Molecular engineering of supramolecular polymer adhesive with confined water and a single crown ether.

Here, we report a water-induced supramolecular polymer adhesive formed from confined water and an intrinsically amphiphilic macrocyclic self-assembly in a nanophase-separated structure. The selenium-containing crown ether macrocycle, featuring a strong hydrophilic hydrogen-bond receptor (selenoxide) and a synergistic hydrophobic selenium-substituted crown core, confines water within a segregated, interdigitated architecture. While water molecules typically freeze around 0 °C, the confined water in this supramolecular polymer remains in a liquid-like state down to -80 °C.

Dynamic anti-correlations of water hydrogen bonds.

Water is characterized by strong intermolecular hydrogen bonds (H-bonds) between molecules. The two hydrogen atoms in one water molecule can form H-bonds of dissimilar length. Although intimately connected to water's anomalous properties, the details and the origins of the asymmetry have remained elusive.

Deciphering Spectroscopic Signatures of Competing Ca - Peptide Interactions.

Calcium-protein interactions are of paramount importance in biochemistry. They are a key element in a number of biological processes, such as neuronal signaling. Therefore, an understanding of the interaction at the molecular level is highly desirable.

Fast Collective Hydrogen-Bond Dynamics in Hexafluoroisopropanol Related to its Chemical Activity.

Using fluorinated mono-alcohols, in particular hexafluoro-isopropanol (HFIP), as a solvent can enhance chemical reaction rates in a spectacular manner. Previous work has shown evidence that this enhancement is related to the hydrogen-bond structure of these liquids. Here, we investigate the hydrogen-bond dynamics of HFIP and compare it to that of its non-fluorinated analog, isopropanol.

Ion Association and Hydration of Some Heavy-Metal Nitrate Salts in Aqueous Solution.

Aqueous solutions of four heavy-metal nitrate salts (AgNO, TlNO, Cd(NO) and Pb(NO)) have been studied at 25 °C using broadband dielectric relaxation spectroscopy (DRS) at frequencies 0.27 ≤ ν/GHz ≤ 115 over the approximate concentration range 0.2 ≲ /mol L ≲ 2.

Flipping Water Orientation at the Surface of Water-in-Salt and Salt-in-Water Solutions.

Salt-in-water and water-in-salt mixtures are promising for battery applications and fine-tuning of room-temperature ionic liquid (RTIL) properties. Although critical processes take place at interfaces of these systems, including charge transfer and heterogeneous catalytic reactions, the microscopic interfacial structures remain unclear. Here, we apply heterodyne-detected sum-frequency generation spectroscopy to aqueous solutions of imidazolium-based RTILs to unveil the microscopic structure of the interfaces of these solutions with air.

Weight-Inclusive Approaches to Nutrition and Dietetics: A Needed Paradigm Shift.

This Perspective article encourages the field of nutrition and dietetics to move away from a weight-centric paradigm that emphasizes weight loss and weight management as primary health outcomes. This approach can perpetuate weight stigma, which is associated with poorer health behaviors, poorer mental health, disordered eating, and even increased mortality risk. We propose an alternative approach-adopting a weight-inclusive paradigm-that focuses on providing care across the weight spectrum by centering health behaviors rather than weight.

Pushing redox potentials to highly positive values using inert fluorobenzenes and weakly coordinating anions.

While the development of weakly coordinating anions (WCAs) received much attention, the progress on weakly coordinating and inert solvents almost stagnated. Here we study the effect of strategic F-substitution on the solvent properties of fluorobenzenes CFH (xFB, x = 1-5). Asymmetric fluorination leads to dielectric constants as high as 22.

Predicting and Probing the Local Temperature Rise Around Plasmonic Core-Shell Nanoparticles to Study Thermally Activated Processes.

Ultrafast spectroscopy can be used to study dynamic processes on femtosecond to nanosecond timescales, but is typically used for photoinduced processes. Several materials can induce ultrafast temperature rises upon absorption of femtosecond laser pulses, in principle allowing to study thermally activated processes, such as (catalytic) reactions, phase transitions, and conformational changes. Gold-silica core-shell nanoparticles are particularly interesting for this, as they can be used in a wide range of media and are chemically inert.

Ion and Molecular Sieving With Ultrathin Polydopamine Nanomembranes.

In contrast to biological cell membranes, it is still a major challenge for synthetic membranes to efficiently separate ions and small molecules due to their similar sizes in the sub-nanometer range. Inspired by biological ion channels with their unique channel wall chemistry that facilitates ion sieving by ion-channel interactions, the first free-standing, ultrathin (10-17 nm) nanomembranes composed entirely of polydopamine (PDA) are reported here as ion and molecular sieves. These nanomembranes are obtained via an easily scalable electropolymerization strategy and provide nanochannels with various amine and phenolic hydroxyl groups that offer a favorable chemical environment for ion-channel electrostatic and hydrogen bond interactions.

Ecological Momentary Assessment of Weight Stigma and Eating Behavior in Everyday Life.

Background: Weight stigma is widespread, but the existing literature on its harmful consequences remains largely limited to lab-based experiments and large-scale longitudinal designs.

Purpose: The purpose of this study was to understand how weight stigma unfolds in everyday life, and whether it predicts increased eating behavior.

Methods: In this event-contingent ecological momentary assessment study, 91 participants reported every time they experienced weight stigma and documented whether they ate, how much they ate, and what they ate.

Social class stigma and poorer health behaviors: Evidence from the eating in America study.

Although the association between objective markers of low socioeconomic status (SES) and poor health is well established, one underexamined possibility is that over and above objective SES, social class stigma-experiences and anticipation of discrimination based on social class-might undermine people's ability to engage in healthy behaviors. Participants (N = 2022) were recruited between December 2019 and January 2020 via a national Qualtrics panel that was census-matched to the U.S.

Elucidating the role of water in collagen self-assembly by isotopically modulating collagen hydration.

Water is known to play an important role in collagen self-assembly, but it is still largely unclear how water-collagen interactions influence the assembly process and determine the fibril network properties. Here, we use the H[Formula: see text]O/D[Formula: see text]O isotope effect on the hydrogen-bond strength in water to investigate the role of hydration in collagen self-assembly. We dissolve collagen in H[Formula: see text]O and D[Formula: see text]O and compare the growth kinetics and the structure of the collagen assemblies formed in these water isotopomers.

Examining the effect of weight-related recruitment information on participant characteristics: A randomized field experiment.

Objective: Although 82% of American adults have a body mass index (BMI) of over 25, individuals with elevated BMI are considered difficult to recruit for studies. Effective participant identification and recruitment are crucial to minimize the likelihood of sampling bias. One understudied factor that could lead to sampling bias is the study information presented in recruitment materials.

Delayed diagnosis of a transient ischemic attack caused by ChatGPT.

Techniques of artificial intelligence (AI) are increasingly used in the treatment of patients, such as providing a diagnosis in radiological imaging, improving workflow by triaging patients or providing an expert opinion based on clinical symptoms; however, such AI techniques also hold intrinsic risks as AI algorithms may point in the wrong direction and constitute a black box without explaining the reason for the decision-making process.This article outlines a case where an erroneous ChatGPT diagnosis, relied upon by the patient to evaluate symptoms, led to a significant treatment delay and a potentially life-threatening situation. With this case, we would like to point out the typical risks posed by the widespread application of AI tools not intended for medical decision-making.

A systematic review of weight stigma and disordered eating cognitions and behaviors.

Weight stigma is persistent across contexts and is associated with disordered eating cognitions and behaviors. This systematic review aimed to examine the existing literature that has explored the relationship between weight stigma and disordered eating cognitions and behaviors. We specifically examined three dimensions of weight stigma - experienced, anticipated, and internalized - and adopted an inclusive conceptualization of outcomes related to disordered eating (including constructs such as binge eating, body dissatisfaction, and other cognitions and behaviors such as dietary restraint, unhealthy weight control behaviors, and drive for thinness).

Liquid-Liquid Phase Separation of the Intrinsically Disordered Domain of the Fused in Sarcoma Protein Results in Substantial Slowing of Hydration Dynamics.

Formation of liquid condensates plays a critical role in biology via localization of different components or via altered hydrodynamic transport, yet the hydrogen-bonding environment within condensates, pivotal for solvation, has remained elusive. We explore the hydrogen-bond dynamics within condensates formed by the low-complexity domain of the fused in sarcoma protein. Probing the hydrogen-bond dynamics sensed by condensate proteins using two-dimensional infrared spectroscopy of the protein amide I vibrations, we find that frequency-frequency correlations of the amide I vibration decay on a picosecond time scale.

nanoparticle-based T cell imaging can predict therapy response towards adoptive T cell therapy in experimental glioma.

Intrinsic brain tumors, such as gliomas are largely resistant to immunotherapies including immune checkpoint blockade. Adoptive cell therapies (ACT) including chimeric antigen receptor (CAR) or T cell receptor (TCR)-transgenic T cell therapy targeting glioma-associated antigens are an emerging field in glioma immunotherapy. However, imaging techniques for non-invasive monitoring of adoptively transferred T cells homing to the glioma microenvironment are currently lacking.

Longitudinal Stability of Disordered-Eating Symptoms From Age 12 to 40 in Black and White Women.

The purpose of the current study was to test the longitudinal association between disordered eating symptoms (body dissatisfaction, drive for thinness and bulimia) in adolescence (ages 12, 14, 16, 18, 19) and adulthood (age 40) in a sample of 883 white and Black women. We also investigated moderation by race. Adolescent symptoms at each time point significantly predicted adulthood symptoms for the body dissatisfaction and drive for thinness subscales, for both Black and white women.

Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis.

Photoactive complexes with earth-abundant metals have attracted increasing interest in the recent years fueled by the promise of sustainable photochemistry. However, sophisticated ligands with complicated syntheses are oftentimes required to enable photoactivity with nonprecious metals. Here, we combine a cheap metal with simple ligands to easily access a photoactive complex.

A Cellular Ground Truth to Develop MRI Signatures in Glioma Models by Correlative Light Sheet Microscopy and Atlas-Based Coregistration.

Glioblastoma is the most common malignant primary brain tumor with poor overall survival. Magnetic resonance imaging (MRI) is the main imaging modality for glioblastoma but has inherent shortcomings. The molecular and cellular basis of MR signals is incompletely understood.