bluuebunny/crossref_metadata_2025 huggingface dataset:
Clinical Outcomes After Admission of Patients With COVID-19 to Skilled Nursing Facilities
Authors: McGarry Brian E. , Gandhi Ashvin D. , Chughtai Mah Afroze , Yin Jiamin , Barnett Michael L.
Published: June 2024

Importance

During the COVID-19 pandemic, stabilized COVID-19–positive patients were discharged to skilled nursing facilities (SNFs) to alleviate hospital crowding. These discharges generated controversy due to fears of seeding outbreaks, but there is little empirical evidence to inform policy.

Objective

To assess the association between the admission to SNFs of COVID-19–positive patients and subsequent COVID-19 cases and death rates among residents.

Design, Setting, and Participants

This cohort study analyzed survey data from the National Healthcare Safety Network of the Centers for Disease Control and Prevention. The cohort included SNFs in the US from June 2020 to March 2021. Exposed facilities (ie, with initial admission of COVID-19–positive patients) were matched to control facilities (ie, without initial admission of COVID-19–positive patients) in the same county and with similar preadmission case counts. Data were analyzed from June 2023 to February 2024.

Exposure

The week of the first observable admission of COVID-19–positive patients (defined as those previously diagnosed with COVID-19 and continued to require transmission-based precautions) during the study period.

Main Outcomes and Measures

Weekly counts of new cases of COVID-19, COVID-19–related deaths, and all-cause deaths per 100 residents in the week prior to the initial admission. A stacked difference-in-differences approach was used to compare outcomes for 10 weeks before and 15 weeks after the first admission. Additional analyses examined whether outcomes differed in facilities with staff or personal protective equipment (PPE) shortages.

Results

A matched group of 264 exposed facilities and 518 control facilities was identified. Over the 15-week follow-up period, exposed SNFs had a cumulative increase of 6.94 (95% CI, 2.91-10.98) additional COVID-19 cases per 100 residents compared with control SNFs, a 31.3% increase compared with the sample mean (SD) of 22.2 (26.4). Exposed facilities experienced 2.31 (95% CI, 1.39-3.24) additional cumulative COVID-19–related deaths per 100 residents compared with control facilities, representing a 72.4% increase compared with the sample mean (SD) of 3.19 (5.5). Exposed facilities experiencing potential staff shortage and PPE shortage had larger increases in COVID-19 cases per 100 residents (additional 10.97 [95% CI, 2.76-19.19] cases and additional 14.81 [95% CI, 2.38-27.25] cases, respectively) compared with those without such shortages.

Conclusion

This cohort study suggests that admission of COVID-19–positive patients into SNFs early in the pandemic was associated with preventable COVID-19 cases and mortality among residents, particularly in facilities with potential staff and PPE shortages. The findings speak to the importance of equipping SNFs to adhere to infection-control best practices as they continue to face COVID-19 strains and other respiratory diseases.
Weight Indices, Cognition, and Mental Health From Childhood to Early Adolescence
Authors: Li Zhaolong Adrian , Ray Mary Katherine , Gu Yueping , Barch Deanna M. , Hershey Tamara
Published: June 2024

This cohort study evaluates the association between weight indices in childhood and changes in cognition and psychopathology.
Adaptive NNs asymptotic tracking control for high‐order nonlinear systems under prescribed performance and asymmetric output constraints
Authors: Jiang Kun , Zhang Xuxi
Published: June 2024

This article studies the adaptive neural networks (NNs) asymptotic tracking control of high‐order nonlinear systems subject to prescribed performance, non‐strict‐feedback structure, and output constraints. To address the output constraint issue while guaranteeing that the tracking error stays within the specified area, a variable fused with the time‐varying constraint functions is introduced. Then, a pivotal form of coordinate transformation is developed, which plays a key role in achieving asymptotic tracking performance. Based on the backstepping and Lyapunov method, the designed control scheme assures that all system variables are semi‐globally uniformly ultimately bounded, the output constraints are never broken, and the tracking error always stays within the predefined function and asymptotically converges to zero. Finally, the effectiveness of theoretical findings is verified via simulation studies.
Advances in Engineering Toolkits for Construction of Ultralow Disordered Van der Waals Heterostructures
Authors: Huang Zhujun , Shahrjerdi Davood
Published: June 2024

The exploration of emerging quantum phenomena by stacking dissimilar atomic layered materials into van der Waals (vdW) heterostructures has driven the development of layer assembly techniques. Achieving ultralow disorder within these heterostructures is crucial for unlocking their novel physical properties. However, current fabrication methods for designer heterostructures have limitations in throughput, yield, and scalability. Over the past decade, engineering toolkits have evolved to address some of these challenges, but their adoption for fabricating designer heterostructures remains limited. In this review, an overview of these emerging engineering toolkits is provided, and examine their utility and limitations in achieving ultralow disordered heterostructures. It is hoped that the insights from this review article can help guide future research directions on advancing the fabrication process of designer heterostructures.
Surface Passivation with Tailoring Organic Potassium Salt for Efficient FAPbI3 Perovskite Solar Cells and Modules
Authors: Zhang Shujie , Tian Ting , Li Jing , Su Zhiwei , Jin Chengkai , Su Jie , Li Wenke , Yuan Ye , Tong Jinhui , Peng Yong , Bai Sai , Müller‐Buschbaum Peter , Huang Fuzhi , Cheng Yi‐Bing , Bu Tongle
Published: June 2024

Passivating surface defects on perovskite films with tailored functional materials has emerged as one of the most effective strategies for achieving high‐performance perovskite solar cells (PSCs). Among existing material selections, potassium salts stand out for their effective passivation of defects surrounding perovskite grain boundaries. However, the widely used potassium salts are inorganic and only soluble in highly polar solvents, which limits their practical application for surface passivation. Herein, a novel organic potassium salt (KCFSO), with multiple organic functional groups and good solubility in low polar isopropanol, is reported to function as a post‐treatment agent for perovskite. Combined with experimental results and theoretical calculations, the formed multiple intermolecular interactions between KCFSO and perovskite are revealed to play a vital role in determining the defect passivation effect. Thus, the KCFSO‐modified film shows a more uniform surface potential distribution, dramatically decreased defect density, and improved charge transfer, leading to a champion power conversion efficiency (PCE) of 25.11%, and good stability for the derived PSCs. As a demonstration of scalability, the centimeter‐sized PSCs and 5 cm × 5 cm mini‐modules also demonstrate impressive PCEs of 24.17% and 20.18%, respectively. These findings provide insights into passivator design principles to achieve efficient and stable perovskite photovoltaics.
Polarization‐Dependent and Color‐Tunable Electrochromic Smart Windows: Uniaxially Oriented and Polymer‐Stabilized Viologen‐Based Liquid Crystal Networks
Authors: Pham Huan Huu , Rim Minwoo , Wi Youngjae , Ko Hyeyoon , Yu Dongmin , Hyeong Jaeseok , Tran Duy Thanh , Ha Minjeong , Na Seok‐In , Jeong Kwang‐Un
Published: June 2024

Viologen‐based reactive mesogen (VRM) is newly designed and synthesized for the development of polarization‐dependent, color‐tunable, and transparent electrochromic (EC) smart windows. By controlling electric field, the color of VRM can be intentionally tuned due to the formation of dication (D state), cation‐radical (C state), and neutral state (N state). Based on the deep understanding of phase transition of VRM, a uniaxially oriented VRM hierarchical nanostructure is successfully constructed on the macroscopic area by simple coating and self‐assembly processes. The subsequent photopolymerization significantly improves thermal, mechanical, and chemical stabilities of the VRM thin film. In addition to the control of color, the transmittance of uniaxially oriented VRM‐based EC smart window can be precisely tuned by rotating a linear polarizer.
Bioprinted Multi‐Composition Array Mimicking Tumor Microenvironments to Evaluate Drug Efficacy with Multivariable Analysis
Authors: Lee Gihyun , Kim Soo Jee , Park Je‐Kyun
Published: June 2024

Current organ‐on‐a‐chip technologies confront limitations in effectively recapitulating the intricate in vivo microenvironments and accommodating diverse experimental conditions on a single device. Here, a novel approach for constructing a multi‐composition tumor array on a single microfluidic device, mimicking complex transport phenomena within tumor microenvironments (TMEs) and allowing for simultaneous evaluation of drug efficacy across 12 distinct conditions is presented. The TME array formed by bioprinting on a microfluidic substrate consists of 36 individual TME models, each characterized by one of three different compositions and tested under four varying drug concentrations. Notably, the TME model exhibits precise compartmentalization, fostering the development of self‐organized vascular endothelial barriers surrounding breast cancer spheroids affecting substance transport. Multivariable screening and analysis of diverse conditions, including model complexity, replicates, and drug concentrations, within a single microfluidic platform, highlight the synergistic potential of integrating bioprinting with microfluidics to evaluate drug responses across diverse TME conditions comprehensively.
Fast‐Curing of Liquid Crystal Thermosets Enabled by End‐Groups Regulation and In Situ Monitoring by Triboelectric Spectroscopy
Authors: Zhang Haiyang , Han Yufei , Guan Qingbao , You Zhengwei , Zhu Meifang
Published: June 2024

The development of high‐performance polymer is crucial for the fabrication of triboelectric nanogenerators (TENGs) used in extreme conditions. Liquid crystal polyarylate thermosets (LCTs) demonstrate great potential as triboelectric material by virtue of exceptional comprehensive properties. However, there are only a few specific end‐groups like phenylethynyl matching the LCT polycondensation temperature (above 300 °C). Moreover, the excellent properties of LCTs rely on the crosslinked network formed with long curing time at high temperature, restricting their further application in triboelectric material. Herein, a fast‐curing LCT is designed by terminating with 4‐maleimidophenol possessing appropriate reactivity. The resultant LCT (MA‐LC‐MA) exhibits much lower polycondensation temperature (250–270 °C) and curing temperature of 300 °C within only 1 min compared to typical LCTs (cured at 370 °C for 1 h). Furthermore, the cured MA‐LC‐MA retains a high glass transition temperature of 135 °C, storage modulus of 6 MPa even at 350 °C, and great electrical output performance. Additionally, triboelectric measurement related to the dielectric properties that vary with crosslinked network is innovatively utilized as an analysis technique of curing progress. This work provides a new strategy to design high‐performance TENGs and promotes the development of next generation thermosets in extreme conditions.
Organocatalytic Asymmetric Decarboxylative Mannich Reaction for the Synthesis of Non‐Natural α‐Amino Acids Bearing Alkynyl Groups
Authors: Xu Xueting , Tu Shengyi , Sun Jiani , Lu Xuehe , Wu Xiaoyu
Published: June 2024

Asymmetric decarboxylative Mannich addition of β‐keto acids or malonic acid half‐esters to β,γ‐alkynyl‐α‐ketimino esters catalyzed by cinchona alkaloid‐derived squaramide has been developed. The reaction proceeded by forming a nucleophilic enolate after decarboxylation, followed by its addition to β,γ‐alkynyl‐α‐ketimino esters facilitated by the bifunctional catalyst. A broad range of substrates with various substituents are tolerated in this reaction, yielding a series of α,α‐disubstituted amino acid derivatives bearing alkynyl functional groups in high yields with good to excellent enantioselectivities. The practicality of this method was demonstrated by a gram‐scale reaction and subsequent elaboration of the Mannich adducts.
Fully Printed PTC Based Heat Transfer Sensor Array as Liquid Level Sensor
Authors: Bäuerle Rainer , Nazari Pariya , Zimmermann Johannes , Melzer Christian , Hernandez‐Sosa Gerardo , Kowalsky Wolfgang
Published: June 2024

Liquid levels must be monitored in almost any process involving liquids. Most level sensors are mounted inside the vessel containing the liquid. Herein, a fully screen‐printed level sensor is demonstrated for external use. It consists of a vertical array of 16 pixels, each comprising a voltage divider of a positive temperature coefficient (PTC) element and a shunt resistor. The self‐regulating PTC elements are heated with constant voltage. Heat flow out of the PTCs dictate their resistances and enables inference about their thermal surrounding. Water in a polypropylene container changes voltage levels by (33 ± 2) % compared to air. Applications with a glass container and household oil instead of water are also successfully tested. Both liquids yield a distinctive difference in signal and the sensor determines the height of the oil/water interface as well as the surfaces of the liquid. To further demonstrate the capabilities of the sensor, segregation of a water‐oil mixture, slowed by a mixing agent, is observed in real time. This work offers an adaptable and simple alternative for external level sensing.
A Facile Chemical Reduction Approach of Li–Sn Modified Li Anode for Dendrite Suppression
Authors: Amardeep Amardeep , Freschi Donald J. , Sang Lingzi , Liu Jian
Published: June 2024

Lithium dendrites are among the most significant threats associated with the practical application of lithium metal anode in lithium batteries. Lithium dendrites are caused by the slow Li‐ion diffusivity in the bulk lithium, which results in a non‐uniform electric field‐cum‐uneven Li plating/stripping at the electrode/electrolyte interface over prolonged cycling. Herein, a facile chemical reduction method is utilized to construct a Li‐ion diffusive Li–Sn protective layer on the electrolyte‐exposed surface of lithium metal to overcome the aforementioned challenge. A systematic study on the SnCl4 precursor concentration variation demonstrated that 25 mM SnCl4 concentration is the most effective and displays a cumulative areal capacity beyond 700 mAh cm−2 at 1 mA cm−2 for 1 h. Moreover, it exhibits superior cumulative capacities than bare Li metal at higher current densities of 2 and 3 mA cm−2. In situ optical microscopy reveals more uniform lithium deposition on the Li–Sn‐modified electrode, while mossy and dendritic lithium growth is observed on the bare lithium electrode. Full cells fabricated with Li–Sn modified anode and NMC532 cathode exhibited 83% capacity retention after 150 cycles, outperforming bare Li‐containing cells, which shows a catastrophic decay post 100 cycles, illustrating the propensity for safer Li metal batteries with Li–Sn modified anode.
Magnetic nanoparticle‐induced sorbent regeneration for direct air capture
Authors: Li Kai , Kesler Michael S. , McGuire Michael A. , Zhang Mingkan , Aytug Tolga , Jiang Huixin , Sholl David S. , Lara‐Curzio Edgar , Thompson Michael J. , Li Yanfei , Tener Zack P. , Nawaz Kashif
Published: June 2024

Direct air capture (DAC) is a promising technology for decarbonization through the removal of CO2 from the atmosphere. In many DAC processes, the regeneration energy used to restore the capture capacity of sorbents accounts for a significant fraction of the energy required by the whole process. Here we report an effective and scalable sorbent regeneration method for liquid DAC solvents based on magnetic nanoparticles (MNPs) heating with AC magnetic fields. MNPs can be directly heated to provide uniform and rapid volumetric heating, as we demonstrate by promoting the release of captured CO2 from an aqueous solution of potassium sarcosinate. Our results showed that 90% of the solvent can be regenerated within 7.5 min of heating through proposed technique. The MNPs and solvent are found to be stable during the regeneration process and the MNPs showed long‐term stability in the CO2‐saturated solvent. Cyclic experiments showed that the nanoparticles can be reused for multiple cycles without performance deterioration. The process is operated in a noncontact mode through electromagnetic waves, making it an adoptable approach for existing carbon capture systems. The MNPs heating provides an effective regeneration strategy for liquid solvents used in carbon capture processes, in particular for DAC.
Unprecedented Packing Polymorphism of Oxindole: An Exploration Inspired by Crystal Structure Prediction
Authors: Wu Emily J. , Kelly Andrew W. , Iuzzolino Luca , Lee Alfred Y. , Zhu Xiaolong
Published: June 2024

Crystal polymorphism, characterized by different packing arrangements of the same compound, strongly ties to the physical properties of a molecule. Determining the polymorphic landscape is complex and time‐consuming, with the number of experimentally observed polymorphs varying widely from molecule to molecule. Furthermore, disappearing polymorphs, the phenomenon whereby experimentally observed forms cannot be reproduced, pose a significant challenge for the pharmaceutical industry. Herein, we focused on oxindole (OX), a small rigid molecule with four known polymorphs, including a reported disappearing form. Using crystal structure prediction (CSP), we assessed OX solid‐state landscape and thermodynamic stability by comparing predicted structures with experimentally known forms. We then performed melt and solution crystallization in bulk and nanoconfinement to validate our predictions. These experiments successfully reproduced the known forms and led to the discovery of four novel polymorphs. Our approach provided insights into reconstructing disappearing polymorphs and building more comprehensive polymorph landscapes. These results also establish a new record of packing polymorphism for rigid molecules.
Tailoring Metallosupramolecular Glycoassemblies for Enhancing Lectin Recognition
Authors: Stauber Julia M.
Published: June 2024

Multivalency is a fundamental principle in nature that leads to high‐affinity intermolecular recognition through multiple cooperative interactions that overcome the weak binding of individual constituents. For example, multivalency plays a critical role in lectin‐carbohydrate interactions that participate in many essential biological processes. Designing high‐affinity multivalent glycoconjugates that engage lectins results in systems with the potential to disrupt these biological processes, offering promising applications in therapeutic design and bioengineering. Here, a versatile and tunable synthetic platform for the synthesis of metallosupramolecular glycoassemblies is presented that leverages subcomponent self‐assembly, which employs metal ion templates to generate complex supramolecular architectures from simple precursors in one pot. Through ligand design, this approach provides precise control over molecular parameters such as size, shape, flexibility, valency, and charge, which afforded a diverse family of well‐defined hybrid glyconanoassemblies. Evaluation of these complexes as multivalent binders to Concanavalin A (Con A) by isothermal titration calorimetry (ITC) demonstrates the optimal saccharide tether length and the effect of electrostatics on protein affinity, revealing insights into the impact of synthetic design on molecular recognition. The presented studies offer an enhanced understanding of structure‐function relationships governing lectin‐saccharide interactions at the molecular level and guide a systematic approach towards optimizing glyconanoassembly binding parameters.
In Situ pH Modulation for Enhanced Chemical Sensing: Strategies and Applications
Authors: Steininger Fabian , Koren Klaus
Published: June 2024

pH is one of the key parameters in chemistry and impacts almost all chemical and biological processes. Also, within analytical chemistry and sensing, pH plays a critical role. This review underscores the critical role of pH manipulation in overcoming analytical challenges posed by complex sample matrices and dynamic environmental conditions. It explores the available tools to control pH at a local scale and how those are or can be applied to improve sensor performance. We focus on four key areas where pH modulation has been or could be leveraged to advance chemical sensing capabilities: i) sensing alkalinity and buffer capacity, ii) sample pretreatment, iii) sensing pH dependent analytes and iv) reducing biofouling. We analyze existing strategies, but also try to identify unexplored possibilities which may have potential and can be exploited for sensing.
Light‐activated 3D printed fish‐like actuator
Authors: Pendlmayr Stefan , Ramos‐Docampo Miguel Alexandre , Bento David H. , Brodszkij Edit , Juhl Dennis Wilkens , Nielsen Niels Chr , Städler Brigitte
Published: June 2024

Hydrogel‐based actuators are innovative materials that exhibit responsive and dynamic behavior in response to external stimuli, making them promising candidates for a wide range of applications in fields such as soft robotics. We employ 3D printing to create layered rectangles, using a passive ink composed of gelatin methacryloyl (GelMA) and an active ink consisting of GelMA and poly(N‐isopropylacrylamide) (PNIPAM). Our aim is to assess and compare the bending capabilities of these structures based on their layer arrangements in a buffer above the lower critical solution temperature. Therefore, an asymmetric rectangular structure is selected as the shape‐changing component in the tail of a 3D printed fish‐shaped hydrogel actuator. We show that gold nanostars integrated into the actuators serve as photothermal elements, enabling the fish tail to repeatedly bend when near infrared light is turned on and off. Our effort illustrates the potential of combining 3D printing, responsive hydrogels and photothermal elements with near infrared light towards soft robotic applications. This combination yields actuators capable of shape‐shifting without requiring localized light or transitioning between environments with varying temperatures.
Optimized poly(methyl methacrylate)/mixed‐phase silver vanadate nanocomposites with tuned optical properties and hydrophobicity
Authors: Yousef Ezz , Ali M. K. M. , Allam Nageh K.
Published: June 2024

The fast advancements in technology have generated significant interest in optoelectronic materials. Nevertheless, the difficulty of creating affordable materials with exceptional optical characteristics is an ongoing challenge. Therefore, the objective of this work was to tune the optical properties of poly(methyl methacrylate) (PMMA) by embedding silver vanadate (SV) in the polymer matrix. Moreover, the wettability test of the fabricated composite membranes showed a hydrophobic behavior, with the PMMA film containing 0.6 wt.% SV showed a contact angle of 86.75 ± 0.7°. Furthermore, SV showed high thermal stability with a maximum weight loss of 0.74% at 830°C, which is very high thermal stability at high temperatures. In addition, the 0.6 wt.% SV@PMMA film exhibited a maximum weight loss of 96.7% at 785°C. Moreover, the 0.6 wt.% SV@PMMA film showed the lowest indirect band gap energy (2.02 eV) compared to the other films and pure SV NPs. The findings demonstrate the potential of the synthesized films for optoelectronic applications.
Recent Advances in Direct Regioselective C−H Chlorination at Aromatic and Aliphatic
Authors: Kachore Ankit , Aggarwal Varun , Bala Ekta , Singh Hemant , Guleria Saksham , Sharma Sakshi , Pathan Sameer , Saima  , Selvaraj Manickam , Assiri Mohammed A. , Kumar Verma Praveen
Published: June 2024

Direct installation of key functionalities in a molecule through C−H bond activation is one of the thrust areas as well as challenging task in organic synthesis. Particularly, introduction of chlorine in a molecule imparts additional benefits for further functionalizations as well as improves the electronic behaviour such as lipophilicity and polarity towards drug development process. The chlorinated molecules have also been established as efficient biologically relevant scaffolds. Current manuscript has been focused on the direct installation of the chlorine atom at various aromatic and aliphatic positions to produce functional molecules. The key highlight of the manuscript belongs to the site selectivity (regioselectivity) for the installation of chlorine functionality. Manuscript describes the advanced methods developed for the direct C−H chlorination reactions and further simplified for the chlorination reactions at various positions including aromatic (o‐, m‐, and p‐), benzylic, heteroaromatic, and aliphatic positions. Directing groups (DGs) and the coordination with the catalyst is the key for the enhancement of regioselectivities during direct C−H chlorination reactions.
A novel equivalent reciprocal convex combination technique to sampled‐data master–slave synchronization for chaotic Lur'e systems with time‐varying delays
Authors: Ji Wenchengyu , Jiang Yulian , Wang Shenquan
Published: June 2024

For a class of master–slave (M‐S) systems in chaotic Lur'e systems with time‐varying delays, a sampled‐data synchronization controller is designed, and a new synchronization stability condition is proposed in the form of linear matrix inequality. A novel Lyapunov‐Krasovskii functional (LKF) is constructed by using the looped‐functional method, and the positive definiteness condition of LKF including sampled‐data parts is exchanged with a looping condition by constructing a functional, which should be equal at adjacent sampling times. The M‐S synchronization condition is obtained utilizing the equivalent reciprocal convex combination approach combined with Bessel‐Legendre integral inequality to estimate the LKF derivative. Different from previous methods, due to fully utilizing both nonlinearity and state information at the sampling time via the integral of error systems from the sampling time to current one, the M‐S synchronization condition is less conservative, and obtained sampled‐data controller possesses a longer sampling period. Finally, two numerical examples verify the superiority and validity of the approach.
Language growth in verbal autistic children from 5 to 11 years
Authors: Brignell Amanda , Williams Katrina J. , Reilly Sheena , Morgan Angela T.
Published: June 2024

To examine predictors and growth in language for verbal autistic and non‐autistic children with/without low language from 4 to 11 years. Receptive and expressive language trajectories were compared in a community sample of 1026 children at ages 5, 7, and 11 years, across four groups: two autistic groups; one with and one without low language; and two non‐autistic groups; one with and one without low language. Groups were delineated on baseline assessment at 4 years. Non‐autistic and autistic children with low language had lower mean expressive language scores than the non‐autistic typical language group (22.26 and 38.53 units lower, respectively, p < 0.001), yet demonstrated faster language growth across 5 to 11 years (p < 0.001 and p = 0.002, respectively). Both groups without low language had similar mean expressive language scores (p = 0.864) and a comparable rate of growth (p = 0.645). Language at 4 years was the only consistent predictor of language at 11 years for autistic children. Results were similar for receptive language in all analyses except there was no significant difference in rate of progress (slope) for the autistic with low language group compared with the typical language group (p = 0.272). Findings suggest early language ability, rather than a diagnosis of autism, is key to determining language growth and outcomes at 11 years in verbal children. Furthermore, children with low language showed developmental acceleration compared with same age peers.
Loneliness in daily life: A comparison between youths with autism spectrum disorders and 22q11.2 deletion syndrome (22q11DS)
Authors: Feller Clémence , Ilen Laura , Eliez Stephan , Schneider Maude
Published: June 2024

Loneliness is a negative emotional experience that can stem from a gap between desires and the reality of social relationships. It is also a predictor of mental health. Loneliness is therefore important to investigate in neurodevelopmental populations known for having difficulties in the social sphere. This co‐registered study involved 48 youths with autism spectrum disorders (ASD), 54 youths with 22q11.2 deletion syndrome (22q11DS) and 65 typically developing youths (TD) aged 12–30. State loneliness was assessed with an ecological momentary assessment. Paper–pencil questionnaires assessing attitude toward aloneness, trait loneliness, and mental health, were completed by the youths and their caregivers. A comparable level of state loneliness between clinical groups and TD were found, with greater loneliness when alone than in a social context. Clinical groups showed a greater intra‐individual variability. Both individuals with ASD and 22q11DS revealed a greater affinity toward being alone than TD, but only individuals with ASD reported greater trait loneliness. However, no significant association was found between attitude toward aloneness, trait and state loneliness. Emotional reactivity to loneliness was different between the clinical groups. Self‐reported mental health only was associated with loneliness in the clinical groups. These results provide new insights into the understanding of loneliness in these clinical populations and have an impact on clinical care by highlighting the need to remain vigilant when encountering youths who report feeling lonely, and that these youths need to be supported in developing their social network, which appears to be a protective factor against loneliness.
An activatable azophenyl fluorescent probe for hypoxic fluorescence imaging in living cells
Authors: Liu Zhiyang , Zhang Zongyu , Li Juping , Zhu Guanqun , Li Quan
Published: June 2024

Cellular hypoxia is a common pathological process in various diseases. Detecting cellular hypoxia is of great scientific significance for early diagnosis of tumors. The hypoxia fluorescence probe analysis method can efficiently and conveniently evaluate the hypoxia status in tumor cells. These probes are covalently linked by hypoxic recognition groups and organic fluorescent molecules. Currently, the fluorescent molecules used in these probes often exhibit the aggregation‐caused quenching effect, which is not conducive to fluorescence imaging in water. Herein, an activatable hypoxia fluorescence probe was constructed by covalently linking aggregation‐induced emission luminogens to the hypoxic recognition group azobenzene. It does not emit fluorescence in solution and in solid state under light excitation due to the presence of photosensitive azo bonds. It can be cleaved by intracellular azoreductase into fluorescent amino derivatives with aggregation‐induced emission characteristic. As the concentration of oxygen in cells decreases, its fluorescence intensity increases, making it suitable for fluorescence imaging to detect hypoxic environment in live cancer cells. This work broadens the molecular design approach for activatable hypoxia fluorescent probes.
A rare case report of heterotopic cesarean scar pregnancy in the 8th week of gestation that was managed successfully by exploratory laparotomy with dilation and curettage
Authors: Karbasi Mahsa , Aletaha Reza , Ahangar‐Sirous Ramin , Alamdari Amir Honarmand , Gharepapagh Esmaeil , Rezaei Sahar
Published: June 2024

Key Clinical Message

Swift and precise identification of heterotopic cesarean scar pregnancy, coupled with standardized treatment approaches for handling possible serious complications, form an essential component in reaching favorable outcomes for patients experiencing this rare type of pregnancy.

Heterotopic pregnancy (HP) denotes a form of multiple gestation where intrauterine and ectopic pregnancies coexist. Cesarean scar ectopic pregnancy, on the other hand, involves the implantation of a fetus over the previous cesarean scar. This condition poses a significant risk of uterine rupture, which may lead to serious health complications, and even death. We report a case of a fit 37‐year‐old woman with two previous cesarean deliveries who was diagnosed with a heterotopic cesarean scar pregnancy at 8 weeks gestation following symptoms of lower abdominal pain and delayed menstruation. Both pregnancies demonstrated cardiac activity and the portion of the myometrium located between the bladder wall and the gestational sac was noted to exhibit considerable thinness. The patient underwent an exploratory laparotomy coupled with dilation and curettage and recovered uneventfully. The proper management of a HCSP requires timely diagnosis through ultrasonography. Early diagnosis allows for immediate intervention to prevent complications such as uterine rupture or potentially lethal bleeding.
Insights into the Interfacial Charge Transfer Dynamics in Semiconductor–Molecular Catalyst Assemblies for Photo–Induced CO2 Reduction
Authors: Chatterjee Tamal , Domingo‐Tafalla Beatriu , Ballester Pablo , Palomares Emilio
Published: June 2024

This mini–review summarises examples of photo and photoelectrochemical CO2 reduction reactions (CO2RR) using semiconductor–molecular catalyst–based hybrid assemblies in which studies of charge transfer dynamics were also performed. In these catalysts, the grand challenges are controlling ultra–fast one–electron charge separation and simultaneously governing its impact on the efficiency and product selectivity in the multielectron and multi–proton–assisted CO2RR. In practice, several unwanted electron recombination processes occur in the femtosecond to millisecond timescale range impacting the overall catalysis efficiency. Titanium di‐oxide (TiO2) nanoparticle, mesoporous TiO2 film, copper indium sulphide (CuInS2) quantum dots were used as semiconductor materials, in turn rhenium (I) bipyridine, cobalt (II) terpyridine, cobaloxamine complex, and iron (III) porphyrins were investigated as molecular catalysts. The results of the charge transfer dynamic studies operating in such hybrid systems shed light on their charge accumulation processes, their rate constants for the intramolecular charge transfer processes and the decay lifetimes of the different excited state species that are produced. Moreover, a comprehensive understanding of the catalysts’ charge transfer dynamics is crucial to identifying detrimental charge recombination pathways. These undesired pathways can be used as rational basis for improving the design of future multi–redox–driven hybrid catalysts.
Copper‐Catalyzed Tunable Oxygenative Rearrangement of Tetrahydrocarbazoles
Authors: Ren Hai , Yang Bing‐Qing , Shi Jun , Wu Wei , Jiang Biaobiao , Chi Qin
Published: June 2024

Herein, we report a general copper‐catalyzed method for the tunable oxygenative rearrangement of tetrahydrocarbazoles to cyclopentyl‐bearing spiroindolin‐2‐ones and spiroindolin‐3‐ones. The method demonstrates excellent chemoselectivity, regioselectivity, and product control simply by using the H2O and O2 as oxygen source, respectively. This open‐flask method is safe and simple to operate, and no other chemical oxidants are required. Besides, inspired from the unique pathway of 1, 2‐migration rearrangement, a highly controllable hydroxylation of indoles for the construction of C3a‐hydroxyl iminium indolines was also developed. Mechanistic experiments suggest that a single‐electron transfer‐induced oxidation process is responsible for the tunable selectivity control.
Diastereo‐ and Enantioselective Construction of Stereochemical Arrays Exploiting Non‐Classical Hydrogen Bonding in Enolborates
Authors: Li Matthew , Scheeff Stephan , Chen Jiahua , Johnston Ryne C. , Rizzo Antonio , Krenske Elizabeth H. , Chiu Pauline
Published: June 2024

We report a copper‐catalyzed reductive aldol addition to aldehydes and ketones, with pinacolborane as stoichiometric reductant, that results in the generation of stereodefined syn‐aldol products. Cyclic, acyclic, fused and spirocyclic aldols bearing contiguous stereocenters are obtained with excellent yields and diastereoselectivities. Moreover, enantioselective reactions could be carried out with cycloalkenones to deliver aldols bearing three contiguous stereocenters and with up to 98 % ee. Computations reveal that the enolborate intermediate undergoes the syn‐aldol reaction via a twist‐boat transition state that is stabilized by non‐classical hydrogen bonding interactions.
Photoredox Catalysis by 21‐Thiaporphyrins: A Green and Efficient Approach for C−N Borylation and C−H Arylation
Authors: Janaagal Anu , Kushwaha Apoorv , Jhaldiyal Pranjali , Dhilip Kumar T. J. , Gupta Iti
Published: June 2024

Photoredox catalysis provides a green and sustainable alternative for C−H activation of organic molecules that eludes harsh conditions and use of transition metals. The photocatalytic C−N borylation and C−H arylation mostly depend on the ruthenium and iridium complexes or eosin Y and the use of porphyrin catalysts is still in infancy. A series of novel 21‐thiaporphyrins (A2B2 and A3B type) were synthesized having carbazole/phenothiazine moieties at their meso‐positions and screened as catalysts for C−N borylation and C−H arylation. This paper demonstrates the 21‐thiaporphyrin catalyzed C−N borylation and het‐arylation of anilines under visible light. The method utilizes only 0.1 mol % of 21‐thiaporphyrin catalyst under blue light for the direct C−N borylation and het‐arylation reactions. A variety of substituted anilines were used as source for expensive and unstable aryl diazonium salts in the reactions. The heterobiaryls and aryl boronic esters were obtained in decent yields (up to 88 %). Versatility of the 21‐thiaporphyrin catalyst was tested by thiolation and selenylation of anilines under similar conditions. Mechanistic insight was obtained from DFT studies, suggesting that 21‐thiaporphyrin undergo an oxidative quenching pathway. The photoredox process catalyzed by 21‐thiaporphyrins offers a mild, efficient and metal‐free alternative for the formation of C−C, C−S, and C−Se bonds in aryl compounds; it can also be extended to borylation reaction.
Color Polymorphism and Room Temperature Phosphorescence of 4‐Bromo‐2,7‐Di‐Tert‐Butyl‐ 9‐Methoxypyrene
Authors: Morawski Olaf W. , Karpiuk Jerzy , Grzybowski Marek
Published: June 2024

Color polymorphism combined with crystal packing‐dependent luminescence properties of polymorphs reflects differences in intermolecular interactions in different molecular arrangements. The title compound has two polymorphic crystal structures having strikingly different absorption and luminescence spectra that result from different packing motifs in the crystal lattice. The polymorph with brick wall‐like packing of molecules is white and shows very weak violet fluorescence whereas the second polymorph, where molecules are arranged in columnar stacks, is bright yellow and displays intense green fluorescence with maximum at 487 nm (20530 cm−1). In the white polymorph, where the distance between neighboring chromophores is increased, absorption and fluorescence spectra are similar to those of monomer in solution, and intersystem crossing to triplet manifold is the dominant pathway of relaxation. In the yellow polymorph, molecules within the columnar stacks are rotated which mitigates the steric hindrance and leads to closer π‐stacking of the pyrene cores. That increases the ππ overlap and strengthens intermolecular interactions decreasing energy of the excited states. This affects emission spectra and photophysical processes–fluorescence yield grows whereas triplet formation yield decreases when S1 is lowered below higher triplet states and conditions for effective vibronic spin‐orbit coupling are not favorable. The effect is not observed for other similar pyrene derivatives, testifying the uniqueness of the phenomenon.
Comparing two recurrent selection methods for developing superior apomictic hybrids in Paspalum notatum
Authors: Marcón Florencia , Galanter Iru N. Lezcano , Brugnoli Elsa A. , Zilli Alex L. , Martínez Eric J. , Acuña Carlos A.
Published: June 2024

Recurrent selection methods have been successful in generating superior Paspalum notatum families through the accumulation of favorable alleles. However, the effectiveness of these methods in producing apomictic hybrids with superior agronomic traits has not been thoroughly evaluated. The aim of this study was to characterize the reproductive behavior of P. notatum progenies obtained through recurrent selection based on combining ability (RSCA) and recurrent phenotypic selection (RPS) and assess the performance of the apomictic hybrids concerning various agronomic traits. The reproductive mode of 144 RSCA and 144 RPS hybrids was determined using a molecular marker tightly linked to the apospory trait (BCU243‐377). The expressivity of apospory was estimated observing mature embryo sacs. The apomictic hybrids were then evaluated for six agronomic traits. A segregation ratio of 5:1 between sexual and apomictic hybrids was observed for the RSCA progeny, while 4.3:1 was registered for the RPS progeny. Although apospory expressivity was variable among hybrids, 75% and 86% of the RSCA and RPS hybrids, respectively, exhibited a high expression (>81%). Non‐significant differences between breeding methods in the number of apomictic hybrids and the level of apospory expressivity were observed. Variations for all agronomic traits were observed among apomictic hybrids within each breeding method. However, no differences between methods in the performance of the highly apomictic hybrids were observed. This demonstrates that the reproductive behavior of P. notatum is not affected by the recurrent selection method. Therefore, the RPS method would be the most suitable since it was equally effective than RSCA but it is cheaper, faster, and easier to apply.
Sulfonate Group Improves the Solubility and Electrocatalytic Performance of Ru‐Based bda‐ and pda‐Type Water Oxidation Catalysts under Neutral Conditions
Authors: Kerkhof Jake T. , Breyer Colton J. , Smith Diane K. , Mao Yuezhi , Grotjahn Douglas B.
Published: June 2024

Four ruthenium water oxidation catalysts that bear carboxylate and sulfonate groups in the active site have been synthesized and analyzed for their catalytic activity. The sulfonate‐containing catalysts show higher electrochemical activity in pH 7 phosphate buffer with 4 times larger catalytic current, improved durability with sacrificial oxidant, and increased solubility compared to similar species containing two carboxylate groups. Density functional theory calculations suggest that the sulfonate group provides a more favorable geometry for water nucleophilic attack, which is both the energetically most favorable mechanism calculated and the experimentally predicted mechanism under electrochemical conditions. Further experimental studies have been performed to show that under certain conditions catalysts can perform well electrochemically under pH conditions as low as 1.6 and that various structural components can greatly change solubility and catalytic operation.
Alpha‐Gal Syndrome: An Underrated Serious Disease and a Potential Future Challenge
Authors: Zhan Mengyuan , Yin Jia , Xu Tengda , Wen Liping
Published: June 2024

Over the past decades, red meat allergy, also known as mammalian meat allergy, which manifests differently from classic food allergies, has been reported in different countries and regions, including China. The allergen of this disease is not a protein but an oligosaccharide: galactose‐α‐1,3‐galactose, i.e., alpha‐gal or α‐gal. Therefore, this clinical syndrome is also called α‐gal syndrome (AGS). It clinically manifests as delayed anaphylaxis, i.e., patients generally develop allergic symptoms 2–6 h after ingesting red meat. This clinical manifestation is believed to be related to sensitization to α‐gal after tick bites. Sensitized individuals may also develop anaphylaxis after ingesting food and medicine or being exposed to medical equipment containing α‐gal, such as cetuximab and gelatin. Here, the literature on AGS is reviewed for a better understanding of its pathogenesis, clinical diagnosis, and treatment.
The effects of spatial leakage correction on the reliability ofEEG‐based functional connectivity networks
Authors: Nagy Péter , Tóth Brigitta , Winkler István , Boncz Ádám
Published: June 2024

Electroencephalography (EEG) functional connectivity (FC) estimates are confounded by the volume conduction problem. This effect can be greatly reduced by applying FC measures insensitive to instantaneous, zero‐lag dependencies (corrected measures). However, numerous studies showed that FC measures sensitive to volume conduction (uncorrected measures) exhibit higher reliability and higher subject‐level identifiability. We tested how source reconstruction contributed to the reliability difference of EEG FC measures on a large (n = 201) resting‐state data set testing eight FC measures (including corrected and uncorrected measures). We showed that the high reliability of uncorrected FC measures in resting state partly stems from source reconstruction: idiosyncratic noise patterns define a baseline resting‐state functional network that explains a significant portion of the reliability of uncorrected FC measures. This effect remained valid for template head model‐based, as well as individual head model‐based source reconstruction. Based on our findings we made suggestions how to best use spatial leakage corrected and uncorrected FC measures depending on the main goals of the study.
Response of runoff and its components to climate change and its future trend in the source region of the Yangtze River
Authors: Gao Tailai , Li Jiadi , Tang Yuanzhi , Jiang Xiaoxuan , Huo Junjun
Published: June 2024

Under global climate changes, the temperature and precipitation on the Tibetan Plateau changed significantly, causing accelerated melting of glaciers and snow and changes in runoff. The response of runoff and its components to climate change is important for water resource management and ecology conservation in the region. Therefore, the Spatial Processes in Hydrology model, a distributed cold‐zone hydrological model that contains a glacial ablation module, was used to simulate runoff in the Yangtze River source located in the middle of the Tibetan Plateau during 2000–2050, and the Nash‐Sutcliffe efficiency coefficient, relative error and coefficient of determination (R2) for the calibration period and validation period revealed that the model performed well in most years. The results showed that rainfall runoff contributed the most to the total runoff (61%), followed by baseflow (23%), snowmelt runoff (12%) and glacier runoff (4%) in the Yangtze River source during 2000–2020. The runoff amounts of the three source rivers, Dangqu River, Tuotuo River and Chumar River, accounted for approximately 53% of the total runoff in the Yangtze River source basin, with rainfall runoff (52%) contributing the most and glacier runoff (6%) contributing the least. Compared to the contributions of glacial runoff in the Dangqu River (9%) and Tuotuo River (7%), the proportion of glacial runoff in the Chumar River is small (1%). Under the CMIP6 climate model, the mean runoff depth is predicted to increase by approximately 13.5 mm from 2020 to 2050 compared with that from 2000 to 2020.