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Angewandte Chemie (International Ed. in... Jul 2024Metallo-supramolecular cages have garnered tremendous attention for their diverse yet molecular-level precision structures. However, physical properties of these...
Metallo-supramolecular cages have garnered tremendous attention for their diverse yet molecular-level precision structures. However, physical properties of these supramolecular ensembles, which are of potential significance in molecular electronics, remain largely unexplored. We herein constructed a series of octahedral metallo-cages and cage-fullerene complexes with notably enhanced structural stability. As such, we could systematically evaluate the electrical conductivity of these ensembles at both single-molecule level and aggregated bulk state (as well-defined films). Our findings reveal that counteranions and fullerene guests play a pivotal role in determining the electrical conductivity of aggregated state, while such effects are less significant for single-molecule conductance. Both counteranions and fullerenes effectively tune the electronic structures and packing density of metallo-supramolecular assemblies, and facilitate efficient charge transfer between the cage hosts and fullerenes, resulting in a notable one order of magnitude increase in electrical conductivity of the aggregated state.
PubMed: 38949854
DOI: 10.1002/anie.202410710 -
Angewandte Chemie (International Ed. in... Jul 2024Pd(II)-based low-symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such cages utilize either...
Pd(II)-based low-symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such cages utilize either more than one type of symmetrical ligands (e.g., Laa, Lbb, etc.) or only one type of unsymmetrical ligand (e.g., Lab). To significantly enhance the anisotropy, we have designed two unsymmetrical bidentate ligands i.e., Lab and Lcd, aiming a low-symmetry Pd2Lab2Lcd2-type cage. It was accomplished by high-fidelity integrative self-sorting of two different low-symmetry cages having Pd2Lab4 and Pd4Lcd8-type architectures (homoleptic complexes of the designed ligands). Structural constraints and geometry complementarity in the ligand design drive the non-statistical exclusive self-assembly of the Pd2Lab2Lcd2-type cage. By taking advantage of the complemental geometries between ligands, a low-symmetry Pd2Lab2Lcc2-type cage was also obtained. Heteromeric completive self-sorting of three homoleptic assemblies (Pd2Lab4, Pd4Lcc8 and Pd4Lcd8-type cages) into an exclusive mixture of Pd2Lab2Lcd2 and Pd2Lab2Lcc2-type mixed ligated assemblies was demonstrated through cage-to-cage transformations.
PubMed: 38949846
DOI: 10.1002/anie.202410219 -
JAMA Pediatrics Jul 2024Lesbian, gay, bisexual, transgender, queer, and/or questioning (LGBTQ+) youth face worse mental health outcomes than non-LGBTQ+ peers. Family support may mitigate this,...
IMPORTANCE
Lesbian, gay, bisexual, transgender, queer, and/or questioning (LGBTQ+) youth face worse mental health outcomes than non-LGBTQ+ peers. Family support may mitigate this, but sparse evidence demonstrates this in clinical settings.
OBJECTIVES
To compare depression and suicide risk between LGBTQ+ and non-LGBTQ+ youth in primary care settings and to investigate whether family support mitigates these negative mental health outcomes.
DESIGN, SETTING, AND PARTICIPANTS
This cross-sectional study uses data from well care visits completed by adolescents aged 13 to 19 years from February 2022 through May 2023, including the Patient Health Questionnaire-9 Modified for Teens (PHQ-9-M) and the Adolescent Health Questionnaire (AHQ; an electronic screener assessing identity, behaviors, and guardian support), at 32 urban or suburban care clinics in Pennsylvania and New Jersey.
EXPOSURES
The primary exposure was self-reported LGBTQ+ status. Family support moderators included parental discussion of adolescent strengths and listening to feelings. Race and ethnicity (determined via parent or guardian report at visit check-in), sex, payer, language, age, and geography were covariates.
MAIN OUTCOMES AND MEASURES
PHQ-9-M-derived mental health outcomes, including total score, recent suicidal ideation, and past suicide attempt.
RESULTS
The sample included 60 626 adolescents; among them, 9936 (16.4%) were LGBTQ+, 15 387 (25.5%) were Black, and 30 296 (50.0%) were assigned female sex at birth. LGBTQ+ youth, compared with non-LGBTQ+ youth, had significantly higher median (IQR) PHQ-9-M scores (5 [2-9] vs 1 [0-3]; P < .001) and prevalence of suicidal ideation (1568 [15.8%] vs 1723 [3.4%]; P < .001). Fewer LGBTQ+ youth endorsed parental support than non-LGBTQ+ youth (discussion of strengths, 8535 [85.9%] vs 47 003 [92.7%]; P < .001; and listening to feelings, 7930 [79.8%] vs 47 177 [93.1%]; P < .001). In linear regression adjusted for demographic characteristics and parental discussion of strengths, LGBTQ+ status was associated with a higher PHQ-9-M score (mean difference, 3.3 points; 95% CI, 3.2-3.3 points). In logistic regression, LGBTQ+ youth had increased adjusted odds of suicidal ideation (adjusted odds ratio, 4.3; 95% CI, 4.0-4.7) and prior suicide attempt (adjusted odds ratio, 4.4; 95% CI, 4.0-4.7). Parental support significantly moderated the association of LGBTQ+ status with PHQ-9-M score and suicidal ideation, with greater protection against these outcomes for LGBTQ+ vs non-LGBTQ+ youth.
CONCLUSIONS AND RELEVANCE
Compared with non-LGBTQ+ youth, LGBTQ+ youth at primary care visits had more depressive symptoms and higher odds of suicidal ideation and prior suicide attempt. Youth-reported parental support was protective against these outcomes, suggesting potential benefits of family support-focused interventions to mitigate mental health inequities for LGBTQ+ youth.
PubMed: 38949835
DOI: 10.1001/jamapediatrics.2024.1956 -
Law and Human Behavior Jun 2024The presence of callous-unemotional (CU) traits in adolescence predisposes youth to negative behavioral and social outcomes and may be particularly damaging to youth...
OBJECTIVE
The presence of callous-unemotional (CU) traits in adolescence predisposes youth to negative behavioral and social outcomes and may be particularly damaging to youth involved in the justice system. Whereas research has shown that CU traits predict later arrest, it remains unknown whether rearrest predicts changes in CU traits and whether these associations may be modified by maternal relationship quality. The present study assessed whether being rearrested predicted changes in CU traits and whether these associations varied by maternal warmth and maternal hostility.
HYPOTHESES
We hypothesized that self-reported CU traits would increase at data collection time points following rearrest. Further, we hypothesized that maternal warmth would buffer the negative effects of rearrest, whereas maternal hostility would not have a significant moderating effect on the associations.
METHOD
Hypotheses were tested using a large, multisite longitudinal data set of 1,216 justice-involved male youth (Mage = 15.82 years at baseline; 47% Latino, 38% Black/African American, 15% White). Data from a series of nine interviews (across a 7-year period) were used to determine associations between rearrest at one-time point and CU traits at the subsequent time point.
RESULTS
Rearrest is associated with a significant increase in CU traits. However, these associations are not moderated by either maternal warmth or maternal hostility.
CONCLUSIONS
Rearrest predicts increases in a known risk factor for healthy socioemotional development among justice-involved youths (CU traits). Moreover, the way rearrest is associated with CU traits does not change depending on maternal warmth; rearrest is associated with increases in CU traits irrespective of the quality of a youth's relationship with their mother. (PsycInfo Database Record (c) 2024 APA, all rights reserved).
Topics: Humans; Male; Adolescent; Mother-Child Relations; Female; Juvenile Delinquency; Longitudinal Studies; Hostility; Emotions; Antisocial Personality Disorder
PubMed: 38949766
DOI: 10.1037/lhb0000567 -
Methods in Molecular Biology (Clifton,... 2024The use of animal models is still widespread in science but there is a movement away from this manner of experimentation. One option approved by the FDA for human-like...
The use of animal models is still widespread in science but there is a movement away from this manner of experimentation. One option approved by the FDA for human-like studies is the hollow fiber bioreactor (HFS). HFSs are highly controllable, self-contained systems that allow for the modeling of individual tissues and disease phenotypes. Oxygen, drug concentration & half-life, and immune cell invasion are all scalable to human and veterinary conditions using a HFS. There are drawbacks to the systems including cost and contamination so the use of these systems must be carefully managed.With these limitations in mind, the scope of the technology is great. Antimicrobial susceptibility testing (AST) is possible with greater accuracy and clinical validity than classical in vitro techniques making minimal inhibitory concentration (MIC) data generated on the bench more translatable to the clinic.In this chapter, we will outline the background of the HFS and some typical uses.
Topics: Humans; Microbial Sensitivity Tests; Bioreactors; Animals; Anti-Bacterial Agents; Drug Resistance, Bacterial
PubMed: 38949701
DOI: 10.1007/978-1-0716-3981-8_7 -
ACS Applied Materials & Interfaces Jul 2024An essential requirement for biomedical devices is the capability of conformal adaptability on diverse irregular 3D (three-dimensional) nonflat surfaces in the human...
An essential requirement for biomedical devices is the capability of conformal adaptability on diverse irregular 3D (three-dimensional) nonflat surfaces in the human body that may be covered with liquids such as mucus or sweat. However, the development of reversible adhesive interface materials for biodevices that function on complex biological surfaces is challenging due to the wet, slippery, smooth, and curved surface properties. Herein, we present an ultra-adaptive bioadhesive for irregular 3D oral cavities covered with saliva by integrating a kirigami-metastructure and vertically self-aligning suction cups. The flared suction cup, inspired by octopus tentacles, allows adhesion to moist surfaces. Additionally, the kirigami-based auxetic metastructure with a negative Poisson's ratio relieves the stress caused by tensile strain, thereby mitigating the stress caused by curved surfaces and enabling conformal contact with the surface. As a result, the adhesive strength of the proposed auxetic adhesive is twice that of adhesives with a flat backbone on highly curved porcine palates. For potential application, the proposed auxetic adhesive is mounted on a denture and performs successfully in human subject feasibility evaluations. An integrated design of these two structures may provide functionality and potential for biomedical applications.
PubMed: 38949691
DOI: 10.1021/acsami.4c03363 -
Organic Letters Jul 2024A new self-cyclopropanation of 1,3-diphenylpropane-1,3-dione, leading to tetrasubstituted cyclopropane containing three contiguous stereogenic centers with high...
A new self-cyclopropanation of 1,3-diphenylpropane-1,3-dione, leading to tetrasubstituted cyclopropane containing three contiguous stereogenic centers with high stereoselectivity, has been achieved through violet-light-emitting diode-irradiated photocatalysis, featuring both cycloaddition and a distinctive rearrangement. Diverging from conventional cyclopropanation pathways, this reaction yields a tetrasubstituted cyclopropane through unprecedented rearrangement and cascade reactions.
PubMed: 38949643
DOI: 10.1021/acs.orglett.4c01875 -
Stress and Health : Journal of the... Jul 2024Findings have revealed a strong link between exposure to child maltreatment (CM) and later chronic pain. Concurrently, other findings have been grounded in the...
Findings have revealed a strong link between exposure to child maltreatment (CM) and later chronic pain. Concurrently, other findings have been grounded in the understanding that CM consequences may not end with the exposed individual, rather, they extend to their offspring. However, little is known regarding the possible intergenerational transmission of chronic pain following CM. This study examines whether chronic pain among parents and their young adult offspring may be associated with parental exposure to CM. Three hundred ninety-three parent-offspring dyads (parents' mean age = 58, SD = 5.91 years; offspring's mean age = 27, SD = 3.91 years) completed self-report questionnaires, assessing CM (CTQ), posttraumatic stress (PTS) and disturbances in self-organisation (DSO) symptoms (ITQ), and chronic pain. CM was associated with chronic pain mediated by DSO symptoms among parents (indirect effect = 0.77; p = 0.007) and PTS symptoms among offspring (indirect effect = 0.285; p = 0.005). Offspring chronic pain was significantly associated with parental CM through two intergenerational paths: the mediation of parents' DSO symptoms and chronic pain (indirect effect = 0.298; p = 0.011), and through parents' PTS symptoms and offspring's PTS symptoms (indirect effect = 0.077; p = 0.004). This study's findings support the relevance of the intergenerational transmission of chronic pain following parental exposure to CM. Furthermore, the findings reveal complex PTS symptoms as a possible underlying mechanism for the intergenerational associations of chronic pain following CM.
PubMed: 38949630
DOI: 10.1002/smi.3441 -
Journal of the American Chemical Society Jul 2024Advanced in vitro diagnosis technologies are highly desirable in early detection, prognosis, and progression monitoring of diseases. Here, we engineer a multiplex...
Advanced in vitro diagnosis technologies are highly desirable in early detection, prognosis, and progression monitoring of diseases. Here, we engineer a multiplex protein biosensing strategy based on the tunable liquid confinement self-assembly of multi-material heterochains, which show improved sensitivity, throughput, and accuracy compared to standard ELISA kits. By controlling the material combination and the number of ligand nanoparticles (NPs), we observe robust near-field enhancement as well as both strong electromagnetic resonance in polymer-semiconductor heterochains. In particular, their optical signals show a linear response to the coordination number of the semiconductor NPs in a wide range. Accordingly, a visible nanophotonic biosensor is developed by functionalizing antibodies on central polymer chains that can identify target proteins attached to semiconductor NPs. This allows for the specific detection of multiple protein biomarkers from healthy people and pancreatic cancer patients in one step with an ultralow detection limit (1 pg/mL). Furthermore, rapid and high-throughput quantification of protein expression levels in diverse clinical samples such as buffer, urine, and serum is achieved by combining a neural network algorithm, with an average accuracy of 97.3%. This work demonstrates that the heterochain-based biosensor is an exemplary candidate for constructing next-generation diagnostic tools and suitable for many clinical settings.
PubMed: 38949598
DOI: 10.1021/jacs.4c04460 -
Medical Physics Jul 2024MR-integrated proton therapy is under development. It consists of the unique challenge of integrating a proton pencil beam scanning (PBS) beam line nozzle with an...
BACKGROUND
MR-integrated proton therapy is under development. It consists of the unique challenge of integrating a proton pencil beam scanning (PBS) beam line nozzle with an magnetic resonance imaging (MRI) scanner. The magnetic interaction between these two components is deemed high risk as the MR images can be degraded if there is cross-talk during beam delivery and image acquisition.
PURPOSE
To create and benchmark a self-consistent proton PBS nozzle model for empowering the next stages of MR-integrated proton therapy development, namely exploring and de-risking complete integrated prototype system designs including magnetic shielding of the PBS nozzle.
MATERIALS AND METHODS
Magnetic field (COMSOL ) and radiation transport (Geant4) models of a proton PBS nozzle located at OncoRay (Dresden, Germany) were developed according to the manufacturers specifications. Geant4 simulations of the PBS process were performed by using magnetic field data generated by the COMSOL simulations. In total 315 spots were simulated which consisted of a scan pattern with 5 cm spot spacings and for proton energies of 70, 100, 150, 200, and 220 MeV. Analysis of the simulated deflection at the beam isocenter plane was performed to determine the self-consistency of the model. The magnetic fringe field from a sub selection of 24 of the 315 spot simulations were directly compared with high precision magnetometer measurements. These focused on the maximum scanning setting of 20 cm beam deflection as generated from the second scanning magnet in the PBS for a proton beam energy of 220 MeV. Locations along the beam line central axis (CAX) were measured at beam isocenter and downstream of 22, 47, 72, 97, and 122 cm. Horizontal off-axis positions were measured at 22 cm downstream of isocenter ( 50, 100, and 150 cm from CAX).
RESULTS
The proton PBS simulations had good spatial agreement to the theoretical values in all 315 spots examined at the beam line isocenter plane (0-2.9 mm differences or within 1.5 % of the local spot deflection amount). Careful analysis of the experimental measurements were able to isolate the changes in magnetic fields due solely to the scanning magnet contribution, and showed 1.9 1.2 -9.4 1.2 changes over the range of measurement locations. Direct comparison with the equivalent simulations matched within the measurement apparatus and setup uncertainty in all but one measurement point.
CONCLUSIONS
For the first time a robust, accurate and self-consistent model of a proton PBS nozzle assembly has been created and successfully benchmarked for the purposes of advancing MR-integrated proton therapy research. The model will enable confidence in further simulation based work on fully integrated designs including MRI scanners and PBS nozzle magnetic shielding in order to de-risk and realize the full potential of MR-integrated proton therapy.
PubMed: 38949569
DOI: 10.1002/mp.17279