Structure and Photonic Properties of a Perylenediimide Monolayer Assembled by the Langmuir-Blodgett Technique.

The photonic responses of densely packed dye molecule assemblies are strongly dependent on their organization and environment. The precise control of molecular orientations and distances relative to the substrate and to each other is thus a key point in the design of photonic molecular materials. Herein, we report the preparation of a homogeneous and well-organized single monolayer of the perylenediimide (PDI) derivative by means of the Langmuir-Blodgett technique. Its optical properties disclose an intense charge-transfer excitonic absorption band related to important intermolecular coupling. Furthermore, an important immunity to photobleaching is observed for such a molecular assembly. The dipolar orientations of the molecules along the substrate have been unambiguously determined by angle-of-incidence-resolved polarized absorption and back-focal-plane fluorescence mapping. In addition, time-resolved spectroscopy reveals a fast two-dimensional diffusion of excitons consistent with strong π-stacking of adjacent PDI molecules.

Quantum Metrology Using Time-Frequency as Quantum Continuous Variables: Resources, Sub-Shot-Noise Precision and Phase Space Representation.

We study the role of the electromagnetic field's frequency on the precision limits of time measurements from a quantum perspective, using single photons as a paradigmatic system. We demonstrate that a quantum enhancement of precision is possible only when combining both intensity and spectral resources and, in particular, that spectral correlations enable a quadratic scaling of precision with the number of probes. We identify the general mathematical structure of nonphysical states that achieve the Heisenberg limit and show how a finite spectral variance may cause a quantum-to-classical-like transition in precision scaling for pure states similar to the one observed for noisy systems. Finally, we provide a clear and consistent geometrical time-frequency phase space interpretation of our results, identifying what should be considered as spectral classical resources.

Daphnanes diterpenes from the latex of Hura crepitans L. and their PKCζ-dependent anti-proliferative activity on colorectal cancer cells.

Hura crepitans L. (Euphorbiaceae) is a thorn-covered tree widespread in South America, Africa and Asia which produces an irritating milky latex containing numerous secondary metabolites, notably daphnane-type diterpenes known as Protein Kinase C activators. Fractionation of a dichloromethane extract of the latex led to the isolation of five new daphnane diterpenes (1-5), along with two known analogs (6-7) including huratoxin. Huratoxin (6) and 4',5'-epoxyhuratoxin (4) were found to exhibit significant and selective cell growth inhibition against colorectal cancer cell line Caco-2 and primary colorectal cancer cells cultured as colonoids. The underlying mechanism of 4 and 6 was further investigated revealing the involvement of PKCζ in the cytostatic activity.

Dissemination, Implementation, and Evaluation of an Effective School-Based Intervention to Promote Physical Activity in Adolescents: A Study Protocol.

Adolescents around the world do not engage in sufficient physical activity and the Spanish context is no exception. Understanding the educational context as a complex system, school-based multi-level and multi-component interventions seem to be an effective strategy to reverse this trend. Moreover, a co-creational approach seems to facilitate the mobilization of community partnerships and the engagement of stakeholders in the intervention process. This study aims to describe the dissemination, implementation, and evaluation process of an effective school-based intervention program in another setting using the replicating effective programs framework and a co-participatory approach. This study will be conducted in two Spanish secondary schools located in the region of Aragon (experimental vs. control school) in a sample of adolescents in the second grade (13-14 years old). To evaluate the effectiveness, different health behaviors such as physical activity, sleep, sedentary time with screens, nutrition, and psychosocial variables will be quantitatively measured at baseline and after the implementation of the intervention. Qualitative methods will also be used to better understand the implementation process and the co-creation approach, as well as to provide insights into the sustainability of the intervention program. The current study has the potential to provide strong information about the dissemination, implementation, and evaluation process of school-based programs to promote healthy behaviors among adolescents.

Dynamics of the energy transfer involved in a diarylethene-perylenebisimide dyad: comparison between the molecule and the nanoparticle level.

Photochromic materials are widely used to achieve fluorescence photoswitching. Understanding the energy transfer processes occurring in these systems would be an advantage for their use and better optimization of their properties. In this scope, we studied a diarylethene-perylenebisimide (DAE-PBI) dyad that presents a bright red emission and a large ON-OFF contrast, both in solution and in an aqueous suspension of nanoparticles (NPs). Using ultrafast transient absorption spectroscopy, the excited state dynamics was characterized for this dyad in THF solution and compared to its behavior in NPs state. An efficient energy transfer process between the PBI fluorophore and the DAE photochromic unit in its closed form was demonstrated, occurring in a few hundreds of femtoseconds.

Accelerometer-Based Physical Activity Assessment During Intermittent Conditions: Effect of Epoch Length on Energy Expenditure Estimate.

Purpose: This study analyzed the effect of epoch length on energy expenditure (EE) estimates and on the moderate-to-vigorous physical activity (MVPA) measure obtained from EE estimates during accelerometer-based assessment. Methods: Ten active students exercised on a treadmill for four 5-min bouts, using two effort intensities (running and walking) and two physical activity (PA) patterns (continuous or intermittent) wearing an accelerometer. The criterion measure of EE was achieved using indirect calorimetry. Data obtained from the accelerometer were reintegrated into 1-sec, 10-sec, 30-sec and 60-sec epochs. Results: During the running intermittent condition, EE and MVPA estimates from the accelerometer were no different from the criterion measure with 30- and 60-sec epoch lengths but they were different with shorter epoch lengths. During the walking intermittent condition, no difference was observed between EE estimates and the criterion measure, regardless of the epoch length. During the running continuous condition, EE estimated from the accelerometer was significantly lower than the EE obtained with the criterion measure, regardless of the epoch length. During the walking continuous condition, no difference was observed. Conclusion: During the intermittent running condition, longer epoch lengths gave the best EE and MVPA estimates. This conclusion is contrary to the current general view that shorter epochs are the most accurate for PA assessment. However, PA estimates are closer to an external load estimates whereas EE estimates are closer to the internal load estimate. Depending on the objective of their study, researchers should be aware of these findings.

Variable electro-optic shearing interferometry for ultrafast single-photon-level pulse characterization.

Despite the multitude of available methods, the characterization of ultrafast pulses remains a challenging endeavor, especially at the single-photon level. We introduce a pulse characterization scheme that maps the magnitude of its short-time Fourier transform. Contrary to many well-known solutions it does not require nonlinear effects and is therefore suitable for single-photon-level measurements. Our method is based on introducing a series of controlled time and frequency shifts, where the latter is performed via an electro-optic modulator allowing a fully-electronic experimental control. We characterized the full spectral and temporal width of a classical and single-photon-level pulse and successfully tested the applicability of the reconstruction algorithm of the spectral phase and amplitude. The method can be extended by implementing a phase-sensitive measurement and is naturally well-suited to partially-incoherent light.

Comparison of the Phytochemical Variation of Non-Volatile Metabolites within Mother Tinctures of Arnica montana Prepared from Fresh and Dried Whole Plant Using UHPLC-HRMS Fingerprinting and Chemometric Analysis.

Arnica montana L. has been recognized for centuries as an herbal remedy to treat wounds and promote healing. It also has a long tradition of use in homeopathy. Depending on its medicinal utilization, standardization regulations allow different manufacturing processes, implying different raw materials, such as the whole arnica plant in its fresh or dried state. In this study, an untargeted metabolomics approach with UHPLC-HRMS/MS was used to cross-compare the phytochemical composition of mother tinctures of A. montana that were prepared from either fresh whole plant (fMT) matter or from oven-dried whole plant (dMT) matter. The multivariate data analysis showed significant differences between fMT and dMT. The dereplication of the HRMS and MS/MS spectra of the more discriminant compounds led to annotated quinic acid, dicaffeoyl quinic acids, ethyl caffeate, thymol derivatives and dehydrophytosphingosine, which were increased in fMT, while Amadori rearrangement products (ARP) and methoxyoxaloyl-dicaffeoyl quinic acid esters were enhanced in dMT. Neither sesquiterpene lactones nor flavonoids were affected by the drying process. This is the first time that a sphingosine, ethyl caffeate and ARP are described in A. montana. Moreover, putative new natural products were detected as 10-hydroxy-8,9-epoxy-thymolisobutyrate and an oxidized proline fructose conjugate, for which isolation and full structure elucidation will be necessary to verify this finding.

Cordiasecosides G-J, 9,10-Seco-29-norcycloartane glycosides isolated from Cordia lutea and their antibacterial activities.

Four undescribed secocycloartane monoglycosides (1-4) were isolated from an ethanolic extract of the dry flowers of Cordia lutea Lam. Their structural assignment is based on NMR and MS analysis. Their stereochemistry is confirmed by molecular modelling studies using DFT-NMR calculations done for compound 3. In vitro antibacterial activity of the four compounds was moderate on Helicobacter pylori (MIC = 15.6 µg/mL), and much weaker on Staphylococcus aureus, Pseudomonas aeruginosa or Escherichia coli (MIC >125 µg/mL). Toxicity evaluated against RAW 264.7 cells was weak (IC50 values ranging from 24 to 41 µM i.e. 15 to 24 µg/mL), but in the same range as anti-Helicobacter activity.

Quality assessment of Curcuma dietary supplements: Complementary data from LC-MS and 1H NMR.

Due to the numerous potential health benefits of Curcuma, turmeric dietary supplements (DS) are among the top selling products. To assess the quality of these formulations, thirty Curcuma DS along with five standard Curcuma rhizomes were analyzed with UHPLC-MS and 1H NMR. The chemometric treatment of the UHPLC-MS spectra showed a significant variability of their chemical composition that was confirmed by 1H NMR which allowed the absolute quantification of the Curcuma major bioactive components, i.e. curcuminoids (curcumin, demethoxycurcumin and bisdemethoxycurcumin), and turmerones (aryl-, α- and ß-) as well as piperine, a commonly associated curcumin bioavailability enhancer: respectively 3.5-556, 0-8.6, 0.18-8.1 mg/capsule or tablet. The comparison of the actual and claimed quantities of curcuminoids and piperine showed that 58% of the DS contained the expected amounts of actives.

Pharmacological validation of Solanum mammosum L. as an anti-infective agent: Role of solamargine.

ETHNOPHARMACOLOGICAL RELEVANCE: Fungal and bacterial infections remain a major problem worldwide, requiring the development of effective therapeutic strategies. Solanum mammosum L. (Solanaceae) ("teta de vaca") is used in traditional medicine in Peru to treat fungal infections and respiratory disorders via topical application. However, the mechanism of action remains unknown, particularly in light of its chemical composition. MATERIALS AND METHODS: The antifungal activity of TDV was determined against Trichophyton mentagrophytes and Candida albicans using bioautography-TLC-HRMS to rapidly identify the active compounds. Then, the minimum inhibitory concentration (MIC) of the fruit crude extract and the active compound was determined to precisely evaluate the antifungal activity. Additionally, the effects of the most active compound on the formation of Pseudomonas aeruginosa biofilms and pyocyanin production were evaluated. Finally, a LC-HRMS profile and a molecular network of TDV extract were created to characterize the metabolites in the fruits' ethanolic extract. RESULTS: Bioautography-TLC-HRMS followed by isolation and confirmation of the structure of the active compound by 1D and 2D NMR allowed the identification solamargine as the main compound responsible for the anti-Trichophyton mentagrophytes (MIC = 64 µg mL-1) and anti-Candida albicans (MIC = 64 µg mL-1) activities. In addition, solamargine led to a significant reduction of about 20% of the Pseudomonas aeruginosa biofilm formation. This effect was observed at a very low concentration (1.6 µg mL-1) and remained fairly consistent regardless of the concentration. In addition, solamargine reduced pyocyanin production by about 20% at concentrations of 12.5 and 50 µg mL-1. Furthermore, the LC-HRMS profiling of TDV allowed us to annotate seven known compounds that were analyzed through a molecular network. CONCLUSIONS: Solamargine has been shown to be the most active compound against T. mentoagrophytes and C. albicans in vitro. In addition, our data show that this compound affects significantly P. aeruginosa pyocyanin production and biofilm formation in our conditions. Altogether, these results might explain the traditional use of S. mammosum fruits to treat a variety of fungal infections and respiratory disorders.

Advances in Wheat Physiology in Response to Drought and the Role of Plant Growth Promoting Rhizobacteria to Trigger Drought Tolerance.

In the coming century, climate change and the increasing human population are likely leading agriculture to face multiple challenges. Agricultural production has to increase while preserving natural resources and protecting the environment. Drought is one of the major abiotic problems, which limits the growth and productivity of crops and impacts 1-3% of all land.To cope with unfavorable water-deficit conditions, plants use through sophisticated and complex mechanisms that help to perceive the stress signal and enable optimal crop yield are required. Among crop production, wheat is estimated to feed about one-fifth of humanity, but faces more and more drought stress periods, partially due to climate change. Plant growth promoting rhizobacteria are a promising and interesting way to develop productive and sustainable agriculture despite environmental stress. The current review focuses on drought stress effects on wheat and how plant growth-promoting rhizobacteria trigger drought stress tolerance of wheat by highlighting several mechanisms. These bacteria can lead to better growth and higher yield through the production of phytohormones, osmolytes, antioxidants, volatile compounds, exopolysaccharides and 1-aminocyclopropane-1-carboxylate deaminase. Based on the available literature, we provide a comprehensive review of mechanisms involved in drought resilience and how bacteria may alleviate this constraint.

Effects of an Intervention to Promote Physical Activity and Reduce Sedentary Time in Disadvantaged Children: Randomized Trial.

BACKGROUND: In our society, children are particularly vulnerable to physical inactivity and excessive sedentary time (ST). The aim of this study was to evaluate the effectiveness of a school-based intervention designed to promote physical activity (PA) and reduce ST in 6- to 10-years-old children from a disadvantaged neighborhood. METHODS: The first intervention of this randomized trial was carried out in School 1 in 2017/2018 and 2018/2019, School 2 benefited from the same intervention in 2018/2019. Baseline assessments were realized using accelerometers prior to the intervention (T1-T2), after the first intervention (T3) and after the second intervention (T4). School-based actions targeted children, parents, teachers, physical, and organizational environment of school and politics. The chi-square test of independence was used to analyze the evolution of the moderate and vigorous physical activity (MVPA) and ST. RESULTS: For School 1, an increase in the percentage of very active children (over 40 minutes MVPA/day) and of having a very low ST (less 240 minutes/day) (p = .00) was found. No further evolution was revealed during the intervention (T2-T3) and 1 year after (T3-T4). For School 2, similar effects on PA and ST were found at T3 (p < .05). CONCLUSIONS: Positive effects occurred before the intervention in each school and then remained stable.

A Citrullus colocynthis fruit extract acutely enhances insulin-induced GLUT4 translocation and glucose uptake in adipocytes by increasing PKB phosphorylation.

ETHNOPHARMACOLOGICAL RELEVANCE: Citrullus colocynthis (L.) Schrad is a common fruit in traditional medicine and used as remedy against various diseases, especially diabetes. Up to now, its anti-diabetic effects have been fully attributed to its enhancement of pancreatic insulin secretion. Whether C. colocynthis also ameliorates insulin action in peripheral tissues has not been investigated. AIM OF THE STUDY: In the present study, using 3T3-L1 adipocytes as cell model, we have investigated whether colocynth fruit extracts affect insulin action. MATERIALS AND METHODS: Various extracts were prepared from the C. colocynthis fruit and screened using a cell-based 96 well plate GLUT4 translocation assay. Promising extracts were further studied for their effects on glucose uptake and cell viability. The effect on insulin signal transduction was determined by Western blot and the molecular composition was established by LC-MS. RESULTS: The ethyl acetate fractions of aqueous non-defatted extracts of seed and pulp, designated Sna1 and Pna1, acutely enhanced insulin-induced GLUT4 translocation. In accordance, both extracts increased insulin-stimulated cellular glucose uptake. Pna1, which displayed greater effects on GLUT4 and glucose uptake than Sna1, was further investigated and was demonstrated to increase GLUT4 translocation without changing the half-maximum dose (ED50) of insulin, nor changing GLUT4 translocation kinetics. At the molecular level, Pna1 was found to enhance insulin-induced PKB phosphorylation without changing phosphorylation of the insulin receptor. Pna1 appeared not to be toxic to cells and, like insulin, restored cell viability during serum starvation. By investigating the molecular composition of Pna1, nine compounds were identified that made up 87% of the mass of the extract, one of which is likely to be responsible for the insulin-enhancing effects of Pna1. CONCLUSIONS: The C. colocynthis fruit possesses insulin-enhancing activity. This activity may explain in part its anti-diabetic effects in traditional medicine. It also identifies the C. colocynthis as a source of a potential novel insulin enhancer that may prove to be useful to reduce hyperglycemia in type 2 diabetes.

Dynamics of Chemical Diversity during Co-Cultures: An Integrative Time-Scale Metabolomics Study of Fungal Endophytes Cophinforma mamane and Fusarium solani.

A rapid and efficient metabolomic study of Cophinforma mamane and Fusarium solani co-cultivation in time-series based analysis was developed to study metabolome variations during their fungal interactions. The fungal metabolomes were studied through the integration of four metabolomic tools: MS-DIAL, a chromatographic deconvolution of liquid-chromatography-mass spectrometry (LC/MS); MS-FINDER, a structure-elucidation program with a wide range metabolome database; GNPS, an effective method to organize MS/MS fragmentation spectra, and MetaboAnalyst, a comprehensive web application for metabolomic data analysis and interpretation. Co-cultures of C. mamane and F. solani induced different patterns of metabolite production over 10 days of incubation and induced production of five de novo compounds not occurring in monocultures. These results emphasize that co-culture in time-frame analysis is an interesting method to unravel hidden metabolome in the investigation of fungal chemodiversity.

School-Based Multicomponent Intervention to Promote Physical Activity and Reduce Sedentary Time of Disadvantaged Children Aged 6-10 Years: Protocol for a Randomized Controlled Trial.

BACKGROUND: In our modern society, physical activity (PA) is decreasing and sedentary time (ST) is increasing, especially for children from disadvantaged neighborhoods. School-based interventions to promote PA and decrease ST are therefore required among this population in order to change children's lifestyle habits. Moreover, attentional capacities and academic achievement can be enhanced by chronic PA during childhood. The relationships between these variables have been poorly studied with this population. OBJECTIVE: The objective of this study is to present the rationale and methods for a randomized controlled trial among 6-10-year-old children with low socioeconomic status that will (1) evaluate the effectiveness of a school-based intervention designed to promote PA and reduce ST and (2) study the relationships between PA, ST, motor skills, attentional capacities, and academic achievement. METHODS: A randomized controlled trial was conducted in 2 eligible primary schools. During academic year 2016-2017, 1 school was randomly assigned as the experiment one and the other was assigned as the control one. Five assessments times were used: baseline (T1 [November 2016] to T2 [June 2017]), follow-up (T3 [November 2017] to T4 [June 2018]), and final assessment (T5 [June 2019]). The school-based intervention included various components on different levels of the socioecological model: (1) curriculum-based program for children; (2) sensitization workshops and newsletters for parents; (3) training workshops for teachers; (4) environmental adaptation of playgrounds and reorganization of recess time; (5) time adaptation of lunch breaks; and (6) collaboration with political groups. PA, ST, motor skills, and attentional capacities were evaluated and academic achievement was recorded. RESULTS: The presented intervention and its different assessments have been successfully implemented. In order to achieve the 2 objectives of this randomized controlled trial, data analyses are about to be completed. CONCLUSIONS: The implementation of this randomized controlled trial can help to determine effective strategies to promote PA in the context of increasing prevalence of physical inactivity among children with sedentary lifestyle which will be useful for researchers, stakeholders, and public policy makers. TRIAL REGISTRATION: ClinicalTrials.gov NCT03983447; https://clinicaltrials.gov/ct2/show/NCT03983447. INTERNATIONAL REGISTERED REPORT IDENTIFIER (IRRID): RR1-10.2196/17815.

Daphnanes diterpenes from the latex of Hura crepitans L. And activity against human colorectal cancer cells Caco-2.

Hura crepitans (Euphorbiaceae) is a tree from South America that produces an irritant latex used as a fish poison. A bio-guided fractionation of an ethanolic extract of the latex led to the isolation and structural identification of three known daphnane-type diterpenes (1-3) including huratoxin (1), together with two new analogs (4, 5). Compound 1 was found to exhibit significant and selective cell growth inhibition against the colorectal cancer cell line Caco-2, with morphological modifications suggesting formations mimicking the intestinal crypt architecture. The underlying mechanism of 1 was further investigated, in comparison with 12-O-tetradecanoylphorbol-13-acetate (TPA), revealing two different mechanisms.

Effect of epoch length on intensity classification and on accuracy of measurement under controlled conditions on treadmill: Towards a better understanding of accelerometer measurement.

PURPOSE: The aim of this study was to analyze the effect of epoch length on intensity classification during continuous and intermittent activities. METHODS: Ten active students exercised under controlled conditions on a treadmill for four 5-min bouts by combining two effort intensities (running and walking) and two physical activity (PA) patterns (continuous or intermittent). The testing session was designed to generate a known level of moderate to vigorous PA (MVPA) for each condition. These PA levels were used as criterion measures to compare with the accelerometer measures. Data obtained from the accelerometer were reintegrated into 1-sec, 10-sec, 30-sec and 60-sec epochs. Equivalence testing was used to examine measurement agreements between MVPA values obtained with the different epochs and the reference values. Mean absolute percent errors (MAPE) were also calculated to provide an indicator of overall measurement error. RESULTS: During the intermittent conditions, only the value obtained with the 1-sec epoch was significantly equivalent to the reference value. With longer epochs the difference increased for both intermittent conditions but in an opposite way: with longer epochs, MVPA decreased during walking but increased during running. Regarding the measurement accuracy, the pattern of variations according to the epoch length selected during the intermittent conditions was identical between walking and running: MAPE increased with the increase in epoch length. MAPE remained low only for the 1-sec epoch (7.6% and 2.7% for walking and running, respectively), increased at 31.3% and 34% for the 10-sec epoch and until near 100% with the 30- and 60-sec epoch lengths. CONCLUSION: This study highlighted the misclassification of exercise intensity based on accelerometer measurement and described for the first time the extent and the direction of this misclassification. Moreover, we can confirm that the shorter epochs are more accurate to measure the real exercise intensity during intermittent PA whatever the intensity.

Structural Characterization and Anti-infective Activity of 9,10-Seco-29-norcycloartane Glycosides Isolated from the Flowers of the Peruvian Medicinal Plant Cordia lutea.

Six new secocycloartane glycosides (1-6) were isolated from the ethanol extract of the flowers of Cordia lutea Lam. on the basis of bioassay-guided fractionation. Their structures were determined by the application of NMR and MS data analyses together with X-ray crystallographic analyses for compounds 1 and 2. Compounds 1-6 represent the first examples of 9,10-seco-29-norcycloartane glycosides. These compounds showed significant in vitro anti-Helicobacter pylori activity, and no activity against either Escherichia coli or Pseudomonas aeruginosa. Significant activity was observed for 5 and 6 against Staphylococcus aureus. All compounds displayed weak cytotoxicity against RAW 264.7 cells. The in vitro antileishmanial and antiplasmodial activities of 1-6 were also evaluated.

Comparison of the Phytochemical Composition of Serenoa repens Extracts by a Multiplexed Metabolomic Approach.

Phytochemical extracts are highly complex chemical mixtures. In the context of an increasing demand for phytopharmaceuticals, assessment of the phytochemical equivalence of extraction procedures is of utmost importance. Compared to routine analytical methods, comprehensive metabolite profiling has pushed forward the concept of phytochemical equivalence. In this study, an untargeted metabolomic approach was used to cross-compare four marketed extracts from Serenoa repens obtained with three different extraction processes: ethanolic, hexanic and sCO2 (supercritical carbon dioxide). Our approach involved a biphasic extraction of native compounds followed by liquid chromatography coupled to a high-resolution mass spectrometry based metabolomic workflow. Our results showed significant differences in the contents of major and minor compounds according to the extraction solvent used. The analyses showed that ethanolic extracts were supplemented in phosphoglycerides and polyphenols, hexanic extracts had higher amounts of free fatty acids and minor compounds, and sCO2 samples contained more glycerides. The discriminant model in this study could predict the extraction solvent used in commercial samples and highlighted the specific biomarkers of each process. This metabolomic survey allowed the authors to assess the phytochemical content of extracts and finished products of S. repens and unequivocally established that sCO2, hexanic and ethanolic extracts are not chemically equivalent and are therefore unlikely to be pharmacologically equivalent.