bluuebunny/crossref_metadata_2025 huggingface dataset:
Recent Progress in Flow Energy Harvesting and Sensing Based on Triboelectric Nanogenerators
Authors: Wu Mengwei , Zhu Chuanqing , Si Jicang , Wang Hao , Xu Minyi , Mi Jianchun
Published: August 2023

Triboelectric nanogenerators (TENGs), as a novel energy harvesting technology, have attracted increasing attention. This review paper focuses on the application of TENGs in flow energy harvesting and self‐powered flow sensing systems, as well as the latest research progress in this field. First, the working principle of TENG is introduced in detail, including the electrification mechanism and four basic working modes. Subsequently, the common applications of TENG‐based flow energy harvesting are systematically classified and summarized. In addition, the designs and principles for harnessing wind energy, wave energy, water flow energy, and droplet energy are illustrated individually. Furthermore, the common applications of TENG in flow sensing are elucidated, involving flow velocity and direction, flow rate measurement, respiration monitoring, water level, and wave motion monitoring. Finally, the current challenges in this field, such as the stability of TENG performance, scalability and integration, environmental impact and durability, etc., are discussed and future research directions, such as developing new TENG materials and designing more high‐efficiency TENG structure, are proposed. It is hoped that this review paper can actively promote the research and application of TENGs and contribute to the development of this field.
Palmitoyltransferase ZDHHC3 Aggravates Nonalcoholic Steatohepatitis by Targeting S‐Palmitoylated IRHOM2
Authors: Xu Minxuan , Tan Jun , Zhu Liancai , Ge Chenxu , Zhang Yi , Gao Fufeng , Dai Xianling , Kuang Qin , Chai Jie , Zou Benkui , Wang Bochu
Published: August 2023

Underestimation of the complexity of pathogenesis in nonalcoholic steatohepatitis (NASH) significantly encumbers development of new drugs and targeted therapy strategies. Inactive rhomboid protein 2 (IRHOM2) has a multifunctional role in regulating inflammation, cell survival, and immunoreaction. Although cytokines and chemokines promote IRHOM2 trafficking or cooperate with partner factors by phosphorylation or ubiquitin ligases‐mediated ubiquitination to perform physiological process, it remains unknown whether other regulators induce IRHOM2 activation via different mechanisms in NASH progression. Here the authors find that IRHOM2 is post‐translationally S‐palmitoylated at C476 in iRhom homology domain (IRHD), which facilitates its cytomembrane translocation and stabilization. Fatty‐acids challenge can directly promote IRHOM2 trafficking by increasing its palmitoylation. Additionally, the authors identify Zinc finger DHHC‐type palmitoyltransferase 3 (ZDHHC3) as a key acetyltransferase required for the IRHOM2 palmitoylation. Fatty‐acids administration enhances IRHOM2 palmitoylation by increasing the direct association between ZDHHC3 and IRHOM2, which is catalyzed by the DHHC (C157) domain of ZDHHC3. Meanwhile, a metabolic stresses‐triggered increase of ZDHHC3 maintains palmitoylated IRHOM2 accumulation by blocking its ubiquitination, consequently suppressing its ubiquitin‐proteasome‐related degradation mediated by tripartite motif containing 31 (TRIM31). High‐levels of ZDHHC3 protein abundance positively correlate with the severity of NASH phenotype in patient samples. Hepatocyte‐specific dysfunction of ZDHHC3 significantly inhibits palmitoylated IRHOM2 deposition, therefore suppressing the fatty‐acids‐mediated hepatosteatosis and inflammation in vitro, as well as NASH pathological phenotype induced by two different high‐energy diets (HFHC & WTDF) in the in vivo rodent and rabbit model. Inversely, specific restoration of ZDHHC3 in hepatocytes markedly provides acceleration over the course of NASH development via increasing palmitoylation of IRHOM2 along with suppression of ubiquitin degradation. The current work uncovers that ZDHHC3‐induced palmitoylation is a novel regulatory mechanism and signal that regulates IRHOM2 trafficking, which confers evidence associating the regulation of palmitoylation with NASH progression.
Enhancing the Photocatalytic Activity of Zirconium‐Based Metal–Organic Frameworks Through the Formation of Mixed‐Valence Centers
Authors: Wei Zihao , Song Shaojia , Gu Hongfei , Li Yaqiong , Sun Qi , Ding Ning , Tang Hao , Zheng Lirong , Liu Shuhu , Li Zhenxing , Chen Wenxing , Li Shenghua , Pang Siping
Published: August 2023

Despite the desirability of metal–organic frameworks (MOFs) as heterogeneous photocatalysts, current strategies available to enhance the performance of MOF photocatalysts are complicated and expensive. Herein, a simple strategy is presented for improving the activity of MOF photocatalysts by regulating the atomic interface structure of the metal active sites on the MOF. In this study, MOF (PCN‐222) is hybridized with cellulose acetate (CA@PCN‐222) through an optimized atomic interface strategy, which lowers the average valence state of Zr ions. The electronic metal‐support interaction mechanism of CA@PCN‐222 is revealed by evaluating the photocatalytic CO2 reduction reaction (CO2RR). The experimental results suggested that the electron migration efficiency at the atomic interface of the MOFs strongly coupled with cellulose is significantly improved. In particular, the CO2RR to formate activity of CA@PCN‐222 photocatalyst greatly increased from 778.2 to 2816.0 µmol g−1 compared with pristine PCN‐222 without cellulose acetate. The findings suggest that the strongly coupled metal–ligand moiety at the atomic interface of MOFs may play a synergistic role in heterogeneous catalysts.
Untethered Magnetic Soft Robot with Ultra‐Flexible Wirelessly Rechargeable Micro‐Supercapacitor as an Onboard Power Source
Authors: Nardekar Swapnil Shital , Kim Sang‐Jae
Published: August 2023

Soft robotics has developed rapidly in recent years as an emergent research topic, offering new avenues for various industrial and biomedical settings. Despite these advancements, its applicability is limited to locomotion and actuation due to the lack of an adequate charge storage system that can support the robot's sensory system in challenging conditions. Herein, an ultra‐flexible, lightweight (≈50 milligrams), and wirelessly rechargeable micro‐supercapacitor as an onboard power source for miniaturized soft robots, capable of powering a range of sensory is proposed. The simple and scalable direct laser combustion technique is utilized to fabricate the robust graphene‐like carbon micro‐supercapacitor (GLC‐MSC) electrode. The GLC‐MSC demonstrates superior areal capacitance (8.76 mF cm−2), and maintains its original capacitance even under extreme actuation frequency (1–30 Hz). As proof of conceptthe authors fabricate a fully integrated magnetic‐soft robot that shows outstanding locomotion aptitude and charged wirelessly (up to 2.4 V within 25s), making it an ideal onboard power source for soft robotics.
Intra‐Operative Definition of Glioma Infiltrative Margins by Visualizing Immunosuppressive Tumor‐Associated Macrophages
Authors: Cao Chong , Yin Hang , Yang Biao , Yue Qi , Wu Guoqing , Gu Meng , Zhang Yuwen , Fan Yang , Dong Xiaoyan , Wang Ting , Wang Cong , Zhu Xiao , Mao Ying , Zhang Xiao‐Yong , Lei Zuhai , Li Cong
Published: August 2023

Accurate delineation of glioma infiltrative margins remains a challenge due to the low density of cancer cells in these regions. Here, a hierarchical imaging strategy to define glioma margins by locating the immunosuppressive tumor‐associated macrophages (TAMs) is proposed. A pH ratiometric fluorescent probe CP2‐M that targets immunosuppressive TAMs by binding to mannose receptor (CD206) is developed, and it subsequently senses the acidic phagosomal lumen, resulting in a remarkable fluorescence enhancement. With assistance of CP2‐M, glioma xenografts in mouse models with a tumor‐to‐background ratio exceeding 3.0 for up to 6 h are successfully visualized. Furthermore, by intra‐operatively mapping the pH distribution of exposed tissue after craniotomy, the glioma allograft in rat models is precisely excised. The overall survival of rat models significantly surpasses that achieved using clinically employed fluorescent probes. This work presents a novel strategy for locating glioma margins, thereby improving surgical outcomes for tumors with infiltrative characteristics.
Thermal Stability of Sulfide Solid Electrolyte with Lithium Metal
Authors: Wu Yujing , Xu Jing , Lu Pushun , Lu Jiaze , Gan Luyu , Wang Shuo , Xiao Ruijuan , Li Hong , Chen Liquan , Wu Fan
Published: August 2023

All solid–state battery (ASSB) is widely recognized as one of the most promising high‐energy‐density systems/technologies. However, thermal safety issues induced by highly reactive materials still exist for solid electrolytes (SEs). Insights on thermal behaviors at elevated temperatures and the underlying mechanism for thermal stability of SE‐based systems are still missing. Herein, thermal stability performance of typical sulfide SEs is systematically investigated with metal Li, whose order of interfacial thermal stability is concluded to be Li6PS5Cl > Li3PS4 > Li9.54Si1.74P1.44S11.7Cl0.3 > Li4SnS4 > Li7P3S11 after a comprehensive evaluation. Interestingly, Li4SnS4, which achieves good air stability, has poor thermal stability with Li metal. This is possibly caused by Li─Sn alloy products generated during thermal decomposition, and their great thermodynamic driving force towards SE for accelerated thermal runaway. Moreover, electrolytes with poor material‐level thermal stability (e.g., Li7P3S11) may form a dense passivation layer by self‐decomposition with Li metal to retard thermal runaway. Conclusively, the material structure affects the thermodynamic stability of the system, but the reaction products (interphase) affects the kinetic process of the thermal reaction within a certain temperature range. Therefore, thermal stability with both metallic lithium and decomposition products is a necessary condition for interfacial thermal stability of sulfide SEs.
Self‐Healing of Proton‐Irradiated Organic Photodiodes and Photovoltaics
Authors: Parkhomenko Hryhorii P. , Mostovyi Andriy I. , Akhtanova Gulnur , Solovan Mykhailo M. , Kaikanov Marat , Schopp Nora , Brus Viktor V.
Published: August 2023

In this study, a comprehensive quantitative analysis of the photodiode (PD) is conducted and photovoltaic (PV) characteristics of organic non‐fullerene PCE10:ITIC‐4F devices before and after exposure to a 150 ns pulse of 170 keV proton irradiation with the fluence of 2·1012 p cm−2 that is equivalent to ≈6 years of operation at a low Earth orbit. While an expected initial performance reduction happened in the photodiode and photovoltaic operation modes, a hitherto unknown self‐healing effect in the organic devices is observed several days after the proton irradiation. The organic bulk‐heterojunction (BHJ) material properties and the multi‐mechanisms recombination processes before and after irradiation and during self‐healing are investigated. This analysis provides a quantitative understanding of the changes occurring in the device physics and points toward the relevant aspects of the self‐healing mechanism related to the dynamics of proton‐induced traps in the bulk of the organic active layer. Ultimately, the synergy of record lightweight features and newly discovered self‐healing of proton‐induced damage in organic PDs and solar cells highlights their great potential for applications in rapidly emerging space technology.
Review of Emerging Atomically Precise Composite Site‐Based Electrocatalysts
Authors: Yang Xinyi , Song Wanqing , Zhang Tao , Huang Zechuan , Zhang Jinfeng , Ding Jia , Hu Wenbin
Published: August 2023

Atomically precise composite site‐based catalysts with new electrocatalytic synergistic mechanisms and enhanced electrocatalytic activities have emerged as a frontier in the electrocatalysis community. This topical review focuses on the recent research advances of atomically precise metal composite sites‐based electrocatalysts. This work first demonstrates an overview of the configurations of atomically precise composite sites, including a discussion of the advanced methods employed for understanding the composite sites. The review then provides a comprehensive organization of the previously reported methodologies of synthesizing electrocatalysts with atomically precise composite sites. Representative case studies are provided, starting from the simple one‐step pyrolysis strategy to the species‐by‐species multi‐step pyrolysis strategy. Based on the preceding discussions of the catalyst materials, the review further discusses the unique electrocatalysis mechanisms raised by the composite sites, that are different from the routine single species sites. The electrocatalytic systems mainly involve the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, nitrogen reduction reaction, and carbon dioxide reduction reaction. The themes of this section include the true active center determination for composite sites and various types of electrocatalytic synergy mechanisms. Finally, critical unanswered questions and remaining challenges, as well as promising underexplored research directions are identified.
The prevalence of frailty and its relationship with sociodemographic factors, regional healthcare disparities, and healthcare utilization in the aging population across India
Authors: Singhal Sunny , Singh Sumitabh , Dewangan Gevesh Chand , Dey Sharmistha , Banerjee Joyita , Lee Jinkook , Upadhyaya Ashish Datt , Hu Peifeng , Dey Aparajit Ballav
Published: August 2023

Objective

To estimate frailty prevalence and its relationship with the socio‐economic and regional factors and health care outcomes.

Methods

In this study, participants from the harmonized Diagnostic Assessment of Dementia for the Longitudinal Aging Study in India (LASI‐DAD) were included. The frailty index (FI) was calculated using a 32‐variable deficit model, with a value of ≥ 25% considered as frail. Data on demographic (including caste and religion) and socioeconomic profiles and health care utilization were obtained. The state‐wise health index maintained by the government based on various health‐related parameters was used to group the participants' residential states into high‐, intermediate‐, and low‐performing states. Multivariable and zero‐inflated negative binomial regression was used to assess the relationship of frailty index with sociodemographic characteristics, health index, and health care expenditure or hospitalization.

Results

Among the 3953 eligible participants, the prevalence of frailty was 42.34% (men = 34.99% and women = 49.35%). Compared to high‐performing states, intermediate‐ and low‐performing states had a higher proportion of frail individuals (49.7% vs. 46.8% vs. 34.5%, P < 0.001). In the adjusted analysis, frailty was positively associated with age, female sex, rural locality, lower education level, and caste (scheduled caste and other backward classes). After adjusting for the socio‐economic profile, FI was inversely associated with the composite health index of a state (P < 0.001). FI was also significantly correlated with total 1‐year health care expenditure and hospitalization (P < 0.001 and 0.020, respectively).

Conclusion

There is a high prevalence of frailty among older Indian adults that is associated with sociodemographic factors and regional health care performance. Furthermore, frailty is associated with increased health care utilization and expenditure.
Self‐assembly multifunctional DNA tetrahedron for efficient elimination of antibiotic‐resistant bacteria
Authors: Wu Tiantian , Fu Yu , Guo Shuang , Shi Yanqiang , Zhang Yuxin , Fan Zhijin , Yang Bin , Ding Baoquan , Liao Yuhui
Published: August 2023

Antibiotic resistance is a major challenge in the clinical treatment of bacterial infectious diseases. Herein, we constructed a multifunctional DNA nanoplatform as a versatile carrier for bacteria‐specific delivery of clinical antibiotic ciprofloxacin (CIP) and classic nanoantibiotic silver nanoparticles (AgNP). In our rational design, CIP was efficiently loaded in the self‐assembly double‐bundle DNA tetrahedron through intercalation with DNA duplex, and single‐strand DNA‐modified AgNP was embedded in the cavity of the DNA tetrahedron through hybridization. With the site‐specific assembly of targeting aptamer in the well‐defined DNA tetrahedron, the bacteria‐specific dual‐antibiotic delivery system exhibited excellent combined bactericidal properties. With enhanced antibiotic accumulation through breaking the out membrane of bacteria, the antibiotic delivery system effectively inhibited biofilm formation and promoted the healing of infected wounds in vivo. This DNA‐based antibiotic delivery system provides a promising strategy for the treatment of antibiotic‐resistant infections.
Experimental and computational design tools for industrial drying processes: Challenges in process‐limit prediction
Authors: Parrish Chance , Bell Nelson , Larsen Marvin E. , Tjiptowidjojo Kristianto , Schunk P. Randall
Published: August 2023

The coating and drying of inks and slurries are important steps to manufacture a plethora of products. Drying processes, particularly, comprise energy‐intensive steps that affect product cost and quality. Prior work has highlighted failures of various multicomponent diffusivity models to conserve mass in dryer modeling and challenges in predicting process limits given variability in published values of key thermodynamic parameters. Herein, we develop a computational model and benchtop drying experiments to investigate these concerns for drying polymer‐laden coatings. Model predictions of process limits in a single‐zone drying oven demonstrate that published variability in Flory–Huggins parameter yields large variations in predicted operating temperatures above which blistering occurs. This indicates that caution should be exercised when choosing approaches to obtain or predict the Flory–Huggins parameter, and that both benchtop drying experiments and a set of additional experiments, such as sorption experiments, are needed to fully characterize and optimize a given drying process.
Cardiovascular health, infection burden, and incident dementia in the UK Biobank
Authors: Beydoun Hind A. , Beydoun May A. , Meirelles Osorio , Erickson Lance D. , Gamaldo Alyssa A. , Weiss Jordan , Launer Lenore J. , Evans Michele K. , Zonderman Alan B.
Published: August 2023

INTRODUCTION

Among older adults, total and hospitalized infection may be associated with incidence of all‐cause and Alzheimer's disease (AD) dementias, with variation by cardiovascular health (CVH).

METHODS

We used Cox proportional hazards (PH) models to examine the relationships between International Classification of Diseases‐10th revision (ICD‐10)‐specific viral and bacterial infectious agents and incident all‐cause and AD dementia among 355,046 UK Biobank participants ≥50 years at baseline. Life's Essential 8 (LE8) index reflected CVH.

RESULTS

In both sexes, total infection burden (yes vs. no) was associated with all‐cause dementia, with significant interactions by LE8 tertiles, whereby this relationship was significant only in the lowest LE8 tertile. Hospital‐treated infection burden (yes vs no) was significantly related to all‐cause and AD dementia, with no significant interaction with LE8 tertile. Age group patterns were detected.

DISCUSSION

AD and all‐cause dementia were related to hospital‐treated infections, while CVH modified the relationship of total infection burden with all‐cause dementia.

Highlights

Secondary analysis on >355,000 UK Biobank participants ≥50 years at baseline.

Alzheimer's disease and all‐cause dementia are both related to hospital‐treated infection.

Cardiovascular health modifies association of infection burden with all‐cause dementia.
Severity of GNAO1‐Related Disorder Correlates with Changes in G‐Protein Function
Authors: Domínguez‐Carral Jana , Ludlam William Grant , Junyent Segarra Mar , Fornaguera Marti Montserrat , Balsells Sol , Muchart Jordi , Čokolić Petrović Dunja , Espinoza Iván , Ortigoza‐Escobar Juan Dario , Martemyanov Kirill A. ,   GNAO1‐Study Group
Published: August 2023

Objective

GNAO1‐related disorders (OMIM #615473 and #617493), caused by variants in the GNAO1 gene, are characterized by developmental delay or intellectual disability, hypotonia, movement disorders, and epilepsy. Neither a genotype–phenotype correlation nor a clear severity score have been established for this disorder. The objective of this prospective and retrospective observational study was to develop a severity score for GNAO1‐related disorders, and to delineate the correlation between the underlying molecular mechanisms and clinical severity.

Methods

A total of 16 individuals with GNAO1‐related disorders harboring 12 distinct missense variants, including four novel variants (p.K46R, p.T48I, p.R209P, and p.L235P), were examined with repeated clinical assessments, video‐electroencephalogram monitoring, and brain magnetic resonance imaging. The molecular pathology of each variant was delineated using a molecular deconvoluting platform.

Results

The patients displayed a wide variability in the severity of their symptoms. This heterogeneity was well represented in the GNAO1‐related disorders severity score, with a broad range of results. Patients with the same variant had comparable severity scores, indicating that differences in disease profiles are not due to interpatient variability, but rather, to unique disease mechanisms. Moreover, we found a significant correlation between clinical severity scores and molecular mechanisms.

Interpretation

The clinical score proposed here provides further insight into the correlation between pathophysiology and phenotypic severity in GNAO1‐related disorders. We found that each variant has a unique profile of clinical phenotypes and pathological molecular mechanisms. These findings will contribute to better understanding GNAO1‐related disorders. Additionally, the severity score will facilitate standardization of patients categorization and assessment of response to therapies in development. ANN NEUROL 2023;94:987–1004
Discovering Dynamic Plant Enzyme Complexes in Yeast for Kratom Alkaloid Pathway Identification**
Authors: Wu Yinan , Liu Chang , Koganitsky Anna , Gong Franklin L. , Li Sijin
Published: August 2023

Discovering natural product biosynthetic pathways of medicinal plants is challenging and laborious. Capturing the coregulation patterns of pathway enzymes, particularly transcriptomic regulation, has proven an effective method to accelerate pathway identification. In this study, we developed a yeast‐based screening method to capture the protein‐protein interactions (PPI) between plant enzymes, which is another useful pattern to complement the prevalent approach. Combining this method with plant multiomics analysis, we discovered four enzyme complexes and their organized pathways from kratom, an alkaloid‐producing plant. The four pathway branches involved six enzymes, including a strictosidine synthase, a strictosidine β‐D‐glucosidase (MsSGD), and four medium‐chain dehydrogenase/reductases (MsMDRs). PPI screening selected six MsMDRs interacting with MsSGD from 20 candidates predicted by multiomics analysis. Four of the six MsMDRs were then characterized as functional, indicating the high selectivity of the PPI screening method. This study highlights the opportunity of leveraging post‐translational regulation features to discover novel plant natural product biosynthetic pathways.
Die Rolle von unreaktiven Polyanionen in aktiven, chemisch regulierten komplexen Koazervaten
Authors: Späth Fabian , Maier Anton S. , Stasi Michele , Bergmann Alexander M. , Halama Kerstin , Wenisch Monika , Rieger Bernhard , Boekhoven Job
Published: August 2023

Komplexe Koazervation beschreibt die Flüssig‐Flüssig‐Phasentrennung entgegengesetzt geladener Polymere. Aktive Koazervate sind Tröpfchen, in denen die Affinität eines der Elektrolyte durch chemische Reaktionen gesteuert wird. Diese Tröpfchen sind besonders interessant, weil ihre Eigenschaften durch die Reaktionskinetik streng reguliert werden. Sie dienen beispielsweise als Modell für membranlose Organellen, die häufig auch durch biochemische Transformationen, wie z. B. posttranslationale Modifikationen, gesteuert werden. Sie sind auch ein gutes Modell für Protozellen oder könnten zur Synthese von künstlichem Leben verwendet werden – sie entstehen spontan als Reaktion auf Reagenzien, konkurrieren und zerfallen, sobald alle Nährstoffe verbraucht sind. Allerdings ist die Rolle der unreaktiven Bausteine, z. B. der Polymere, bisher kaum verstanden. Mit unserer Arbeit zeigen wir die wichtige Rolle des unreaktiven Polyanions unserer chemisch betriebenen Koazervattropfen. Wir zeigen, dass das Polyanion den Lebenszyklus der resultierenden Tröpfchen drastisch beeinflusst, ohne den chemischen Reaktionszyklus selbst zu beeinflussen – entweder sind sie sehr dynamisch oder lösen sich nur verzögert auf. Darüber hinaus leiten wir den Mechanismus dahinter ab und zeigen, wie Additive und rationales Polymerdesign dazu beitragen können, die gewünschten Lebenszyklen von Koazervatemulsionen zu erzeugen.
Photoinduzierte Metallonitrenbildung durch N2 Abspaltung aus Azid‐Diradikal‐Liganden
Authors: Domenianni Luis I. , Bauer Markus , Schmidt‐Räntsch Till , Lindner Jörg , Schneider Sven , Vöhringer Peter
Published: August 2023

Übergangsmetallnitride/nitrene sind vielversprechende Reagenzien für katalytischen Stickstoffatomtransfer, die in situ durch optisch induzierte N2‐Eliminierung aus Azidkomplexen zugänglich sind. Um ihr synthetisches Potenzial für die Katalyse voll ausschöpfen zu können, ist ein grundlegendes Verständnis der primären photoinduzierten Prozesse und der stereoelektronischen Faktoren, welche die N2‐Dissoziation kontrollieren, unerlässlich. Mit Hilfe von Femtosekunden‐Infrarotspektroskopie klären wir hier die primären molekularen Mechanismen auf, die für die Bildung eines einzigartigen Platin(II)nitrens mit Triplett‐Grundzustand aus einem geschlossenschaligen Platin(II)azidkomplex verantwortlich sind. Die spektroskopischen Daten in Kombination mit quantenchemischen Rechnungen ergeben einen konsistenten Mechanismus: Produktbildung erfordert die anfängliche Besetzung eines angeregten Singulett‐Zustands mit anionischen Azid‐Diradikal‐Liganden, der an ein low‐spin d8‐konfiguriertes PtII‐Ion gebunden ist. Anschließende Interkombination erzeugt das an Platin gebundene Triplett‐Aziddiradikal, welches sich durch N2‐Verlust in einer nahezu barrierelosen, adiabatischen Dissoziation nahtlos in das Triplett‐Nitren umwandelt. Unsere Daten unterstreichen die Bedeutung des produktiven, N2‐freisetzenden Zustands mit Azid ππ* Charakter als Konstruktionsprinzip für den Zugang zu effizienten Stickstoffatomtransfer‐Katalysatoren.
Photoinduced Metallonitrene Formation by N2 Elimination from Azide Diradical Ligands
Authors: Domenianni Luis I. , Bauer Markus , Schmidt‐Räntsch Till , Lindner Jörg , Schneider Sven , Vöhringer Peter
Published: August 2023

Transition‐metal nitrides/nitrenes are highly promising reagents for catalytic nitrogen‐atom‐transfer reactivity. They are typically prepared in situ upon optically induced N2 elimination from azido precursors. A full exploitation of their catalytic potential, however, requires in‐depth knowledge of the primary photo‐induced processes and the structural/electronic factors mediating the N2 loss with birth of the terminal metal‐nitrogen core. Using femtosecond infrared spectroscopy, we elucidate here the primary molecular‐level mechanisms responsible for the formation of a unique platinum(II) nitrene with a triplet ground state from a closed‐shell platinum(II) azide precursor. The spectroscopic data in combination with quantum‐chemical calculations provide compelling evidence that product formation requires the initial occupation of a singlet excited state with an anionic azide diradical ligand that is bound to a low‐spin d8‐configured PtII ion. Subsequent intersystem crossing generates the Pt‐bound triplet azide diradical, which smoothly evolves into the triplet nitrene via N2 loss in a near barrierless adiabatic dissociation. Our data highlight the importance of the productive, N2‐releasing state possessing azide ππ* character as a design principle for accessing efficient N‐atom‐transfer catalysts.
Structural and biological studies of mononuclear metal (II) complexes containing hetero ligand based on 3‐acetylpyridine thiosemicarbazone
Authors: BenGuzzi Salima A. , S. Abubakr Amrajaa , Hassan Safaa S.
Published: August 2023

The Schiff base (3‐APT) was a bidentate ligand produced from the condensation between 3‐acetylpyridine and the amine group of thiosemicarbazide. Metal chelates were successfully obtained with formulas [Cu(3‐APT)2X]X, [Ni(3‐APT)2]X2.H2O and [Pd(3‐APT)X2] (where 3‐APT = 3‐acetylpyridine thiosemicarbazone and X = Cl−). The characterization was performed by various physicochemical tools. The studied (3‐APT) ligand had two donor sites through both azomethine nitrogen and thiocarbonyl sulfur. The characterization tools observed the presence of two different geometric shapes. The square planar structure in the case of both nickel (II) and palladium (II) chelates and the square pyramidal structure in the case of copper (II) complex. The characterization involved a1HNMR study for the (3‐APT) ligand and its square planar Pd (II) and Ni (II) chelates. The density functional theory was used to structurally optimize the synthesized ligand and its chelates. The antibacterial activity was evaluated using different types of bacteria showing superior results. The breast (MCF‐7) cell line was selected to investigate the cytotoxic effect of formed compounds. The palladium (II) complex was the most cytotoxic effective compound with the least IC50value. Further theoretical molecular docking study was performed to observe the active sites in the selected proteins during their interactions with our compounds.
A nitrogen‐rich DOPO‐based phosphoramide for improving the fire resistance of polycarbonate with comparable mechanical property
Authors: Cai Boyu , Jiang Qing , Xu Wendi , Wang Luze , Luo Zhonglin , Wang Biaobing
Published: August 2023

A nitrogen‐rich DOPO‐based phosphoramide (DPAPZ) was synthesized using aminopyrazine and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as raw materials, and blended with polycarbonate (PC) through melting method. The chemical structure of DPAPZ was validated by FTIR, 1H NMR and 31P NMR. The presence of DPAPZ endowed PC/DPAPZ composites with better fire safety and smoke suppression. With the incorporation of 6 wt% DPAPZ, PC/DPAPZ‐6 composite reached UL‐94 V‐0 rating and 30.2% of limiting oxygen index value. Simultaneously, the peak of heat release rate and total heat release of PC/DPAPZ‐6 were reduced by 44.8% and 47.0% as compared with the pure PC, respectively. The DPAPZ displayed bi‐phase flame retardant roles. In the gas phase, the decomposition of DPAPZ released phosphorus‐containing free radicals acting as the quencher of reactive H·/OH· and nonflammable NH3 diluting O2/combustible volatiles. In the condensed phase, the phosphorus‐containing components were dehydrated into metaphosphoric acid or polymetaphosphate covering the surface to protect the PC matrix from further combustion, and to promote the formation of a dense carbon layer to interrupt the transmission of O2 and volatiles between the combustion zone and the inner. The tensile strength of the composites displayed almost no change but the elongation at break decreased slightly with the addition of DPAPZ.
Fabrication ofAg2S‐incorporated polyamide thin film nanocomposite reverse osmosis membranes with antifouling properties
Authors: Nchoe Obakeng B. , Matshetshe Kabo , As' Ballim Muhammed , Tetyana Phumlani , Sikhwivhilu Keneiloe , Moloto Nosipho
Published: August 2023

Herein we report on the fabrication of polyamide (PA) thin‐film composites (TFC) as reverse osmosis (RO) membranes with embedded silver sulfide (Ag2S) nanoparticles (NPs) to form thin‐film nanocomposites (TFN) and mitigate fouling. The fabrication of TFN membranes was done via interfacial polymerization on a polysulfone support membrane. Varied amounts of Ag2S NPs (20, 30, and 50 mg) were added to the aqueous phase to form membranes with enhanced antifouling and permselectivity performance. The chemical composition, surface topography, resistance to organic fouling and biofouling, water flux, and salt rejection, were tested on all membranes. The formation of Ag2S was confirmed by XRD and transmission electron microscopy. The pure water flux (Jo) obtained by all TFN membranes was above 25 L/m2h. Moreover, the 30 mg loaded TFN membrane attained the highestJoof 32.7 L/m2h. Salt rejection of the nanocomposite membranes were observed to be above 98%, which deems them suitable materials for desalination. TFN demonstrated resistance to fouling by bovine serum albumin and was able to retard bacterial colony formation. This was attributed to antibacterial properties of Ag2S NPs. Moreover, surface roughness decreased with increased NP loading, which also reduced the propensity of fouling.
Designing Magnetic Properties in CrSBr through Hydrostatic Pressure and Ligand Substitution
Authors: Telford Evan J. , Chica Daniel G. , Ziebel Michael E. , Xie Kaichen , Manganaro Nicholas S. , Huang Chun‐Ying , Cox Jordan , Dismukes Avalon H. , Zhu Xiaoyang , Walsh James P. S. , Cao Ting , Dean Cory R. , Roy Xavier
Published: August 2023

Magnetic van der Waals (vdW) materials are a promising platform for producing atomically thin spintronic and optoelectronic devices. The A‐type antiferromagnet CrSBr has emerged as a particularly exciting material due to its high magnetic ordering temperature, semiconducting electrical properties, and enhanced chemical stability compared to other vdW magnets. Exploring mechanisms to tune its magnetic properties will facilitate the development of nanoscale devices based on vdW materials with designer magnetic properties. Here it is investigated how the magnetic properties of CrSBr change under pressure and ligand substitution. Pressure compresses the unit cell, increasing the interlayer exchange energy while lowering the Néel temperature. Ligand substitution, realized synthetically through Cl alloying, anisotropically compresses the unit cell and suppresses the Cr‐halogen covalency, reducing the magnetocrystalline anisotropy energy and decreasing the Néel temperature. A detailed structural analysis combined with first‐principles calculations reveals that alterations in the magnetic properties are intricately related to changes in direct Cr–Cr exchange interactions and the Cr–anion superexchange pathways. Further, it is demonstrated that Cl alloying enables chemical tuning of the interlayer coupling from antiferromagnetic to ferromagnetic, which is unique among known two‐dimensional magnets.
Melon and rostral muscle morphology of Gervais' beaked whale (Mesoplodon europaeus): Alternating patterns of bilateral asymmetry
Authors: Denk Michael , McLellan William , Pabst D. Ann , Rommel Sentiel , Keenan Tiffany , Sharp Sarah , Niemeyer Misty , Hunter Nicole , Block Gary , Nelson Nathan , Harms Craig , Thornton Steven , Costidis Alexander , Moore Michael
Published: August 2023

Toothed whales utilize specialized nasal structures such as the lipid‐rich melon to produce sound and propagate it into the aquatic environment. Very little nasal morphology of mesoplodont beaked whales has been described in the literature, and the anatomy of the melon and associated musculature of Gervais' beaked whale (Mesoplodon europaeus) remains undescribed. Heads of three (n = 3) Gervais' beaked whales were examined in detail via dissection as well as computed tomography (CT) and magnetic resonance imaging (MRI). Two additional Gervais' beaked whale individuals (n = 2) were studied via archived CT and MRI scans. Representative transverse dissection sections of the melon were processed for polarized light imaging to verify the presence of tendons inserting into the melon tissue. Three‐dimensional (3D) CT reconstructions of the melon, rostral muscles, and associated structures were performed to assess morphology and spatial relationships. In all individuals, the melon's main body demonstrated a bilaterally asymmetrical, curvilinear geometry. This curvilinear shape was defined by a pattern of alternating asymmetry in the medial rostral muscles that projected into the melon's tissue. In transverse polarized light imaging, a network of tendons originating from these asymmetrical rostral muscle projections was observed permeating the melon's lipid tissue. This curvilinear melon morphology and associated asymmetrical musculature suggest a means of lengthening the lipid pathway within a relatively short dimensional footprint. In addition, the species‐specific arrangement of muscular projections suggests complex fine‐tuning of the melon's geometry during echolocation. Further studies may lend additional insight into the function of this unusual melon morphology.
Facts in the machine: Systems of record and the performance of sociotechnical truth
Authors: Hauser Elliott
Published: August 2023

Information systems serve as the “source of truth” for much of social reality, from credit scores to eligibility for boarding an airplane to the current time. In contexts of practical consensus, the system makes it so. I label this phenomenon system‐dependent truth. This paper advances a theory of performative truthmaking, wherein the agencies of giving as and taking as produce facts and truth as relations. I introduce the term systems of record to denote information systems that contain facts rather than propositions. I develop a suitable performative approach to the phenomenon of system‐dependent truth by synthesizing John Searle's social ontology, an account of truth, facts, and social reality, with Karen Barad's agential realism, an onto‐epistemology of human and nonhuman agency. Using several specific examples drawn from travel and migration contexts, including the US government's No Fly List, I show that system‐dependent truth arises when an agent takes information from a system as fact during the performance of sociotechnical truth. I argue that the agencies of truthmaking and factmaking are a distinct form of power, that the coordination of these agencies constitutes institutional rationalities of potentially global scale, and that systems of record are therefore critical sites for justice‐oriented information studies.
Empathy deficits, callous‐unemotional traits and structural underpinnings in autism spectrum disorder and conduct disorder youth
Authors: Tkalcec Antonia , Bierlein Maria , Seeger‐Schneider Gudrun , Walitza Susanne , Jenny Bettina , Menks Willeke M. , Felhbaum Lynn V. , Borbas Reka , Cole David M. , Raschle Nora , Herbrecht Evelyn , Stadler Christina , Cubillo Ana
Published: August 2023

Distinct empathy deficits are often described in patients with conduct disorder (CD) and autism spectrum disorder (ASD) yet their neural underpinnings and the influence of comorbid Callous‐Unemotional (CU) traits are unclear. This study compares the cognitive (CE) and affective empathy (AE) abilities of youth with CD and ASD, their potential neuroanatomical correlates, and the influence of CU traits on empathy. Adolescents and parents/caregivers completed empathy questionnaires (N = 148 adolescents, mean age = 15.16 years) and T1 weighted images were obtained from a subsample (N = 130). Group differences in empathy and the influence of CU traits were investigated using Bayesian analyses and Voxel‐Based Morphometry with Threshold‐Free Cluster Enhancement focusing on regions involved in AE (insula, amygdala, inferior frontal gyrus and cingulate cortex) and CE processes (ventromedial prefrontal cortex, temporoparietal junction, superior temporal gyrus, and precuneus). The ASD group showed lower parent‐reported AE and CE scores and lower self‐reported CE scores while the CD group showed lower parent‐reported CE scores than controls. When accounting for the influence of CU traits no AE deficits in ASD and CE deficits in CD were found, but CE deficits in ASD remained. Across all participants, CU traits were negatively associated with gray matter volumes in anterior cingulate which extends into the mid cingulate, ventromedial prefrontal cortex, and precuneus. Thus, although co‐occurring CU traits have been linked to global empathy deficits in reports and underlying brain structures, its influence on empathy aspects might be disorder‐specific. Investigating the subdimensions of empathy may therefore help to identify disorder‐specific empathy deficits.
A universal surrogate matrix assay for urea measurement in clinical pharmacokinetic studies of respiratory diseases
Authors: Tang Yang , Van Parys Michael , Walker Abigail , Drelick Alexandra , Liang Xiaorong , Dean Brian , Chen Liuxi
Published: August 2023

In pharmacokinetic studies for respiratory diseases, urea is a commonly used dilution marker for volume normalization of various biological matrices, owing to the fact that urea diffuses freely throughout the body and is minimally affected by disease states. In this study, we developed a convenient liquid chromatography–tandem mass spectrometry (LC–MS/MS) surrogate matrix assay for accurate urea quantitation in plasma, serum and epithelial lining fluid. Different mass spectrometer platforms and ionization modes were compared in parallel. The LC method and mass spectrometer parameters were comprehensively optimized to reduce interferences, to smooth the baseline and to maximize the signal‐to‐noise ratio. Saline was selected as the surrogate matrix, and its suitability was confirmed by good parallelism and accurate quality control sample measurements. Reliable and robust assay performance was demonstrated by precision and accuracy, dilution integrity, sensitivity, recovery and stability, all of which met bioanalysis requirements to support clinical studies. The assay performance was also verified and better understood by comparing it with a colorimetric assay and to a surrogate analyte assay. The newly developed surrogate matrix assay has the potential to be further expanded for urea quantitation in numerous physiological matrices.
Accelerometer‐derived sleep measures in idiopathic dystonia: A UK Biobank cohort study
Authors: Bailey Grace A , Wadon Megan E. , Komarzynski Sandra , Matthews Clare , Davies Elin Haf , Peall Kathryn J.
Published: August 2023

Background

Sleep disturbance is an increasingly recognized non‐motor trait in dystonia, with varying findings reported to date. Here, we examine sleep in a UK Biobank derived dystonia cohort using subjective self‐reported sleep symptoms and objective accelerometer‐derived sleep measures, with comparison to a control population.

Methods

A total of 241 dystonia cases were compared to 964 matched controls in analysis of self‐reported sleep symptoms and changes in sleep architecture using wrist‐worn triaxial accelerometers.

Results

Dystonia participants had poorer self‐reported sleep patterns compared to controls. Accelerometery measurements demonstrated later sleep times, reduced time in bed, and shifts in circadian rhythm. No association was observed with pain, and only limited relationships with psychiatric symptoms.

Discussion

This study demonstrates the utility of accelerometers in longer term evaluation of sleep in dystonia, for measurement of disturbance and response to treatment. Compared to controls, altered sleep and circadian rhythm were more common in dystonia patients which may contribute to the clinical phenotype.
Establishment of a facial nerve trunk crush injury model and evaluation of facial nerve self‐healing in rats
Authors: Fei Jing , Guan Xirui , Gao Lin , Ni Ping , Zheng Hongdi , Duan Kunling , Liao Na , Li Leiji
Published: August 2023

Introduction/aims

To facilitate further investigation into the mechanisms of facial nerve regeneration, a simple and reliable model of facial nerve crush injury is essential. Nevertheless, the establishment of such models lacks standardization and repeatability, while the healing capacity of the nerve is often overlooked, potentially affecting future studies.

Methods

We made facial nerve trunk crush injury models with different pressing times and detected the changes from the distal nerves to the motoneurons via behavior analysis, electrophysiological test, and histomorphometry analysis.

Results

It revealed a particular capacity for self‐healing following facial nerve crush damage because there was almost no facial motoneuron apoptosis in the MC group during the observation period, and rats in MC group had total facial paralysis in behavioral tests following surgery and varying degrees of recovery 28 days postoperatively with no treatments. As the pressing time increased, the latency, wave amplitude, nerve fiber damage degree, nerve axon ratio, myelin thickness, electroneurograph (ENoG) value, ultrastructural damage, abnormal morphological changes, and the buccal muscle atrophy of each MC group gradually increased or got worse during the observation period. However, after 28 postoperative days, only the ENoG values of the M10min and M12min groups were beyond 90%, indicating no self‐healing.

Discussion

It suggests that a stable model of peripheral facial palsy may be created by applying a 12.5 cm mosquito clamped to the facial nerve trunk for at least 10 min, which laid the foundation for the subsequent research to objectively evaluate facial nerve regeneration.
Sustainable business models for smallholder farmers: Challenges for and lessons from theBarshapump experience
Authors: Intriago Zambrano Juan Carlo , Diehl Jan‐Carel , Ertsen Maurits W.
Published: August 2023

Smallholder farmers (SFs) are cornerstone actors in eradicating poverty and hunger. Companies have recently focused on SFs as potential customers and suppliers. Several hindrances yet prevent SFs to be commercially viable actors. In this respect, sustainable business models (SBMs) bring opportunities for companies to increase profit, improve SFs' livelihoods, and promote environmental sustainability. Recognizing these opportunities, the Dutch company aQysta provides the Barsha pump (BP) as a sustainable irrigation solution for SFs. The challenges for BP adoption that remain for SFs illustrate that there is still limited understanding of how SBMs can support companies in engaging with SFs. To expand this understanding, we conducted a multiple‐case analysis of 10 organizations providing SF‐tailored products and/or services. Based on this analysis, we have drawn lessons for aQysta (and similar companies) to improve the BP's value proposition and we elaborate on the implications of this study for other organizations engaging commercially with SFs.