Atomically precise copper(
i
) nanoclusters (CuNCs) with high photoluminescence (PL) efficiency and a relatively short lifetime could be promising non-precious metal-based phosphorescent emitters for ...organic light-emitting diodes (OLEDs), but the synthesis of such CuNCs still remains a great challenge. Herein, we have prepared a parallelepiped-like and green emissive atomically precise
Cu
10
alkynyl cluster with a moderate PLQY of 35% and lifetime (
τ
av
) of 8.4 μs. Interestingly, upon addition of hexane to a DCM solution of
Cu
10
, it turns into an hourglass-like, orange emissive
Cu
18
cluster with an enhanced PL efficiency (PLQY = 63%, and
τ
av
= 2.8 μs) at room temperature, which is rarely achieved in high-nuclearity alkynyl-protected CuNCs. Experiments and theoretical calculations suggested that the excellent PL performance of
Cu
18
is due to reduced nonradiative transition, a larger d orbital contribution of Cu ions, an enhanced transition dipole moment and reduced HOMO-LUMO gap. This work will not only pave a novel approach for constructing alkynyl-protected CuNCs with a high PLQY and short lifetime, which might be explored for other CuNCs for fabricating high-performance OLEDs, but also shed light on the structure-luminescence relationship.
Atomically precise alkynyl-protected copper(
i
) nanoclusters (CuNCs) have been prepared, and they exhibit high phosphorescence quantum yield, short lifetime, and fast radiative decay rate, which are rarely observed in atomically precise CuNCs.
•The present study addresses sources of error affecting the validity of mobile-based dietary assessments in a free-living setting.•A two-stage data modification process that included manual data ...cleaning and reanalyzing of prepackaged foods improved the accuracy of an image-assisted mobile nutrition app.•Stage 1 errors were commonly observed and associated with wrong food code selections, portion size estimates, misreporting, and missing condiments.•Stage 2 errors related to the mobile nutrition app were associated with prepackaged and restaurant/street foods that only provide limited micronutrient information.•Reanalyzing food codes with missing nutrients substantially improved the accuracy of micronutrient intake levels and enhanced correlations between the app and 24-h dietary recall.•Results highlight the importance of addressing errors in mobile-based dietary assessments and continually updating and expanding prepackaged food databases with full nutrient information.
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Mobile nutrition applications (apps) provide a simple way for individuals to record their diet, but the validity and inherent errors need to be carefully evaluated. The aim of this study was to assess the validity and clarify the sources of measurement errors of image-assisted mobile nutrition apps.
This was a cross-sectional study with 98 students recruited from School of Nutrition and Health Sciences, Taipei Medical University. A 3-d nutrient intake record by Formosa Food and Nutrient Recording App (FoodApp) was compared with a 24-h dietary recall (24-HDR). A two-stage data modification process, manual data cleaning, and reanalyzing of prepackaged foods were employed to address inherent errors. Nutrient intake levels obtained by the two methods were compared with the recommended daily intake (DRI), Taiwan. Paired t test, Spearman's correlation coefficients, and Bland–Altman plots were used to assess agreement between the FoodApp and 24-HDR.
Manual data cleaning identified 166 food coding errors (12%; stage 1), and 426 food codes with missing micronutrients (32%) were reanalyzed (stage 2). Positive linear trends were observed for total energy and micronutrient intake (all Ptrend < 0.05) after the two stages of data modification, but not for dietary fat, carbohydrates, or vitamin D. There were no statistical differences in mean energy and macronutrient intake between the FoodApp and 24-HDR, and this agreement was confirmed by Bland–Altman plots. Spearman's correlation analyses showed strong to moderate correlations (r = 0.834 ∼ 0.386) between the two methods. Participants’ nutrient intake tended to be lower than the DRI, but no differences in proportions of adequacy/inadequacy for DRI values were observed between the two methods.
Mitigating errors significantly improved the accuracy of the Formosa FoodApp, indicating its validity and reliability as a self-reporting mobile-based dietary assessment tool. Dietitians and health professionals should be mindful of potential errors associated with self-reporting nutrition apps, and manual data cleaning is vital to obtain reliable nutrient intake data.
A fluorescence–phosphorescence dual-emissive Cu3pyrazolate3 (Cu3Pz3) complex is reported here, whose ligand is a product of Diels–Alder cycloaddition between a simple anthrylpyrazole and ...N-phenylmaleimide. In contrast to the green-fluorescent Cu3Pz3 complex with the anthrylpyrazolate, the dual-emissive complex exhibits a switching between blue fluorescence and orange or red phosphorescence by modulating excitation energies or temperatures, although the intermolecular Cu–Cu distance (2.953 Å at 100 K) is remarkably shorter than those of most of the phosphorescent Cu(i) cyclic trinuclear complexes (CTCs). Based on theoretical investigations, the origins of distinct luminescence behaviors of these two complexes have been clarified as the different contributions from ligand-based orbitals in the frontier orbitals of the complexes, leading to the ligand-based fluorescence of both complexes and the metal-sensitized ligand-localized phosphorescence of the dual-emissive complex. Finally, an anticounterfeiting code and a luminescent molecular thermometer have been simply fabricated utilizing the dual-emissive Cu(i) complex. Therefore, Diels–Alder cycloaddition can be a convenient and feasible way to functionalize a given pyrazole ligand for enriching the luminescence behaviors of Cu3Pz3 complexes, which usually demonstrate yellow-to-red phosphorescence.
•Diurnal temperature fluctuations mitigate the heat stress on the coral host.•The holobionts adopt different strategies in response to temperature fluctuations.•Acinetobacter and Rhodobacteraceae are ...identified as coral heat stress indicators.
Corals and their associated microbiota form a “holobiont,” which includes symbiotic algae and other associated microbiota dominated by bacteria. The composition of holobiont is influenced by various environmental factors, such as increasing sea water temperatures. Previous studies of the effects of temperature changes on coral physiology and associated bacterial communities have been conducted based on stable water temperatures set by mean temperatures, or by slowly increasing/decreasing temperatures. However, the daily temperature fluctuations that corals experience in nature are not stable. The current understanding of the effects of large daily temperature fluctuations on coral and associated bacterial community dynamics is limited. Hence, we conducted a four-week tank experiment using different large daily temperature fluctuations (±5 °C and ±7 °C) accompanied by continuous warming conditions (26 °C to 29 °C) to investigate the effects on two common reef-building corals, Stylophora pistillata and Pocillopora acuta. During the experiment, the activity of coral host catalase and superoxide dismutase were measured, the photosynthetic ability of symbiotic algae was recorded, and the variation in bacterial communities was analyzed using the V6-V8 region of 16S rDNA. According to the results, different parts of the holobionts of two coral species exhibited varying response rates to the continuous warming conditions and diurnal temperature fluctuations. Additionally, it was found that diurnal temperature fluctuations may mitigate the heat stress on the host and reduce the changes in bacterial response to warming. Therefore, it is suggested that the holobionts of different coral species may adopt different adaptation and survival strategies in response to diurnal temperature fluctuations and warming. Finally, based on the response of these two coral species under the conditions of diurnal temperature fluctuations and continuous warming, Acinetobacter and Rhodobacteraceae were identified as potential indicator coral-associated bacteria. This is the first study to investigate the tripartite dynamic response of coral, symbiotic algae and bacteria to daily temperature fluctuations.
Assimilable organic carbon (AOC) serves as an indicator of the biostability of drinking water distribution systems; however, the properties of the released organic metabolites by Pseudomonas ...fluorescens (P17) and Spirillum (NOX) used in AOC bioassays are seldom discussed. In this study, fluorescence excitation emission matrix (FEEM) was selected to characterize organic metabolites after substrate biotransformation and their divergences at different growth stages of both strains in AOC bioassay. Excellent correlation between ATP and colony-forming units (CFUs) was observed for both strains. The concentration of ATP per colony was six times higher in the P17 strain than in the NOX strain. A retarding phenomenon was observed for the NOX strain in the presence of high acetate-C content (100–150 μg acetate-C/L). The fluorescence wavelength peaks were wider for the protein-like substance released by the P17 strain than for those released by the NOX strain. However, fluorescent fulvic-like substances only existed in the NOX strain. Relative humus accumulation (RHA), the ratio of protein-like fluorescence intensity to humus-like fluorescence intensity, decreased in the P17 strain but substantially increased in the NOX strain in the logarithmic growth phase. RHA showed a descending trend for the P17 strain as compared to that of the NOX strain during the progress from logarithmic to stationary growth phase at three different acetate-C concentrations; however, the opposite was observed at 100 μg acetate-C/L, indicating that high acetate-C content may affect the properties of released organic matter from both strains.
•Retarding phenomena were observed in NOX strain at high acetate concentration.•Wider range of protein-like substances from P17 strain than NOX strain were found.•Fulvic acid-like substances was only observed in NOX strain.•Both strains grown in high acetate-C may affect the released organic properties.•Organic distributions were opposite in the logarithmic phase for both strains.
Summary
A systematic review and meta‐analysis was conducted to evaluate the relative effectiveness of different dietary macronutrient patterns on changes in resting energy expenditure (REE) in ...relation to weight loss, categorized as minimal (<5%) and moderate to high (>5%). Changes in REE were assessed using a DerSimonian and Laird random‐effects meta‐analysis. A diet lower in carbohydrates (CHO) or higher in fat and protein was associated with smaller reductions in REE, with these trends being more pronounced among participants who experienced moderate to high weight loss. Adjusted meta‐regression analysis indicated that, within the participants who experienced moderate to high weight loss, each 1% increase in CHO intake was associated with a reduction of 2.30 kcal/day in REE (95% CI: −4.11 to −0.47, p = 0.013). In contrast, a 1% increase in protein and fat intake was correlated with an increase in REE by 3.00 (95% confidence interval CI 1.02, 5.07, p = 0.003) and 0.5 (95% CI −2.43, 3.41, p = 0.740) kcal/day, respectively. No significant associations were found among participants who experienced minimal weight loss. These findings indicate that, under a caloric deficit, the impact of dietary macronutrient composition on REE may vary depending on the degree of weight loss and individual metabolic responses.
Oysters and barnacles are dominant inhabitants of natural and restored oyster reefs around the world, and high areal coverage of barnacles at natural or restored reefs commonly decreases substrate ...accessibility for oyster settlement. The overall understanding of oyster and barnacle recruitment dynamics provides invaluable information on site selection and strategies employed for oyster reef restoration. This study documented the temporal and spatial patterns of oyster and barnacle recruitment on and near the largest natural intertidal oyster reef (Liyashan) in China during 2019–2020. The oyster
Crassostrea sikamea
recruitment appeared as a continuous process from June through late November or early December, with the peak in August. Greater recruits of oyster spat occurred on the sheltered inshore at the upstream of the natural oyster reef than on the reef and the nearby open coast (
p
< 0.05). The barnacle recruitment extended from spring to early winter, with mid-spring and mid-summer peaks. Conversely, higher barnacle recruitment appeared on the natural oyster reef and the nearby open coast than on the sheltered inshore. Across all the monitoring sites, the cumulative recruits of oysters in each of 2019 and 2020 was negatively correlated with those of barnacles (
p
< 0.05). The inshore sites (SH1 and SH2) with high oyster recruitment and low barnacle recruitment should be recognized as the natural spatfall sites for the natural oyster reef restoration. The separation in the recruitment peak between the oyster and the barnacle indicated that August was the most favorable window for capturing oyster spat through substratum addition to the water around the natural reef.
Multistimuli-responsive luminescent materials, showing obvious alteration of emission colours or intensity toward multiple external stimuli, have attracted extensive interest from researchers for ...decades, but the tailored synthesis of such materials with a single phase remains a tough challenge. Herein, we investigate a Cu(i) cyclic trinuclear complex with the pyridyl-substituted pyrazolate ligand (denoted as complex 1), manifesting reversible multistimuli-responsive behavior in response to mechanical stimuli, temperature, organic solvents and vapor stimuli related to metal-sensitized ligand-based phosphorescence. In particular, the ground complex 1 showed remarkable alteration of emission colours after contact with CH2Cl2 or CHCl3, thereby photoluminescence sensing towards these two organic molecules was realized. Further taking advantage of this feature, the luminescent AND and IMPLICATION logic gates and microarray data with the function of encrypted information transformation were designed. Experimental and theoretical evidence revealed that the introduction of the pyridyl group provided an effective site to interact with CH2Cl2 or CHCl3, hence affecting the lowest triplet state and finally modulating the emission colours. This work demonstrates an effective route to construct multistimuli-responsive material via the supramolecular interaction of the pyridyl group for the application of logic gates and encrypted information transformation.
For using targeted covalent inhibitors (TCIs) as anticancer and antiviral drugs, we establish that the model compounds PCMPS (p-chloromercuriphenyl sulfate) and PCMB (p-chloromercuribenzoate) are ...inhibitors of the DEDDh family of exonucleases. The underlying mechanism is analyzed by X-ray crystallography, activity/nucleic acid-binding assays, and all-atom molecular dynamics (MD) simulations. The first TCI-complexed structures of a DEDDh enzyme, the Lassa fever virus NP exonuclease (NPexo), are resolved to elucidate that the Cys409 binding site is away from the active site and the RNA-binding lid. The NPexo C409A structures indicate Cys461 as the alternative distal site for obstructing the equally active mutant. All-atom MD simulations of the wild type and mutant NPexos in explicit solvent uncover an allosteric inhibition mechanism that the local perturbation induced by PCMPS sulfonate propagates to impact the RNA-binding lid conformation. Binding assay studies confirm that PCMPS does affect the RNA binding of NPexo. The predicted relative potency between PCMPS and PCMB is also in line with experiments. The structural data and inhibition mechanism established in this work provide an important molecular basis for the drug development of TCIs.
The extent of oyster stocks and their habitat loss experienced on the Chinese coasts suggests that oyster restoration will be necessary to rebuild direct fisheries and recover lost ecosystem ...services. Limited understanding of oyster biology and ecology is among the potential barriers to successful restoration along the Chinese coasts. At a natural oyster bed in Jiantiao Bay, Sanmen County, China, the study compared gonad development and spawn duration of the Sumonie oyster Crassostrea ariakensis and the Kumamoto oyster Crassostrea sikamea through histological sections from May 2020 to March 2021. Their temporal and vertical recruitment patterns were simultaneously observed along an increasing tidal elevation gradient (0.1 m, 0.6 m, 1.1 m, 1.6 m, 2.1 m). The gonad index did not differ between the oysters (P>0.05), with the maximum values in June–August, but C. sikamea had a longer spawning duration (May–December) than C. ariakensis (May–October). Crassostrea ariakensis recruited to only the lower 3 tidal zones (0.1 m, 0.6 m, 1.1 m), and its recruits varied linearly and significantly as an inverse function of tidal elevation. Significant 2nd degree polynomial fits best described the relationships for C. sikamea recruits and tidal elevation. The greatest recruits were commonly observed at the mid intertidal zones (0.6 m, 1.1 m and 1.6 m). An evident vertical settlement pattern emerged for C. sikamea at both 1-day and 3-day experiments; the greatest settlement rates occurred in the 1.6 m tidal zone, intermediate rates occurred in the 1.1 m and 0.6 m, the lowest rates occurred in the 0.1 m and 2.1 m. The study concluded that C. sikamea sustained longer spawning and recruitment durations than C. ariakensis, and a strong zonation pattern in recruitment emerged; C. sikamea achieved its maximum recruits in the mid-tidal zone, while the recruits of C. ariakensis linearly decreased with increasing tidal elevation.
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