Acid/Base-Responsive Circularly Polarized Luminescence Emitters with Configurationally Stable Nitrogen Stereogenic Centers.

A way to prevent the fast configurational interconversion of tertiary amines is to invoke Tröger's base analogs, which display methano- or ethano-bridged diazocine cores fused to aromatic rings. These derivatives are configurationally stable, even in acidic media when their structures bear ethylene bridges. Here, a two- to three-step synthesis is presented of methano- and ethano-bridged Tröger's base analogs with two peripheral fluorophores, i.

Can Deep Learning Search for Exceptional Chiroptical Properties? The Halogenated [6]Helicene Case.

The relationship between chemical structure and chiroptical properties is not always clearly understood. Nowadays, efforts to develop new systems with enhanced optical properties follow the trial-error method. A large number of data would allow us to obtain more robust conclusions and guide research toward molecules with practical applications.

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-]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).

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 (Ψ) can help in irrigation management decisions. To compare the response of the Ψ 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.

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.

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.

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

Unlabelled: 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.

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 ( L.

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.

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 C and C , with remarkably large binding constants (ca. 10  M ), as estimated by fluorescence measurements.

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

The combined effects of deficit irrigation and crop load level on sweet cherry ( 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 (ET) and (ii) a deficit irrigation treatment (DI) irrigated at 70% ET.

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(ONO) (en = ethylenediamine) complexes of ditopic ligands incorporating both ,'-dialkyl-4,4'-bipyridinium and -monoalkyl-4,4'-bipyridinium or -monoalkyl-2,7-diazapyrenium moieties leads to constitutionally dynamic systems responsive to the concentration of the components. At low concentrations, the metallamacrocyclic mononuclear [M] species is formed. In contrast, when the concentration is increased, a defined dinuclear [M] structure appears as a second species in equilibrium, becoming the major one at high concentrations.

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.

Microtensiometers Accurately Measure Stem Water Potential in Woody Perennials.

Stem water potential (Ψ) 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.

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.

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.

Polyethylenimine-Bisphosphonate-Cyclodextrin Ternary Conjugates: Supramolecular Systems for the Delivery of Antineoplastic Drugs.

Bisphosphonates (BPs) are bone-binding molecules that provide targeting capabilities to bone cancer cells when conjugated with drug-carrying polymers. This work reports the design, synthesis, and biological evaluation of polyethyleneimine-BP-cyclodextrin (PEI-BP-CD) ternary conjugates with supramolecular capabilities for the loading of antineoplastic drugs. A straightforward, modular, and versatile strategy based on the click aza-Michael addition reaction of vinyl sulfones (VSs) allows the grafting of BPs targeting ligands and βCD carrier appendages to the PEI polymeric scaffold.

Chiral Distorted Hexa-peri-hexabenzocoronenes Bearing a Nonagon-Embedded Carbohelicene.

A new family of chiral saddle-helix hybrid nanographenes is reported. The first hexa-peri-hexabenzocoronene (HBC) analogues bearing a nine-membered carbocycle are presented. Furthermore, for the first time, π-extended carbo[n]helicenes containing a nine-membered ring as part of the helical moiety have been synthesized.

Game of Cruxes: co-designing a game for scientists and stakeholders for identifying joint problems.

Unlabelled: Scientists increasingly cross their disciplinary boundaries and connect with local stakeholders to jointly solve complex problems. Working with stakeholders means higher legitimacy and supports practical impact of research. Games provide a tool to achieve such transdisciplinary collaboration.

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.

Octagon-Embedded Carbohelicene as a Chiral Motif for Circularly Polarized Luminescence Emission of Saddle-Helix Nanographenes.

We report a new family of hexa-peri-hexabenzocoronene (HBC)-based helical nanographenes incorporating π-extended carbo[5]helicenes bearing an octagonal carbocycle. This family represents a new kind of highly distorted saddle-helix hybrid nanographenes. For the first time, the eight-membered ring becomes a constituent of both a carbo[5]helicene and a HBC and thus, the negative curvature is responsible for twisting both units.