Characterization of CO Adsorbed to Clean and Partially Oxidized Cu(211) and Cu(111).

Copper-based catalysts gain activity through the presence of poorly coordinated Cu atoms and incomplete oxidation at the surface. The catalytic mechanisms can in principle be observed by controlled dosing of reactants to single-crystal substrates. However, the interconnected influences of surface defects, partial oxidation, and adsorbate coverage present a large matrix of conditions that have not been fully explored in the literature. We recently characterized oxygen and carbon monoxide coadsorption on Cu(111), a nominally defect-free surface, and now extend our study to the stepped surface Cu(211). Temperature-programmed desorption of CO adsorbed to bare metal surfaces confirms that two sites dominate desorption from a saturated layer: atop terrace atoms of local (111) character and atop step edge atoms with CO bound more strongly to the latter. At low coverage, discrete CO resonances in reflection adsorption infrared spectra can be assigned to these sites: 2077 cm-1 for extended (111) terraces, 2093 cm-1 for step sites, and additional kink-adsorbed molecules at 2110 cm-1. With increasing coverage, in contrast to Cu(111), the infrared spectral features on Cu(211) evolve and shift as a consequence of dipole-dipole coupling between differentially occupied types of sites. Auger electron spectroscopy shows that exposure to background O2 oxidizes the (211) surface at a rate nearly 1 order of magnitude greater than (111); we argue that the resulting surface is stoichiometric Cu2O, as previously found for Cu(111). This oxide binds CO less strongly than the bare metal and the underlying crystal cut continues to influence the adsorption sites available to CO. On oxidized (111) terraces, broad absorption peaks at 2115-2120 cm-1; on oxidized Cu(211), CO adsorbed to step sites appears as a resolved secondary peak at 2144 cm-1. This suite of spectroscopic signatures, obtained under carefully controlled conditions, will help to determine the origin and fate of adsorbed species in future studies of reaction mechanisms on copper.

Muscle strength is reduced in children with pulmonary arterial hypertension.

Muscle strength is decreased in adults with pulmonary arterial hypertension (PAH). We aim to investigate muscle strength in children with PAH in relation to a cohort of healthy children, and investigate correlations with disease severity markers. This prospective study included children with PAH aged 4-18 years, who visited the Dutch National Referral Center for Pulmonary Hypertension in Childhood between October 2015 and March 2016. Muscle strength was assessed using handgrip strength and maximum voluntary isometric contractility (MVIC) of four peripheral muscles. Dynamic muscle function was evaluated with the Bruininks-Oseretsky test of motor proficiency (BOT-2). These measurements were compared with those in two cohorts of healthy children and correlated with 6-minute walk distance (6MWD), World Health Organization functional class (WHO-FC), N-terminal pro-brain natriuretic peptide (NT-proBNP), and time since diagnosis. Eighteen children with PAH aged 14.0 [interquartile range: 9.9-16.0] years showed reduced muscle strength. Handgrip strength z-score -2.4 ± 1.2, p < 0.001, total MVIC z-score -2.9 ± 1.2, p < 0.001, and BOT-2 z-score -1.0 ± 0.9, p < 0.001. 6MWD (67 ± 11% predicted) correlated with most muscle measurements (r = 0.49-0.71, p = 0.001). Dynamic muscle function (BOT-2) differed between WHO-FC, whereas handgrip strength and MVIC did not. NT-proBNP and time since diagnosis did not show significant correlations with muscle strength measurements. Muscle strength was significantly reduced in children with PAH and correlated with 6MWD, but not with disease severity markers WHO-FC and NT-pro-BNP. The nature of this reduced muscle strength is yet unclear, but its occurrence in children with seemingly mild or well-controlled PAH supports the concept of PAH being a systemic syndrome involving peripheral skeletal muscles.

Decreased Muscle Strength in Children With Repaired Tetralogy of Fallot: Relation With Exercise Capacity.

Background The aim of this study is to describe muscle strength in pediatric patients with repaired tetralogy of Fallot compared with healthy peers and to analyze the correlation between muscle strength and peak oxygen uptake, exercise capacity (mL/min). Methods and Results A prospective, cross-sectional study was carried out in the University Medical Center Groningen between March 2016 and December 2019, which included 8 -to-19-year-old patients with repaired tetralogy of Fallot. Exclusion criteria comprised the following: Down syndrome, unstable pulmonary disease and severe scoliosis affecting pulmonary function, neuromuscular disease, and mental or physical limitations that prohibit the execution of the functional tests. Muscle strength was compared with 2 healthy pediatric cohorts from the Northern Netherlands. Handgrip strength, maximal voluntary isometric contraction, and dynamic muscle strength in correlation with peak oxygen uptake, exercise capacity (mL/min) were the main outcomes of the study. The 67 patients with repaired tetralogy of Fallot (42% female; aged 12.9 [interquartile range, 10.0-16.3] years old) were compared with healthy children. The patients showed reduced grip strength (z-score [mean±SD] -1.5±1.2, P<0.001), and total muscle strength (z-score -0.9±1.3, P<0.001). Dynamic strength (Bruininks-Oseretsky test) was significantly reduced (z-score -0.3±0.8, P=0.001), but running, speed, and agility were normal (z-score 0.1±0.7, P=0.4). Univariate correlation analyses showed strong correlations between absolute peak oxygen uptake, exercise capacity (mL/min), and muscle strength (grip strength r=0.83, total muscle strength r=0.88; P<0.001). In multivariate analyses, including correction for age and sex, total muscle strength (B 0.3; P=0.009), and forced vital capacity (B 0.5; P=0.02) correlated with peak oxygen uptake, exercise capacity (mL/min), independent of conventional cardiovascular parameters. Conclusions Children with repaired tetralogy of Fallot show reduced muscle strength, which strongly correlated with their exercise performance.

Changes in body size and body composition in survivors of childhood cancer: seven years follow-up of a prospective cohort study.

BACKGROUND & AIMS: Cancer treatment is known to have impact on nutritional status, and both underweight and overweight have been reported in several studies in survivors. A limitation of most studies is that they relied on retrospective data or were limited to a subgroup of patients. The current study aims to describe changes in body size and body composition prospectively seven years after diagnosis in a heterogeneous sample of childhood cancer survivors and to evaluate associated factors. METHODS: The study population consisted of children diagnosed with hematological, solid and brain malignancies aged 0-18 years at diagnosis. Data of body size, body composition, and associated factors were collected at diagnosis, one year and seven years after diagnosis. RESULTS: In the total cohort mean BMI z-score increased during treatment. In children with hematological and brain malignancies BMI z-score continued to increase after end of treatment leading to quadrupling of the prevalence of obesity seven years after diagnosis. BMI at diagnosis (ß = -0.34, P = 0.007) and maternal BMI (ß = 0.25, P = 0.046) were associated with the increase in BMI z-score. Mean fat mass (FM) z-score, already high at diagnosis, increased during treatment in children with hematological and brain malignancies and evened out during follow-up. Changes in FM z-score were predicted by type of malignancy (hematologic malignancy versus solid tumor ß = 0.48, P = 0.008; brain tumor versus solid tumor ß = 0.45, P = 0.012). Mean fat free mass (FFM) z-scores started low at diagnosis, particularly in patients with brain tumors, increased during treatment in patients with solid and brain malignancies, though decreased in children with hematological malignancies. At 7 years follow-up a clear increase to normal was seen. Age at diagnosis (ß = 0.43, P = 0.004) and initial FFM (ß = -0.49, P = 0.001) were found to be significant predictors for changes in FFM z-scores. CONCLUSIONS: The finding that the once obtained extra weight and FM during treatment persisted after termination of treatment in children with hematological and brain malignancies, stresses the importance to create awareness about the risk of developing overweight in children during cancer treatment.

RAIRS Characterization of CO and O Coadsorption on Cu(111).

In a study preliminary to investigating CO2 dissociation, we report our results on oxygen and carbon monoxide coadsorption on Cu(111). We use reflection adsorption infrared spectroscopy and Auger electron spectroscopy to characterize and quantify adsorbed species. On clean Cu(111), the CO internal stretch mode appears initially at 2077 cm-1 for a surface temperature of ∼80 K. We accurately reproduce the previously determined redshift of the absorption band with increasing CO coverage. We subsequently oxidize the surface by exposure to O2 at 300 K to ensure O2 dissociation. The band's frequency and line shape of subsequently adsorbed CO at ∼80 K are not affected. However, the maximum absorbance and integrated peak intensities drop with increasing O coverage. The data suggest that CO is not adsorbed near O, likely as a consequence of the mechanism of Cu(111) surface oxidation by O2 at 300 K. We discuss whether our RAIRS results may be used to quantify CO2 dissociation in the zero-coverage limit.

The first use of olives in Africa around 100,000 years ago.

The olive tree was an iconic plant for most of the past Mediterranean civilizations, for which it had important economic value. Here we report the earliest use of fruits and wood from olive trees in Africa so far, around 100,000 years ago. These findings suggest the presence of olive trees on the Atlantic coast of Morocco during most of the last glacial period, and the use of olives by the early Homo sapiens for fuel management and most probably for consumption.

Cell Death Signaling From Endoplasmic Reticulum Stress: Plant-Specific and Conserved Features.

The endoplasmic reticulum (ER) stress response is triggered by any condition that disrupts protein folding and promotes the accumulation of unfolded proteins in the lumen of the organelle. In eukaryotic cells, the evolutionarily conserved unfolded protein response is activated to clear unfolded proteins and restore ER homeostasis. The recovery from ER stress is accomplished by decreasing protein translation and loading into the organelle, increasing the ER protein processing capacity and ER-associated protein degradation activity. However, if the ER stress persists and cannot be reversed, the chronically prolonged stress leads to cellular dysfunction that activates cell death signaling as an ultimate attempt to survive. Accumulating evidence implicates ER stress-induced cell death signaling pathways as significant contributors for stress adaptation in plants, making modulators of ER stress pathways potentially attractive targets for stress tolerance engineering. Here, we summarize recent advances in understanding plant-specific molecular mechanisms that elicit cell death signaling from ER stress. We also highlight the conserved features of ER stress-induced cell death signaling in plants shared by eukaryotic cells.

Task-induced subjective fatigue and resting-state striatal connectivity following traumatic brain injury.

BACKGROUND: People with traumatic brain injury (TBI) often experience fatigue, but an understanding of the neural underpinnings of fatigue following TBI is still lacking. This study used resting-state functional magnetic resonance imaging (rs-fMRI) to examine associations between functional connectivity (FC) changes and task-induced changes in subjective fatigue in people with moderate-severe TBI. METHODS: Sixteen people with moderate-severe TBI and 17 matched healthy controls (HC) performed an adaptive N-back task (working memory task) to induce cognitive fatigue. Before and after the task they rated their state fatigue level and underwent rs-fMRI. Seed-to-voxel analyses with seeds in areas involved in cognitive fatigue, namely the striatum and default mode network (DMN) including, medial prefrontal cortex and posterior cingulate cortex, were performed. RESULTS: The adaptive N-back task was effective in inducing fatigue in both groups. Subjective task-induced fatigue was positively associated with FC between striatum and precuneus in people with TBI, while there was a negative association in HC. In contrast, subjective task-induced fatigue was negatively associated with FC between striatum and cerebellum in the TBI group, while there was no association in HC. Similar associations between task-induced subjective fatigue and DMN FC were found across the groups. CONCLUSIONS: Our results suggest that the subjective experience of fatigue was linked to DMN connectivity in both groups and was differently associated with striatal connectivity in people with moderate-severe TBI compared to HC. Defining fatigue-induced neuronal network changes is pertinent to the development of treatments that target abnormal neuronal activity after TBI.

[Urinary bladder microbiome analysis and probiotic treatment options for women with recurrent urinary tract infections]. / Mikrobiomanalyse der Harnblase und probiotische Therapieoptionen bei Frauen mit rezidivierenden Harnwegsinfektionen.

Novel preventive measures and therapeutic approaches are needed to reduce the frequency of recurrent urinary tract infections (rUTI) and the associated emergence of multidrug-resistant uropathogens. The aim of this review is to systematically present the available evidence on the urinary bladder microbiome of healthy women and those with rUTIs. In addition, relevant studies on the efficacy of probiotics in rUTIs are presented in a structured manner. This will provide an overview on the current state of research and an outlook on treatment strategies beyond the usual antimicrobial options.

Physical and Psychosocial Health in Pediatric Uveitis Patients.

BACKGROUND: To investigate the possible associations between childhood noninfectious uveitis and cardio-respiratory fitness, physical activity, health related quality of life and fatigue. METHODS: Cross-sectional analysis of 23 patients with noninfectious uveitis, aged 8-18 years. BMI, exercise capacity, muscle strength and physical activity were measured. Health-related quality of life and fatigue were assessed. The results were compared to standardized values for age matched healthy children. RESULTS: Twenty-three patients were included. Children with uveitis had a higher bodyweight and body mass index. Children with uveitis had lower cardio-respiratory fitness and they were less physically active, but they experienced a normal quality of life and normal fatigue. Parents of children with uveitis reported a lower quality of life and more fatigue for their children than parents of healthy children. CONCLUSION: Our study indicates that children with noninfectious uveitis are at risk of developing lower physical and psychosocial health.

Behavioral consequences of the downstream products of ethanol metabolism involved in alcohol use disorder.

Research concerning Alcohol Use Disorder (AUD) has previously focused primarily on either the behavioral or chemical consequences experienced following ethanol intake, but these areas of research have rarely been considered in tandem. Compared with other drugs of abuse, ethanol has been shown to have a unique metabolic pathway once it enters the body, which leads to the formation of downstream metabolites which can go on to form biologically active products. These metabolites can mediate a variety of behavioral responses that are commonly observed with AUD, such as ethanol intake, reinforcement, and vulnerability to relapse. The following review considers the preclinical and chemical research implicating these downstream products in AUD and proposes a chemobehavioral model of AUD.

Impact of new operational dosimetric quantities on individual monitoring services.

The new operational dosimetric quantities framework, proposed in the ICRU95 report, has stimulated the scientific community to start investigations that aim to assess its impact on radiation protection practices. As part of this effort, the present study describes an inter-comparison exercise among individual monitoring services (IMSs) on passive whole-body dosimetry. The inter-comparison is performed in terms of both the existing operational dose quantityHp(10)and its proposed replacementHp, to allow an evaluation of the actions that may be necessary to adapt dosimetry systems to the proposed quantity. For two of the tested IMSs, simple modifications to the detector response function, or the dose calculation algorithm, were sufficient to obtain results within acceptable limits. However, these approaches are not sufficient to give a level of performance comparable to that achieved in terms ofHp(10). This may require a modification to dosemeter design.

GmNAC81 Inversely Modulates Leaf Senescence and Drought Tolerance.

Glycine max NAC81 (GmNAC81) is a downstream effector of the DCD/NRP-mediated cell death signaling, which interacts with GmNAC30 to fully induce the caspase 1-like vacuolar processing enzyme (VPE) expression, the executioner of the cell death program. GmNAC81 has been previously shown to positively modulate leaf senescence via the NRP/GmNAC81/VPE signaling module. Here, we examined the transcriptome induced by GmNAC81 overexpression and leaf senescence and showed that GmNAC81 further modulates leaf senescence by regulating an extensive repertoire of functionally characterized senescence-associated genes (SAGs). Because the NRP/GmNAC81/VPE signaling circuit also relays stress-induced cell death signals, we examined the effect of GmNAC81 overexpression in drought responses. Enhanced GmNAC81 expression in the transgenic lines increased sensitivity to water deprivation. Under progressive drought, the GmNAC81-overexpressing lines displayed severe leaf wilting, a larger and faster decline in leaf Ψw, relative water content (RWC), photosynthesis rate, stomatal conductance, and transpiration rate, in addition to higher Ci/Ca and lower Fm/Fv ratios compared to the BR16 control line. Collectively, these results indicate that the photosynthetic activity and apparatus were more affected by drought in the transgenic lines. Consistent with hypersensitivity to drought, chlorophyll loss, and lipid peroxidation were higher in the GmNAC81-overexpressing lines than in BR16 under dehydration. In addition to inducing VPE expression, GmNAC81 overexpression uncovered the regulation of typical drought-responsive genes. In particular, key regulators and effectors of ABA signaling were suppressed by GmNAC81 overexpression. These results suggest that GmNAC81 may negatively control drought tolerance not only via VPE activation but also via suppression of ABA signaling.

Motor development in children 0-2 years pre- and post-LTX, a prospective study.

To determine prospectively gross and fine motor development of children <2 years of age, who undergo LTX. In this prospective study, children aged <2 years who undergo LTX were tested using the motor scale of the Bayley Scales of infant and toddler development, 3rd edition Dutch version. Testing was done during screening pre- and post-LTX: at the time of hospital discharge (2-6 weeks), at 3 months, 6 months, and 1 year. Z-scores were calculated. Twenty-nine children participated in this study, 14 boys, median age 6 months, at screening for LTX. Gross motor skills were delayed pre-LTX (Z-score -1.3). Fine motor skills were normal (Z-score 0.3). Immediately post-LTX, both skills reduced, and at 1 year post-LTX, gross motor skills Z-score was -1.0 and fine motor skills Z-score 0.0. Both gross and fine motor skills Z-scores decline post-LTX and tend to recover after 1 year, gross motor skills to low normal and fine motor skills to normal levels. Monitoring of gross motor development and attention on stimulating gross motor development post-LTX remains important, to enable participation in physical activity and sport for health benefits later in life.

Physical activity and aerobic fitness in children after liver transplantation.

To determine physical activity (PA), aerobic fitness, muscle strength, health-related quality of life (HRQOL), fatigue, and participation in children after liver transplantation. Children, 6-12 years, at least one year after liver transplantation, participated in this cross-sectional study. Measurements: Time spent in moderate to vigorous PA (MVPA) was measured using an accelerometer, and aerobic fitness (VO2 peak ) was measured by cardiopulmonary exercise testing. Muscle strength was measured by hand-held dynamometry. Fatigue was measured using the multidimensional fatigue scale, and HRQOL with the Pediatric Quality of life Core scales and leisure activities was measured using the Children's Assessment of Participation and Enjoyment. Outcomes (medians and interquartile range (IQR)) were compared to norm values. Twenty-six children participated in this study (14 boys, age 9.7 years, IQR 7.7;11.4). Children spent 0.8 hours/d (IQR 0.6;1.1) on MVPA. One child met the recommendation of at least 1 hour of MVPA every day of the week. Aerobic fitness was similar to norms (VO2 peak 1.4 L/min , IQR 1.1;1.7, Z-score -0.3). Z-scores of muscle strength ranged between -1.4 and -0.4 and HRQOL and fatigue between -2.3 and -0.4. Participation was similar to published norms (Z-scores between -0.6 and 0.6). Young children after liver transplantation have similar MVPA patterns and aerobic fitness compared to published norms. Despite lower HRQOL, more fatigue, and less muscle strength, these children have similar participation in daily activities. Although children do well, it remains important to stimulate PA in children after liver transplantation in the context of long-term management.

Dutch juvenile idiopathic arthritis patients, carers and clinicians create a research agenda together following the James Lind Alliance method: a study protocol.

BACKGROUND: Research on Juvenile Idiopathic Arthritis (JIA) should support patients, caregivers/parents (carers) and clinicians to make important decisions in the consulting room and eventually to improve the lives of patients with JIA. Thus far these end-users of JIA-research have rarely been involved in the prioritisation of future research. MAIN BODY: Dutch organisations of patients, carers and clinicians will collaboratively develop a research agenda for JIA, following the James Lind Alliance (JLA) methodology. In a 'Priority Setting Partnership' (PSP), they will gradually establish a top 10 list of the most important unanswered research questions for JIA. In this process the input from clinicians, patients and their carers will be equally valued. Additionally, focus groups will be organised to involve young people with JIA. The involvement of all contributors will be monitored and evaluated. In this manner, the project will contribute to the growing body of literature on how to involve young people in agenda setting in a meaningful way. CONCLUSION: A JIA research agenda established through the JLA method and thus co-created by patients, carers and clinicians will inform researchers and research funders about the most important research questions for JIA. This will lead to research that really matters.

Holocene evolution of Portus Pisanus, the lost harbour of Pisa.

The ancient harbour of Pisa, Portus Pisanus, was one of Italy's most influential seaports for many centuries. Nonetheless, very little is known about its oldest harbour and the relationships between environmental evolution and the main stages of harbour history. The port complex that ensured Pisa's position as an economic and maritime power progressively shifted westwards by coastal progradation, before the maritime port of Livorno was built in the late 16th century AD. The lost port is, however, described in the early 5th century AD as being "a large, naturally sheltered embayment" that hosted merchant vessels, suggesting an important maritime structure with significant artificial infrastructure to reach the city. Despite its importance, the geographical location of the harbour complex remains controversial and its environmental evolution is unclear. To fill this knowledge gap and furnish accurate palaeoenvironmental information on Portus Pisanus, we used bio- and geosciences. Based on stratigraphic data, the area's relative sea-level history, and long-term environmental dynamics, we established that at ~200 BC, a naturally protected lagoon developed and hosted Portus Pisanus until the 5th century AD. The decline of the protected lagoon started at ~1350 AD and culminated ~1500 AD, after which time the basin was a coastal lake.

Revisiting the Soybean GmNAC Superfamily.

The NAC (NAM, ATAF, and CUC) genes encode transcription factors involved with the control of plant morph-physiology and stress responses. The release of the last soybean (Glycine max) genome assembly (Wm82.a2.v1) raised the possibility that new NAC genes would be present in the soybean genome. Here, we interrogated the last version of the soybean genome against a conserved NAC domain structure. Our analysis identified 32 putative novel NAC genes, updating the superfamily to 180 gene members. We also organized the genes in 15 phylogenetic subfamilies, which showed a perfect correlation among sequence conservation, expression profile, and function of orthologous Arabidopsis thaliana genes and NAC soybean genes. To validate our in silico analyses, we monitored the stress-mediated gene expression profiles of eight new NAC-genes by qRT-PCR and monitored the GmNAC senescence-associated genes by RNA-seq. Among ER stress, osmotic stress and salicylic acid treatment, all the novel tested GmNAC genes responded to at least one type of stress, displaying a complex expression profile under different kinetics and extension of the response. Furthermore, we showed that 40% of the GmNACs were differentially regulated by natural leaf senescence, including eight (8) newly identified GmNACs. The developmental and stress-responsive expression profiles of the novel NAC genes fitted perfectly with their phylogenetic subfamily. Finally, we examined two uncharacterized senescence-associated proteins, GmNAC065 and GmNAC085, and a novel, previously unidentified, NAC protein, GmNAC177, and showed that they are nuclear localized, and except for GmNAC065, they display transactivation activity in yeast. Consistent with a role in leaf senescence, transient expression of GmNAC065 and GmNAC085 induces the appearance of hallmarks of leaf senescence, including chlorophyll loss, leaf yellowing, lipid peroxidation and accumulation of H2O2. GmNAC177 was clustered to an uncharacterized subfamily but in close proximity to the TIP subfamily. Accordingly, it was rapidly induced by ER stress and by salicylic acid under late kinetic response and promoted cell death in planta. Collectively, our data further substantiated the notion that the GmNAC genes display functional and expression profiles consistent with their phylogenetic relatedness and established a complete framework of the soybean NAC superfamily as a foundation for future analyses.

The ICRU Proposal for New Operational Quantities for External Radiation.

Report Committee 26 of the ICRU proposes a set of operational quantities for radiation protection for external radiation, directly based on effective dose and for an extended range of particles and energies. It is accompanied by quantities for estimating deterministic effects to the eye lens and the local skin. The operational quantities are designed to overcome the conceptual and technical shortcomings of those presently in use. This paper describes the proposed operational quantities, and highlights the improvements with respect to the present, legal monitoring quantities.