Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer.

Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

'That is because we are alone': A relational qualitative study of socio-spatial inequities in maternal and newborn health programme coverage in rural Uttar Pradesh, India.

This qualitative study was conducted in Uttar Pradesh state, India to explore how interrelated socio-economic position and spatial characteristics of four diverse villages may have influenced equity in coverage of community-based maternal and newborn health (MNH) services. We conducted social mapping and three focus group discussions in each village, among women of lower and higher socio-economic position who recently gave birth, and with community health workers (n = 134). Data were analysed in NVivo 11.0 using thematic framework analysis. The extent of socio-economic hierarchies and spatial disparateness within the village, combined with distance to larger centers, together shaped villages' level of socio-spatial remoteness. Disadvantaged socio-economic groups expressed being more often spatially isolated, with less access to infrastructure, resources or services, which was heightened if the village was physically distant from larger centers. In more socio-spatially remote villages, inequities in coverage of MNH services that disadvantaged lower socio-economic position groups were compounded as these groups more often experienced ASHA vacancies, as well as greater distance to and poorer perceived quality of health services nearest the village. The results inform a conceptual framework of 'socio-spatial remoteness' that can guide public health research and programmes to more comprehensively address health inequities within India and beyond.

Structural and functional characterization of the IgSF21-neurexin2α complex and its related signaling pathways in the regulation of inhibitory synapse organization.

The prevailing model behind synapse development and specificity is that a multitude of adhesion molecules engage in transsynaptic interactions to induce pre- and postsynaptic assembly. How these extracellular interactions translate into intracellular signal transduction for synaptic assembly remains unclear. Here, we focus on a synapse organizing complex formed by immunoglobulin superfamily member 21 (IgSF21) and neurexin2α (Nrxn2α) that regulates GABAergic synapse development in the mouse brain. We reveal that the interaction between presynaptic Nrxn2α and postsynaptic IgSF21 is a high-affinity receptor-ligand interaction and identify a binding interface in the IgSF21-Nrxn2α complex. Despite being expressed in both dendritic and somatic regions, IgSF21 preferentially regulates dendritic GABAergic presynaptic differentiation whereas another canonical Nrxn ligand, neuroligin2 (Nlgn2), primarily regulates perisomatic presynaptic differentiation. To explore mechanisms that could underlie this compartment specificity, we targeted multiple signaling pathways pharmacologically while monitoring the synaptogenic activity of IgSF21 and Nlgn2. Interestingly, both IgSF21 and Nlgn2 require c-jun N-terminal kinase (JNK)-mediated signaling, whereas Nlgn2, but not IgSF21, additionally requires CaMKII and Src kinase activity. JNK inhibition diminished de novo presynaptic differentiation without affecting the maintenance of formed synapses. We further found that Nrxn2α knockout brains exhibit altered synaptic JNK activity in a sex-specific fashion, suggesting functional linkage between Nrxns and JNK. Thus, our study elucidates the structural and functional relationship of IgSF21 with Nrxn2α and distinct signaling pathways for IgSF21-Nrxn2α and Nlgn2-Nrxn synaptic organizing complexes in vitro. We therefore propose a revised hypothesis that Nrxns act as molecular hubs to specify synaptic properties not only through their multiple extracellular ligands but also through distinct intracellular signaling pathways of these ligands.

Ligand-Directed Self-Assembly of Organic-Semiconductor/Quantum-Dot Blend Films Enables Efficient Triplet Exciton-Photon Conversion.

Blends comprising organic semiconductors and inorganic quantum dots (QDs) are relevant for many optoelectronic applications and devices. However, the individual components in organic-QD blends have a strong tendency to aggregate and phase-separate during film processing, compromising both their structural and electronic properties. Here, we demonstrate a QD surface engineering approach using electronically active, highly soluble semiconductor ligands that are matched to the organic semiconductor host material to achieve well-dispersed inorganic-organic blend films, as characterized by X-ray and neutron scattering, and electron microscopies. This approach preserves the electronic properties of the organic and QD phases and also creates an optimized interface between them. We exemplify this in two emerging applications, singlet-fission-based photon multiplication (SF-PM) and triplet-triplet annihilation-based photon upconversion (TTA-UC). Steady-state and time-resolved optical spectroscopy shows that triplet excitons can be transferred with near unity efficiently across the organic-inorganic interface, while the organic films maintain efficient SF (190% yield) in the organic phase. By changing the relative energy between organic and inorganic components, yellow upconverted emission is observed upon 790 nm NIR excitation. Overall, we provide a highly versatile approach to overcome longstanding challenges in the blending of organic semiconductors with QDs that have relevance for many optical and optoelectronic applications.

Implementation and Adaptation of the Safewards Model in the New Zealand Context. Perspectives of Tangata Whai Ora and Staff.

The safety of service users and staff is paramount in cultivating a therapeutic environment within inpatient mental health units. The Safewards model, originating in the United Kingdom, aims to reduce conflict and containment rates through 10 interventions. This study used participatory action research to explore the perspective of tangata whai ora and staff regarding the adaptation of the Safewards model to the unique New Zealand context. Such adaptation is critical due to significant health outcome disparities between Maori and non-Maori populations and the disproportionate representation of Maori within mental health services. In adhering to the principles of Te Tiriti o Waitangi, cultural adaptation becomes an imperative obligation. The study utilised qualitative content analysis and thematic analysis, drawing data from focus groups of staff (n = 15) and tangata whai ora (n = 3). This study describes a New Zealand Safewards model, which must include Te Ao Maori, align with current practices, adapt Safewards interventions and gain acceptance. Organisational change management is pivotal in the integration of this model into nursing practice. The outcomes of this study hold the potential to contribute to the formulation and implementation of a New Zealand Safewards model, while also bearing relevance for the international adaptation of Safewards to culturally diverse countries and healthcare systems.

Understanding radiation-generated electronic traps in radiation dosimeters based on organic field-effect transistors.

Organic dosimeters offer unique advantages over traditional technologies, and they can be used to expand the capabilities of current radiation detection systems. In-depth knowledge of the mechanisms underlying the interaction between radiation and organic materials is essential for their widespread adoption. Here, we identified and quantitatively characterized the electronic traps generated during the operation of radiation dosimeters based on organic field-effect transistors. Spectral analysis of the trap density of states, along with optical and structural studies, revealed the origin of trap states as local structural disorder within the crystalline films. Our results provide new insights into the radiation-induced defects in organic dosimeters, and pave the way for the development of more efficient and reliable radiation detection devices.

In vivo human medial gastrocnemius fascicle behaviour and belly gear during submaximal eccentric contractions are not affected by concentric fatiguing exercise.

Changes in muscle geometry and belly gearing during eccentric contractions influence fibre strain and susceptibility to muscle damage. They are modulated by the interaction between connective tissues and intracellular-intrafascicular fluid pressures and external pressures from neighbouring structures. Fatiguing exercise triggers fluid shifts (muscle swelling) and muscle activation changes that may influence these modulators. Our purpose was to measure medial gastrocnemius (MG) geometric changes in vivo during eccentric contractions before and after maximal concentric muscle work to test the hypothesis that fatigue would reduce fascicle rotation and muscle gear and provoke greater fascicle strain. Submaximal eccentric plantar flexor contractions at 40% and 60% of maximal eccentric torque were performed on an isokinetic dynamometer at 5°.s-1 before and immediately after the fatiguing exercise. MG fascicles and muscle-tendon junction were captured using ultrasonography during contractions, allowing quantification of geometric changes, whole-MG length, and belly gear (Δmuscle length/Δfascicle length). Triceps surae (TS) activation was estimated using surface electromyography and the distribution of activations between synergistic muscles was then determined. After exercise, concentric torque decreased ∼39% and resting muscle thickness increased by 4%, indicating muscle fatigue and swelling, respectively. While soleus (Sol) activation and the Sol/TS ratio increased, no changes in MG, MG/TS ratio or fascicle rotation during the contraction were detected. Thus, fascicle lengthening and belly gear remained unaltered. Changes in muscle thickness during contraction was also similar before and after exercise, suggesting that changes in muscle shape were relatively unaffected by the exercise. Consequently, the muscle maintained mechanical integrity after the fatiguing muscle work.

Molecular Control of Triplet-Pair Spin Polarization and Its Optoelectronic Magnetic Resonance Probes.

ConspectusPreparing and manipulating pure magnetic states in molecular systems are the key initial requirements for harnessing the power of synthetic chemistry to drive practical quantum sensing and computing technologies. One route for achieving the requisite higher spin states in organic systems exploits the phenomenon of singlet fission, which produces pairs of triplet excited states from initially photoexcited singlets in molecular assemblies with multiple chromophores. The resulting spin states are characterized by total spin (quintet, triplet, or singlet) and its projection onto a specified molecular or magnetic field axis. These excited states are typically highly polarized but exhibit an impure spin population pattern. Herein, we report the prediction and experimental verification of molecular design rules that drive the population of a single pure magnetic state and describe the progress toward its experimental realization.A vital feature of this work is the close partnership among theory, chemical synthesis, and spectroscopy. We begin by presenting our theoretical framework for understanding spin manifold interconversion in singlet fission systems. This theory makes specific testable predictions about the intermolecular structure and orientation relative to an external magnetic field that should lead to pure magnetic state preparation and provides a powerful tool for interpreting magnetic spectra. We then test these predictions through detailed magnetic spectroscopy experiments on a series of new molecular architectures that meet one or more of the identified structural criteria. Many of these architectures rely on the synthesis of molecules with features unique to this effort: rigid bridges between chromophores in dimers, heteroacenes with tailored singlet/triplet-pair energy level matching, or side-group engineering to produce specific crystal structures. The spin evolution of these systems is revealed through our application and development of several magnetic resonance methods, each of which has different sensitivities and relevance in environments relevant to quantum applications.Our theoretical predictions prove to be remarkably consistent with our experimental results, though experimentally meeting all the structural prescriptions demanded by theory for true pure-state preparation remains a challenge. Our magnetic spectra agree with our model of triplet-pair behavior, including funneling of the population to the ms = 0 magnetic sublevel of the quintet under specified conditions in dimers and crystals, showing that this phenomenon is subject to control through molecular design. Moreover, our demonstration of novel and/or highly sensitive detection mechanisms of spin states in singlet fission systems, including photoluminescence (PL), photoinduced absorption (PA), and magnetoconductance (MC), points the way toward both a deeper understanding of how these systems evolve and technologically feasible routes toward experiments at the single-molecule quantum limit that are desirable for computational applications.

Free and open-source software for object detection, size, and colour determination for use in plant phenotyping.

BACKGROUND: Object detection, size determination, and colour detection of images are tools commonly used in plant science. Key examples of this include identification of ripening stages of fruit such as tomatoes and the determination of chlorophyll content as an indicator of plant health. While methods exist for determining these important phenotypes, they often require proprietary software or require coding knowledge to adapt existing code. RESULTS: We provide a set of free and open-source Python scripts that, without any adaptation, are able to perform background correction and colour correction on images using a ColourChecker chart. Further scripts identify objects, use an object of known size to calibrate for size, and extract the average colour of objects in RGB, Lab, and YUV colour spaces. We use two examples to demonstrate the use of these scripts. We show the consistency of these scripts by imaging in four different lighting conditions, and then we use two examples to show how the scripts can be used. In the first example, we estimate the lycopene content in tomatoes (Solanum lycopersicum) var. Tiny Tim using fruit images and an exponential model to predict lycopene content. We demonstrate that three different cameras (a DSLR camera and two separate mobile phones) are all able to model lycopene content. The models that predict lycopene or chlorophyll need to be adjusted depending on the camera used. In the second example, we estimate the chlorophyll content of basil (Ocimum basilicum) using leaf images and an exponential model to predict chlorophyll content. CONCLUSION: A fast, cheap, non-destructive, and inexpensive method is provided for the determination of the size and colour of plant materials using a rig consisting of a lightbox, camera, and colour checker card and using free and open-source scripts that run in Python 3.8. This method accurately predicted the lycopene content in tomato fruit and the chlorophyll content in basil leaves.

Cushing Syndrome due to Adrenocortical Carcinoma During Pregnancy.

Cushing syndrome resulting from adrenocortical carcinoma in pregnancy is exceedingly rare. There are no validated guidelines to establish a diagnosis or guide management in pregnancy. We provide a case of a 31-year-old woman presenting for management of diabetes in pregnancy who appeared cushingoid. She was subsequently diagnosed with ACTH-independent Cushing syndrome and experienced preterm labor at 33 weeks' gestation, delivering a healthy infant. Four weeks postpartum, the patient underwent a left adrenalectomy and was subsequently diagnosed with adrenocortical carcinoma.

Multiexciton quintet state populations in a rigid pyrene-bridged parallel tetracene dimer.

The multiexciton quintet state, 5TT, generated as a singlet fission intermediate in pairs of molecular chromophores, is a promising candidate as a qubit or qudit in future quantum information science schemes. In this work, we synthesize a pyrene-bridged parallel tetracene dimer, TPT, with an optimized interchromophore coupling strength to prevent the dissociation of 5TT to two decorrelated triplet (T1) states, which would contaminate the spin-state mixture. Long-lived and strongly spin-polarized pure 5TT state population is observed via transient absorption spectroscopy and transient/pulsed electron paramagnetic resonance spectroscopy, and its lifetime is estimated to be >35 µs, with the dephasing time (T2) for the 5TT-based qubit measured to be 726 ns at 10 K. Direct relaxation from 1TT to the ground state does diminish the overall excited state population, but the exclusive 5TT population at large enough persistent density for pulsed echo determination of spin coherence time is consistent with recent theoretical models that predict such behavior for strict parallel chromophore alignment and large exchange coupling.

Development and validation of the student ratings in clinical teaching scale in Australia: a methodological study

PURPOSE: This study aimed to devise a valid measurement for assessing clinical students' perceptions of teaching practices. METHODS: A new tool was developed based on a meta-analysis encompassing effective clinical teaching-learning factors. Seventy-nine items were generated using a frequency (never to always) scale. The tool was applied to the University of New South Wales year 2, 3, and 6 medical students. Exploratory and confirmatory factor analysis (exploratory factor analysis [EFA] and confirmatory factor analysis [CFA], respectively) were conducted to establish the tool's construct validity and goodness of fit, and Cronbach's α was used for reliability. RESULTS: In total, 352 students (44.2%) completed the questionnaire. The EFA identified student-centered learning, problem-solving learning, self-directed learning, and visual technology (reliability, 0.77 to 0.89). CFA showed acceptable goodness of fit (chi-square P<0.01, comparative fit index=0.930 and Tucker-Lewis index=0.917, root mean square error of approximation=0.069, standardized root mean square residual=0.06). CONCLUSION: The established tool­Student Ratings in Clinical Teaching (STRICT)­is a valid and reliable tool that demonstrates how students perceive clinical teaching efficacy. STRICT measures the frequency of teaching practices to mitigate the biases of acquiescence and social desirability. Clinical teachers may use the tool to adapt their teaching practices with more active learning activities and to utilize visual technology to facilitate clinical learning efficacy. Clinical educators may apply STRICT to assess how these teaching practices are implemented in current clinical settings.

Integrated Radiology, Pathology, and Pharmacy Program to Accelerate Access to Osimertinib.

PURPOSE: Targeted therapy yields superior outcomes relative to genotype-agnostic therapy for patients with epidermal growth factor receptor (EGFR)-mutant lung cancer. Workflows that facilitate timely detection of EGFR mutations and early dispensation of osimertinib can improve management of this disease. METHODS: We developed an Integrated Radiology, Pathology, and Pharmacy Program to minimize delays in initiating osimertinib. The intervention consisted of parallel workflows coupling interventional radiology, surgical pathology, and analysis of nucleic acids from frozen tissue with early pharmacy engagement. We compared time to EGFR testing results and time to treatment for participating patients with those of historical cohorts. RESULTS: Between January 2020 and December 2021, 222 patients participated in the intervention. The median turnaround time from biopsy to EGFR results was 1 workday. Forty-nine (22%) tumors harbored EGFR exon 19 deletions or EGFR L858R. Thirty-one (63%) patients were prescribed osimertinib via the intervention. The median interval between osimertinib prescription and osimertinib dispensation was 3 days; dispensation occurred within 48 hours for 42% of patients. The median interval between biopsy and osimertinib dispensation was 5 days. Three patients received osimertinib within 24 hours of EGFR results. Compared with patients with EGFR-mutant non-small-cell lung cancer who were diagnosed through routine workflows, the intervention led to a significant reduction in median time between biopsy and EGFR results (1 v 7 days; P < .01) and median time to treatment initiation (5 v 23 days; P < .01). CONCLUSION: Combining radiology and pathology workflows with early parallel pharmacy engagement leads to a significant reduction in time to initiating osimertinib. Multidisciplinary integration programs are essential to maximize clinical utility of rapid testing.

The metabolic function of pyruvate kinase M2 regulates reactive oxygen species production and microbial killing by neutrophils.

Neutrophils rely predominantly on glycolytic metabolism for their biological functions, including reactive oxygen species (ROS) production. Although pyruvate kinase M2 (PKM2) is a glycolytic enzyme known to be involved in metabolic reprogramming and gene transcription in many immune cell types, its role in neutrophils remains poorly understood. Here, we report that PKM2 regulates ROS production and microbial killing by neutrophils. Zymosan-activated neutrophils showed increased cytoplasmic expression of PKM2. Pharmacological inhibition or genetic deficiency of PKM2 in neutrophils reduced ROS production and Staphylococcus aureus killing in vitro. In addition, this also resulted in phosphoenolpyruvate (PEP) accumulation and decreased dihydroxyacetone phosphate (DHAP) production, which is required for de novo synthesis of diacylglycerol (DAG) from glycolysis. In vivo, PKM2 deficiency in myeloid cells impaired the control of infection with Staphylococcus aureus. Our results fill the gap in the current knowledge of the importance of lower glycolysis for ROS production in neutrophils, highlighting the role of PKM2 in regulating the DHAP and DAG synthesis to promote ROS production in neutrophils.

An analysis of the barriers and enablers to implementing the Safewards model within inpatient mental health services.

Mental health inpatient units can provide a sanctuary for people to recover from mental illness. To support a therapeutic environment, the safety and well-being of service users and staff need protection through reduced conflict and containment rates. The Safewards model identifies 10 interventions to prevent conflict and containment. This paper aims to present barriers and enablers to implementing Safewards by analysing current literature on the Safewards model. It will also compare the Safewards model to New Zealand's Six Core Strategies. In a systematic search of 12 electronic databases following the PRISMA flow chart, 22 primary studies were included in this analysis. JBI tools were used for quality appraisal and deductive content analysis was used to organize and interpret data. Four categories were identified: (a) designing the Safewards interventions and implementation; (b) staff participation and perception of Safewards; (c) healthcare system influences on Safewards implementation; (d) service user participation and perception of Safewards. To support successful Safewards implementation in future practice, this review recommends that Safewards implementation is enabled through robust design of the Safewards interventions and implementation methods; staff participation and positive perception of the Safewards model; a resourced healthcare system that prioritizes Safewards implementation; service user awareness and participation in Safewards interventions. Interactionist perspectives may support the implementation of Safewards. This analysis is limited by research settings mostly being inpatient adult services and inadequate capturing of the service user voice. An ongoing review of barriers and enablers is important for supporting future Safewards implementation.

The role of hyaluronan in endothelial glycocalyx and potential preventative lifestyle strategy with advancing age.

The endothelial glycocalyx (EG) is a gel-like structure that forms a layer in between the surface of the endothelium and lumen. EG was once thought to be merely a structural support for the endothelium. However, in recent years, the importance of EG as a first line of defense and a key regulator to endothelial integrity has been illuminated. With advanced age, EG deterioration becomes more noticeable and at least partially associated with endothelial dysfunction. Hyaluronan (HA), one of the critical components of the EG, has distinct properties and roles to the maintenance of EG and endothelial function. Therefore, given the intimate relationship between the EG and endothelium during the aging process, HA may serve as a promising therapeutic target to prevent endothelial dysfunction.

Mixed Small-Molecule Matrices Improve Nanoparticle Dispersibility in Organic Semiconductor-Nanoparticle Films.

Controlling the dispersibility of nanocrystalline inorganic quantum dots (QDs) within organic semiconductor (OSC):QD nanocomposite films is critical for a wide range of optoelectronic devices. This work demonstrates how small changes to the OSC host molecule can have a dramatic detrimental effect on QD dispersibility within the host organic semiconductor matrix as quantified by grazing incidence X-ray scattering. It is commonplace to modify QD surface chemistry to enhance QD dispersibility within an OSC host. Here, an alternative route toward optimizing QD dispersibilities is demonstrated, which dramatically improves QD dispersibilities through blending two different OSCs to form a fully mixed OSC matrix phase.