Adaptation of sea turtles to climate warming: Will phenological responses be sufficient to counteract changes in reproductive output?

Sea turtles are vulnerable to climate change since their reproductive output is influenced by incubating temperatures, with warmer temperatures causing lower hatching success and increased feminization of embryos. Their ability to cope with projected increases in ambient temperatures will depend on their capacity to adapt to shifts in climatic regimes. Here, we assessed the extent to which phenological shifts could mitigate impacts from increases in ambient temperatures (from 1.5 to 3°C in air temperatures and from 1.4 to 2.3°C in sea surface temperatures by 2100 at our sites) on four species of sea turtles, under a "middle of the road" scenario (SSP2-4.5). Sand temperatures at sea turtle nesting sites are projected to increase from 0.58 to 4.17°C by 2100 and expected shifts in nesting of 26-43 days earlier will not be sufficient to maintain current incubation temperatures at 7 (29%) of our sites, hatching success rates at 10 (42%) of our sites, with current trends in hatchling sex ratio being able to be maintained at half of the sites. We also calculated the phenological shifts that would be required (both backward for an earlier shift in nesting and forward for a later shift) to keep up with present-day incubation temperatures, hatching success rates, and sex ratios. The required shifts backward in nesting for incubation temperatures ranged from -20 to -191 days, whereas the required shifts forward ranged from +54 to +180 days. However, for half of the sites, no matter the shift the median incubation temperature will always be warmer than the 75th percentile of current ranges. Given that phenological shifts will not be able to ameliorate predicted changes in temperature, hatching success and sex ratio at most sites, turtles may need to use other adaptive responses and/or there is the need to enhance sea turtle resilience to climate warming.

Enhancing chlamydospore production in Duddingtonia flagrans on solid substrate: The impact of mannitol and varied cultivation conditions.

Duddingtonia flagrans is a nematophagous fungus which has shown promising results as a non-chemical parasitic control tool. The fungus disrupts the parasite's life cycle by trapping larvae in the environment through the networks generated from chlamydospores, thus preventing the reinfection of animals. One barrier to the development of a commercial product using this tool is the need to increase chlamydospore production in the laboratory for its administration to livestock. The purpose of this study was to evaluate the addition of mannitol to an enriched culture medium and the effect of adverse cultivation conditions on chlamydospore production. D. flagrans was cultivated on Petri dishes with corn agar for 4 weeks at 27 °C and 70% relative humidity (RH). Four groups were then formed, all with Sabouraud agar as a base, to which different growth inducers were added: GSA (glucose Sabouraud agar), GSA-MI (glucose Sabouraud agar + meso inositol), GSA-E (enriched glucose Sabouraud agar), and AE-M (enriched agar + mannitol). After 4 weeks, chlamydospores were recovered by washing the surface of each plate with distilled water and then quantified. The medium that yielded the highest amount of chlamydospores was subjected to different cultivation conditions: NC (normal conditions): 70% RH and 27 °C, AC (adverse conditions) 1: 20% RH and 40 °C, CA2: 60% RH and 27 °C, and CA3: 55% RH and 24 °C. It was determined that mannitol increases chlamydospore production (65x106 chlamydospores/plate), and when reducing humidity by 10% under cultivation conditions it resulted in an approximately 10% increase in chlamydospore production compared to the control group. These results suggest that the addition of polyols, as well as its cultivation under certain environmental conditions, can improve chlamydospore production on a laboratory scale.

Low levels of miR-143-3p are associated with severe chronic rhinosinusitis with nasal polyps.

microRNAs (miRNAs) are small, single-stranded, non-coding RNA molecules that regulate post-transcriptional gene expression. Accumulating evidence suggests their involvement in regulating various biological and pathological processes, including inflammation. Studies have revealed distinct expression patterns of miRNAs in Chronic Rhinosinusitis with (CRSwNP) and without (CRSsNP) nasal polyps (1). Specifically, miR-155 and miR-21 have been observed to be upregulated in CRSwNP, increasing and attenuating the expression of pro-inflammatory cytokines, respectively (2,3). Conversely, the downregulation of miR-34, miR-449, and members of the miR-200 family has been associated with impaired ciliogenesis and the regulation of epithelial-mesenchymal transition, respectively (4,5). Nonetheless, the direct role of miRNAs in CRSwNP is still being investigated.

Effect of an additional bonding resin on the 5-year performance of a universal adhesive: a randomized clinical trial.

OBJECTIVES: To evaluate the effect of the application of an additional hydrophobic bonding resin on the clinical performance of a universal adhesive applied in etch-and-rinse (ER) or self-etch adhesive (SE) strategy in non-carious cervical lesions (NCCLs) after 5 years. MATERIALS AND METHODS: Scotchbond Universal Adhesive (3M Oral Care) was applied in 134 NCCLs of 39 subjects using different adhesion approaches: 3-step ER (3-ER), 2-step ER (2-ER), 2-step SE (2-SE), and 1-step SE (1-SE). Enamel and dentin were acid etched prior to application of the universal adhesive for the 3-ER and 2-ER groups. An extra layer of a hydrophobic bonding resin was applied for groups 3-ER and 2-SE. All lesions were restored with Filtek Supreme XTE resin composite (3M Oral Care). Restorations were evaluated at baseline and at 5 years using the modified USPHS criteria. Mann-Whitney U and Wilcoxon tests were performed, and the survival rates (retention/fracture) were analyzed using Kaplan-Meier and log-rank tests (p < 0.05). RESULTS: The recall rate was 66.7% at 5 years. The cumulative survival rate was 96.9% for 3-ER, 96.8% for 2-ER, 71.4% for 2-SE, and 81.3% for 1-SE strategies. The log-rank test was statistically significant (p = 0.006). Retention rates were 100% for both ER groups, 75% for 2-SE and 81.3% for 1-SE. At 5 years, 2- and 1-SE approaches showed similar retention rates, but lower than those for 3- and 2-ER. A significant decrease in retention rate was detected for 2-SE (p = 0.007) and 1-SE (p = 0.014) groups between baseline and 5 years. All groups, except 2-ER, showed an increase in marginal discoloration. For this parameter, significant differences were detected between 2-ER and 1-SE (p = 0.004). CONCLUSIONS: The addition of a hydrophobic bonding resin to the recommended application sequence of Scotchbond Universal Adhesive did not improve its clinical performance in NCCLs after 5 years. Higher retention rates were measured when this adhesive was applied in ER mode. TRIAL REGISTRATION: This manuscript is a 5-year follow-up of a randomized clinical trial that started in 2012 when there was no strong recommendation for registration in clinicaltrials.gov. The results after 36 months of clinical service were previously published in this journal.

Rubric vs. numeric rating scale: agreement among evaluators on endodontic treatments performed by dental students.

BACKGROUND: Students´ assessment should be carried out in an effective and objective manner, which reduces the possibility of different evaluators giving different scores, thus influencing the qualification obtained and the consistency of education. The aim of the present study was to determine the agreement among four evaluators and compare the overall scores awarded when assessing portfolios of endodontic preclinical treatments performed by dental students by using an analytic rubric and a numeric rating scale. METHODS: A random sample of 42 portfolios performed by fourth-year dental students at preclinical endodontic practices were blindly assessed by four evaluators using two different evaluation methods: an analytic rubric specifically designed and a numeric rating scale. Six categories were analyzed: radiographic assessment, access preparation, shaping procedure, obturation, content of the portfolio, and presentation of the portfolio. The maximum global score was 10 points. The overall scores obtained with both methods from each evaluator were compared by Student's t, while agreement among evaluators was measured by Intraclass correlation coefficients (ICC). The influence of the difficulty of the endodontic treatment on the evaluators´ scores was analyzed by one-way ANOVA. Statistical tests were performed at a pre-set alpha of 0.05 using Stata 16. RESULTS: Difficulty of canal treatment did not influence the scores of evaluators, irrespective of the evaluation method used. When the analytic rubric was used, inter-evaluator agreement was substantial for radiographic assessment, access preparation, shaping procedure, obturation, and overall scores. Inter-evaluator agreement ranged from moderate to fair with the numeric rating scale. Mean higher overall scores were achieved when numeric rating scale was used. Presentation and content of the portfolio showed slight and fair agreement, respectively, among evaluators, regardless the evaluation method applied. CONCLUSIONS: Assessment guided by an analytic rubric allowed evaluators to reach higher levels of agreement than those obtained when using a numeric rating scale. However, the rubric negatively affected overall scores.

Application of the Midi Parasep® SF technique for the detection of L1 larvae of Angiostrongylus cantonensis in faeces of infected rats.

We investigated parasitic zoonoses caused by protozoans and helminths in urban and peri-urban rat populations (Rattus norvegicus and R. rattus) in Spanish cities. Rats were trapped and then dissected to remove adult helminths, and the contents of the large intestine were retrieved for the study of parasitic forms. The Midi Parasep® solvent free (SF) technique was used to concentrate the parasites in the intestinal contents. Some of the rats studied (n = 8) were infected by the rat lungworm, Angiostongylus cantonensis, whose first stage larvae (L1) are shed in rat faeces. After the concentration technique, L1 larvae were found in the sediment of 6 of the 8 positive rats. The two negative sediment samples were due to the presence of either only adult females or, in addition to males, only young females in the lungs of the rats. In view of our results, Midi Parasep® SF turned out to be a simple, rapid, inexpensive, and sensitive method to detect nematode larvae, such as the L1 larvae of A. cantonensis (or A. costaricensis), in natural and experimentally infected rats.

Oral cancer knowledge in adults evaluated through a phone survey in the context of the SARS-CoV2 health emergency in Colombia.

BACKGROUND: in Colombia, oral cancer is the eighth most common type of cancer, with an estimated survival rate of 52%. Lack of knowledge about oral cancer and its risk factors is associated with late detection. MATERIAL AND METHODS: a descriptive cross-sectional study was carried out on 268 patients attending the School of Dentistry of the University of Antioquia clinics, to whom a validated 47-question questionnaire was applied by phone during the COVID-19 pandemic (2020 and 2021). Data were analyzed using the SPSS software. RESULTS: the mean age was 58.9. 58.6% of the participants had heard of oral cancer, 42% acquire knowledge from the media, and 96.7% considered screening necessary. Most of the patients expressed not feeling worried (54.5%), fearful (59.7%), or anxious (56.3%) in the case of being submitted to an examination for early detection of oral cancer. A correlation between low socioeconomic status and educational level with less knowledge of oral cancer was found. The dimensions of experience and attitude towards screening were not associated with sociodemographic variables. CONCLUSIONS: There is little knowledge about oral cancer, especially in low socioeconomic and educational status, although this does not occur in the dimensions of attitude and experience toward screening. In contrast, patients participating in this study presented high knowledge about oral cancer risk. This population recognizes the situations most related to the development of cancer. This level of knowledge was similar for the demographic conditions except for people with no education, who presented less knowledge of the risks. The need for educational campaigns on oral cancer knowledge is reaffirmed, especially in socially disadvantaged groups, considering that there would be no barriers related to screening.

Bioavailability of once-daily tacrolimus formulations used in clinical practice in the management of De Novo kidney transplant recipients: the better study.

Multicenter, prospective, observational study to compare the relative bioavailability of once-daily tacrolimus formulations in de novo kidney transplant recipients. De novo kidney transplant recipients who started a tacrolimus-based regimen were included 14 days post-transplant and followed up for 6 months. Data from 218 participants were evaluated: 129 in the LCPT group (Envarsus) and 89 in the PR-Tac (Advagraf) group. Patients in the LCPT group exhibited higher relative bioavailability (Cmin /total daily dose [TDD]) vs. PR-Tac (61% increase; P < .001) with similar Cmin and 30% lower TDD levels (P < .0001). The incidence of treatment failure was 3.9% in the LCPT group and 9.0% in the PR-Tac group (P = .117). Study discontinuation rates were 6.2% in the LCPT group and 12.4% in the PR-Tac group (P = .113). Adverse events, renal function and other complications were comparable between groups. The median accumulated dose of tacrolimus in the LCPT group from day 14 to month 6 was 889 mg. Compared to PR-Tac, LCPT showed higher relative bioavailability, similar effectiveness at preventing allograft rejection, comparable effect on renal function, safety, adherence, treatment failure and premature discontinuation rates.

Characterizing Determinants of Near-Road Ambient Air Quality for an Urban Intersection and a Freeway Site.

INTRODUCTION: Near-road ambient air pollution concentrations that are affected by vehicle emissions are typically characterized by substantial spatial variability with respect to distance from the roadway and temporal variability based on the time of day, day of week, and season. The goal of this work is to identify variables that explain either temporal or spatial variability based on case studies for a freeway site and an urban intersection site. The key hypothesis is that dispersion modeling of near-road pollutant concentrations could be improved by adding estimates or indices for site-specific explanatory variables, particularly related to traffic. Based on case studies for a freeway site and an urban intersection site, the specific aims of this project are to (1) develop and test regression models that explain variability in traffic-related air pollutant (TRAP) ambient concentration at two near-roadway locations; (2) develop and test refined proxies for land use, traffic, emissions and dispersion; and (3) prioritize inputs according to their ability to explain variability in ambient concentrations to help focus efforts for future data collection and model development.The key pollutants that are the key focus of this work include nitrogen oxides (NOx), carbon monoxide (CO), black carbon (BC), fine particulate matter (PM2.5; PM ≤ 2.5 µm in aerodynamic diameter), ultrafine particles (UFPs; PM ≤ 0.1 µm in aerodynamic diameter), and ozone (O3). NOx, CO, and BC are tracers of vehicle emissions and dispersion. PM2.5 is influenced by vehicle table emissions and regional sources. UFPs are sensitive to primary vehicle emissions. Secondary particles can form near roadways and on regional scales, influencing both PM2.5 and UFP concentrations. O3 concentrations are influenced by interaction with NOx near the roadway. Nitrogen dioxide (NO2), CO, PM2.5, and O3 are regulated under the National Ambient Air Quality Standards (NAAQS) because of demonstrated health effects. BC and UFPs are of concern for their potential health effects. Therefore, these pollutants are the focus of this work. METHODS: The methodological approach includes case studies for which variables are identified and assesses their ability to explain either temporal or spatial variability in pollutant ambient concentrations. The case studies include one freeway location and one urban intersection. The case studies address (1) temporal variability at a fixed monitor 10 meters from a freeway; (2) downwind concentrations perpendicular to the same location; (3) variability in 24-hour average pollutant concentrations at five sites near an urban intersection; and (4) spatiotemporal variability along a walking path near that same intersection.The study boundary encompasses key factors in the continuum from vehicle emissions to near-road exposure concentrations. These factors include land use, transportation infrastructure and traffic control, vehicle mix, vehicle (traffic) flow, on-road emissions, meteorology, transport and evolution (transformation) of primary emissions, and production of secondary pollutants, and their resulting impact on measured concentrations in the near-road environment. We conducted field measurements of land use, traffic, vehicle emissions, and near-road ambient concentrations in the vicinity of two newly installed fixed-site monitors. One is a monitoring station jointly operated by the U.S. Environmental Protection Agency (U.S. EPA) and the North Carolina Department of Environmental Quality (NC DEQ) on I-40 between Airport Boulevard and I-540 in Wake County, North Carolina. The other is a fixed-site monitor for measuring PM2.5 at the North Carolina Central University (NCCU) campus on E. Lawson Street in Durham, North Carolina. We refer to these two locations as the freeway site and the urban site, respectively. We developed statistical models for the freeway and urban sites. RESULTS: We quantified land use metrics at each site, such as distances to the nearest bus stop. For the freeway site, we quantified lane-by-lane total vehicle count, heavy vehicle (HV) count, and several vehicle-activity indices that account for distance from each lane to the roadside monitor. For the urban site, we quantified vehicle counts for all 12 turning movements through the intersection. At each site, we measured microscale vehicle tailpipe emissions using a portable emission measurement system.At the freeway site, we measured the spatial gradient of NOx, BC, UFPs, and PM, quantified particle size distributions at selected distances from the roadway and assessed partitioning of particles as a function of evolving volatility. We also quantified fleet-average emission factors for several pollutants.At the urban site, we measured daily average concentrations of nitric oxide (NO), NOx, O3, and PM2.5 at five sites surrounding the intersection of interest; we also measured high resolution (1-second to 10-second averages) concentrations of O3, PM2.5, and UFPs along a pedestrian transect. At both sites, the Research LINE-source (R-LINE) dispersion model was applied to predict concentration gradients based on the physical dispersion of pollution.Statistical models were developed for each site for selected pollutants. With variables for local wind direction, heavy-vehicle index, temperature, and day type, the multiple coefficient of determination (R2) was 0.61 for hourly NOx concentrations at the freeway site. An interaction effect of the dispersion model and a real-time traffic index contributed only 24% of the response variance for NOx at the freeway site. Local wind direction, measured near the road, was typically more important than wind direction measured some distance away, and vehicle-activity metrics directly related to actual real-time traffic were important. At the urban site, variability in pollutant concentrations measured for a pedestrian walk-along route was explained primarily by real-time traffic metrics, meteorology, time of day, season, and real-world vehicle tailpipe emissions, depending on the pollutant. The regression models explained most of the variance in measured concentrations for BC, PM, UFPs, NO, and NOx at the freeway site and for UFPs and O3 at the urban site pedestrian transect. CONCLUSIONS: Among the set of candidate explanatory variables, typically only a few were needed to explain most of the variability in observed ambient concentrations. At the freeway site, the concentration gradients perpendicular to the road were influenced by dilution, season, time of day, and whether the pollutant underwent chemical or physical transformations. The explanatory variables that were useful in explaining temporal variability in measured ambient concentrations, as well as spatial variability at the urban site, were typically localized real-time traffic-volume indices and local wind direction. However, the specific set of useful explanatory variables was site, context (e.g., next to road, quadrants around an intersection, pedestrian transects), and pollutant specific. Among the most novel of the indicators, variability in real-time measured tailpipe exhaust emissions was found to help explain variability in pedestrian transect UFP concentrations. UFP particle counts were very sensitive to real-time traffic indicators at both the freeway and urban sites. Localized site-specific data on traffic and meteorology contributed to explaining variability in ambient concentrations. HV traffic influenced near-road air quality at the freeway site more so than at the urban site. The statistical models typically explained most of the observed variability but were relatively simple. The results here are site-specific and not generalizable, but they are illustrative that near-road air quality can be highly sensitive to localized real-time indicators of traffic and meteorology.

A review on role of solar photovoltaic (PV) modules in enhancing sustainable water production capacity of solar distillation units.

Sustainable production of potable water is one of the United Nations sustainable development goals set for 2030. Among available renewable energy resources, solar energy is abundantly available in most of the fresh water scarce rural and remote locations. Moreover, solar distillation units and solar photovoltaic (PV) modules have been acknowledged as suitable candidates for addressing rising fresh water and electricity demands in these regions. In recent years, researchers have proposed a number of novel hybrid solar distillation units where the solar PV modules are integrated with solar thermal distillation units in different ways to harvest both electric power and potable water. In this work, a detailed review highlighting the classification, working principle, performance and features of these novel hybrid units have been carried out. In most of these hybrid units, integration is highly beneficial for solar thermal distillation units rather than for PV modules. Direct utilization of PV module as absorber, condenser and reflector in solar stills has few drawbacks. However, indirect utilization like utilizing electric power and waste heat energy recovered from PV module in distillation units has posed significant distillate yield enhancement up to 300.0%. In some cases, the integrated PV module has even generated sufficient power for carrying out essential domestic activities. Integrated PV module's performance has also improved significantly in few studies but the magnitude of improvement has not been disclosed clearly in most of the studies as more focus has been given to distillation units rather than PV modules. However, these novel hybrid configurations have not been fully explored & optimized and their techno-enviro-economic aspects have not yet been disclosed in these available precious literatures and they are still available as a potential research gap.

Performance of the SolWat system operating in static mode vs. dynamic for wastewater treatment: Power generation and obtaining reclaimed water.

Two hybrid SolWat systems operating in static (without flow circulation) versus dynamic (with flow circulation) mode were simultaneously compared. This work aims to demonstrate the viability of SolWat in dynamic mode to: a) adapt to the operation of the WWTP with a continuous flow, in which the wastewater flows continuously for treatment, b) treat a larger volume of water in the system and c) increase the cooling of the PV modules thanks to the cooling of the temperature of the water sample to improve the energy efficiency in the system. Real secondary wastewater effluents from wastewater treatment plants were used, using solar energy for water disinfection and photovoltaic energy production, in order to use the SolWat systems and implement it as a tertiary treatment. A total of five experiments were performed during autumn, winter, spring and summer. Solar disinfection of Escherichia coli, Enterococcus faecalis and Clostridium perfringens was assessed, and physicochemical parameters were also analysed. The UV dose received by the SolWat systems was the same, but not for the microorganisms in the water sample. The static SolWat irradiated a particle (microorganism) for 4 h, while the dynamic SolWat irradiated intermittently, so the latter system received a shorter UV exposure time, and therefore a lower UV dose. Results indicated that, although the microorganisms did not obtain the absolute bacterial inactivation during the SODIS treatment in any SolWat system, adequate inactivation levels were achieved to allow the reuse of the water for various uses (Royal Decree 1620/2007, Regulation (EU) 2020/741), although to a lesser extent for SolWat in dynamic mode, which treated twice the volume of water and reached cooler temperatures. C. perfringens proved to be the most resistant bacterium tested. The total photovoltaic energy production in the dynamic mode system was more energy efficient than the static mode, being even more efficient than the single PV reference system during the spring (3.5%) and summer (2.7%) test, due to the compensating effect by the cooling of the water on the photovoltaic module against the losses caused by radiation.

Oral microbiome and systemic antineoplastics in cancer treatment: A systematic review.

BACKGROUND: Oral mucositis is one of the most common side effects in cancer patients receiving systemic antineoplastics. However, the underlying biological mechanisms leading to this condition are still unclear. For this reason, it has been hypothesised that systemic antineoplastics may cause an imbalance on the oral microbiota that subsequently triggers oral mucosa damage. MATERIAL AND METHODS: A systematic review was performed following the PRISMA protocol and the PICO question established was: patients diagnosed with cancer, who are candidates for receiving systemic antineoplastics (P=Patients), that undergo oral microbiome determinations (I=Intervention), before and after systemic antineoplastics administration (C=Comparison), to analyse changes in the oral microbiome composition (O=Outcome). The bibliographic search was carried out in PubMed and other scientific repositories. RESULTS: Out of 166 obtained articles, only 5 met eligibility criteria. Acute myeloid leukaemia (AML) was the most frequent type of cancer (40 %) among the participants. Only one of the studies included a control group of healthy subjects. Heterogeneity in the protocols and approaches of the included studies hindered a detailed comparison of the outcomes. However, it was stated that a decrease in bacteria α diversity is often associated with oral mucositis. On the other hand, fungal diversity was not associated with oral mucositis although α diversity was lower at baseline on patients developing oral candidiasis. CONCLUSIONS: There is insufficient scientific evidence of oral microbiological changes in patients undergoing systemic antineoplastics. Further investigations ought to be carried out to identify microorganisms that might play a key role in the pathogenesis of oral mucosa damage in patients undergoing systemic antineoplastics.

Partnering a Three-Coordinate Gallium Cation with a Hydroborate Counter-Ion for the Catalytic Hydrosilylation of CO2.

A novel ß-diketiminate stabilized gallium hydride, (Dipp L)Ga(Ad)H (where (Dipp L)={HC(MeCDippN)2 }, Dipp=2,6-diisopropylphenyl and Ad=1-adamantyl), has been synthesized and shown to undergo insertion of carbon dioxide into the Ga-H bond under mild conditions. In this case, treatment of the resulting κ1 -formate complex with triethylsilane does not lead to regeneration of the hydride precursor. However, when combined with B(C6 F5 )3 , (Dipp L)Ga(Ad)H catalyses the reductive hydrosilylation of CO2 . Under stoichiometric conditions, the addition of one equivalent of B(C6 F5 )3 to (Dipp L)Ga(Ad)H leads to the formation of a 3-coordinate cationic gallane complex, partnered with a hydroborate anion, [(Dipp L)Ga(Ad)][HB(C6 F5 )3 ]. This complex rapidly hydrometallates carbon dioxide and catalyses the selective reduction of CO2 to the formaldehyde oxidation level at 60 °C in the presence of Et3 SiH (yielding H2 C(OSiEt3 )2 ). When catalysis is undertaken in the presence of excess B(C6 F5 )3 , appreciable enhancement of activity is observed, with a corresponding reduction in selectivity: the product distribution includes H2 C(OSiEt3 )2 , CH4 and O(SiEt3 )2 . While this system represents proof-of-concept in CO2 hydrosilylation by a gallium hydride system, the TOF values obtained are relatively modest (max. 10 h-1 ). This is attributed to the strength of binding of the formatoborate anion to the gallium centre in the catalytic intermediate (Dipp L)Ga(Ad){OC(H)OB(C6 F5 )3 }, and the correspondingly slow rate of the turnover-limiting hydrosilylation step. In turn, this strength of binding can be related to the relatively high Lewis acidity measured for the [(Dipp L)Ga(Ad)]+ cation (AN=69.8).

Dietary patterns are related to cognitive functioning in elderly enriched with individuals at increased risk for Alzheimer's disease.

PURPOSE: To investigate cross-sectional associations between dietary patterns and cognitive functioning in elderly free of dementia. METHODS: Data of 389 participants from the German DELCODE study (52% female, 69 ± 6 years, mean Mini Mental State Score 29 ± 1) were included. The sample was enriched with elderly at increased risk for Alzheimer's disease (AD) by including participants with subjective cognitive decline, mild cognitive impairment (MCI) and siblings of AD patients. Mediterranean and MIND diets were derived from 148 Food Frequency Questionnaire items, and data-driven patterns by principal component analysis (PCA) of 39 food groups. Associations between dietary patterns and five cognitive domain scores were analyzed with linear regression analyses adjusted for demographics (model 1), and additionally for energy intake, BMI, other lifestyle variables and APOe4-status (model 2). For PCA-derived dietary components, final model 3 included all other dietary components. RESULTS: In fully adjusted models, adherence to Mediterranean and MIND diet was associated with better memory. The 'alcoholic beverages' PCA component was positively associated with most cognitive domains. Exclusion of MCI subjects (n = 60) revealed that Mediterranean and MIND diet were also related to language functions; associations with the alcoholic beverages component were attenuated, but most remained significant. CONCLUSION: In line with data from elderly population samples, Mediterranean and MIND diet and some data-derived dietary patterns were related to memory and language function. Longitudinal data are needed to draw conclusions on the putative effect of nutrition on the rate of cognitive decline, and on the potential of dietary interventions in groups at increased risk for AD.

Approaching a "Naked" Boryl Anion: Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes.

Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3 Si)2 N}M{B(NDippCH)2 }(thf)n (M=Ca, n=2; M=Sr, n=3), through the reactions of the corresponding bis(amides), M{N(SiMe3 )2 }2 (thf)2 , with (thf)2 Li- {B(NDippCH)2 }. Most notably, this approach can also be applied to the analogous potassium amide K{N(SiMe3 )2 }, leading to the formation of the solvent-free borylpotassium dimer [K{B(NDippCH)2 }]2 , which is stable in the solid state at room temperature for extended periods (48 h). A dimeric structure has been determined crystallographically in which the K+ cations interact weakly with both the ipso-carbons of the flanking Dipp groups and the boron centres of the diazaborolyl heterocycles, with K⋅⋅⋅B distances of >3.1 Å. These structural features, together with atoms in molecules (QTAIM) calculations imply that the boron-containing fragment closely approaches a limiting description as a "free" boryl anion in the condensed phase.

Copper-Catalyzed Dehydrogenative Amidation of Light Alkanes.

The functionalization of C-H bonds in light alkanes, particularly to form C-N bonds, remains a challenge. We report the dehydrogenative coupling of amides with C1-C4 hydrocarbons to form N-alkyl amide products with tBuOOtBu as oxidant, and a copper complex of a phenanthroline-type ligand as catalyst. The reactions occurred in good yields in benzene or supercritical carbon dioxide as solvents. This strategy allowed for the determination of the relative reactivity of these alkane C-H bonds toward this amination process and showed, in contrast to prior work with larger alkanes, that the reactivity correlated with bond dissociation energies.

Walking in pregnancy and prevention of insomnia in third trimester using pedometers: study protocol of Walking_Preg project (WPP). A randomized controlled trial.

BACKGROUND: Previous studies in pregnancy have not focused in evaluating the effect of walking during pregnancy and prevention of insomnia. Our general objective is to determine the effect of a walking program in preventing the appearance of insomnia in the third trimester of pregnancy, increasing sleep quality and improving quality of life throughout pregnancy. METHODS: Randomized Controlled trial in parallel in healthy sedentary pregnant women (n = 265), Walking_Preg Project (WPP), from university hospital in Granada, Spain. At 12th gestational week (GW), they will be invited to participate and randomly assigned to one of the three arms of study: the intervention group I1 (pedometer, goal of 11,000 steps/day), intervention group I2 (pedometer, no goal) and control (no pedometer). Duration of intervention: 13-32 GW. At 12th, 19th and 31st GW the average steps/day will be measured in groups I1 and I2. At 13th, 20th and 32nd GW, Athens Insomnia Scale (AIS), Pittsburgh Sleep Quality Index (PSQI), Adherence to Mediterranean Diet (AMD), physical activity (short IPAQ), quality of life (PSI), and consumption of toxic substances (caffeine, illegal drugs, alcohol and tobacco) will be collected. Student t test or Mann-Whitney U will be used to compare 19th and 31st GW mean of daily steps between I1 and I2 groups. To compare differences between groups in terms of frequency of insomnia/quality of life for each trimester of pregnancy, Pearson's Chi-square test or Fisher's exact test will be used. To determine differences in hours of sleep and quality of sleep throughout each trimester of pregnancy, analysis of variance or Friedman test will be used. McNemar-Bowker test will be used to assess differences in life quality in pre-post analyses in the 3 arms. We will use Stata 15 statistical software. DISCUSSION: promoting walking in second half of pregnancy through use of pedometer and health pre-registration of a goal to be achieved -'10,000-11,000 steps a day'- should prevent appearance of insomnia in third trimester, will increase sleep quality and quality of life in pregnant women. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT03735381 . Registered 8th November, 2018.

An Acid-Free Anionic Oxoborane Isoelectronic with Carbonyl: Facile Access and Transfer of a Terminal B═O Double Bond.

We disclose the synthesis and structural characterization of the first acid-free anionic oxoborane, [K(2.2.2-crypt)][(HCDippN)2BO] (1) (Dipp = 2,6- iPr2C6H3), which is isoelectronic with classical carbonyl compounds. 1 can readily be accessed from its borinic acid by a simple deprotonation/sequestration sequence. Crystallographic and density functional theory (DFT) analyses support the presence of a polarized terminal B═O double bond. Subsequent π bond metathesis converts the B═O bond to a heavier B═S containing system, affording the first anionic thioxoborane [K(2.2.2-crypt)][(HCDippN)2BS] (2), isoelectronic with thiocarbonyls. Facile B═O bond cleavage can also be achieved to access B-H and B-Cl bonds and, via a remarkable oxide (O2-) ion abstraction, to generate a borenium cation [(HCDippN)2B(NC5H5)][OTf] (4). By extension, 1 can act as an oxide transfer agent to organic substrates, a synthetic role traditionally associated with transition-metal compounds. Hence we show that B-O linkages, which are often considered to be thermodynamic sinks, can be activated under mild conditions toward bond cleavage and transfer, by exploiting the higher reactivity inherent in the B═O double bond.

Suspended LRSPP for the development of highly integrated active plasmonic devices.

We present a novel long-range surface plasmon polariton (LRSPP) device consisting of a suspended dielectric matrix in which an electrically active, millimeter-long metallic waveguide is embedded. We show that, by opening an air gap under the lower cladding, the influence of the substrate is suppressed and the symmetry of the thermo-optical distribution around the LRSPP waveguide is preserved over extended ranges of applied electrical current with minimal optical losses. Experimental results show that, compared to a standard nonsuspended structure, our device allows either the induction of a phase change that is three times larger, for a fixed electrical power, or, equivalently, a scaling down of the device to one-tenth of its original length, for a fixed phase change.

Borylated N-Heterocyclic Carbenes: Rearrangement and Chemical Trapping.

This study details attempts to access N-heterocyclic carbenes (NHCs) featuring the diazaborolyl group, {(HCNDipp)2 B}, as one or both of the N-bound substituents, to generate strongly electron-donating and sterically imposing new carbene ligands. Attempts to isolate N-heterocyclic carbenes based around imidazolylidene or related heterocycles, are characterized by facile N-to-C migration of the boryl substituent. In the cases of imidazolium precursors bearing one N-bound diazaborolyl group and one methyl substituent, deprotonation leads to the generation of the target carbenes, which can be characterized in situ by NMR measurements, and trapped by reactions with metal fragments and elemental selenium. The half-lives of the free carbenes at room temperature range from 4-50 h (depending on the pattern of ancillary substituents) with N-to-C2 migration of the boryl function being shown to be the predominant rearrangement pathway. Kinetic studies show this to be a first-order process that occurs with an entropy of activation close to zero. DFT calculations imply that an intramolecular 1,2-shift is mechanistically feasible, with calculated activation energies of the order of 90-100 kJ mol-1 , reflecting the retention of significant aromatic character in the imidazole ring in the transition state. Trapping of the carbene allows for evaluation of steric and electronic properties through systems of the type LAuCl, LRh(CO)2 Cl, and LSe. A highly unsymmetrical (but nonetheless bulky) steric profile and moderately enhanced σ-donor capabilities (compared with IMes) are revealed.