A Configurationally Stable Helical Indenofluorene.

We report the synthesis and study of the optoelectronic, magnetic, and chiroptical properties of a helically chiral diradicaloid based on dibenzoindeno[2,1-c]fluorene. The molecule shows a small HOMO-LUMO gap and a moderate singlet-triplet gap, which agrees with the results of DFT calculations. The helical structure of the compound, confirmed by X-ray diffraction, is configurationally stable, which allows the isolation of both enantiomers and the evaluation of the chiroptical properties (ECD).

Catalogue of drought events in peninsular Spanish along 1916-2020 period.

We leveraged the most extensive and detailed gridded database of monthly precipitation data across the Spanish mainland (MOPREDAScentury), encompassing 1916-2020 time period, to pinpoint the most severe drought events within this timeframe and analyse their spatio-temporal dynamics. To identify these events, we employed the Standardized Precipitation Index (SPI) at a 12-month timescale. Drought events were identified as periods of at least three months where significantly dry conditions affected 20% or more of the study area, defined as grid cells with SPI values lower than -0.84. Our analysis revealed a total of 40 major drought events. Our catalogue contains detailed information on each episode's spatial extent, duration, severity, and spatio-temporal dynamics. The analysis of the propagation patterns of the events unveils substantial heterogeneity, implying that droughts stem from diverse atmospheric mechanisms, further influenced by complex local topography. The open-licensed drought database serves as a valuable resource. It not only facilitates exploration of drought onset and evolution mechanisms but also aids in assessing drought impact on agricultural and other socio-economic sectors.

Curved Nanographenes as Stoppers in a [2]Rotaxane with Two-Photon Excited Emission.

Heptagon-containing distorted nanographenes are used as stoppers for the capping of a [2]rotaxane through a Michael-type addition reaction to vinyl sulfone groups. These curved aromatics are bulky enough to prevent the disassembly of the rotaxane but also give emissive and nonlinear (two-photon absorption and emission) optical properties to the structure.

Relating microtensiometer-based trunk water potential with sap flow, canopy temperature, and trunk and fruit diameter variations for irrigated 'Honeycrisp' apple.

Instrumentation plays a key role in modern horticulture. Thus, the microtensiomenter, a new plant-based sensor that continuously monitors trunk water potential (Ψtrunk) can help in irrigation management decisions. To compare the response of the Ψtrunk with other continuous tree water status indicators such as the sap flow rate, the difference between canopy and air temperatures, or the variations of the trunk and fruit diameter, all the sensors were installed in 2022 in a commercial orchard of 'Honeycrisp' apple trees with M.9 rootstocks in Washinton State (USA). From the daily evolution of the Ψtrunk, five indicators were considered: predawn, midday, minimum, daily mean, and daily range (the difference between the daily maximum and minimum values). The daily range of Ψtrunk was the most linked to the maximum daily shrinkage (MDS; R2 = 0.42), the canopy-to-air temperature (Tc-Ta; R2 = 0.32), and the sap flow rate (SF; R2 = 0.30). On the other hand, the relative fruit growth rate (FRGR) was more related to the minimum Ψtrunk (R2 = 0.33) and the daily mean Ψtrunk (R2 = 0.32) than to the daily range of Ψtrunk. All indicators derived from Ψtrunk identified changes in tree water status after each irrigation event and had low coefficients of variation and high sensitivity. These results encourage Ψtrunk as a promising candidate for continuous monitoring of tree water status, however, more research is needed to better relate these measures with other widely studied plant-based indicators and identify good combinations of sensors and threshold values.

The Waste-to-Biomethane Logistic Problem: A Mathematical Optimization Approach.

In this paper, we propose a new mathematical optimization approach to make decisions on the optimal design of the complex logistic system required to produce biogas from waste. We provide a novel and flexible decision-aid tool that allows decision makers to optimally determine the locations of different types of plants (pretreatment, anaerobic digestion, and biomethane liquefaction plants) and pipelines involved in the logistic process, according to a given budget, as well as the most efficient distribution of the products (from waste to biomethane) along the supply chain. The method is based on a mathematical optimization model that we further analyze and that, after reducing the number of variables and constraints without affecting the solutions, is able to solve real-size instances in reasonable CPU times. The proposed methodology is designed to be versatile and adaptable to different situations that arise in the transformation of waste to biogas. The results of our computational experiments, both in synthetic and in a case study instance, prove the validity of our proposal in practical applications. Synthetic instances with up to 200 farms and potential locations for pretreatment plants and 100 potential locations for anaerobic digestion and biomethane liquefaction plants were solved, exactly, within <20 min, whereas the larger instances with 500 farms were solved within <2 h. The CPU times required to solve the real-world instance range from 2 min to 6 h, being highly affected by the given budget to install the plants and the percent of biomethane that is required to be injected in the existing gas network.

Supramolecular Large Nanosheets Assembled at Air/Water Interfaces and in Solution from Amphiphilic Heptagon-Containing Nanographenes.

We report the synthesis of a new set of amphiphilic saddle-shaped heptagon-containing polycyclic aromatic hydrocarbons (PAHs) functionalized with tetraethylene glycol chains and their self-assembly into large two-dimensional (2D) polymers. An in-depth analysis of the self-assembly mechanism at the air/water interface has been carried out, and the proposed arrangement models are in good agreement with the molecular dynamics simulations. Quite remarkably, the number and disposition of the tetraethylene glycol chains significantly influence the disposition of the PAHs at the interface and conditionate their packing under pressure. For the three compounds studied, we observed three different behaviors in which the aromatic core is parallel, perpendicular, and tilted with respect to the water surface. We also show that these curved PAHs are able to self-assemble in solution into remarkably large sheets of up to 150 µm2. These results show the relationship, within a family of curved nanographenes, between the monomer configuration and their self-assembly capacity in air/water interfaces and organic-water mixtures.

Intervenciones hacia la Prueba de Antígeno Prostático: Una revisión rápida de literatura / Interventions for Prostate-Specific Antigen Testing: A Rapid Literature Review

Objetivo: Identificar la mejor evidencia disponible relacionada a las intervenciones dirigidas hacia la aceptación de la prueba de antígeno prostático. Metodología: Revisión rápida de literatura, siguiendo los pasos establecidos por Tapia-Benavente, los cuales son: 1.- pregunta de investigación, para lo cual se utilizó la estructura PICO acotada a la definición del problema, intervención y resultado; 2.- búsqueda de bibliografía en bases de datos reconocidas; 3.- selección de estudios y extracción de datos; 4.- evaluación del riesgo de sesgo, para lo cual se utilizó la guía de comprobación de ensayos clínicos del grupo CONSORT; y 5.- la elaboración de la síntesis además de la conclusión de la evidencia encontrada. Resultados: La búsqueda rápida de literatura arrojó un total de 51 publicaciones de tres bases de datos, PubMed (27), EBSCO (13) y SCOPUS (11); de los cuales 11 cumplían con los criterios de inclusión. El 100% de los estudios indican un cambio significativo entre el grupo experimental y control (p < .05). Las estrategias más utilizadas incluyen la visita domiciliaria, conferencias, debates en grupo, lluvia de ideas, dinámicas de pregunta y respuesta con diapositivas, así como presentación de folletos educativos, mismos que se ejecutan en un periodo de un día, hasta seis meses. Conclusiones: Se hace evidente el vacío de conocimiento referente al desarrollo e implementación de estrategias para abordar la conducta de prevención relacionada al Cancer de Próstata hacia varones de pueblos originarios, así como la falta de modelos de intervención de enfermería enfocadas en este padecimiento. (AU)

Objective: To identify the best available evidence related to interventions for the acceptance of the prostate-specific antigen test. Methodology: Rapid literature review following the steps established by Tapia-Benavente, which are: 1.- research question, for which the PICO structure limited to the definition of the problem, intervention, and result was used; 2.- bibliography search in recognized databases; 3.- study selection and data extraction; 4.- bias risk assessment, for which the CONSORT group clinical trial verification guidelines were used; and 5.- preparation of a summary and conclusion of the evidence found. Results: The rapid literature search yielded a total of 51 publications from three databases, PubMed (27), EBSCO (13), and SCOPUS (11); 11 of which met the inclusion criteria. One hundred percent of the studies indicated a significant difference between the experimental and control groups (p < .05). The most frequently used strategies included home visits, conferences, group discussions, brainstorming, question-and-answer dynamics with slides, as well as the use of educational brochures, and were carried out in a period of one day and up to six months. Conclusions: There is an evident knowledge gap in the development and implementation of strategies for Prostate Cancer prevention behavior directed to indigenous men, as well as a lack of nursing intervention models focused on this disease. (AU)

Study of Mineral Composition and Quality of Fruit Using Vascular Restrictions in Branches of Sweet Cherry.

Calcium (Ca) and carbohydrate (CHO) supply in sweet cherry have been associated with fruit quality at harvest and during storage. There is little published information integrating CHO and Ca availability and distribution in sweet cherry and their effects on fruit quality. Accordingly, in the 2019-20 season, vascular restrictions were imposed on the phloem (girdling, G, stopping phloem flow) and xylem (transverse incision, S, cutting 50% of xylem cross-section area) of individual vertical branches of the sweet cherry combination 'Lapins'/Colt trained as Kym Green Bush system to modify mineral and CHO composition in fruit and associate such changes with quality at harvest and storage. The girdling to the phloem was used to induce changes in CHO distribution. The transverse incision to the xylem was a tool to modify Ca distribution. Five treatments (TR) were implemented: TR1-CTL = Control (without vascular restriction), TR2-G, at its base, TR3-G + G: at its base, and G further up at the change of year between the second and the third years of growth TR4--S and TR5-S + G. The vegetative (i.e., shoot and leaf growth), reproductive (i.e., fruit set and yield) development and stomatal conductance were monitored. Each branch was divided into the upper (1-and 2-year-old wood) and the lower (3-and 4-year-old wood) segments of the restriction applied. The quality and mineral composition (Ca, Mg, K, and N) of fruit borne on each segment were measured at harvest. The upper segment of TR3-G + G branches were harvested 10 d before the lower segment. The fruit from the upper segment of TR3-G + G was the largest, the sweetest, and had the higher titratable acidity concentration. However, fruits of this segment were the softest, had the lowest Ca concentrations, and had the highest ratios of N:Ca and K:Ca, compared with the other TRs. TR3-G + G branches developed the highest number of lateral current season shoots including shoots below the second girdling in the lower segment of the branch. This vegetative flow of growth would explain the mineral unbalance produced in the fruit from the upper segment of the branch. TR2-G did not register changes in fruit quality and mineral concentration compared with TR1-CTL. Surprisingly, the fruit from the branches with xylem restriction did not show changes in Ca concentration, suggesting that the xylem stream was enough to supply the fruit in branches without lateral shoot development. Fruit firmness was positively related to fruit Ca concentration and negatively related to the ratios of K:Ca and N:Ca.

Aligning social networks and co-designed visions to foster systemic innovation in the Alps.

Mountain regions face substantial challenges and opportunities arising from global change. The capacity of mountain regions for (systemic) innovation will be determinant to the success of system transformations envisioned by social actors of mountain communities. By analysing the social networks of two regions in the Alps and relating them to desired future visions of sustainable regional development, we provide insights about innovative capacities in mountain regions and propose how to strengthen these capacities in order to support regional transformations. In particular, we analyse innovation systems' collaboration networks to evaluate the innovative capacity of communities, co-construct visions with mountain stakeholders, and assess innovation requirements to meet these visions. Accordingly, we propose changes to the collaboration networks for addressing regional innovation system (RIS) capacities to help achieve visions through systemic innovation. Our analysis furthers the understanding on the type and magnitude of regional innovation system changes required to more effectively address desired transformative visions in mountain regions. We close by discussing implications of our approach for the assessment of innovative capacity and the transformation of mountain regions. Supplementary Information: The online version contains supplementary material available at 10.1007/s10113-023-02099-y.

Combining thermal imaging and soil water content sensors to assess tree water status in pear trees.

Volumetric soil water content is commonly used for irrigation management in fruit trees. By integrating direct information on tree water status into measurements of soil water content, we can improve detection of water stress and irrigation scheduling. Thermal-based indicators can be an alternative to traditional measurements of midday stem water potential and stomatal conductance for irrigation management of pear trees (Pyrus communis L.). These indicators are easy, quick, and cost-effective. The soil and tree water status of two cultivars of pear trees 'D'Anjou' and 'Bartlett' submitted to regulated deficit irrigation was measured regularly in a pear orchard in Rock Island, WA (USA) for two seasons, 2021 and 2022. These assessments were compared to the canopy temperature (Tc), the difference between the canopy and air temperature (Tc-Ta) and the crop water stress index (CWSI). Trees under deficit irrigation had lower midday stem water potential and stomatal conductance but higher Tc, Tc-Ta, and CWSI. Tc was not a robust method to assess tree water status since it was strongly related to air temperature (R = 0.99). However, Tc-Ta and CWSI were greater than 0°C or 0.5, respectively, and were less dependent on the environmental conditions when trees were under water deficits (midday stem water potential values< -1.2 MPa). Moreover, values of Tc-Ta = 2°C and CWSI = 0.8 occurred when midday stem water potential was close to -1.5 MPa and stomatal conductance was lower than 200 mmol m-2s-1. Soil water content (SWC) was the first indicator in detecting the deficit irrigation applied, however, it was not as strongly related to the tree water status as the thermal-based indicators. Thus, the relation between the indicators studied with the stem water potential followed the order: CWSI > Tc-Ta > SWC = Tc. A multiple regression analysis is proposed that combines both soil water content and thermal-based indices to overcome limitations of individual use of each indicator.

Mathematical optimization models for reallocating and sharing health equipment in pandemic situations.

In this paper we provide a mathematical programming based decision tool to optimally reallocate and share equipment between different units to efficiently equip hospitals in pandemic emergency situations under lack of resources. The approach is motivated by the COVID-19 pandemic in which many Heath National Systems were not able to satisfy the demand of ventilators, sanitary individual protection equipment or different human resources. Our tool is based in two main principles: (1) Part of the stock of equipment at a unit that is not needed (in near future) could be shared to other units; and (2) extra stock to be shared among the units in a region can be efficiently distributed taking into account the demand of the units. The decisions are taken with the aim of minimizing certain measures of the non-covered demand in a region where units are structured in a given network. The mathematical programming models that we provide are stochastic and multiperiod with different robust objective functions. Since the proposed models are computationally hard to solve, we provide a divide-et-conquer math-heuristic approach. We report the results of applying our approach to the COVID-19 case in different regions of Spain, highlighting some interesting conclusions of our analysis, such as the great increase of treated patients if the proposed redistribution tool is applied.

Heptagon-Containing Nanographene Embedded into [10]Cycloparaphenylene.

We report the synthesis and characterization of a novel type of nanohoop, consisting of a cycloparaphenylene derivative incorporating a curved heptagon-containing π-extended polycyclic aromatic hydrocarbon (PAH) unit. We demonstrate that this new macrocycle behaves as a supramolecular receptor of curved π-systems such as fullerenes C60 and C70 , with remarkably large binding constants (ca. 107  M-1 ), as estimated by fluorescence measurements. Nanosecond and femtosecond spectroscopic analysis show that these host-guest complexes are capable of quasi-instantaneous charge separation upon photoexcitation, due to the ultrafast charge transfer from the macrocycle to the complexed fullerene. These results demonstrate saddle-shaped PAHs with dibenzocycloheptatrienone motifs as structural components for new macrocycles displaying molecular receptor abilities and versatile photochemical responses with promising electron-donor properties in host-guest complexes.

Metal-directed self-assembly of constitutionally dynamic systems: control of the nuclearity of Pd(II)/Pt(II) metallacycles.

Self-assembly with the square-planar Pd(II) or Pt(II) (en)M(ONO2)2 (en = ethylenediamine) complexes of ditopic ligands incorporating both N,N'-dialkyl-4,4'-bipyridinium and N-monoalkyl-4,4'-bipyridinium or N-monoalkyl-2,7-diazapyrenium moieties leads to constitutionally dynamic systems responsive to the concentration of the components. At low concentrations, the metallamacrocyclic mononuclear [ML]5+ species is formed. In contrast, when the concentration is increased, a defined dinuclear [M2L2]10+ structure appears as a second species in equilibrium, becoming the major one at high concentrations. Besides concentration changes, the addition of an aromatic guest also allows the control of the system speciation, shifting the outcome of the metal-directed self-assembly towards the mononuclear metallacycle. This dynamic behavior enables the control of the nuclearity of the metallacycles assembled by external stimuli.

Irrigation and Crop Load Management Lessen Rain-Induced Cherry Cracking.

The combined effects of deficit irrigation and crop load level on sweet cherry (Prunus avium L.) physiological and agronomic response were evaluated during the 2019 season in a commercial orchard located in southeastern Spain. Two irrigation treatments were imposed: (i) control treatment (CTL) irrigated above crop water requirements at 110% of crop evapotranspiration (ETC) and (ii) a deficit irrigation treatment (DI) irrigated at 70% ETC. Within each irrigation treatment, crop load was adjusted to three levels: 100% (natural crop load-high), 66% (medium crop load), and 33% (low crop load). The water relations results were more affected by the irrigation strategies applied than by the crop load management. The deficit irrigation strategy applied reduced soil water availability for DI trees, which led to a continuous decrease in their gas exchange and stem water potential. At harvest, the fruit water potential and osmotic potential of cherries from the DI treatment resulted in significantly lower values than those measured in cherries from CTL trees. On the other hand, both the irrigation strategies imposed and the crop load management used impacted fruit quality. Trees with the lowest level of crop load had fruits of greater size, regardless of the irrigation treatment assayed, and in the DI treatment, cherries from the trees with the lowest crop load were darker and more acidic than those from the trees with the highest crop load. Our results emphasize the different effects that rainfall before harvest has on mature cherries. Thus, cracked cherries at harvest represented 27.1% of the total yield of CTL trees while they were 8.3% of the total yield in DI trees. Cherries from CTL trees also showed a greater cracking index than those from DI trees. Moreover, a linear relationship between crop load and fruit cracked at harvest was observed, particularly for the CTL treatment; thus, the lower the crop load, the greater the proportion of cracked cherries.

Aggregation-Induced Emission and Circularly Polarized Luminescence Duality in Tetracationic Binaphthyl-Based Cyclophanes.

Here, we report an approach to the synthesis of highly charged enantiopure cyclophanes by the insertion of axially chiral enantiomeric binaphthyl fluorophores into the constitutions of pyridinium-based macrocycles. Remarkably, these fluorescent tetracationic cyclophanes exhibit a significant AIE compared to their neutral optically active binaphthyl precursors. A combination of theoretical calculations and time-resolved spectroscopy reveal that the AIE originates from limited torsional vibrations associated with the axes of chirality present in the chiral enantiomeric binaphthyl units and the fine-tuning of their electronic landscape when incorporated within the cyclophane structure. Furthermore, these highly charged enantiopure cyclophanes display CPL responses both in solution and in the aggregated state. This unique duality of AIE and CPL in these tetracationic cyclophanes is destined to be of major importance in future development of photonic devices and bio-applications.

Short-Term Effectiveness and Reduction in Insulin Requirements in Patients With Type 2 Diabetes Treated With IdegLira in a Real-World Setting.

Background: Type 2 diabetes mellitus (T2DM) is a chronic, highly prevalent disease with a significant impact on health. Appropriate treatment requires effective and timely escalation to achieve metabolic control. To evaluate the effectiveness and safety of IDegLira on adults with T2DM previously treated with oral antidiabetics and/or insulin in a real-life setting. Methods: An observational study in a real-world setting was conducted. Patients were selected from the outpatient clinic of two centers dedicated to specialized diabetes care. Main outcomes were HbA1c, body weight, insulin dose changes, hypoglycemia, and other adverse events. Results: 67 T2DM patients treated with IDegLira were monitored between 3 and 7 months. At the end of foll ow-up, the median change in HbA1c was -1.05% (CI95% -1.45, -0.65), and a decrease in insulin requirement was also observed (mean difference -10 TDD units (CI95% - 17 to -2.5). No treatment discontinuation was reported, hypoglycemia events were reported in 3 patients at the end of follow-up versus 8 patients at baseline. Conclusions: This real-life study shows the effectiveness in glycemic control of IDegLira use in T2DM patients who do not achieve goals with other therapies, with an adequate safety profile. The findings need to be confirmed with evaluation of therapeutic results in larger cohorts.

The effectiveness of a comprehensive diabetes program for glycemic control and adherence, and the selection of candidates for sensor-augmented insulin pump therapy.

OBJECTIVE: This study aimed to estimate the effectiveness of a comprehensive diabetes program (CDP) in terms of glycemic control, adherence, and the selection of candidates for sensor-augmented insulin pump therapy (SAP). METHODS: We compared diabetes control before and 6 months after CDP. The program was based on disease management using a logical model dealing with the following: case management, education and coaching, nutritional assessment, and mental health. RESULTS: The CDP improved glycemic control, HbA1c decreased by 0.56% (p-value=0.004; 95% CI: 0.14-0.98) and 19.1% of the patients reached the HbA1c goal without hypoglycemia. The CDP reduced by 52.4% the indication for SAP due to better glycemic control (36.4%) or non-adherence issues (63.6%); the remaining 47.6% persisted with poor glycemic control despite good adherence and were scaled to SAP. Among the 30 suitable candidates for SAP therapy, 60% did not reach the HbA1c goal and 40% had either hypoglycemic episodes (severe or persistent) or dawn phenomenon. The overall non-adherence rate was 33.3%. CONCLUSIONS: CDP optimized the selection of suitable candidates for SAP by improving glycemic control and identifying adherence issues early. These results provide evidence of the impact of the implementation of patient selection and educational protocols in the real-life setting of a highly experienced clinic.

Real-world effectiveness and safety of sensor-augmented insulin pump therapy in adults with type 1 diabetes: Long-term follow-up.

OBJECTIVE: To evaluate the effectiveness and safety of sensor-augmented insulin pump therapy (SAP) in addition to a comprehensive diabetes program on glycated hemoglobin (HbA1c), severe hypoglycemia, ketoacidosis, and the hospital admission rate in patients with type 1 diabetes under real-world settings during a 2-year follow-up. METHODS: This was a retrospective real-life study comparing diabetes control before and after SAP therapy initiation. Patients ≥18 years old with type 1 diabetes were included. They were followed for 2 years with clinical assessments at months 3, 6, 12, 18, and 24. Effectiveness was estimated by difference in medians of HbA1c from baseline and at each follow-up visit. Safety was assessed by comparing the annual rates of severe hypoglycemia, hyperglycemic crisis, and hospital admission related to diabetes. RESULTS: 162 patients were included, median age 32 years, women 73%). The main indication for SAP was poor metabolic control (51.2%). At 2 years HbA1c decreased from 8.4% to 7.5% (-0.9%, 95% CI: 0.5-1.2; p<0.0001), HbA1c ≤7% improved from 14.2% to 25.3% (11.1%, 95% CI: 19.7-2.5; p=0.006), and severe hypoglycemia decreased from 22.2% to 14.1% (-8.1%, 95% CI: -16.5 to 0.3; p=0.03). CONCLUSIONS: SAP therapy improved glycemic control after the third month of use and for up to 2 years of follow-up, with lower rates of hospital admission and severe hypoglycemia. More studies are needed to assess the add-on impact of education programs and technologies for diabetes care.

Microtensiometers Accurately Measure Stem Water Potential in Woody Perennials.

Stem water potential (Ψstem) is considered to be the standard measure of plant water status. However, it is measured with the pressure chamber (PC), an equipment that can neither provide continuous information nor be automated, limiting its use. Recent developments of microtensiometers (MT; FloraPulse sensors), which can continuously measure water tension in woody tissue of the trunk of the tree, can potentially highlight the dynamic nature of plant water relations. Thus, this study aimed to validate and assess the usefulness of the MT by comparing the Ψstem provided by MT with those same measurements from the PC. Here, two irrigation treatments (a control and a deficit treatment) were applied in a pear (Pyrus communis L.) orchard in Washington State (USA) to capture the full range of water potentials in this environment. Discrete measurements of leaf gas exchange, canopy temperature and Ψstem measured with PC and MT were made every two hours for four days from dawn to sunset. There were strong linear relationships between the Ψstem-MT and Ψstem-PC (R2 > 0.8) and with vapor pressure deficit (R2 > 0.7). However, Ψstem-MT was more variable and lower than Ψstem-PC when Ψstem-MT was below -1.5 MPa, especially during the evening. Minimum Ψstem-MT occurred later in the afternoon compared to Ψstem-PC. Ψstem showed similar sensitivity and coefficients of variation for both PC and MT acquired data. Overall, the promising results achieved indicated the potential for MT to be used to continuously assess tree water status.