87), and vapor pressure deficit (R2= 0.86 and 0.70). Our results suggest that site‐specific studies can help establish T/ET ratios, as well as identify dominant climatic drivers, which could then be used to partition T from reliable ET measurements. Moreover, our results suggest that the TEA method is a suitable tool for ET partitioning in short‐statured croplands. To reduce water losses linked to agriculture, we need to understand how much water the crops transpire and how much water is evaporated from irrigation surplus. Measuring how much water plants transpire is however difficult, especially for short‐statured crops like wheat or barley, because they are too small for the usual measurement techniques. In our study, we use detailed climate and vegetation measurements at a cropland in Switzerland combined with a model, and compare with two other data‐driven partitioning approaches (Transpiration Estimation Algorithm (TEA), underlying Water Use Efficiency (uWUE)). Our results show that the measurements combined with a model compared well with one of the approach (TEA), while the other (uWUE) was less well suited for our cropland. Our results demonstrate that there are ratios of the transpiration to evapotranspiration (i.e., including evaporation) that tend to be stable for specific ecosystems, and that could therefore be used once they are known for an ecosystem. Our results also show that the amount of light and the atmospheric demand for water vapor are important drivers for transpiration on a daily basis, while the plant cover determines the overall rate. High agreement between transpiration (T) from measurements combined with a process‐based model (Soil‐Plant‐Atmosphere Crop) and a data‐driven method (Transpiration Estimation Algorithm)Diurnal and seasonal T to evapotranspiration ratios were relatively similar despite differences in crop and productivity between yearsDetailed crop specific models are a powerful method for partitioning T in short‐statured croplands to address lack of measurement methods High agreement between transpiration (T) from measurements combined with a process‐based model (Soil‐Plant‐Atmosphere Crop) and a data‐driven method (Transpiration Estimation Algorithm) Diurnal and seasonal T to evapotranspiration ratios were relatively similar despite differences in crop and productivity between years Detailed crop specific models are a powerful method for partitioning T in short‐statured croplands to address lack of measurement methods

Purpose. There is limited documentation regarding the potential quality of life (QOL) benefits associated with use of a worksite wellness center. Therefore, the aim of this study was to examine the relationship between potential QOL change and use of a worksite wellness center during a 12-month period.Design. Analysis of an annual QOL wellness center member survey and wellness center use during a 12-month time period.Setting. A worksite wellness center.Participants. A total of 1151 employee wellness center members, average age of 39.5 years, 69.7% female, and 43.5% reported being overweight.Intervention. Members of the worksite wellness center have access to a range of fitness options, including exercise classes, water aerobics, an indoor track, strength training, and aerobic conditioning equipment. Additionally, nutritional classes are offered, and there is a wellness café. For resiliency, members can participate in wellness coaching or a stress-reduction group program.Method. Participants completed a baseline QOL survey and a second QOL survey 1 year later. An electronic entry system tracked use of the wellness center.Results. Participants were divided into four wellness center use quartiles: low users (less than once every 2 weeks), below-average users, above-average users, and high users (two to three visits per week). High users reported experiencing improvements in their physical QOL (p < .0001) compared with the low users. Additionally, low users experienced a greater decline in their mental QOL (p = .05) compared with high users.Conclusion. In a large sample of employees, use of a wellness center during a 12-month period was associated with benefits for physical QOL. QOL is an important domain of wellness; therefore, in addition to measuring physiologic changes, examining potential QOL changes may be another important outcome measure for wellness centers.

Several barriers to colorectal cancer screening have been identified including limited access to trained endoscopists and highlight insufficient capacity to meet projected demand for colonoscopies. Two European studies have found that nonphysician providers can perform colonoscopies as safely and accurately as physicians. Training nurse practitioners (NP) to perform colonoscopy may be an effective strategy to increase access. The goal of this study was to compare accuracy, safety, and patient satisfaction in screening colonoscopy performed by board certified gastroenterologists (GI-MD) and a gastroenterology trained nurse practitioner (GI-NP). A consecutive sample of average risk participants referred for screening colonoscopy was randomized to have their procedure performed by either a GI-MD (n= 100) or a GI-NP (n= 50). Participants completed a preprocedure and postprocedure questionnaire. Endoscopists completed a postprocedure questionnaire. Cecal intubation rates, duration of procedure, sedative, and analgesic use, and patient reported procedural pain scores were equivalent among the groups. The GI-NP group had a higher adenoma detection rate compared with the combined GI-MD groups (42 and 17, respectively, p= .0001) and a higher satisfaction score when compared with the combined GI-MD groups (mean 5.9 ± 13.81 and 8.6 ± 16.11, respectively, p= .042; visual analog scale 0–100 mm, “0” = completely satisfied, “100” = completely dissatisfied). There were no immediate complications reported in any group. The properly trained GI-NP in our study performed screening colonoscopy as safely, accurately, and satisfactorily as the GI-MDs. Using well-trained NPs for screening colonoscopy can be an effective strategy to increase access to colorectal screening.

We present a spectroscopic analysis of white dwarfs found in the Kiso survey. Spectroscopic observations at high signal-to-noise ratio have been obtained for all DA and DB stars in the Kiso Schmidt ultraviolet excess survey (KUV stars). These observations led to the reclassification of several KUV objects, including the discovery of three unresolved DA+DB double-degenerate binaries. The atmospheric parameters (T eff and log g) are obtained from detailed model atmosphere fits to optical spectroscopic data. The mass distribution of our sample is characterized by a mean value of 0.606 M and a dispersion of 0.135 M for DA stars, and 0.758 M and a dispersion of 0.192 M for DB stars. Absolute visual magnitudes obtained from our spectroscopic fits allow us to derive an improved luminosity function for the DA and DB stars identified in the Kiso survey. Our luminosity function is found to be significantly different from earlier estimates based on empirical photometric calibrations of MV for the same sample. The results for the DA stars now appear entirely consistent with those obtained for the PG survey using the same spectroscopic approach. The space density for DA stars with MV [?] 12.75 is 2.80 x 10-4 pc-3 in the Kiso survey, which is 9.6% smaller than the value found in the PG survey. The completeness of both surveys is briefly discussed.

It is unclear whether pregnancy is a trigger or accelerant for idiopathic pulmonary arterial hypertension (PAH). Alternatively, its frequency close to the onset of symptoms and diagnosis in the idiopathic PAH population may represent a coincidence in a disease that predominates in young women. We describe a carrier of a BMPR2gene mutation who had an uneventful first pregnancy but had aggressive PAH during her second pregnancy and now has ongoing heritable PAH. The possible role of pregnancy as a trigger in this vulnerable patient is discussed. Databases of patients with heritable PAH should be explored to see whether pregnancy is related to overt manifestation of the disease.

Several letters to the editor are presented in response to articles in previous issues, including "How to Raise a South Dakotan" in the January/February 2016 issue, "Custer Stayed West" in the March/April 2016 issue and "Boe's Legacy" in the March/April 2016 issue.

The electrochemical reduction of phenylazide or phenylacetylene diazonium salts leads to the grafting of azido or ethynyl groups onto the surface of carbon electrodes. In the presence of copper(I) catalyst, these azide‐ or alkyne‐modified surfaces react efficiently and rapidly with compounds bearing an acetylene or azide function, thus forming a covalent 1,2,3‐triazole linkage by means of click chemistry. This was illustrated with the surface coupling of ferrocenes functionalized with an ethynyl or azido group and the biomolecule biotin terminated by an acetylene group.

The formation of a dense monolayer of histidine‐tagged recombinant laccase on gold electrodes by using a short thiol‐NTA linker is described, as well as a kinetic analysis of the process by cyclic voltammetry. From a detailed analysis of the catalytic reduction of dioxygen by laccase in the presence of a one‐electron redox mediator it can be concluded that the immobilized enzyme remains as active as in homogeneous solution.

The catalytic responses obtained with step-by-step neutravidin-biotin deposition of successive monolayers of HRP are analyzed by means of cyclic voltammetry. The theoretical tools that have been developed allowed full characterization of the multilayered HRP coatings by means of a combination between closed-form analysis of limiting behaviors and finite difference numerical computations. An analysis of the experiments in which the number of monolayers was extended to 16 allowed an approximate determination of the average thickness of each monolayer, pointing to a compact arrangement of neutravidin and biotinylated HRP. The piling up of so many monolayers on the electrode allowed an improvement of the catalytic current by a factor of ca. 10, leading to very good sensitivities in term of cosubstrate detection.

Very small amounts of various vanadium or iron substituted Heteropoly acids (HPA) are strongly adsorbed on to commercial XC-72R based carbon gas diffusion electrodes. The electrochemical activity of these adsorbed HPA for both the hydrogen oxidation reaction and the oxygen reduction reaction is investigated as non-platinum electro-catalysts and it is shown that these materials have a moderate activity at the extremely low doping levels achieved. On the cathode rearrangement of the precursor HPA induced by moderate heating (vanadium) or cycling the fuel cell in the absence of oxygen (iron) occurs to give a more active electro-catalyst. The HPA studied are also proposed for use in CO tolerant anodes and as mixed electronic/protonic conductors in platinized fuel cell electrodes.

After showing the failure of conventional gold-enhancement procedures to amplify the gold nanoparticle-based electrochemical transduction of DNA hybridization in polystyrene microwells, a new efficient protocol was developed and evaluated for the sensitive quantification of a 35 base-pair human cytomegalovirus nucleic acid target (tDNA). In this assay, the hybridization of the target adsorbed on the bottom of microwells with an oligonucleotide-modified Au nanoparticle detection probe (pDNA-Au) was monitored by the anodic stripping detection of the chemically oxidized gold label at a screen-printed microband electrode (SPMBE). Thanks to the combination of the sensitive AuIIIdetermination at a SPMBE with the large amount of AuIIIreleased from each pDNA-Au, picomolar detection limits of tDNA can be achieved. Further enhancement of the hybridization signal based on the autocatalytic reductive deposition of ionic gold (AuIII) on the surface of the gold nanoparticle labels anchored on the hybrids was first envisaged by incubating the commonly used mixture of AuIIIand hydroxylamine (NH2OH). However, due to a considerable nonspecific current response of poor reproducibility it was not possible to significantly improve the analytical performances of the method under these conditions. Complementary transmission electronic microscopy experiments indicated the loss of most of the grown gold labels during the post-enlargement rinsing step. To circumvent this drawback, a polymeric solute containing polyethyleneglycol and sodium chloride was introduced in the growth media to act as an aggregating agent during the catalytic process and thus retain the enlarged labels on the bottom of the microwell. This strategy, which led to an efficient increase of the hybridization response, allowed detection of tDNA concentrations as low as 600 aM (i.e., 104lower than without amplification), and thus offers great promise for ultrasensitive detection of other hybridization events.

Polylactides (PLA) have been known for several decades and are recently of considerable commercial significance. However, the literature on basic chain properties and solution characterization is divided and inconsistent. In this study, a comprehensive and well‐controlled set of experiments is combined with rigorous quantitative analysis to resolve existing apparent contradictions. Homopolymers and copolymers spanning wide ranges of molecular weight and stereoisomer proportions were prepared by ring‐opening polymerizations of L‐ and D‐lactides using stannous octanoate as the catalyst. Samples were characterized by means of: (1) dilute‐solution viscometry in three different solvents; (2) size exclusion chromatography in tetrahydrofuran (THF) with light scattering detection; (3) static multiangle light scattering in a mixed acetonitrile–dichloromethane solvent; (4) variable‐angle spectroscopic ellipsometry; and (5) melt rheology. The data imply that PLA are typical linear flexible polymers; unperturbed PLA chain dimensions are describable in terms of a characteristic ratio of 6.5 ± 0.9, regardless of stereoisomer content. The Schulz‐Blaschke and Mark‐Houwink constants for dilute PLA solutions in chloroform and in THF are determined. For chloroform at 30°C, the correct values are kSB = 0.302, K = 0.0131 (mL/g), and a = 0.759, while for THF at 30°C, the correct values are kSB = 0.289, K = 0.0174 (mL/g), and a = 0.736. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3100–3111, 2005

A growing body of evidence indicates that people with autism frequently experience sleep disorders and exhibit atypical sleep architecture. In order to establish whether sleep disorders truly belong to the autism spectrum disorder (ASD) phenotype, we conducted a subjective and objective study of sleep in a group of high-functioning adults with ASD but without sleep complaints, psychiatric disorders or neurological comorbidity. We compared the subjective data of 27 ASD participants with those of 78 healthy controls matched for chronological age and gender. Subjective measures of sleep in the clinical group were compatible with insomnia and/or a tolerable phase advance of the sleep–wake cycle. Subjective data were confirmed by objective laboratory sleep recordings in a subset of 16 patients and 16 controls. Persons with autism presented with a longer sleep latency (P < 0.04), more frequent nocturnal awakenings (P < 0.03), lower sleep efficiency (P < 0.03), increased duration of stage 1 sleep (P < 0.02), decreased non-REM sleep (stages 2 + 3 + 4, P < 0.04) and slow-wave sleep (stages 3 + 4, P < 0.05), fewer stage 2 EEG sleep spindles (P < 0.004), and a lower number of rapid eye movements during REM sleep (P < 0.006) than did control participants. On clinical scales, the scores of persons with ASD on the Beck Depression Inventory were similar to those of persons without, but their trait anxiety scores on the Spielberger Anxiety Scale were higher (P < 0.02). The state anxiety scores of the Spielberger scale and cortisol levels were the same in the two groups. Objective total sleep time correlated negatively with the Social (−0.52, P < 0.05) and Communication (−0.54, P < 0.02) scales of the Autism Diagnostic Interview—Revised. The sleep of clinical subgroups (10 with high-functioning autism, six with Asperger syndrome) did not differ, except for the presence of fewer EEG sleep spindles in the Asperger syndrome subgroup (P < 0.05). In conclusion, these findings indicate that atypicalities of sleep constitute a salient feature of the adult ASD phenotype and this should be further investigated in younger patients. Moreover, the results are consistent with an atypical organization of neural networks subserving the macro- and microstructure of sleep in ASD. We are furthering this research with quantified analysis of sleep EEG.

In this work, monolayers of metal complexes were covalently attached to the surface of carbon electrodes with the goal of binding monolayers of histidine-tagged proteins with a controlled molecular orientation and a maintained biological activity. In this novel method, which is simple, versatile, and efficient, the covalent attachment was accomplished in a single step by the electrochemical reduction of aryl diazonium ions that were substituted with a nitrilotriacetic (NTA) or an imminodiacetic (IDA) ligand at the para position. The transient aryl radicals that were generated in the reduction were grafted to the surfaces of glassy carbon, highly oriented pyrolitic graphite, and graphite-based screen-printed electrodes, producing dense monolayers of the ligands. The NTA- and IDA-modified electrodes were shown to efficiently chelate Cu(II) and Ni(II) ions. The presence of the metal was established using X-ray photoelectron spectroscopy and electrochemistry. Surface coverages of the ligands were indirectly determined from the electroactivity of the copper(II) complex formed on the electrode surface. Studies on the effect of electrodeposition time and potential showed that, at sufficiently negative potentials, the surface coverage reached a saturating value in less than 2 min of electrodeposition time, which corresponds to the formation of a close-packed monolayer of ligand on the electrode surface. Once loaded with a metal ion, the modified electrode was able to bind specifically to histidine-tagged proteins such as the horseradish peroxidase (His-HRP) or to an enhanced, recombinant green-fluorescent protein via its N-terminal hexahistidine tail. In the case of His-HRP, the amount of active enzyme specifically immobilized by metal-chelating binding was determined from the analysis of electrocatalytic currents using cyclic voltammetry. The electrochemical grafting makes it possible to accurately controlled and electronically address the amount of deposited ligand on the conductive surfaces of carbon electrodes with any size and shape.

Within the framework of environmental studies regarding radioactive waste management, the speciation of M3+f-elements in concentrated carbonate solutions was investigated. Solubility measurements of NaEu(CO3)2·5H2O(s) were performed at 23 ± 1 °C under fixed [Na+], by using NaClO4. In 3 mol l−1Na+aqueous solutions, the limiting complex Eu(CO3)33−was identified in the range 0.01 < [CO32−] < 2 mol l−1; experimental solubilities were modelled with the equilibrium: NaEu(CO3)2·5H2O(s) + CO32− Na++ Eu(CO3)33−+ 5H2O, and the logarithm of the corresponding equilibrium constant was found to be logKs,3= −4.2 ± 0.2. To interpret the measurements at different [Na+], the activity coefficients of the species were calculated with the SIT formula. Time-resolved laser-induced fluorescence spectroscopy was used to verify the presence of a single complex of Eu(iii) in aqueous solutions. From fluorescence lifetime measurements in 1 mol l−1Na2CO3solutions in H2O–D2O mixtures, it was determined that about two water molecules remained in the first coordination sphere of Eu(CO3)33−. From a critical review of literature data and sensitivity analysis, it was concluded that solubility results should be more reliable than solvent extraction and spectroscopic results in determining the stoichiometry of limiting carbonate complexes. Tricarbonate complexes of most M3+f-elements appeared to be the limiting stable species in Na+aqueous solutions, except for Ce(iii), for which a tetracarbonate complex was indeed observed. Interestingly, supporting electrolytes based on K+can favour tetracarbonate complexes at high ionic strength. Available values of thermodynamic constants related to various ionic media are compared on the basis of the SIT formula.