bluuebunny/crossref_metadata_2025 huggingface dataset:
Association of Active Postnatal Care With Infant Survival Among Periviable Infants in the US
Authors: Silva Emani R. , Shukla Vivek V. , Tindal Rachel , Carlo Waldemar A. , Travers Colm P.
Published: January 2023

Importance

Active postnatal care has been associated with center differences in survival among periviable infants. Regional differences in outcomes among periviable infants in the US may be associated with differences in active postnatal care.

Objective

To determine if regions with higher rates of active postnatal care will have higher gestational age-specific survival rates among periviable infants.

Design, Setting, and Participants

This cohort study included live births from 22 to 25 weeks’ gestation weighing 400 to 999 g in the US Centers for Disease Control and Prevention (CDC) WONDER 2017 to 2020 (expanded) database. Infants with congenital anomalies were excluded. Active postnatal care was defined using the CDC definition of abnormal conditions of newborn as presence of any of the following: neonatal intensive care unit (NICU) admission, surfactant, assisted ventilation, antibiotics, and seizures. Data were analyzed from August to November 2022.

Main Outcomes and Measures

Regional gestational age-specific survival rates were compared with rates of active postnatal care in the 10 US Health and Human Services regions using Kendall τ test.

Results

We included 41 707 periviable infants, of whom 32 674 (78%) were singletons and 19 467 (46.7%) were female. Among those studied 34 983 (83.9%) had evidence of active care, and 26 009 (62.6%) survived. Regional rates of active postnatal care were positively correlated with regional survival rates at 22 weeks’ gestation (rτ[8] = 0.56; r2 = 0.31; P = .03) but the correlation was not significant at 23 weeks’ gestation (rτ[8] = 0.47; r2 = 0.22; P = .07). There was no correlation between active care and survival at 24 or 25 weeks’ gestation. Regional rates of both NICU admission and assisted ventilation following delivery were positively correlated with regional rates of survival at 22 weeks’ gestation (both P < .05). Regional rates of antenatal corticosteroids exposure were also positively correlated with regional rates of survival at 22 weeks’ gestation (rτ[8] = 0.60; r2 = 0.36; P = .02).

Conclusions and Relevance

In this cohort study of 41 707 periviable infants, regional differences in rates of active postnatal care, neonatal intensive care unit admission, provision of assisted ventilation and antenatal corticosteroid exposure were moderately correlated with survival at 22 weeks’ gestation. Further studies focused on individual-level factors associated with active periviable care are warranted.
Racial Health Equity and Social Needs Interventions
Authors: Cené Crystal W. , Viswanathan Meera , Fichtenberg Caroline M. , Sathe Nila A. , Kennedy Sara M. , Gottlieb Laura M. , Cartier Yuri , Peek Monica E.
Published: January 2023

Importance

Social needs interventions aim to improve health outcomes and mitigate inequities by addressing health-related social needs, such as lack of transportation or food insecurity. However, it is not clear whether these studies are reducing racial or ethnic inequities.

Objective

To understand how studies of interventions addressing social needs among multiracial or multiethnic populations conceptualize and analyze differential intervention outcomes by race or ethnicity.

Evidence Review

Sources included a scoping review of systematic searches of PubMed and the Cochrane Library from January 1, 1995, through November 29, 2021, expert suggestions, and hand searches of key citations. Eligible studies evaluated interventions addressing social needs; reported behavioral, health, or utilization outcomes or harms; and were conducted in multiracial or multiethnic populations. Two reviewers independently assessed titles, abstracts, and full text for inclusion. The team developed a framework to assess whether the study was “conceptually thoughtful” for understanding root causes of racial health inequities (ie, noted that race or ethnicity are markers of exposure to racism) and whether analyses were “analytically informative” for advancing racial health equity research (ie, examined differential intervention impacts by race or ethnicity).

Findings

Of 152 studies conducted in multiracial or multiethnic populations, 44 studies included race or ethnicity in their analyses; of these, only 4 (9%) were conceptually thoughtful. Twenty-one studies (14%) were analytically informative. Seven of 21 analytically informative studies reported differences in outcomes by race or ethnicity, whereas 14 found no differences. Among the 7 that found differential outcomes, 4 found the interventions were associated with improved outcomes for minoritized racial or ethnic populations or reduced inequities between minoritized and White populations. No studies were powered to detect differences.

Conclusions and Relevance

In this review of a scoping review, studies of social needs interventions in multiracial or multiethnic populations were rarely conceptually thoughtful for understanding root causes of racial health inequities and infrequently conducted informative analyses on intervention effectiveness by race or ethnicity. Future work should use a theoretically sound conceptualization of how race (as a proxy for racism) affects social drivers of health and use this understanding to ensure social needs interventions benefit minoritized racial and ethnic groups facing social and structural barriers to health.
Addressing a potential weakness in indices of predation, herbivory, and parasitism
Authors: Adams Jean V.
Published: January 2023

Quantification of predation, herbivory, and parasitism is critical to understanding the dynamics and trophic interactions of populations in an ecosystem. Such quantification can be challenging if the availability or consumption of the taxa are difficult to assess. Sometimes the consumption of a single prey, forage, or host is used as an overall index of the predation, herbivory, or parasitism for a population of interest. Occasionally, human‐manipulated baits are used to derive similar indices. However, all such indices are susceptible to influence by variation in the abundance of the preferred taxon relative to other taxa as the result of preference switching. In this article, I describe a test for preference switching (and an adjustment, if detected) that does not require availability and consumption of the prey (forage, or host) to be measured on the same scale. The ability to detect and adjust for preference switching in such situations may advance the understanding of biological preference in taxa not previously studied in this respect.
Dosimetric accuracy of the Convolution algorithm for Leksell Gamma Plan radiosurgery treatment planning: Evaluation in the presence of clinically relevant inhomogeneities
Authors: Pantelis Evaggelos , Logothetis Andreas , Zoros Emmanouil , Pappas Eleftherios P. , Papagiannis Panagiotis , Paddick Ian , Nordström Håkan , Kollias George , Karaiskos Pantelis
Published: January 2023

Purpose

The Leksell Gamma Plan Convolution algorithm (LGP‐Convolution) has not been widely adopted. This mainly stems from the higher calculated beam‐on times relative to the standard ray tracing‐based LGP‐TMR10 dose calculation algorithm. This study aims to evaluate the accuracy of the LGP‐Convolution in scenarios where the treated lesions are in the vicinity of or encompassed by bone and/or air inhomogeneities.

Methods

The solid water dosimetry phantom provided by the vendor was modified to include bone and air inhomogeneities. Two treatment planning scenarios were investigated involving a single shot and multiple shots, respectively. Treatment planning and dose prescription were performed using the LGP‐Convolution algorithm. Triple channel film dosimetry was performed using GafChromic EBT3 films calibrated in terms of absorbed dose to water in a 60Co beam. Monte Carlo (MC) simulation dosimetry was also performed in the inhomogeneous experimental geometry using the EGSnrc MC platform and a previously validated sector‐based phase‐space source model. MC simulations were also employed to determine correction factors required for converting EBT3 measurements at points within the bone and air inhomogeneities from dose‐to‐water values to the corresponding dose to medium values.

Results and Conclusions

EBT3 dose to medium correction factors ranged with field size (4, 8, or 16 mm) within 0.941–0.946 for bone and 0.745–0.749 for air inhomogeneities. An excellent agreement was found between the LGP‐Convolution calculations with corresponding EBT3 and MC dose to medium results at all measurement points, except those located inside the air inhomogeneity. The latter is of no clinical importance and excluding them yielded gamma index passing rates of nearly 100% for 3% local dose difference and 1 mm distance‐to‐agreement criteria. The excellent agreement observed between LGP‐Convolution calculations and film as well as MC results of dose to medium indicates that the latter is the quantity reported by the LGP‐Convolution.
Ligand Coupling and Decoupling Modulates Stem Cell Fate
Authors: Thangam Ramar , Kim Seong Yeol , Kang Nayeon , Hong Hyunsik , Lee Hyun‐Jeong , Lee Sungkyu , Jeong Daun , Tag Kyong‐Ryol , Kim Kanghyeon , Zhu Yangzhi , Sun Wujin , Kim Han‐Jun , Cho Seung‐Woo , Ahn Jae‐Pyoung , Jang Woo Young , Kim Jong Seung , Paulmurugan Ramasamy , Khademhosseini Ali , Kim Hong‐Kyu , Kang Heemin
Published: January 2023

In natural microenvironment, various proteins containing adhesive ligands in fibrous and non‐fibrous structures dynamically couple and decouple to regulate stem cell fate. Herein, materials presenting movably couplable ligands are developed by grafting liganded gold nanoparticles (AuNPs) to a substrate followed by flexibly grafting liganded movable linear nanomaterials (MLNs) to the substrate via a long bendable linker, thereby creating a space between the MLNs and the AuNPs in the decoupled state. Magnetic control of the MLNs decreases this space via the bending of the linker to couple the MLNs to the AuNPs. Remote control of ligand coupling stimulates integrin recruitment to the coupled ligands, thereby non‐toxically facilitating the focal adhesion, mechanosensing, and potential differentiation of stem cells, which is suppressed by ligand decoupling. Versatile tuning of size, aspect ratio, distributions, and ligands of the MLNs can help to decipher dynamic ligand‐coupling‐dependent stem cell fate to advance regenerative therapies.
A General Route for Encapsulating Monodispersed Transition Metal Phosphides into Carbon Multi‐Chambers toward High‐Efficient Lithium‐Ion Storage with Underlying Mechanism Exploration
Authors: Cui Xiang , Chen Jiaxin , Sun Zhefei , Wang Lei , Peng Qianqian , Xiao Bensheng , Zhao Ligong , Zheng He , Wang Yong , Wang Jianbo , Chen Xianfei , Zhang Qiaobao , Chen Shuangqiang
Published: January 2023

Transition metal phosphides (MPx) with high theoretical capacities and low cost are regarded as the most promising anodes for lithium‐ion batteries (LIBs), but the large volume variations and sluggish kinetics largely restrict their development. To solve the above challenges, herein a generic but effective method is proposed to encapsulate various monodispersed MPx into flexible carbon multi‐chambers (MPx@NC, MNi, Fe, Co, and Cu, etc.) with pre‐reserved voids, working as anodes for LIBs and markedly boosting the Li+ storage performance. Ni2P@NC, one representative example of MPx@NC anode, shows high reversible capacity (613 mAh g−1, 200 cycles at 0.2 A g−1), and superior cycle stability (475 mAh g−1, 800 cycles at 2 A g−1). Full cell coupled with LiFePO4 displays a high reversible capacity (150.1 mAh g−1 at 0.1 A g−1) with stable cycling performance. In situ X‐ray diffraction and transmission electron microscope techniques confirm the reversible conversion reaction mechanism and robust structural integrity, accounting for enhanced rate and cycling performance. Theoretical calculations reveal the synergistic effect between MPx and carbon shells, which can significantly promote electron transfer and reduce diffusion energy barriers, paving ways to design high‐energy‐density materials for energy storage systems.
New‐Generation Anion‐Pillared Metal–Organic Frameworks with Customized Cages for Highly Efficient CO2 Capture
Authors: Hu Yongqi , Jiang Yunjia , Li Jiahao , Wang Lingyao , Steiner Mathias , Neumann Rodrigo F. , Luan Binquan , Zhang Yuanbin
Published: January 2023

The rational design of porous materials for CO2 capture under realistic process conditions is highly desirable. However, trade‐offs exist among a nanopore's capacity, selectivity, adsorption heat, and stability. In this study, a new generation of anion‐pillared metal‐organic frameworks (MOFs) are reported with customizable cages for benchmark CO2 capture from flue gas. The optimally designed TIFSIX‐Cu‐TPA exhibits a high CO2 capacity, excellent CO2/N2 selectivity, high thermal stability, and chemical stability in acid solution and acidic atmosphere, as well as modest adsorption heat for facile regeneration. Additionally, the practical separation performance of the synthesized MOFs is demonstrated by breakthrough experiments under various process conditions. A highly selective separation is achieved at 298–348 K with the impressive CO2 capacity of 2.1–1.4 mmol g−1. Importantly, the outstanding performance is sustained under high humidity and over ten repeat process cycles. The molecular mechanism of MOF's CO2 adsorption is further investigated in situ by CO2 dosed single crystal structure and theoretical calculations, highlighting two separate binding sites for CO2 in small and large cages featured with high CO2 selectivity and loading, respectively. The simultaneous adsorption of CO2 inside these two types of interconnected cages accounts for the high performance of these newly designed anionic pillar‐caged MOFs.
Ferroptosis: The Entanglement between Traditional Drugs and Nanodrugs in Tumor Therapy
Authors: Liu Kexuan , Huang Lei , Qi Shuangyan , Liu Shuchen , Xie Wangni , Du Liuyi , Cui Jing , Zhang Xu , Zhang Boya , Liu Lijun , Li Daowei , Sun Hongchen
Published: January 2023

Ferroptosis is a non‐apoptotic programmed cell death caused by the accumulation of lipid peroxide. System Xc‐/glutathione peroxidase 4 (GPX4) axis and iron axis are two main pathways regulating ferroptosis. Simultaneously, multiple pathways are also involved in the ferroptosis regulation. Ferroptosis is an intense area of the current study. With the improvement of the regulatory mechanisms that underlie ferroptosis, a variety of drugs associated with ferroptosis have been discovered and developed for cancer therapy. Among them, traditional drugs were developed initially. Small molecule compounds that regulate ferroptosis signaling pathway and iron complexes that promote the Fenton reaction have become important drugs for inducing ferroptosis. In recent years, the emerging development of nanotechnology has promoted the research of ferroptosis nanodrugs. Iron‐based nanomaterials are extensively tested as ferroptosis‐inducing agents. Furthermore, nanoscale drug delivery systems offer a suitable scaffold for traditional drug therapies. Traditional drugs and nanodrugs are complementary, each with their own strengths and limitations. This review describes the latest studies on the regulation of ferroptosis in tumor cells and focuses on the entanglement between traditional drugs and nanodrugs. To conclude, the challenges and perspectives in this field are put forward.
Moisture‐Enabled Electricity from Hygroscopic Materials: A New Type of Clean Energy
Authors: Xu Tong , Ding Xiaoteng , Cheng Huhu , Han Gaoyi , Qu Liangti
Published: January 2023

Water utilization is accompanied with the development of human beings, whereas gaseous moisture is usually regarded as an underexploited resource. The advances of highly efficient hygroscopic materials endow atmospheric water harvesting as an intriguing solution to convert moisture into clean water. The discovery of hygroelectricity, which refers to the charge buildup at a material surface dependent on humidity, and the following moisture‐enabled electric generation (MEG) realizes energy conversion and directly outputs electricity. Much progress has been made since then to optimize MEG performance, pushing forward the applications of MEG into a practical level. Herein, the evolvement and development of MEG are systematically summarized in a chronological order. The optimization strategies of MEG are discussed and comprehensively evaluated. Then, the latest applications of MEG are presented, including high‐performance powering units and self‐powered devices. In the end, a perspective on the future development of MEG is given for inspiring more researchers into this promising area.
Copper‐Catalyzed Olefination of 4‐CF3‐Substituted Cyclohexadienones Using Sulfonylmethyl Isocyanides: An Electrostatic Repulsion‐Controlled Regioselectivity Switch Strategy
Authors: Lee Seungwon , Ahmed Abozeid Mohamed , Young Kim Hun , Oh Kyungsoo
Published: January 2023

A Cu(OTf)2‐catalyzed olefination of cyclohexadienones was developed using sulfonylmethyl isocyanides. A CF3 moiety at the 4‐position of cyclohexadienones was shown to exert a pronounced electrostatic repulsion effect to give the olefination products via a preferential [3+2] cycloaddition with the ketone moiety followed by a facile fragmentation of transient oxazoline intermediates. The current Cu(II)‐catalyzed olefination of 4‐CF3‐substituted cyclohexadienones demonstrates the reaction dichotomy involving a CF3‐controlled 1,2‐addition over a Van Leusen 1,4‐addition pathway through the electrostatic repulsion effect.

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Synthesis of o‐Bis(3‐indolyl)arenes under Brønsted Acid Catalysis: Carbonyl Compounds as Sources of Aryl Groups
Authors: Tokunaga Rei , Okusa Takumi , Tsuchimoto Teruhisa
Published: January 2023

A method of synthesizing o‐bis(3‐indolyl)arenes was developed by reacting indoles with 7‐oxabicyclo[2.2.1]hept‐5‐en‐2‐one and derivatives thereof having no aromatic ring. All 23 unknown o‐bis(3‐indolyl)arenes could be obtained using this method. Palladium catalysis is useful for enlarging the π‐conjugated area of o‐bis(3‐indolyl)arenes, delivering aryl‐, alkynyl‐, and alkenyl‐unit‐installed o‐bis(3‐indolyl)arenes, and benzo[c]indolo[2,3‐a]carbazoles, the derivatization to which is effective for raising fluorescence quantum yield. A possible reaction mechanism is proposed based on several mechanistic studies.

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Electrochemical Deoxygenative Hydrogenation and Deuteration of Aldehydes/Ketones by Protic Acids in Water
Authors: Sun Zhihui , Ji Ruixue , Wu Jintao , Zhao Jianyou , Fang Fang , Wang Fan , Jiang Chao , Liu Zhong‐Quan
Published: January 2023

We report herein a modified Clemmensen reduction. When reacted with aqueous H(D)Cl in an undivided cell, aliphatic and aromatic aldehydes and ketones undergo deoxygenative hydrogenation and deuterization to give hydrocarbons and deuterocarbons. The general features of this transformation are: 1) H+/D+ as the sources of H/D; 2) mild reaction conditions (room temperature, open flask, CH3CN and water as cosolvent); 3) easily scaled‐up to 100 grams. A series of D‐labeled drugs were synthesized by this method.

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Exploring the effects of weaning age on adult infectious disease mortality among 18th–19th century Italians
Authors: Smith April K. , Reitsema Laurie J. , Fornaciari Antonio , Sineo Luca
Published: January 2023

Objectives

The developmental origins of health and disease (DOHaD) hypothesis describes how early childhood stress affects morbidity and mortality later in life. The role of early childhood stress in mortality from infectious disease is understudied. Stressors in early childhood that weaken the immune system may result in increased susceptibility to infectious disease in adulthood. Weaning is one of the earliest potential periods of significant stress in early childhood. This research investigates the effect of weaning after ~6 months of age on cholera mortality among 18th–19th‐century Italian populations by determining if earlier breastfeeding cessation is associated with earlier mortality, analyzing childhood dietary variation and physiological stress markers, and determining if age‐at‐weaning completion differs between catastrophic and attritional populations.

Methods

Serial dentin stable carbon and nitrogen isotope analyses from canines are compared between catastrophic (n = 45) and attritional groups (n = 23). Canines are sectioned serially from crown to apex, and the increment's δ15N and δ13C are used to estimate age‐at‐weaning completion.

Results

Catastrophic and attritional groups exhibit similar age‐at‐weaning completion (~2.8 years). Seventy‐four percent of individuals lack elevated δ15N values in dentin that formed during infancy.

Conclusions

Age‐at‐weaning completion was not a predisposing factor in cholera mortality in adulthood in this sample. Age‐at‐weaning completion may not be significantly associated with infectious disease mortality because weaning completion likely occurred after infants had adapted to consuming contaminated weanling foods. Individuals without detectable weaning curves may represent infants who received supplementary foods since birth or were weaned before the age of 6–9 months.
The relationship between objective physical activity and change in cognitive function
Authors: Sewell Kelsey R. , Rainey‐Smith Stephanie R. , Peiffer Jeremiah , Sohrabi Hamid R. , Taddei Kevin , Ames David , Maruff Paul , Masters Colin L. , Rowe Christopher C. , Martins Ralph N. , Erickson Kirk I. , Brown Belinda M.
Published: January 2023

Introduction

The current study investigated the association between objectively measured physical activity and cognition in older adults over approximately 8 years.

Methods

We utilized data from 199 cognitively unimpaired individuals from the Australian Imaging, Biomarkers and Lifestyle (AIBL) study, aged ≥60. Actigraphy was used to measure physical activity (intensity, total activity, and energy expenditure) at baseline. Cognition was assessed using a comprehensive cognitive battery every 18‐months.

Results

Higher baseline energy expenditure predicted better episodic recall memory and global cognition over the follow‐up period (p = 0.031; p = 0.047, respectively). Those with higher physical activity intensity and greater total activity also had better global cognition over time (both p = 0.005). Finally, higher total physical activity predicted improved episodic recall memory over time (p = 0.022).

Discussion

These results suggest that physical activity can preserve cognition and that activity intensity may play an important role in this association.

Highlights

Greater total physical activity predicts preserved episodic memory and global cognition.

Moderate intensity physical activity (>3.7 metabolic equivalents of task [MET]) predicts preserved global cognition.

Expending > 373 kilocalories per day may benefit episodic memory and global cognition.
Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion
Authors: Yang Eric S. , Wilson Daniel W. N. , Goicoechea Jose M.
Published: January 2023

The cyaphide anion, CP−, is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) by Sm(Cp*)2(OEt2) (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl), was found to afford a tetra‐metallic complex containing a 2,3‐diphosphabutadiene‐1,1,4,4‐tetraide fragment. By contrast, non‐reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolidin‐2‐ylidene; Cp=cyclopentadienyl), gives rise to an asymmetric bimetallic complex containing a 1,3‐diphosphacyclobutadiene‐2,4‐diide moiety. Spontaneous trimerization of Sc(Cp*)2(CP) results in the formation of a trimetallic complex containing a 1,3,5‐triphosphabenzene‐2,4,6‐triide fragment. These transformations show that while cyaphido transition metal complexes can be readily accessed using metathesis reactions, many such species are unstable to further oligomerization processes.
Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2O Vapor Sorption
Authors: Azmy Ali , Li Shunran , Angeli Giasemi K. , Welton Claire , Raval Parth , Li Min , Zibouche Nourdine , Wojtas Lukasz , Reddy G. N. Manjunatha , Guo Peijun , Trikalitis Pantelis N. , Spanopoulos Ioannis
Published: January 2023

In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure‐directing agents and counter‐cations. Reaction of the [2.2.2] cryptand (DHS) linker with PbII in acidic media gave rise to the first porous and water‐stable 2D metal halide semiconductor (DHS)2Pb5Br14. The corresponding material is stable in water for a year, while gas and vapor‐sorption studies revealed that it can selectively and reversibly adsorb H2O and D2O at room temperature (RT). Solid‐state NMR measurements and DFT calculations verified the incorporation of H2O and D2O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half‐maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid‐state batteries) for this class of hybrid semiconductors.
Glycinimin – Das schwer fassbare α‐Iminosäure‐Intermediat bei der Reduktiven Aminierung der Glyoxylsäure
Authors: Paczelt Viktor , Wende Raffael C. , Schreiner Peter R. , Eckhardt André K.
Published: January 2023

Einfache ungehinderte Aldimine neigen dazu, zu hydrolysieren oder zu oligomerisieren und sind daher spektroskopisch nicht gut charakterisiert. Wir berichten hier über die Bildung und spektroskopische Charakterisierung der einfachsten Iminosäure, nämlich Glycinimin, mittels kryogener Matrixisolation, IR‐ und UV/Vis‐Spektroskopie. Glycinimin bildet sich nach UV‐Bestrahlung von 2‐Azidoessigsäure durch N2‐Freisetzung in anti‐(E,E)‐ und anti‐(Z,Z)‐Konformationen, die photochemisch ineinander umgewandelt werden können. In Pyrolyseversuchen gekoppelt mit Matrixisolation von 2‐Azidoessigsäure kann Glycinimin nicht isoliert werden, da es weiter zu Aminomethylen decarboxyliert. In wässriger Lösung wird Glycinimin zu Hydroxyglycin und hydratisierter Glyoxylsäure hydrolysiert. Bei höheren Konzentrationen oder in Gegenwart von FeIISO4 als Reduktionsmittel reduziert sich Glycinimin durch oxidative Decarboxylierung selbst. Glycinimin kann als ein Schlüsselintermediat zwischen präbiotischer Aminosäure‐ und Zuckerbildung angesehen werden.
Pressure‐Tuned Multicolor Emission of 2D Lead Halide Perovskites with Ultrahigh Color Purity
Authors: Gao Fei‐Fei , Song Haipeng , Li Zhi‐Gang , Qin Yan , Li Xiang , Yao Zhao‐Quan , Fan Jia‐Hui , Wu Xiang , Li Wei , Bu Xian‐He
Published: January 2023

The chemical diversity and structural flexibility of lead halide perovskites (LHPs) offer tremendous opportunities to tune their optical properties through internal molecular engineering and external stimuli. Herein, we report the wide‐range and ultrapure photoluminescence emissions in a family of homologous 2D LHPs, [MeOPEA]2PbBr4−4xI4x (MeOPEA=4‐methoxyphenethylammonium; x=0, 0.2, 0.425, 0.575, 1) enabled through internal chemical pressure and external hydrostatic pressure. The chemical pressure, induced by the C−H⋅⋅⋅π interactions and halogen doping/substitution strengthens the structural rigidity to give sustained narrow emissions, and regulates the emission energy, respectively. Further manipulation of physical pressure leads to wide‐range emission tuning from 412 to 647 nm in a continuous and reversible manner. This work could open up new pathways for developing 2D LHP emitters with ultra‐wide color gamut and high color purity which are highly useful for pressure sensing.
Concerted and Selective Electrooxidation of Polyethylene‐Terephthalate‐Derived Alcohol to Glycolic Acid at an Industry‐Level Current Density over a Pd−Ni(OH)2 Catalyst
Authors: Liu Fulai , Gao Xutao , Shi Rui , Guo Zhengxiao , Tse Edmund C. M. , Chen Yong
Published: January 2023

Electro‐reforming of Polyethylene‐terephthalate‐derived (PET‐derived) ethylene glycol (EG) into fine chemicals and H2 is an ideal solution to address severe plastic pollution. Here, we report the electrooxidation of EG to glycolic acid (GA) with a high Faraday efficiency and selectivity (>85 %) even at an industry‐level current density (600 mA cm−2 at 1.15 V vs. RHE) over a Pd−Ni(OH)2 catalyst. Notably, stable electrolysis over 200 h can be achieved, outperforming all available Pd‐based catalysts. Combined experimental and theoretical results reveal that 1) the OH* generation promoted by Ni(OH)2 plays a critical role in facilitating EG‐to‐GA oxidation and removing poisonous carbonyl species, thereby achieving high activity and stability; 2) Pd with a downshifted d‐band center and the oxophilic Ni can synergistically facilitate the rapid desorption and transfer of GA from the active Pd sites to the inactive Ni sites, avoiding over‐oxidation and thus achieving high selectivity.
Poly‐Hydride [AuI7(PPh3)7H5](SbF6)2 cluster complex: Structure, Transformation, and Electrocatalytic CO2 Reduction Properties
Authors: Tang Li , Luo Yuting , Ma Xiaoshuang , Wang Bin , Ding Mei , Wang Ru , Wang Pu , Pei Yong , Wang Shuxin
Published: January 2023

Hydride AuI bonds are labile due to the mismatch in electric potential of an oxidizing metal and reducing ligand, and therefore the structure and structure–activity relationships of nanoclusters that contain them are seldom studied. Herein, we report the synthesis and characterization of [Au7(PPh3)7H5](SbF6)2 (abbrev. Au7H52+), an Au cluster complex containing five hydride ligands, which decomposed to give [Au8(PPh3)7]2+ (abbrev. Au82+) upon exposure to light (300 to 450 nm). The valence state of AuI and H− was verified by density functional theory (DFT) calculations, NMR, UV/Vis and XPS. The two nanoclusters behaved differently in the electrocatalytic CO2 reduction reaction (CO2RR): Au7H52+ exhibited 98.2 % selectivity for H2, whereas Au82+ was selective for CO (73.5 %). Further DFT calculations showed that the H− ligand inhibited the CO2RR process compared with the electron‐donor H.
Chemomechanically Stable Small Single‐crystal Mo‐doped LiNi0.6Co0.2Mn0.2O2 Cathodes for Practical 4.5 V‐class Pouch‐type Li‐ion Batteries
Authors: Liang Longwei , Li Xiaoying , Su Maoshui , Wang Lixian , Sun Jinfeng , Liu Yang , Hou Linrui , Yuan Changzhou
Published: January 2023

High voltage can cost‐effectively boost energy density of Ni‐rich cathodes based Li‐ion batteries (LIBs), but compromises their mechanical, electrochemical and thermal‐driven stability. Herein, a collaborative strategy (i.e., small single‐crystal design and hetero‐atom doping) is devised to construct a chemomechanically reliable small single‐crystal Mo‐doped LiNi0.6Co0.2Mn0.2O2 (SS‐MN6) operating stably under high voltage (≥4.5 V vs. Li/Li+). The substantially reduced particle size combined with Mo6+ doping absorbs accumulated localized stress to eradicate cracks formation, subdues the surface side reactions and lattice oxygen missing meanwhile, and improves thermal tolerance at highly delithiated state. Consequently, the SS‐MN6 based pouch cells are endowed with striking deep cycling stability and wide‐temperature‐tolerance capability. The contribution here provides a promising way to construct advanced cathodes with superb chemomechanical stability for next‐generation LIBs.
Electroreduction of CO2 on Au(310)@Cu High‐index Facets
Authors: Liang Liang , Feng Quanchen , Wang Xingli , Hübner Jessica , Gernert Ulrich , Heggen Marc , Wu Longfei , Hellmann Tim , Hofmann Jan P. , Strasser Peter
Published: January 2023

The chemical selectivity and faradaic efficiency of high‐index Cu facets for the CO2 reduction reaction (CO2RR) is investigated. More specifically, shape‐controlled nanoparticles enclosed by Cu {hk0} facets are fabricated using Cu multilayer deposition at three distinct layer thicknesses on the surface facets of Au truncated ditetragonal nanoprisms (Au DTPs). Au DTPs are shapes enclosed by 12 high‐index {310} facets. Facet angle analysis confirms DTP geometry. Elemental mapping analysis shows Cu surface layers are uniformly distributed on the Au {310} facets of the DTPs. The 7 nm Au@Cu DTPs high‐index {hk0} facets exhibit a CH4 : CO product ratio of almost 10 : 1 compared to a 1 : 1 ratio for the reference 7 nm Au@Cu nanoparticles (NPs). Operando Fourier transform infrared spectroscopy spectra disclose reactive adsorbed *CO as the main intermediate, whereas CO stripping experiments reveal the high‐index facets enhance the *CO formation followed by rapid desorption or hydrogenation.
Correlating the Experimentally Determined CO Adsorption Enthalpy with the Electrochemical CO Reduction Performance on Cu Surfaces
Authors: Xiong Haocheng , Sun Qiwen , Chen Kedang , Xu Yifei , Chang Xiaoxia , Lu Qi , Xu Bingjun
Published: January 2023

CO binding energy has been widely employed as a descriptor for effective catalysts in the electrochemical CO2and CO reduction reactions (CO(2)RR), however, it has yet to be determined experimentally at electrochemical interfaces due to the lack of suitable techniques. In this work, we developed a method to determine the standard adsorption enthalpy of CO on Cu surfaces with quantitative surface enhanced infrared absorption spectroscopy. On dendritic Cu at −0.75 V vs. SHE, the standard adsorption enthalpy, entropy and Gibbs free energy were determined to 1.5±0.5 kJ mol−1, ≈37.9±13.4 J/(mol K), and ≈−9.8±4.0 kJ mol−1, respectively. Comparison of the standard adsorption enthalpy of oxide‐derived Cu and dendritic Cu, as well as their CORR activities, suggests the presence of stronger binding sites on OD Cu, which could favor multicarbon products. The method developed in this work will help establish the correlation between the CO binding energy and the CO(2)RR activity.
Biased Borate Esterification during Nucleoside Phosphorylase‐Catalyzed Reactions: Apparent Equilibrium Shifts and Kinetic Implications**
Authors: Kaspar Felix , Brandt Felix , Westarp Sarah , Eilert Lea , Kemper Sebastian , Kurreck Anke , Neubauer Peter , Jacob Christoph R. , Schallmey Anett
Published: January 2023

Biocatalytic nucleoside (trans‐)glycosylations catalyzed by nucleoside phosphorylases have evolved into a practical and convenient approach to the preparation of modified nucleosides, which are important pharmaceuticals for the treatment of various cancers and viral infections. However, the obtained yields in these reactions are generally determined exclusively by the innate thermodynamic properties of the nucleosides involved, hampering the biocatalytic access to many sought‐after target nucleosides. We herein report an additional means for reaction engineering of these systems. We show how apparent equilibrium shifts in phosphorolysis and glycosylation reactions can be effected through entropically driven, biased esterification of nucleosides and ribosyl phosphates with inorganic borate. Our multifaceted analysis further describes the kinetic implications of this in situ reactant esterification for a model phosphorylase.
Glycine Imine—The Elusive α‐Imino Acid Intermediate in the Reductive Amination of Glyoxylic Acid
Authors: Paczelt Viktor , Wende Raffael C. , Schreiner Peter R. , Eckhardt André K.
Published: January 2023

Simple unhindered aldimines tend to hydrolyze or oligomerize and are therefore spectroscopically not well characterized. Herein we report the formation and spectroscopic characterization of the simplest imino acid, namely glycine imine, by cryogenic matrix isolation IR and UV/Vis spectroscopy. Glycine imine forms after UV irradiation of 2‐azidoacetic acid by N2 extrusion in anti‐(E,E)‐ and anti‐(Z,Z)‐conformation that can be photochemically interconverted. In matrix isolation pyrolysis experiments with 2‐azidoacetic acid, glycine imine cannot be trapped as it further decarboxylates to aminomethylene. In aqueous solution glycine imine is hydrolyzed to hydroxy glycine and hydrated glyoxylic acid. At higher concentrations or in the presence of FeIISO4 as a reducing agent glycine imine undergoes self‐reduction by oxidative decarboxylation chemistry. Glycine imine may be seen as one of the key reaction intermediates connecting prebiotic amino acid and sugar formation chemistry.
One‐Dimensional Covalent Organic Frameworks for the 2e− Oxygen Reduction Reaction
Authors: An Shuhao , Li Xuewen , Shang Shuaishuai , Xu Ting , Yang Shuai , Cui Cheng‐Xing , Peng Changjun , Liu Honglai , Xu Qing , Jiang Zheng , Hu Jun
Published: January 2023

Two‐dimensional covalent organic frameworks (2D COFs) are often employed for electrocatalytic systems because of their structural diversity. However, the efficiency of atom utilization is still in need of improvement, because the catalytic centers are located in the basal layers and it is difficult for the electrolytes to access them. Herein, we demonstrate the use of 1D COFs for the 2e− oxygen reduction reaction (ORR). The use of different four‐connectivity blocks resulted in the prepared 1D COFs displaying good crystallinity, high surface areas, and excellent chemical stability. The more exposed catalytic sites resulted in the 1D COFs showing large electrochemically active surface areas, 4.8‐fold of that of a control 2D COF, and thus enabled catalysis of the ORR with a higher H2O2 selectivity of 85.8 % and activity, with a TOF value of 0.051 s−1 at 0.2 V, than a 2D COF (72.9 % and 0.032 s−1). This work paves the way for the development of COFs with low dimensions for electrocatalysis.
Preparation of fluorinated epoxy‐phthalonitrile resins with excellent thermal stability and low dielectric constant
Authors: Dong Jinghui , Sang Xiaoming , Yin Weihao , Chen Xinggang
Published: January 2023

Fluoropolymers find applications in heat‐resistant cables, chemical‐resistant linings, electronic components, cladding materials, and weather‐resistant films. Therefore, it is imperative to improve their temperature resistance level and dielectric properties. In this study, a series of new fluorinated epoxy‐phthalonitrile resins with different mass ratios were prepared by adding phthalonitrile to the epoxy resin matrix, followed by a two‐step reaction of the amine with the epoxy resin at low temperature, and then by the reaction of the nitrile with the epoxy resin and the nitrile group at high temperature. The thermal stability and thermal oxidation stability of the cured products were improved; the initial decomposition temperature for 5% weight loss in air was 375.3°C, indicating good heat resistance performance. In addition, the glass transition temperature and storage modulus of the fluorinated epoxy‐phthalonitrile resins cured products increased with an increase in phthalonitrile content. The storage modulus remained above 1500 MPa until 150°C. The glass transition temperature of fluorinated epoxy‐phthalonitrile resins (at a mass ratio of 5:5) was 180°C, much higher than that of the epoxy resin (which was 140°C). Moreover, the dielectric constant of fluorinated phthalonitrile‐epoxy resin (5:5 mass ratio) was 2.01, which was 39.63% lower than that of fluorinated epoxy resin. The thermoset matrix has potential applications in the fabrication of a variety of low dielectric constant composites for electronic device related industries.
Identification and expression analyses of the olfactory‐related genes in different tissues' transcriptome of a predacious soldier beetle,Podabrus annulatus(Coleoptera, Cantharidae)
Authors: Wang Xiaoxiao , Liu Haoyu , Xie Guanglin , Wang Wenkai , Yang Yuxia
Published: January 2023

We sequenced and analyzed the transcriptomes from different tissues of the soldier beetle,Podabrus annulatus(Coleoptera: Cantharidae), and obtained 75.74 Gb clean reads which were assembled into 95,274 unigenes. Among these transcripts, 25,484 unigenes of highly quality were annotated. Based on annotation and tBLASTn results, we identified a total of 101 candidate olfactory‐related genes for the first time, including 11 putative odorant‐binding proteins (OBPs), 6 chemosensory proteins (CSP), 50 olfactory receptors (ORs), 25 gustatory receptors (GRs), 6 ionotropic receptors (IRs), and 3 sensory neuron membrane proteins (SNMPs). BLASTX best‐hit results indicated that these chemosensory genes were most identical to their respective orthologs fromPhotinus pyralis. Phylogenetic analyses also revealed that the ORs, GRs, and IRs ofPodabrus annulatusare closely related to those ofPhotinus pyralis. The fragment per kilobase per million mapped fragments (FPKM) values showed that the PannOBP2, PannOBP3, and PannOBP10 were predominantly expressed in the antennae, PannOBP1 in the abdomen–thorax, while others were not identified to be tissue‐specific. These olfactory‐related differentially expressed genes (DEGs) demonstrated different roles in the olfactory system ofPodabrus annulatus. This study establishes the groundwork for future research into the molecular mechanism of olfactory recognition inPodabrus annulatus.
Retracted: Pan‐neuronal knockdown of Ras GTPase‐activating protein 1 alters Drosophila activity and sleep behavior
Authors: Lagunas‐Rangel Francisco Alejandro
Published: January 2023

The above article, published online on 18 January 2023 in Wiley Online Library (https://onlinelibrary.wiley.com/doi/abs/10.1002/arch.22001), has been retracted by agreement between the author, the journal Editor in Chief, Yonggyun Kim and Wiley Periodicals, LLC.

The retraction has been agreed due to errors identified in the research methodology. The author confirms that repeating the research with corrected methodology has yielded significantly different results; therefore, the results and conclusions of the published article must be considered invalid.
Novel Approach for the Isolation and Immobilization of a Recombinant Transaminase: Applying an Advanced Nanocomposite System
Authors: Koplányi Gábor , Bell Evelin , Molnár Zsófia , Katona Gábor , Lajos Neumann Péter , Ender Ferenc , Balogh György T. , Žnidaršič‐Plazl Polona , Poppe László , Balogh‐Weiser Diána
Published: January 2023

The increasing application of recombinant enzymes demands not only effective and sustainable fermentation, but also highly efficient downstream processing and further stabilization of the enzymes by immobilization. In this study, a novel approach for the isolation and immobilization of His‐tagged transaminase fromChromobacterium violaceum(CvTA) has been developed. A recombinant ofCvTA was simultaneously isolated and immobilized by binding on silica nanoparticles (SNPs) with metal affinity linkers and additionally within poly(lactic acid) (PLA) nanofibers. The linker length and the nature of the metal ion significantly affected the enzyme binding efficiency and biocatalytic activity ofCvTA‐SNPs. The formation of PLA nanofibers by electrospinning enabled rapid embedding ofCvTA‐SNPs biocatalysts and ensured enhanced stability and activity. The developed advanced immobilization method reduces the time required for enzyme isolation, purification and immobilization by more than fourfold compared to a classical stepwise technique.
Imatinib suppresses activation of hepatic stellate cells by targeting STAT3/IL‐6 pathway through miR‐124
Authors: Alavifard Helia , Mazhari Sogol , Meyfour Anna , Tokhanbigli Samaneh , Ghavami Saeid , Zali Mohammad Reza , Aghdaei Hamid Asadzadeh , Hatami Behzad , Baghaei Kaveh
Published: January 2023

The activation of hepatic stellate cells is the primary function of facilitating liver fibrosis. Interfering with the coordinators of different signaling pathways in activated hepatic stellate cells (aHSCs) could be a potential approach in ameliorating liver fibrosis. Regarding the illustrated anti‐fibrotic effect of imatinib in liver fibrosis, we investigated the imatinib′s potential role in inhibiting HSC activation through miR‐124 and its interference with the STAT3/hepatic leukemia factor (HLF)/IL‐6 circuit. The anti‐fibrotic effect of imatinib was investigated in the LX‐2 cell line and carbon tetrachloride (CCl4)‐induced Sprague‐Dawley rat. The expression of IL‐6, STAT3, HLF, miR‐124, and α‐smooth muscle actin (α‐SMA) were quantified by quantitative real‐time PCR (qRT‐PCR) and the protein level of α‐SMA and STAT3 was measured by western blot analysis both in vitro and in vivo. The LX‐2 cells were subjected to immunocytochemistry (ICC) for α‐SMA expression. After administering imatinib in the liver fibrosis model, histopathological examinations were done, and hepatic function serum markers were checked. Imatinib administration alleviated mentioned liver fibrosis markers. The expression of miR‐124 was downregulated, while IL‐6/HLF/STAT3 circuit agents were upregulated in vitro and in vivo. Notably, imatinib intervention decreased the expression of IL‐6, STAT3, and HLF. Elevated expression of miR‐124 suppressed the expression of STAT3 and further inhibited HSCs activation. Our results demonstrated that imatinib not only ameliorated hepatic fibrosis through tyrosine kinase inhibitor (TKI) activity but also interfered with the miR‐124 and STAT3/HLF/IL‐6 pathway. Considering the important role of miR‐124 in regulating liver fibrosis and HSCs activation, imatinib may exert its anti‐fibrotic activity through miR‐124.
PCI for late STEMI: Better late than never?
Authors: Davis Monique G. , Blankenship James C.
Published: January 2023

Key Points

Management of patients presenting with late STEMI (>12 hours) remains controversial.

In this study, outcomes of early and late STEMI were similar despite more critical cardiovascular risk profiles among late presenters, potentially supporting a strategy of PCI in late STEMI presenters.

An algorithm for the management of late STEMI is presented
Nothing to do does not mean any consequences
Authors: Aranzulla Tiziana Claudia , Musumeci Giuseppe
Published: January 2023

Key Points

Post‐TAVR new‐onset left bundle branch block (nLBBB) has clinical and echocardiographic prognostic implications, being associated with higher rates of permanent pacemaker (PPM) implantation and hospitalization for heart failure, and with worse left ventricular ejection fraction and remodeling.

Close monitoring of patients who developed post‐TAVR nLBBB is needed, and predefined clinical, electrocardiographic and echocardiographic follow‐up should be scheduled at discharge

Future studies aimed at identifying predictors of post‐TAVR nLBBB occurrence and regression, as well as the time windows in which it is likely will help in targeting patients at higher risk of PPM
A novel RAD51 variant resulting in Fanconi anemia identified in an infant with multiple congenital anomalies
Authors: Geilmann Shelby , Solstad Rachel , Palmquist Rachel , Flores Daboub Josue , Botto Lorenzo D. , Grubb Peter H. , Bonkowsky Josh L. , Longo Nicola , Malone Jenkins Sabrina
Published: January 2023

Fanconi anemia, FA, is a rare, multi‐system disease caused by pathogenic variants in DNA repair genes. We report a novel RAD51 variant in an infant with FA whose tracheobronchomalacia has not been described in FA. His severe presentation expands the phenotype of RAD51‐associated FA, reported only in three patients previously.
Nonketotic hyperglycemic hemichorea‐hemiballismus in a pediatric patient: A case report
Authors: Saroufim Rita , Hannon Tamara
Published: January 2023

Nonketotic hyperglycemic hemichorea‐hemiballismus (NHHH) is an infrequent complication of diabetes mellitus, and rarely occurs in children. We present an adolescent boy with recent diagnosis of type 1 diabetes who presented with hemichorea and brain imaging findings consistent with NHHH. His symptoms resolved with euglycemia and valproic acid after few weeks.