bluuebunny/crossref_metadata_2025_split huggingface dataset:
Redox‐Modulated Circularly Polarized Luminescence in Chiral Photonic Films Derived from Cellulose Nanocrystals and Polyoxometalate
Authors: Zhang Jing , Niu Chengyan , Yang Xuekang , Liu Jiaqi , Wu Qiulan , Tan Jingjing , Wei Xuehong , Tang Zhiyong 
Published: June 2023

AbstractAchieving smart circularly polarized luminescence (CPL) materials with large luminescence dissymmetry factor (glum) is in high demand for potential technological applications in the chiroptical fields. Herein, a series of chiral photonic crystals (CPCs) derived from cellulose nanocrystals (CNCs) and photosensitive inorganic polyoxometalates (POMs) through an evaporation‐induced self‐assembly strategy are reported. The photonic bandgaps (PBGs) of CPC films are well regulated by controlling the amount of doped POMs, yielding the tunable right‐handed CPL emission with tailored glum. By locating the maximum emission peak of POMs at the center of the PBG of CPC films, the composite shows remarkable CPL performance with a |glum| value up to 0.53. Furthermore, the CPL can be reversibly switched on/off through a fluorescence resonance energy transfer (FRET) process controlled by alternate UV irradiation reduction and air oxidation. The CPC films hold the great promise as next‐generation chiroptical memory devices.
Highly Efficient Doping‐Free Thermally Activated Delayed Fluorescent Organic Light‐Emitting Diodes with an Ultrathin Quasi‐Host‐Guest Emission Layer
Authors: Peng Xiaomei , Gao Kuo , Qiu Weidong , Xu Zhida , Li Mengke , Xie Wentao , Yang Jiaji , Li Deli , Liu Kunkun , Su Shi‐Jian 
Published: June 2023

AbstractDoping‐free organic light‐emitting diodes (OLEDs) are beneficial to reduce manufacturing costs for mass production, which, however, are limited by the ubiquitous aggregation‐caused quenching (ACQ) effect, especially for thermally activated delayed fluorescence (TADF) emitters with relatively long exciton lifetimes. Herein, two typical TADF emitters pACRS and pACRSO with different sulfur atom valence states are developed, where pACRS with a thioether unit exhibits suppressed intermolecular interaction, alleviated ACQ effect, and higher efficiency in a conventional doping‐free device, in contract to pACRSO with a sulfone unit. It is of interest that comparable efficiencies are achieved for both emitters in doping‐free OLEDs with an ultrathin emission layer (UEML), in which the emitter molecules are deposited onto the surface of the underlying organic layer of host material to form an ultrathin quasi‐host‐guest system with alleviated ACQ effect. Besides, the suppressed trap effect is the key to guarantee the efficiency of UEML‐OLEDs, while different intermolecular interactions of emitters that determine the optimized UEML thickness will affect the efficiency roll‐off. Furthermore, benefiting from the UEML structure, highly efficient doping‐free OLEDs are also successfully achieved for red TADF emitters with stronger intermolecular interactions. Such an UEML strategy meeting efficiency and cost demands holds great promise for doping‐free OLEDs.
Modulating the Room Temperature Phosphorescence by Tweaking SOC and P = X Interactions (X = O, S, and Se) in Phosphoramides: Magnetic Circularly Polarized Luminescence from Achiral Phosphoramides
Authors: Jena Satyam , Behera Santosh Kumar , Eyyathiyil Jusaina , Kitahara Maho , Imai Yoshitane , Thilagar Pakkirisamy 
Published: June 2023

AbstractHerein, the synthesis, structure, room temperature phosphorescence, and magnetic chiroptical properties of phosphoramides 1‐6 with donor–acceptor architecture are reported.5). The electronic interactions between donor phenothiazine (PTZ) and acceptor (C6H5)n‐P = X (n = 1, 2; X = O, S, and Se)moieties in 1–6 are modulated by varying the number of donor units. The Lewis acidity of the phosphorus center is controlled by the nature of heteroatoms and the number of phenyl moieties attached to it. All compounds exhibit phosphorescence in the solid state under ambient conditions with a photoluminescence lifetime in the millisecond range (≈8–40 ms). The energy of the phosphorescence bands and their excited state lifetimes are governed by the P=X units. The phosphorescence features observed for 1–6 are in complete contrast to the observations noted for (PTZ)3P = X (X = O, S, and Se), where the phosphorescence process is completely controlled by the PTZ moiety, and there is a negligible contribution from the P = X moiety. Thus, the present and earlier studies together reveal that the steric crowding and the number of C6H5 moieties around the P = X unit play a crucial role in controlling the electronic coupling between the donor and acceptor moieties in phosphoramides containing non‐planar donor moieties. Furthermore, for the first time, the magnetic chiroptical properties of achiral phosphoramides 1–6, exhibiting a luminescence dissymmetry factor (gMCPL) in the order of 10−3 (≈4.0 × 10−3–7.4 × 10−3) are demonstrated.
Self‐Organized Stick Insect‐Like Locomotion under Decentralized Adaptive Neural Control: From Biological Investigation to Robot Simulation
Authors: Larsen Alexander Dupond , Büscher Thies H. , Chuthong Thirawat , Pairam Thipawan , Bethge Hendrik , Gorb Stanislav N. , Manoonpong Poramate 
Published: June 2023

AbstractLiving animals and legged robots share similar challenges for movement control. In particular, the investigation of neural control mechanisms for the self‐organized locomotion of insects and hexapod robots can be informative for other fields. The Annam stick insectMedauroidea extradentatais used as a template to develop a biorobotic model to infer walking self‐organization with strongly heterogeneous leg lengths. Body dimensions and data on the walking dynamics of the actual stick insect are used for the development of a neural control mechanism, generating self‐organized gait patterns that correspond to the real insect observations. The combination of both investigations not only proposes solutions for distributed neural locomotion control but also enables insights into the neural equipment of the biological template. Decentralized neural central pattern generation is utilized with phase modulation based on foot contact feedback to generate adaptive periodic base patterns and a radial basis function premotor network in each leg based on the target trajectories of actual stick insect legs during walking for complex intralimb coordination and self‐organized interlimb coordination control. Furthermore, based on both study objects, a robot with heterogeneous leg lengths is constructed to preliminary validate the findings from the simulations and real insect observations.
Engineering 2D Multienzyme‐Mimicking Pyroptosis Inducers for Ultrasound‐Augmented Catalytic Tumor Nanotherapy
Authors: Song Xinran , Huang Hui , Xia Lili , Jia Wencong , Yang Shaoling , Wang Chenglong , Chen Yu 
Published: June 2023

AbstractOvercoming apoptosis resistance is necessary to ensure an effective cancer treatment; however, it is currently very difficult to achieve. A desirable alternative for cancer treatment is the targeted activation of pyroptosis, a unique type of programmed cell death. However, the pyroptosis inducers that are efficient for cancer therapy are limited. This work reports the engineering of 2D NiCoOx nanosheets as inducers of the production of harmful reactive oxygen species (ROS), which promote intense cell pyroptosis, and that can be applied to ultrasound (US)‐augmented catalytic tumor nanotherapy. The main therapeutic task is carried out by the 2D NiCoOx nanosheets, which have four multienzyme‐mimicking activities: peroxidase‐ (POD), oxidase‐ (OXD), glutathione peroxidase‐ (GPx), and catalase‐ (CAT) mimicking activities. These activities induce the reversal of the hypoxic microenvironment, endogenous glutathione depletion, and a continuous ROS output. The ROS‐induced pyroptosis process is carried out via the ROS‐NLRP3‐GSDMD pathway, and the exogenous US activation boosts the multienzyme‐mimicking activities and favors the incremental ROS generation, thus inducing mitochondrial dysfunction. The anti‐cancer experimental results support the dominance of NiCoOx nanosheet‐induced pyroptosis. This work expands on the biomedical applications of engineering 2D materials for US‐augmented catalytic breast cancer nanotherapy and deepens the understanding of the multienzyme activities of nanomaterials.
Tough Gelatin Hydrogel for Tissue Engineering
Authors: Yuan Ximin , Zhu Zhou , Xia Pengcheng , Wang Zhenjia , Zhao Xiao , Jiang Xiao , Wang Tianming , Gao Qing , Xu Jie , Shan Debin , Guo Bin , Yao Qingqiang , He Yong 
Published: June 2023

AbstractTough hydrogel has attracted considerable interest in various fields, however, due to poor biocompatibility, nondegradation, and pronounced compositional differences from natural tissues, it is difficult to be used for tissue regeneration. Here, a gelatin‐based tough hydrogel (GBTH) is proposed to fill this gap. Inspired by human exercise to improve muscle strength, the synergistic effect is utilized to generate highly functional crystalline domains for resisting crack propagation. The GBTH exhibits excellent tensile strength of 6.67 MPa (145‐fold that after untreated gelation). Furthermore, it is directly sutured to a ruptured tendon of adult rabbits due to its pronounced toughness and biocompatibility, self‐degradability in vivo, and similarity to natural tissue components. Ruptured tendons can compensate for mechanotransduction by GBTH and stimulate tendon differentiation to quickly return to the initial state, that is, within eight weeks. This strategy provides a new avenue for preparation of highly biocompatible tough hydrogel for tissue regeneration.
Modulating Water Splitting Kinetics via Charge Transfer and Interfacial Hydrogen Spillover Effect for Robust Hydrogen Evolution Catalysis in Alkaline Media
Authors: Jiang Yiming , Leng Juncai , Zhang Shiqi , Zhou Tingyi , Liu Mingxuan , Liu Shuoming , Gao Yahui , Zhao Jianwei , Yang Lei , Li Li , Zhao Wei 
Published: June 2023

AbstractDesigning and synthesizing advanced electrocatalysts with superior intrinsic activity toward hydrogen evolution reaction (HER) in alkaline media is critical for the hydrogen economy. Herein, a novel Ir@Rhene heterojunction electrocatalyst is synthesized via epitaxially confining ultrasmall and low‐coordinate Ir nanoclusters on the ultrathin Rh metallene accompanying the formation of Ir/IrO2 Janus nanoparticles. The as‐prepared heterojunctions display outstanding alkaline HER activity, with an overpotential of only 17 mV at 10 mA cm−2 and an ultralow Tafel slope of 14.7 mV dec−1. Both structural characterizations and theoretical calculations demonstrate that the Ir@Rhene heterointerfaces induce charge density redistribution, resulting in the increment of the electron density around the O atoms in the IrO2 site and thus delivering much lower water dissociation energy. In addition, the dual‐site synergetic effects between IrO2 and Ir/Rh interface trigger and improve the interfacial hydrogen spillover, thereby subtly avoiding the steric blocking of the active site and eventually accelerating the alkaline HER kinetics.
3‐Masks‐Processed Sub‐100 nm Amorphous InGaZnO Thin‐Film Transistors for Monolithic 3D Capacitor‐Less Dynamic Random Access Memories
Authors: Zhang Yuqing , Li Jiye , Li Jinxiong , Huang Tengyan , Guan Yuhang , Zhang Yuhan , Yang Huan , Chan Mansun , Wang Xinwei , Lu Lei , Zhang Shengdong 
Published: June 2023

AbstractThe capacitor–less embedded dynamic random access memory (eDRAM) based on oxide semiconductor (OS) transistors exhibits a promising future and thus has lead to a growing demand for nanoscale OS thin–film transistors (TFTs). In this work, a self–aligned top–gate (SATG) amorphous InGaZnO (a‐IGZO) TFT is demonstrated by using the simplest 3‐masks (3M) process, and the downscaling‐related issues are carefully addressed to strengthen its back–end–of–line (BEOL) compatibility and mass producibility. The gate insulator (GI) and associated interface defects of the TFTs are jointly optimized with 4–nm atomic‐layer‐deposited (ALD) AlOx on the pre‐oxidized a‐IGZO. The defects in a‐IGZO channel are further manipulated with a rapid thermal anneal (RTA) in oxygen. By virtue of the strengthened gate controllability and modified channel properties, the fabricated TFT with 97‐nm gate length (Lg) exhibits decent performance, such as a maximum on–state current (ION) of 32.4 µA µm−1, as well as clear linear and saturation characteristics. Based on such 3M SATG a‐IGZO TFTs with high device performance and inherently minimal parasitic capacitances, the developed capacitor‐less eDRAM bit cell achieves a wide sensing margin and a long retention time of over 500 s. A highly manufacturable oxide TFT technology for high–performance and high–density monolithic–3D (M3D) integration is thus well established.
Increased blood reactive oxygen species and hepcidin in obstructive sleep apnea precludes expected erythrocytosis
Authors: Song Jihyun , Sundar Krishna M. , Horvathova Monika , Gangaraju Radhika , Indrak Karel , Christensen Robert D. , Genzor Samuel , Lundby Carsten , Divoky Vladimir , Ganz Tomas , Prchal Josef T. 
Published: June 2023

AbstractObstructive sleep apnea (OSA) causes intermittent hypoxia during sleep. Hypoxia predictably initiates an increase in the blood hemoglobin concentration (Hb); yet in our analysis of 527 patients with OSA, >98% did not have an elevated Hb. To understand why patients with OSA do not develop secondary erythrocytosis due to intermittent hypoxia, we first hypothesized that erythrocytosis occurs in these patients, but is masked by a concomitant increase in plasma volume. However, we excluded that explanation by finding that the red cell mass was normal (measured by radionuclide labeling of erythrocytes and carbon monoxide inhalation). We next studied 45 patients with OSA before and after applying continuous positive airway pressure (CPAP). We found accelerated erythropoiesis in these patients (increased erythropoietin and reticulocytosis), but it was offset by neocytolysis (lysis of erythrocytes newly generated in hypoxia upon return to normoxia). Parameters of neocytolysis included increased reactive oxygen species from expanded reticulocytes' mitochondria. The antioxidant catalase was also downregulated in these cells from hypoxia‐stimulated microRNA‐21. In addition, inflammation‐induced hepcidin limited iron availability for erythropoiesis. After CPAP, some of these intermediaries diminished but Hb did not change. We conclude that in OSA, the absence of significant increase in red cell mass is integral to the pathogenesis, and results from hemolysis via neocytolysis combined with inflammation‐mediated suppression of erythropoiesis.
Heterozygous variants in TBCK cause a mild neurologic syndrome in humans and mice
Authors: Nair Divya , Diaz‐Rosado Abdias , Varella‐Branco Elisa , Ramos Igor , Black Aaron , Angireddy Rajesh , Park Joseph , Murali Svathi , Yoon Andrew , Ciesielski Brianna , O'Brien W. Timothy , Passos‐Bueno Maria Rita , Bhoj Elizabeth 
Published: June 2023

AbstractTBCK‐related encephalopathy is a rare pediatric neurodegenerative disorder caused by biallelic loss‐of‐function variants in the TBCK gene. After receiving anecdotal reports of neurologic phenotypes in both human and mouse TBCK heterozygotes, we quantified if TBCK haploinsufficiency causes a phenotype in mice and humans. Using the tbck+/− mouse model, we performed a battery of behavioral assays and mTOR pathway analysis to investigate potential alterations in neurophysiology. We conducted as well a phenome‐wide association study (PheWAS) analysis in a large adult biobank to determine the presence of potential phenotypes associated to this variant. The tbck+/− mouse model demonstrates a reduction of exploratory behavior in animals with significant sex and genotype interactions. The concurrent PheWAS analysis of 10,900 unrelated individuals showed that patients with one copy of a TBCK loss‐of‐function allele had a significantly higher rate of acquired toe and foot deformities, likely indicative of a mild peripheral neuropathy phenotype. This study presents an example of what may be the underappreciated occurrence of mild neurogenic symptoms in heterozygote individuals of recessive neurogenetic syndromes.
Five siblings expand the spectrum of GPC6‐related skeletal dysplasia
Authors: Crenshaw Molly M. , Meyers Mariana L. , Brown Kathleen , Slegesky Valerie , Duis Jessica , Elias Ellen R. , Saenz Margarita , Shi Wen , Filmus Jorge , Meeks Naomi J. L. 
Published: June 2023

AbstractSkeletal dysplasias broadly include disorders of cartilage or bone. Omodysplasia‐1 is a type of skeletal dysplasia caused by biallelic loss of function variants in the GPC6 gene. GPC6 codes for the protein glypican 6 (GPC6) (OMIM *604404), which stimulates bone growth. We report a family in which five out of nine children were presented with a skeletal dysplasia characterized phenotypically by mild short stature and rhizomelia. All affected individuals were found to have homozygous missense variants in GPC6: c.511 C>T (p.Arg171Trp). Radiograph findings included rhizomelic foreshortening of all four extremities, coxa breva, and ulna minus deformity. Using a Hedgehog (Hh) reporter assay, we demonstrate that the variant found in this family results in significantly reduced stimulation of Hh activity when compared to the wild‐type GPC6 protein, however protein function is still present. Thus, the milder phenotype seen in the family presented is hypothesized due to decreased GPC6 protein activity versus complete loss of function as seen in omodysplasia‐1. Given the unique phenotype and molecular mechanism, we propose that this family's findings widen the phenotypic spectrum of GPC6‐related skeletal dysplasias.
Recent Advances in Carbonyl‐Photoredox/Transition Metal Dual Catalysis
Authors: Zhu Da‐Liang , Li Jie , Young David James , Wang Yanqing , Li Hong‐Xi 
Published: June 2023

AbstractOrganic transformations using carbonyl‐photoredox/metal dual catalysis have attracted much attention in recent years. Abundant and inexpensive carbonyl photosensitizers effectively serve as single electron, energy or hydrogen atom transfer agents to induce metal‐catalyzed cross‐coupling and dicarbofunctionalization of olefins. This review covers literature reports of metal‐catalyzed photocatalytic coupling reactions from 2020 to mid‐2023, with a focus on C−C (C(sp3)−C(sp3), C(sp3)−C(sp2), C(sp2)−C(sp2), C(sp2)−C(sp)) and C‐heteroatom (C(sp3)−S, C(sp3)−N, C(sp2)−O, C(sp2)−S, C(sp2)−P, C(sp2)−B) bond forming reactions.
There is an obstetrical dilemma: Misconceptions about the evolution of human childbirth and pelvic form
Authors: Grunstra N. D. S. , Betti L. , Fischer B. , Haeusler M. , Pavlicev M. , Stansfield E. , Trevathan W. , Webb N. M. , Wells J. C. K. , Rosenberg K. R. , Mitteroecker P. 
Published: June 2023

AbstractCompared to other primates, modern humans face high rates of maternal and neonatal morbidity and mortality during childbirth. Since the early 20th century, this “difficulty” of human parturition has prompted numerous evolutionary explanations, typically assuming antagonistic selective forces acting on maternal and fetal traits, which has been termed the “obstetrical dilemma.” Recently, there has been a growing tendency among some anthropologists to question the difficulty of human childbirth and its evolutionary origin in an antagonistic selective regime. Partly, this stems from the motivation to combat increasing pathologization and overmedicalization of childbirth in industrialized countries. Some authors have argued that there is no obstetrical dilemma at all, and that the difficulty of childbirth mainly results from modern lifestyles and inappropriate and patriarchal obstetric practices. The failure of some studies to identify biomechanical and metabolic constraints on pelvic dimensions is sometimes interpreted as empirical support for discarding an obstetrical dilemma. Here we explain why these points are important but do not invalidate evolutionary explanations of human childbirth. We present robust empirical evidence and solid evolutionary theory supporting an obstetrical dilemma, yet one that is much more complex than originally conceived in the 20th century. We argue that evolutionary research does not hinder appropriate midwifery and obstetric care, nor does it promote negative views of female bodies. Understanding the evolutionary entanglement of biological and sociocultural factors underlying human childbirth can help us to understand individual variation in the risk factors of obstructed labor, and thus can contribute to more individualized maternal care.
Use of the patient portal among older adults with diagnosed dementia and their care partners
Authors: Gleason Kelly T. , Wu Mingche M. J. , Wec Aleksandra , Powell Danielle S. , Zhang Talan , Gamper Mary Jo , Green Ariel R. , Nothelle Stephanie , Amjad Halima , Wolff Jennifer L. 
Published: June 2023

AbstractINTRODUCTIONCare partners are at the forefront of dementia care, yet little is known about patient portal use in the context of dementia diagnosis.METHODSWe conducted an observational cohort study of date/time‐stamped patient portal use for a 5‐year period (October 3, 2017–October 2, 2022) at an academic health system. The cohort consisted of 3170 patients ages 65+ with diagnosed dementia with 2+ visits within 24 months. Message authorship was determined by manual review of 970 threads involving 3065 messages for 279 patients.RESULTSMost (71.20%) older adults with diagnosed dementia were registered portal users but far fewer (10.41%) had a registered care partner with shared access. Care partners authored most (612/970, 63.09%) message threads, overwhelmingly using patient identity credentials (271/279, 97.13%).DISCUSSIONThe patient portal is used by persons with dementia and their care partners. Organizational efforts that facilitate shared access may benefit the support of persons with dementia and their care partners.Highlights
Patient portal registration and use has been increasing among persons with diagnosed dementia.
Two thirds of secure messages from portal accounts of patients with diagnosed dementia were identified as being authored by care partners, primarily using patient login credentials.
Care partners who accessed the patient portal using their own identity credentials through shared access demonstrate similar levels of activity to patients without dementia.
Organizational initiatives should recognize and support the needs of persons with dementia and their care partners by encouraging awareness, registration, and use of proper identity credentials, including shared, or proxy, portal access.
Sustainable and High‐Rate Electrosynthesis of Nitrogen Fertilizer
Authors: Zhao Qinglan , Lu Xinxin , Wang Yinuo , Zhu Shangqian , Liu Yushen , Xiao Fei , Dou Shi Xue , Lai Wei‐Hong , Shao Minhua 
Published: June 2023

AbstractThe conventional industrial production of nitrogen‐containing fertilizers, such as urea and ammonia, relies heavily on energy‐intensive processes, accounting for approximately 3 % of global annual CO2 emissions. Herein, we report a sustainable electrocatalytic approach that realizes direct and selective synthesis of urea and ammonia from co‐reduction of CO2 and nitrates under ambient conditions. With the assistance of a copper (Cu)‐based salphen organic catalyst, outstanding urea (3.64 mg h−1 mgcat−1) and ammonia (9.73 mg h−1 mgcat−1) yield rates are achieved, in addition to a remarkable Faradaic efficiency of 57.9±3 % for the former. This work proposes an appealing sustainable route to converting greenhouse gas and waste nitrates by renewable energies into value‐added fertilizers.