bluuebunny/crossref_metadata_2025 huggingface dataset:
Heterosynaptic MoS2 Memtransistors Emulating Biological Neuromodulation for Energy‐Efficient Neuromorphic Electronics
Authors: Huh Woong , Lee Donghun , Jang Seonghoon , Kang Jung Hoon , Yoon Tae Hyun , So Jae‐Pil , Kim Yeon Ho , Kim Jong Chan , Park Hong‐Gyu , Jeong Hu Young , Wang Gunuk , Lee Chul‐Ho
Published: March 2023

Heterosynaptic neuromodulation is a key enabler for energy‐efficient and high‐level biological neural processing. However, such manifold synaptic modulation cannot be emulated using conventional memristors and synaptic transistors. Thus, reported herein is a three‐terminal heterosynaptic memtransistor using an intentional‐defect‐generated molybdenum disulfide channel. Particularly, the defect‐mediated space‐charge‐limited conduction in the ultrathin channel results in memristive switching characteristics between the source and drain terminals, which are further modulated using a gate terminal according to the gate‐tuned filling of trap states. The device acts as an artificial synapse controlled by sub‐femtojoule impulses from both the source and gate terminals, consuming lower energy than its biological counterpart. In particular, electrostatic gate modulation, corresponding to biological neuromodulation, additionally regulates the dynamic range and tuning rate of the synaptic weight, independent of the programming (source) impulses. Notably, this heterosynaptic modulation not only improves the learning accuracy and efficiency but also reduces energy consumption in the pattern recognition. Thus, the study presents a new route leading toward the realization of highly networked and energy‐efficient neuromorphic electronics.
Bridging Synthesis and Controllable Doping of Monolayer 4 in. Length Transition‐Metal Dichalcogenides Single Crystals with High Electron Mobility
Authors: Li Hui , Yang Junbo , Li Xiaohui , Luo Quankun , Cheng Mo , Feng Wang , Du Ruofan , Wang Yuzhu , Song Luying , Wen Xia , Wen Yao , Xiao Mengmeng , Liao Lei , Zhang Yanfeng , Shi Jianping , He Jun
Published: March 2023

Epitaxial growth and controllable doping of wafer‐scale atomically thin semiconductor single crystals are two central tasks to tackle the scaling challenge of transistors. Despite considerable efforts are devoted, addressing such crucial issues simultaneously under 2D confinement is yet to be realized. Here, an ingenious strategy to synthesize record‐breaking 4 in. length Fe‐doped transition‐metal dichalcogenides (TMDCs) single crystals on industry‐compatible c‐plane sapphire without special miscut angle is designed. Atomically thin transistors with high electron mobility (≈146 cm2 V−1 s−1) and remarkable on/off current ratio (≈109) are fabricated based on 4 in. length Fe‐MoS2 single crystals, due to the ultralow contact resistance (≈489 Ω µm). In‐depth characterizations and theoretical calculations reveal that the introduction of Fe significantly decreases the formation energy of parallel steps on sapphire surfaces and contributes to the edge‐nucleation of unidirectional alignment TMDCs domains (>99%). This work represents a substantial leap in terms of bridging synthesis and doping of wafer‐scale 2D semiconductor single crystals, which should promote the further device downscaling and extension of Moore's law.
Vertical Array of Graphite Oxide Liquid Crystal by Microwire Shearing for Highly Thermally Conductive Composites
Authors: Cao Min , Li Zheng , Lu Jiahao , Wang Bo , Lai Haiwen , Li Zeshen , Gao Yue , Ming Xin , Luo Shiyu , Peng Li , Xu Zhen , Liu Senping , Liu Yingjun , Gao Chao
Published: March 2023

Excellent through‐plane thermally conductive composites are highly demanded for efficient heat dissipation. Giant sheets have large crystalline domain and significantly reduce interface phonon scattering, making them promising to build highly thermally conductive composites. However, realizing vertical orientation of giant sheets remains challenging due to their enormous mass and huge hydrodynamic drag force. Here, we achieve highly vertically ordered liquid crystals of giant graphite oxide (more than 100 µm in lateral dimension) by microwire shearing, which endows the composite with a recorded through‐plane thermal conductivity of 94 W m−1 K−1. Microscale shearing fields induced by vertical motion of microwires conquer huge hydrodynamic energy barrier and vertically reorient giant sheets. The resulting liquid crystals exhibit extremely retarded relaxation and impart large‐scale vertical array with bidirectional ordering degree as high as 0.82. The graphite array‐based composites demonstrate an ultrahigh thermal enhancement efficiency of over 35 times per unit volume. Furthermore, the composites improve cooling efficiency by 93% for thermal management tests compared to commercial thermal interface materials. This work offers a novel methodology to precisely manipulate the orientation of giant particles and promote large‐scale fabrication of vertical array with advanced functionalities.
Amorphous Germanium Nanomaterials as High‐Performance Anode for Lithium and Sodium‐Ion Batteries
Authors: Liu Chao , Jiang Yiming , Meng Chao , Liu Xiaocun , Li Bo , Xia Shengqing
Published: March 2023

Amorphous germanium (a‐Ge) is a promising anode material for lithium and sodium‐ion batteries (LIBs and SIBs) due to its higher capacity than traditional graphite materials. Herein, a method to prepare the a‐Ge nano‐materials with a particle size ≈10 nm is proposed by decomposing the CaGe Zintl phase at room temperature. For LIBs, a‐Ge has a high‐capacity retention of 80% even after 180 cycles (1375 mAh g−1). When employed as the anode for SIBs, two‐dimensional composites with the a‐Ge supported on the graphite nanosheets (a‐Ge@GNS) is configured, and a high reversible capacity of 526 mAh g−1 after 120 cycles is achieved. The preparation of such high‐performance amorphous Ge nanomaterials demonstrated in this work is low‐cost and environmentally‐friendly, and compared with other methods it is especially suitable for scaling‐up or mass production.
Visible and Near‐Infrared Dynamic Electrochromic Modulation With the Plasmon‐Enhanced Two‐Dimensional Ordered Macroporous Au/PProDot‐Me2 Thin Film
Authors: Wu Qiyan , Wang Junxin , Yang Xinyue , Tong Zhangfa , Ji Hongbing , Qu Hui‐Ying
Published: March 2023

Localized surface plasmon resonance (LSPR) is attractive to fabricate visible (VIS) and near‐infrared (NIR) dual‐band electrochromic materials. However, the introduction of the LSPR effect in the available dual‐band electrochromic materials can only be manifested to the spectral enhancement in the NIR region, and difficult issues of electrochromic materials such as low coloration efficiency and unsatisfactory long‐term cycling durability still remain. Here, a dual‐band electrochromic thin film consisting of a 2D ordered macroporous (2DOM) Au LSPR layer and a poly(3,4‐(2,2‐dimethylpropylenedioxy)thiophene) (PProDot‐Me2) electrochromic layer is presented, where LSPR and electrochromism interact in a complementary fashion. The 2DOM Au exhibits LSPR effect at wavelengths of 550 and 1700 nm, leading to a unique electrochromic performance improvement of the film in both of the VIS and NIR spectral regions. Large optical modulation, rapid switching speed, high coloration efficiency, and long‐term durability are achieved due to the collective effect of the near‐field enhancement of the 2DOM Au and the reduced bandgap of PProDot‐Me2. These advantages can be well retained in the dual‐band electrochromic device using the 2DOM Au/PProDot‐Me2 films as the electrochromic layers. This work provides new ideas for designing LSPR‐based devices, especially dual‐band electrochromic materials and devices, both experimentally and theoretically.
MYH10 Combines with MYH9 to Recruit USP45 by Deubiquitinating Snail and Promotes Serous Ovarian Cancer Carcinogenesis, Progression, and Cisplatin Resistance
Authors: Liu Longyang , Chen Chunlin , Liu Ping , Li Jing , Pang Zhanjun , Zhu Jiayu , Lin Zhongqiu , Zhou Haixu , Xie Yingying , Lan Tiancai , Chen Zhe‐Sheng , Zeng Zhaoyang , Fang Weiyi
Published: March 2023

The poor prognosis of serous ovarian cancer (SOC) is due to its high invasive capacity and cisplatin resistance of SOC cells, whereas the molecular mechanisms remain poorly understood. In the present study, the expression and function of non‐muscle myosin heavy chain IIB (MYH10) in SOC are identified by immunohistochemistry, in vitro, and in vivo studies, respectively. The mechanism of MYH10 is demonstrated by co‐immunoprecipitation, GST pull‐down, confocal laser assays, and so on. The results show that the knockdown of MYH10 suppressed SOC cell proliferation, migration, invasion, metastasis, and cisplatin resistance both in vivo and in vitro. Further studies confirm that the MYH10 protein functional domain combines with non‐muscle myosin heavy chain IIA (MYH9) to recruit the deubiquitinating enzyme Ubiquitin‐specific proteases 45 and deubiquitinates snail to inhibit snail degradation, eventually promoting tumorigenesis, progression, and cisplatin resistance in SOC. In clinical samples, MYH10 expression is significantly elevated in SOC samples compared to the paratumor samples. And the expression of MYH10 is positively correlated with MYH9 expression. MYH10+/MYH9+ co‐expression is an independent prognostic factor for predicting SOC patient survival. These findings uncover a key role of the MYH10‐MYH9‐snail axis in SOC carcinogenesis, progression, and cisplatin resistance, and provide potential novel therapeutic targets for SOC intervention.
Abnormal ear development in corn: Does hybrid, environment, and seeding rate matter?
Authors: Ortez Osler A. , McMechan Anthony J. , Robinson Emily , Hoegemeyer Thomas , Howard Reka , Elmore Roger W.
Published: March 2023

Corn (Zea mays L.) yields have increased in the United States since the 1930s and in other parts of the world since the 1950s and 1960s because of improvements in agricultural management and genotypes. Despite these increases, production concerns still exist. In July 2016, abnormal ear development (multi‐ears per node, barbell‐ears, and short‐husks) was reported in cornfields that extended from the Texas Panhandle to eastern Colorado and east through Kansas, Nebraska, Iowa, and Illinois. Surveys in Nebraska farmer fields revealed significant productivity losses due to the issues, but little was known about the underlying causes. A research study was conducted in four Nebraska fields during the 2018 and 2019 growing seasons. The research investigated the effects of hybrids, environments, seeding rates, and their interactions on abnormal ears. Eight hybrids, eight environments, and five seeding rates were studied. About 63,500 plants were individually assessed at or after the dent stage (R5). Grain yield ranged from 4.3 to 20.1 Mg ha−1. In 2018, about 5% of ears were abnormal; in 2019, about 11%, if combined, about 8%. Higher‐yielding hybrids were associated with lower percentages of abnormalities. Hybrids, environments, and seeding rates influenced the occurrence of abnormal ears. In most cases, abnormal ears had lower heights in the canopy, suggesting that primary ear loss may be a factor. The results reinforced the overriding hypothesis that ear abnormalities result from environmental, genetic, and management interactions. Depending on the environment, selecting certain hybrids with optimum seeding rates could help mitigate the occurrence of abnormal ears.
Carbon Quantum Dots with Near‐Unity Quantum Yield Bandgap Emission for Electroluminescent Light‐Emitting Diodes
Authors: Yuan Ting , Yuan Fanglong , Sui Laizhi , Zhang Yang , Li Yunchao , Li Xiaohong , Tan Zhan'ao , Fan Louzhen
Published: March 2023

Carbon quantum dots (CQDs) feature bright and tunable photoluminescence, solution processability, and low toxicity, showing great potential in optoelectronics. However, the large‐scale synthesis of CQDs with near‐unity photoluminescence quantum yield (PLQY) has not been achieved so far. In this study, we perform radical‐assisted synthesis of hexagon‐shaped CQDs (H‐CQDs) delivering near‐unity PLQY (96 %). Experimental and theoretical analyses revealed that the large vertically oriented transition dipole moment of H‐CQDs originating from high symmetry results in nearly 100 % PLQY. The H‐CQDs also exhibited a high electron mobility of up to 0.07 cm2 V−1 s−1. These properties enable the H‐CQD‐based light‐emitting diodes with a high external quantum efficiency of 4.6 % and a record maximum brightness of over 11 000 cd m−2. This study represents a significant advance that CQDs‐based electroluminescent device can be utilized for potential display and lighting applications.
Entropic Contributions to Sodium Solvation and Solvent Stabilization upon Electrochemical Sodium Deposition from Diglyme and Propylene Carbonate Electrolytes
Authors: Karcher Franziska , Uhl Matthias , Geng Tanja , Jacob Timo , Schuster Rolf
Published: March 2023

The formation of an appropriate solid electrolyte interphase (SEI) at the anode of a sodium battery is crucially dependent on the electrochemical stability of solvent and electrolyte at the redox potential of Na/Na+ in the respective system. In order to determine entropic contributions to the relative stability of the electrolyte solution, we measure the reaction entropy of Na metal deposition for diglyme (DG) and propylene carbonate (PC) based electrolyte solutions by electrochemical microcalorimetry at single electrodes. We found a large positive reaction entropy for Na+ deposition in DG of ΔR
234 J mol−1 K−1 (c.f.: ΔR
83 J mol−1 K−1), which signals substantial entropic destabilization of Na+ in DG by about 0.73 eV, thus increasing the stability of solvent and electrolyte relative to Na+ reduction. We attribute this strong entropic destabilization to a highly negative solvation entropy of Na+, due to the low dielectric constant and high freezing entropy of DG.
Messung von Nanometerabständen in Lösung mittels 13C NMR‐Spektroskopie – Schrumpfen von Makrocyclen mit zunehmender Temperatur
Authors: Siera Hannah , Mehrparvar Saber , Fax Jonas , Kreuzahler Mathis , Haberhauer Gebhard
Published: March 2023

Bei molekularen Systemen sind Größe und Form von elementarer Bedeutung für Funktion und Eigenschaften. Daher ist die Bestimmung von Abständen innerhalb eines Moleküls elementar. Die aktuell gängigen Methoden sind jedoch nur für Abstände kleiner als 4 Å oder größer als 15 Å geeignet. Hier zeigen wir, dass wir durch den Einbau einer molekularen Feder Abstände in Makrocyclen im Bereich von 10 Å mit Hilfe der 13C NMR‐Spektroskopie messen können. Die Genauigkeit der Methode erlaubt es auch die Temperaturabhängigkeit der Abstände zu bestimmen. In einem Fall findet man bei Erwärmung ein Schrumpfen der Länge um fast 10 %. Diese Verkürzung durch Erwärmung kann als inverse Thermoelastizität auf molekularer Ebene betrachtet werden und ist ein bisher völlig vernachlässigtes Phänomen, das in Zukunft als Werkzeug zur Veränderung der Länge und damit der Funktion eines Systems genutzt werden kann.
Morphological Profiling Identifies the Motor Protein Eg5 as Cellular Target of Spirooxindoles
Authors: Liu Jie , Mallick Shubhadip , Xie Yusheng , Grassin Corentin , Lucas Belén , Schölermann Beate , Pahl Axel , Scheel Rebecca , Strohmann Carsten , Protzel Christoph , Berg Thorsten , Merten Christian , Ziegler Slava , Waldmann Herbert
Published: March 2023

Oxindoles and iso‐oxindoles are natural product‐derived scaffolds that provide inspiration for the design and synthesis of novel biologically relevant compound classes. Notably, the spirocyclic connection of oxindoles with iso‐oxindoles has not been explored by nature but promises to provide structurally related compounds endowed with novel bioactivity. Therefore, methods for their efficient synthesis and the conclusive discovery of their cellular targets are highly desirable. We describe a selective RhIII‐catalyzed scaffold‐divergent synthesis of spirooxindole–isooxindoles and spirooxindole–oxindoles from differently protected diazooxindoles and N‐pivaloyloxy aryl amides which includes a functional group‐controlled Lossen rearrangement as key step. Unbiased morphological profiling of a corresponding compound collection in the Cell Painting assay efficiently identified the mitotic kinesin Eg5 as the cellular target of the spirooxindoles, defining a unique Eg5 inhibitor chemotype.
Electrically Amplified Circularly Polarized Luminescence by a Chiral Anion Strategy
Authors: Li Zhong‐Qiu , Wang Yu‐Duan , Shao Jiang‐Yang , Zhou Zeyang , Gong Zhong‐Liang , Zhang Chuang , Yao Jiannian , Zhong Yu‐Wu
Published: March 2023

The development of circularly polarized electroluminescence (CPEL) is currently hampered by the high difficulty and cost in the syntheses of suitable chiral materials and the notorious chirality diminishment issue in electrical devices. Herein, diastereomeric IrIII and RuII complexes with chiral (±)‐camphorsulfonate counteranions are readily synthesized and used as the active materials in circularly polarized light‐emitting electrochemical cells to generate promising CPELs. The addition of the chiral ionic liquid (±)‐1‐butyl‐3‐methylimidazole camphorsulfonate into the active layer significantly improves the device performance and the electroluminescence dissymmetry factors (≈10−3), in stark contrast to the very weak circularly polarized photoluminescence of the spin‐coated films of these diastereomeric complexes. Control experiments with enantiopure IrIII complexes suggest that the chiral anions play a dominant role in the electrically‐induced amplification of CPELs.
Upcycling of Polybutadiene Facilitated by Selenium‐Mediated Allylic Amination
Authors: Hodges Mercie N. , Elardo Matthew J. , Seo Jinyoung , Dohoda Alexander F. , Michael Forrest E. , Golder Matthew R.
Published: March 2023

Accumulation of end‐of‐life plastics presents ongoing environmental concerns. One strategy to solve this grand challenge is to invent new techniques that modify post‐consumer waste and impart new functionality. While promising approaches for the chemical upcycling of commodity polyolefins and polyaromatics exist, analogous approaches to repurpose unsaturated polymers (e.g., polybutadiene) are scarce. In this work, we propose a method to upcycle polybutadiene, one of the most widely used commercial rubbers, via a mild, metal‐free allylic amination reaction. The resulting materials have tunable thermal and surface wetting properties as a function of both sulfonamide identity and grafting density. Importantly, this approach maintains the parent alkene microstructure without evidence of olefin reduction, olefin transposition, and/or chain scission. Based on these findings, we anticipate future applications in the remediation of complex elastomers and vulcanized rubbers.
Large‐Scale and Controllable Syntheses of Covalently‐Crosslinked Poly(ionic liquid) Nanoporous Membranes
Authors: Hu Yingyi , Xu Luyao , Zhang Wangqing , Wang Hong
Published: March 2023

Herein, we report an exciting synthetic procedure for the scalable and controllable fabrication of covalently crosslinked poly(ionic liquid) (PIL) nanoporous membranes (CPILMs) in water solution under ambient conditions. We found that the pore sizes, flexibility and compositions of freestanding CPILMs can be finely tailored by a rational structural choice of PIL, diketone and aldehyde. Studies on the CPILM formation mechanism revealed that hydrogen bonding‐induced phase separation of amino‐functionalized homo‐PIL between its polar and apolar domains coupled with structural rearrangements due to the Debus Radsizewski reaction‐triggered ambient covalent crosslinking process created a stable three‐dimensionally interconnected pore system in water solution. Employing structurally stable CPILMs in ion sieving devices resulted in an excellent Li+/Mg2+ separation efficiency due to the positively charged nature and “Donann” effects. This green, facile yet versatile approach to the production of CPILMs is a conceptually distinct and commercially interesting strategy for making useful nanoporous functional polyelectrolyte membranes.
An operation on placental support in a fetus with a nasopharyngeal teratoma
Authors: Yanko F. , Nathani H. , Alden T. , Valika T. , Rastatter J. , Alhajjat A. , Ballard H. A.
Published: March 2023

Airway obstruction diagnosed antenatally in the fetus due to congenital high airway obstruction syndrome or nasopharyngeal masses are the primary indications for performing an operation on placental support. Prenatally diagnosed nasopharyngeal masses pose the risk of total airway obstruction upon delivery. Placental support utilises uteroplacental blood flow to facilitate an airway intervention on the fetus while maintaining oxygenation. These interventions must be completed in under 20 min due to amniotic fluid loss and uterine contractions. This case report describes the anaesthetic management of a fetus with a nasal teratoma. In this report, we discuss the clinical indications and anaesthetic considerations of the operation on placental support procedure for nasopharyngeal masses.
Sulfonamide derived Schiff base Mn (II), Co (II), and Ni (II) complexes: Crystal structures, density functional theory and Hirshfeld surface analysis
Authors: Shehnaz  , Siddiqui Waseeq Ahmad , Ashraf Adnan , Ashfaq Muhammad , Tahir Muhammad Nawaz , Niaz Shanawer
Published: March 2023

The three transition metal complexes of the ligand named as 2,4‐dibromo‐6‐{[2‐(1,1‐dioxo‐1H‐benzoisothiazole‐3‐yl‐amino)‐ethylimino]‐methyl}‐phenol 3 were synthesized with divalent manganese, cobalt and nickel metal ions and characterized by employing different analytical methods including UV–visible, FT‐IR and elemental analyses. The crystal structures of Mn (II) complex 4, Co (II) complex 5, and Ni (II) complex 6 are determined by single beam X‐rays crystallography, which confirm the distorted octahedral coordination of the complexes 4–6. The non‐covalent interactions of the complexes 4–6 are investigated by the Hirshfeld surface analysis. The tendency of the pair of chemical species to form crystal packing interactions are computed, which provide the favorable contacts in the crystal packing for the complexes 4–6. For the sake of computing strength of the crystal packing, void analysis is performed for the complexes 4–6. The non‐electrolytic nature of synthesized metal complexes was confirmed by molar conductance. The spectral analyses suggested that sulfonamide functionalized Schiff base behaves as bidentate ligand and coordinates with the metal center through phenolic oxygen and iminic nitrogen atoms. The density functional theory (DFT) studies were performed for the Mn (II), Co (II), and Ni (II) metal complexes at the B3LYP/LANL2DZ level of theory. The structural characteristics, vibrational analysis (IR), NMR analysis, UV–Vis, natural bonding orbital (NBO), frontier molecular orbital (FMO), charges (Mulliken and NPA), global reactivity descriptors, molecular electrostatic potential (MEP), and dipole moments were investigated using this method. The large values of stabilization energy, that is, 12.02, 15.25, and 23.81 kcal/mol were found for the complexes Mn (II) 4, Co (II) 5, and Ni (II) 6, respectively by NBO analysis. The global reactivity findings suggested the positive values of electron affinity for all complexes, which indicate the involvement of charge transfer reaction. Among these complexes, complex 6 is the most stable and complex 4 is the least. Further, FMO analysis indicated large HOMO‐LUMO gap (3.85–3.97 eV) with higher LUMO values for all metal complexes.
An image reconstruction modeling approach for micro‐fibrous network of cellulose polymer separator concerning tensile and pore properties
Authors: Liu Wangyu , Wu Lin , Dang Yanping , Gou Jingren , Xie Weigui , Tang Aimin
Published: March 2023

Cellulose is applicable for preparing lithium‐ion battery separators due to its excellent properties. Factors affecting the performance of the cellulose separator can be explored via modeling the micro‐fibrous structure, which can provide guidance for preparing design and optimization of separators. In this paper, a three‐dimensional modeling method based on digital image processing is proposed for random fibrous network of cellulose separator, with a strong focus on the fibrous parameters. Finite element simulation on elastic mechanics is conducted, and the modeling accuracy has been discussed, where the effect of the fiber diameter and quantity on the elastic property of fibrous separator is comprehensively investigated. The relationship between porosity and elastic modulus can be predicted by both modeling simulation and experiment with a small error, indicating that the modeling method is credible. The pore property, that is, porosity and tortuosity, of the constructed model is calculated and compared with related work to characterize battery performance of separator. The result has shown the feasibility of the fibrous model in pore study. This work has provided an effective and reliable modeling approach for fibrous network, which can be utilized to investigate the mechanical and pore properties of battery separators.
Pt‐Based Rare Earth Alloy as Efficient and Robust Electrocatalyst for High‐Temperature Proton Exchange Membrane Fuel Cells
Authors: Lin Jiaqi , Wang Jun , Wu Yujie , Yang Pupu , Liu Qie , Li Miaoyu , Du Shiqian , Chen Ru , Tao Li
Published: March 2023

High‐temperature proton exchange membrane fuel cells (HT‐PEMFCs) are crucial in future energy systems. However, the activity and stability of the electrocatalysts are severely restricted by high temperature and phosphoric acid poisoning. Herein, PtCe alloy as oxygen reduction reaction (ORR) electrocatalyst for HT‐PEMFCs exhibits fantastic performance. Ce can increase the electronic density of Pt, weakening phosphoric acid poisoning and improving ORR activity. The optimized electronic structure can also reduce the dipole effect between Pt and O, which suppresses the irreversible oxidation of Pt. Additionally, the dramatically negative heat of formation in PtCe catalyst brings high kinetic barrier of metal diffusion and dissolution. With this electrocatalyst, the HT‐PEMFCs show a preeminent peak power of 605 mW cm−2 with 0.3 mgPt cm−2. After 30000 cycles of accelerated stability test, the peak power density only decreases by 31.6%, achieving the goal of Department of Energy in 2020 (<40% loss).
Gestational exposure to continuous light impairs the development of the female reproductive system in adult Wistar rat offspring
Authors: Ogo Fernanda Mithie , Siervo Glaucia Eloisa Munhoz Lion , Praxedes Ana Maria , Vieira Henrique Rodrigues , da Silva Scarton Suellen Ribeiro , Bitencourt Ana Tereza Guimarães , Arena Arielle Cristina , Simão Andréa Name Colado , Guerra Marina Trevizan , de Freitas Mathias Paulo Cesar , Fernandes Glaura Scantamburlo Alves
Published: March 2023

Introduction

It has been suggested that maternal exposure to constant light during the gestational period could be considered as a chronic stressor, impairing offspring development by interfering in neuroendocrine and behavior responses.

Objective

This study aimed to evaluate whether maternal exposure to continuous light during pregnancy affects the adult reproductive system in the female offspring.

Materials and Methods

Pregnant Wistar rats were allocated into light–dark (LD) group, exposed to light and dark photoperiod during gestation, and the light–light (LL) group, exposed to a photoperiod of constant light during gestation. After birth, pups were maintained under normal light–dark photoperiod until adulthood. At postnatal day 90, blood was collected from the female offspring, to analyze plasma luteinizing hormone (LH) and progesterone levels, and the uterus and ovaries were harvested for morphometric, histological, and oxidative stress evaluations.

Results and Discussion

Female exposure to continuous light during the intrauterine period resulted in the adult reduction of LH and increased progesterone plasma levels, and uterine injuries a higher number of endometrial glands and reduced levels of antioxidant enzymes, such as glutathione reductase and glutathione S‐transferase. In these experimental conditions, gestational continuous light exposure disturbs sex hormone balance and reduces the antioxidant enzymatic activity in the uterus of female offspring in adult life.
Crystallographic, morphological and photoluminescent investigations of Tb3+‐doped YAlO3 perovskites for lighting applications
Authors: Gupta Isha , Singh Devender , Singh Sitender , Kumar Pawan , Bhagwan Shri , Kumar Vinod , Kumar Harish , Chhikara Sunil Kumar
Published: March 2023

Terbium(III)‐doped yttrium aluminate perovskite (YAP:xTb3+) (x = 0.01–0.08 mol) was synthesized using a simple gel‐combustion method. Structural elucidations were performed using X‐ray diffraction (XRD) and Rietveld analysis. Fourier‐transform infrared spectral studies validated the efficient synthesis of designed doped samples. Transmission electron microscopic images showed the agglomerated irregular dimensions of the synthesized nanocrystalline materials. When excited at 251 nm, a strong emissive line attributed to 5D4 → 7F5 electronic transition was observed at 545 nm (green emission). The maximum luminescence was found at the optimized concentration (0.05 mol) of Tb3+ ions; this emission was quenched by dipolar–dipolar (d–d) interactions. Chromaticity (x and y) and correlated colour temperature parameters were obtained by analysing the emission profiles. Finally, the colour coordinates of nanophosphors were closer to the National Television Standards Committee green coordinates, which replicates their potency in the design and architecture of R‐G‐B‐based white LEDs.
Trace elements as potential modulators of puberty‐induced amelioration of oxidative stress and inflammation in childhood obesity
Authors: González‐Domínguez Álvaro , Domínguez‐Riscart Jesús , Millán‐Martínez María , Mateos‐Bernal Rosa María , Lechuga‐Sancho Alfonso María , González‐Domínguez Raúl
Published: March 2023

Although puberty is known to influence obesity progression, the molecular mechanisms underlying the role of sexual maturation in obesity‐related complications remains largely unexplored. Here, we delve into the impact of puberty on the most relevant pathogenic hallmarks of obesity, namely oxidative stress and inflammation, and their association with trace element blood status. To this end, we studied a well‐characterized observational cohort comprising prepubertal (N = 46) and pubertal (N = 48) children with obesity. From all participants, plasma and erythrocyte samples were collected and subjected to metallomics analysis and determination of classical biomarkers of oxidative stress and inflammation. Besides the expected raise of sexual hormones, pubertal children displayed better inflammatory and oxidative control, as reflected by lower levels of C‐reactive protein and oxidative damage markers, as well as improved antioxidant defense. This was in turn accompanied by a healthier multielemental profile, with increased levels of essential elements involved in the antioxidant system and metabolic control (metalloproteins containing zinc, molybdenum, selenium, and manganese) and decreased content of potentially deleterious species (total copper, labile free iron). Therefore, our findings suggest that children with obesity have an exacerbated inflammatory and oxidative damage at early ages, which could be ameliorated during pubertal development by the action of trace element‐mediated buffering mechanisms.
Characterization of ionic strength for X‐MuLV inactivation by low pH treatment for monoclonal antibody purification
Authors: Daya Jena , Cusick Valerie , Mattila John
Published: March 2023

In the production of monoclonal antibodies (mAbs) intended for use in humans, it is a global regulatory requirement that the manufacturing process includes unit operations that are proven to inactivate or remove adventitious agents to ensure viral safety. Viral inactivation by low pH hold (LPH) is typically used to ensure this viral safety in the purification process of mAbs and other biotherapeutics derived from mammalian cell lines. To ascertain the effectiveness of the LPH step, viral clearance studies have evaluated LPH under worst‐case conditions of pH above the manufacturing set point and hold duration at or below the manufacturing minimum. Highly acidic conditions (i.e., pH < 3.60) provide robust and effective enveloped virus inactivation but may lead to reduced product quality of the therapeutic protein. However, when viral inactivation is operated above pH 3.60 to ensure product stability, effective (>4 log10 reduction factor) viral inactivation may not be observed under these worst‐case pH conditions in viral clearance studies. A multivariate design of experiments was conducted to further characterize the operating space for low pH viral inactivation of a model retrovirus, xenotropic murine leukemia virus (X‐MuLV). The statistically designed experiment evaluated the effect of mAb isotype, pH, temperature, acid titrant, sodium chloride (NaCl) concentration, virus spike timing, and post‐spike filtration on X‐MuLV inactivation. Data from the characterization study were used to generate predictive models to identify conditions that reliably achieve effective viral inactivation at pH ≥ 3.60. Results of the study demonstrated that NaCl concentration has the greatest effect on virus inactivation in the range studied, and pH has a large effect when the load material has no additional NaCl. Overall, robust and effective inactivation of X‐MuLV at pH 3.65–3.80 can be achieved by manipulating either the pH or the NaCl concentration of the load material. This study contributes to the understanding of ionic strength as an influential parameter in low pH viral inactivation studies.
A stability‐indicating, reversed‐phase HPLC method for quantification of assay and organic impurities in doxycycline hyclate bulk and parenteral dosage forms
Authors: Pippalla Sreenivas , Nekkalapudi Arjuna Rao , Jillellamudi Suresh Babu , Reddy Mukkala Prasada , Kumar Cholleti Vijay
Published: March 2023

The aim of this study is to develop a stability‐indicating, reversed‐phase HPLC method for the quantification of assay and organic impurities (process and degradation) of doxycycline hyclate in a doxycycline injectable formulation. Both the active and dosage forms are officially present in the USP monograph, and assay and impurity methods are provided by separate UPLC techniques, which are highly sensitive to the flow rate and temperature, considering the quality control requirements and user‐friendliness. A simple stability‐indicating HPLC method with a shorter run time was developed for the simultaneous quantification of assay and impurity. The method was developed using HPLC with a gradient program and a reversed‐phase Waters XBridge BEH C8 column (150 × 4.6 mm, 3.5 μm i.d.). Mobile phase A consisted of phosphate buffer (pH 8.5, 25 mM potassium phosphate, 2 mM ethylenediaminetetraacetic acid, and 0.5 ml of triethylamine). Mobile phase B consisted of methanol with a flow rate of 1.7 ml/min, a column temperature of 55°C, a UV wavelength of 270 nm, and an injection volume of 25 μl. Modern research represents a concomitant method for quantifying assay and organic impurities of doxycycline hyclate (active form) and doxycycline for injection (dosage form). The assay and impurity method were validated per United States Pharmacopeia (USP) 1225 and International Conference on Harmonization (ICH) guidelines. The retention time of doxycycline and degradation impurity, 4‐epidoxycycline, was about 9.8 and 6.4 min, respectively. The linearity range of doxycycline and 4‐epidoxycycline was 0.5–150 and 0.5–18 μg/ml, respectively. The percentage of recovery of doxycycline and 4‐epidoxycycline was 98.7–100.6% and 88.0–112.0%. Validation of the analytical method demonstrated that the method is suitable, specific, linear, accurate, precise, rugged, and stability indicating for estimating the assay, known and degraded impurities of doxycycline, and doxycycline for injection.
‘On Water’‐Promoted Three‐Component Tandem Michael Addition/D−A Cycloaddition Reaction to Construct Polycyclic N‐Heterocycles Derivatives
Authors: Dong Yu , Luo Liang‐Xian , Hua Chen , He Ze‐Jing , Chen Yong , Shi Zhi‐Chuan , Li Zhong‐Hui , He Bing
Published: March 2023

‘On Water’‐promoted the three‐component tandem Michael addition/D−A cycloaddition reaction in 80 °C at 3 h has been developed without employing any catalyst and organic solvent. The process allows facile access to polycyclic N‐heterocycles derivatives contain indole and maleimide from easily accessible starting materials in moderate to high yields (up to 91 %). Compared with conventional reaction conditions, this reaction not only improves the reaction efficiency and rate but also minimizes the side reaction.
Differential Chemoproteomics Reveals MARK2/3 as Cell Migration‐Relevant Targets of the ALK Inhibitor Brigatinib
Authors: Hu Qianqian , Liao Yi , Cao Jessica , Fang Bin , Yun Sang Y. , Kinose Fumi , Haura Eric B. , Lawrence Harshani R. , Doebele Robert C. , Koomen John M. , Rix Uwe
Published: March 2023

Metastasis poses a major challenge in cancer management, including EML4‐ALK‐rearranged non‐small cell lung cancer (NSCLC). As cell migration is a critical step during metastasis, we assessed the anti‐migratory activities of several clinical ALK inhibitors in NSCLC cells and observed differential anti‐migratory capabilities despite similar ALK inhibition, with brigatinib displaying superior anti‐migratory effects over other ALK inhibitors. Applying an unbiased in situ mass spectrometry‐based chemoproteomics approach, we determined the proteome‐wide target profile of brigatinib in EML4‐ALK+ NSCLC cells. Dose‐dependent and cross‐competitive chemoproteomics suggested MARK2 and MARK3 as relevant brigatinib kinase targets. Functional validation showed that combined pharmacological inhibition or genetic modulation of MARK2/3 inhibited cell migration. Consistently, brigatinib treatment induced inhibitory YAP1 phosphorylation downstream of MARK2/3. Collectively, our data suggest that brigatinib exhibits unusual cross‐phenotype polypharmacology as, despite similar efficacy for inhibiting EML4‐ALK‐dependent cell proliferation as other ALK inhibitors, it more effectively prevented migration of NSCLC cells due to co‐targeting of MARK2/3.
Promotional Effect of Zirconium Doping on the NH3‐SCR Activity of CeO2 and CeO2‐TA Modified by Thiourea: A Comparative Study
Authors: Li Jun , Zhou Fei , Xiong Zhibo , Du Yanping , Yang Qiguo , Wang Wei , Lu Wei
Published: March 2023

Zirconium (Zr) was doped to optimize the NH3‐SCR activity of both CeO2 and thiourea modified CeO2‐TA catalysts for comparison. Different from the promotional influence of thiourea modification on the agglomeration of CeO2, the transformation from nanoparticles to nanocubes and the formation of highly crystallized CeOSO4, Zr doping lowers the agglomeration of nanoparticles, loosens the surface morphology of catalyst and promotes the formation of Ce‐Zr solid solution. Furthermore, Zr doping exhibits a synergistic promotional effect of thiourea modification on the dispersion of Ce3+ and S6+ species on the surface of CeO2, and increases the concentrations of the surface total oxygen and chemisorbed oxygen of CeO2‐TA. Interestingly, Zr doping instead decreases the promotional effect of thiourea modification on the high‐temperature or medium/low‐temperature reducibility of catalyst, but increases both Brønsted and Lewis acid sites of CeO2‐TA by inducing the highly dispersive sulfate species rather than the CeOSO4 crystal, which might be crucial to the NH3‐SCR activity of Ce‐based catalyst.
Artificial neural network (ANN) modeling for simultaneous removal of a binary mixture of Pb(II) and Cu(II) by cobalt hydroxide nano‐flakes
Authors: Zolgharnein Javad , Shariatmanesh Tahere , Farahani Saeideh Dermanaki
Published: March 2023

A three‐layer artificial neural network (ANN) model was developed to predict the efficiency of Cu(II) and Pb(II) ion removal from aqueous solution by cobalt hydroxide nano‐flakes. It is based on experimental sets obtained from a D‐optimal design. The input variables to the neural network were as follows: the initial concentration of Pb(II) and Cu (II) ions (mg L−1), initial pH, and sorbent mass (g). The configuration of the backpropagation neural network for both Cu(II) and Pb (II) ions was a tangent sigmoid transfer function (tansig) at the hidden layer, linear transfer function (purelin) at the output layer, and Levenberg–Marquardt training algorithm (LMA). ANN‐predicted results were very close to the experimental results with a coefficient of determination (R2) of 0.9970 and mean square error (MSE) 0.000376. Analysis based on the ANN model indicated that sorbent mass appeared to be the most influential factor in the adsorption process of Cu(II) and Pb(II). Characterization of the cobalt hydroxide nano‐flakes and possible metal ions‐adsorbent interactions were confirmed by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), and scanning electron microscopy (SEM).
Caffeine Biodegradation by Cytochrome P450 1A2. What Determines the Product Distributions?
Authors: Mokkawes Thirakorn , de Visser Sam P.
Published: March 2023

Caffeine is a natural compound found in plant seeds that after consumption by humans effects the central nervous system as well as the cardiovascular system. In general, the cytochrome P450 enzymes in the liver are involved in the biodegradation of caffeine, which gives paraxanthine, theobromine and theophylline products. There has been debate for many years why multiple products are obtained and how their distributions are determined. To this end we performed a high‐level computational study using a combination of molecular dynamics and quantum mechanical approaches. A series of quantum chemical cluster models on the mechanism of caffeine activation by P450 model complexes give hydrogen atom abstraction barriers that predicts the correct ordering and statistical distribution of products. Our studies highlight that second‐coordination sphere effects and thermochemical properties of the substrate determine the product distributions.
Ionic Liquid‐Mediated Approach for the Synthesis of Site‐Specific Thioether Conjugates
Authors: Abujubara Helal , Yang Jie , Birsen Otyakmaz A. , Noisier Anaïs F. M. , Czechtizky Werngard , Lemurell Malin , Tietze Alesia A.
Published: March 2023

Site‐specific conjugation approaches are of great importance in drug discovery, notably for the synthesis of biochemical probes or molecular conjugates for targeted delivery. Herein, we report a mild ionic liquid (IL)‐mediated thiolation technique that relies on the use of 1,3‐ethyl‐methyl imidazolium acetate, [C2mim][OAc] as a solvent and precursor to generate activated IL, as well as a solvent for the conjugation reaction. First, a focused library of active ILs was prepared for functionalizing/conjugating cysteine‐containing small molecules and unprotected peptides. Interestingly, a bifunctional active IL could also be successfully employed as a linker for the conjugation of peptides lacking Cys. This study sets the ground for further investigation of the use of active ILs for modifying, labeling or conjugating larger and more complex therapeutic modalities such as proteins and antibodies.
λ3‐ and λ5‐Iodanes: Substituent Effects and Pseudorotation/Hypervalent Twisting
Authors: Parida Keshaba N. , Moorthy J. Narasimha
Published: March 2023

Hypervalent iodine (III and V) compounds exhibit positional isomerization through pseudorotation or twisting; the latter have been invoked for the stability as well as the reactivity of λ3‐ and λ5‐iodanes. By judicious exploitation of sterics, the twisting process in iodanes can be facilitated to promote reactivity. For example, ortho‐substitution in λ3‐ and λ5‐iodanes accelerates α‐tosyloxylation of ketones and oxidation of alcohols. The enhancement of reactivity arises from sterically‐induced non‐planarity and the resultant weakening of the 3c–4e bonds involving the hypervalent iodine atom. The ortho‐substitution constitutes an important strategy to maneuver reactivity, control selectivity, and develop new catalysts, including chiral, for diverse reactions. This review entails coverage of the literature developments in regard to the effect of substituents and twisting/pseudorotation on the stability as well as the reactivity of hypervalent λ3‐ and λ5‐iodanes, and the application of the latter for synthetic transformations.
Residue‐Selective C−H Sulfenylation Enabled by Acid‐Activated S‐Acetamidomethyl Cysteine Sulfoxide with Application to One‐Pot Stapling and Lipidation Sequence
Authors: Ohkawachi Kento , Anzaki Kaito , Kobayashi Daishiro , Kyan Ryuji , Yasuda Takuma , Denda Masaya , Harada Norio , Shigenaga Akira , Inagaki Nobuya , Otaka Akira
Published: March 2023

A tyrosine (Tyr)‐ or tryptophan (Trp)‐selective metal‐free C−H sulfenylation reaction using an acid‐activated S‐acetamidomethyl cysteine (Cys) sulfoxide, Cys(Acm)(O), has been achieved. The dually protonated intermediate produced from Cys(Acm)(O) under acidic conditions allows the sulfenylation of Tyr. Significantly, the reaction in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) mainly affords a Cys‐Tyr‐linked peptide even in the presence of Trp residues. In contrast, a Cys‐Trp‐linked peptide was selectively obtained from the reaction in the presence of guanidine hydrochloride (Gn ⋅ HCl) under acidic conditions. Established Tyr‐ and Trp‐selective sulfenylation methods were used in the Cys‐Tyr stapling and Trp lipidation of glucagon‐like peptides 1 in a one‐pot/stepwise manner. Investigation of the mechanism showed that orbital‐ and charge‐controlled reactions are responsible for the Trp and Tyr selectivity, respectively.
Hierarchical Self‐assembly of G‐Quadruplexes Based Hydrogel Consisting of Guanine and Peptide Epitope†
Authors: Zhang Hongyue , Yang Xuejiao , Liang Juan , Chen Kaihua , Wang Huaimin
Published: March 2023

Comprehensive Summary

Guanosine‐based hydrogels have attracted considerable attention because of their simplicity and easy preparation. However, the sugar moiety limits its further applications because of the necessity of sugar in the hydrogel formation. This work reports a G‐quadruplexes‐based hydrogel consisting of guanine and peptide epitope to form a supramolecular hydrogel in the presence of metal cations. Using the metal ion‐responsive peptide epitope from the ion channel to replace sugar motif at N9 position of guanosine results in a novel nucleopeptide. The results show that the gelation time, the diameter of nanofibers, the anisotropic property, and the mechanical property of the hydrogel can be simply controlled using metal cations. The magnesium and calcium ions direct the alignment of nanofibers to form anisotropic nano‐bundles. The mechanistic studies indicate the formation of G‐quadruplexes in the hydrogel. Compared to the storage modulus of nucleopeptide without the metal cation, adding zinc ions results in an over three‐order increase in mechanical properties. Cytotoxicity experiment indicates the good biocompatibility of our hydrogel. Moreover, we demonstrate that the guanine‐capped peptide could release STING agonist in a controlled manner. This work illustrates a simple way to modulate the property of the nucleopeptide hydrogel to develop soft materials.