bluuebunny/crossref_metadata_2025 huggingface dataset:
Comparison of MR‐soft tissue based versus biliary stent based alignment for image guidance in pancreatic SBRT
Authors: Han Zhaohui , Sudhyadhom Atchar , Hsu Shu‐Hui , Hu Yue‐Houng , Mak Raymond H. , Huynh Mai Anh , van Dams Ritchell R. , Tanguturi Shyam , Venkatachalam Veena , Mancias Joseph D. , Mamon Harvey J. , Martin Neil E. , Lam Miranda B. , Leeman Jonathan E.
Published: March 2023

Purpose

The role of biliary stents in image‐guided localization for pancreatic cancer has been inconclusive. To date, stent accuracy has been largely evaluated against implanted fiducials on cone beam computed tomography. We aim to use magnetic resonance (MR) soft tissue as a direct reference to examine the geometric and dosimetric impacts of stent‐based localization on the newly available MR linear accelerator.

Methods

Thirty pancreatic cancer patients (132 fractions) treated on our MR linear accelerator were identified to have a biliary stent. In our standard adaptive workflow, patients were set up to the target using soft tissue for image registration and structures were re‐contoured on daily MR images. The original plan was then projected on treatment anatomy and dose predicted, followed by plan re‐optimization and treatment delivery. These online predicted plans were soft tissue‐based and served as reference plans. Retrospective image registration to the stent was performed offline to simulate stent‐based localization and the magnitude of shifts was taken as the geometric accuracy of stent localization. New predicted plans were generated based on stent‐alignment for dosimetric comparison.

Results

Shifts were within 3 mm for 90% of the cases (mean = 1.5 mm); however, larger shifts up to 7.2 mm were observed. Average PTV coverage dropped by 1.1% with a maximum drop of 26.8%. The mean increase in V35Gy was 0.15, 0.05, 0.02, and 0.02 cc for duodenum, stomach, small bowel and large bowel, respectively. Stent alignment was significantly worse for all metrics except for small bowel (p = 0.07).

Conclusions

Overall discrepancy between stent‐ and soft tissue‐alignment was modest; however, large discrepancies were observed for select cases. While PTV coverage loss may be compensated for by using a larger margin, the increase in dose to gastrointestinal organs at risk may limit the role of biliary stents in image‐guided localization.
Drug‐resistant seizures associated with hyperinflammatory monocytes in FIRES
Authors: Howe Charles L. , Johnson Renee K. , Overlee Brittany L. , Sagen Jessica A. , Mehta Niyati , Farias‐Moeller Raquel
Published: March 2023

Objective

Therapeutic strategies for patients with febrile infection‐related epilepsy syndrome (FIRES) are limited, ad hoc, and frequently ineffective. Based on evidence that inflammation drives pathogenesis in FIRES, we used ex vivo stimulation of peripheral blood mononuclear cells (PBMCs) to characterize the monocytic response profile before and after therapy in a child successfully treated with dexamethasone delivered intrathecally six times between hospital Day 23 and 40 at 0.25 mg/kg/dose.

Methods

PBMCs were isolated from serial blood draws acquired during refractory status epilepticus (RSE) and following resolution associated with intrathecal dexamethasone therapy in a previously healthy 9‐year‐old male that presented with seizures following Streptococcal pharyngitis. Cells were stimulated with bacterial or viral ligands and cytokine release was measured and compared to responses in age‐matched healthy control PBMCs. Levels of inflammatory factors in the blood and CSF were also measured and compared to pediatric healthy control ranges.

Results

During RSE, serum levels of IL6, CXCL8, HMGB1, S100A8/A9, and CRP were significantly elevated. IL6 was elevated in CSF. Ex vivo stimulation of PBMCs collected during RSE revealed hyperinflammatory release of IL6 and CXCL8 in response to bacterial stimulation. Following intrathecal dexamethasone, RSE resolved, inflammatory levels normalized in serum and CSF, and the PBMC hyperinflammatory response renormalized.

Significance

FIRES may be associated with a hyperinflammatory monocytic response to normally banal bacterial pathogens. This hyperinflammatory response may induce a profound neutrophil burden and the consequent release of factors that further exacerbate inflammation and drive neuroinflammation. Intrathecal dexamethasone may resolve RSE by resetting this inflammatory feedback loop.
Finite Element Modeling of Crumpling of Metallic Thin Foil
Authors: Kwon Jihye , Bouaziz Olivier , Kim Hyoung Seop , Estrin Yuri
Published: March 2023

Crumpled metallic thin foils are very promising as weight‐saving and energy‐absorption materials that can easily be fabricated. To achieve practical industrial applications, it is necessary to improve the understanding of the process of crumpling and the mechanical behavior of crumpled materials considering their complex internal structures. Herein, two possible strategies for computational simulations of crumpled material under closed‐die compression are presented for the first time. The first one entails computations performed at the scale of the foil (direct method), while the second one considers the structure as a continuum with porosity. The analysis performed shows that the continuum‐based approach is more suitable for representing the macroscopic mechanical behavior of crumpled materials with the relative densities ranging from 2% to 40%. An additional benefit is the low computational cost and high efficacy of the porous continuum approach. However, the direct method is shown to be the preferable computational tool when the internal structural patterns changes need to be adequately reproduced, e.g., for a better prediction of the mechanical response under complex loading conditions.
Single‐Walled Carbon Nanotube Film as an Efficient Conductive Network for Si‐Based Anodes
Authors: He Ziying , Xiao Zhexi , Yue Hongjie , Jiang Yaxin , Zhao Mingyu , Zhu Yukang , Yu Chunhui , Zhu Zhenxing , Lu Feng , Jiang Hairong , Zhang Chenxi , Wei Fei
Published: March 2023

Silicon‐based anodes are considered ideal candidate materials for next‐generation lithium‐ion batteries due to their high capacity. However, the low conductivity and large volume variations during cycling inevitably result in inferior cyclic stability. Herein, a dry method without binders is designed to fabricate Si‐based electrodes with single‐walled carbon nanotubes (SWCNTs) network and to explore the different mechanisms between SWCNT and multiwalled carbon nanotubes (MWCNTs) as a conductive network. As expected, higher initial discharge capacity (1785 mAh g−1), higher initial Coulombic efficiency (ICE, 81.52%) and outstanding cyclic stability are obtained from the SiOx@C|SWCNT anodes. Furthermore, its lithium‐ion diffusion coefficient (DLi+) is 3–4 orders of magnitude higher than that of SiOx@C|MWCNT. The underlying mechanism is clarified by in situ Raman spectroscopy and theoretical analysis. It is found that the SWCNTs can maintain good contact with SiOx@C even under tensile stresses up to 6.2 GPa, while the MWCNTs lose electrical contact due to alternating compressive stress up to 8.9 GPa and tensile stress up to 2.5 GPa during long‐term cycling. Under such very large stresses, the more flexible SWCNTs and their stronger van der Waals forces ensure that SiOx@C still has good contact with SWCNTs.
Aqueous Two‐Phase Emulsion Bioresin for Facile One‐Step 3D Microgel‐Based Bioprinting
Authors: Wang Qingbo , Karadas Özge , Backman Oskar , Wang Luyao , Näreoja Tuomas , Rosenholm Jessica M. , Xu Chunlin , Wang Xiaoju
Published: March 2023

Microgel assembly as void‐forming bioinks in 3D bioprinting has evidenced recent success with a highlighted scaffolding performance of these bottom‐up biomaterial systems in supporting the viability and function of the laden cells. Here, a ternary‐component aqueous emulsion is established as a one‐step strategy to integrate the methacrylated gelatin (GelMA) microgel fabrication and assembly through vat photopolymerization in situ using digital light processing (DLP)‐based bioprinting. The as‐proposed aqueous emulsion is featured with the partitioning of a secondary photo‐crosslinkable polysaccharide, methacrylated galactoglucomannan (GGMMA) derived from plant source in both the dispersed phase of GelMA droplets and the continuous phase of dextran (Dex). As an emulgator, GGMMA renders enhanced stability of the aqueous emulsion bioresins. Strategically, the photo‐crosslinkable GGMMA adheres the GelMA microgels that are conveniently converted from emulsion droplets to form hydrogel construct in layer‐by‐layer curing to accommodate the laden cells directly mixed in the aqueous emulsion. The spatially interconnected void space left by the removal of Dex benefits the cell growth under the guidance of the microgel surface and supports cell colonization within the macroscopic porous hydrogel. This work amends a low‐concentration and cost‐effective bioresin that is highly applicable for facilely fabricating microgel assembly as a porous hydrogel construct in DLP‐based bioprinting.
Near‐Theoretical Thermal Conductivity Silver Nanoflakes as Reinforcements in Gap‐Filling Adhesives
Authors: Chen Lu , Liu Te‐Huan , Wang Xiangze , Wang Yandong , Cui Xiwei , Yan Qingwei , Lv Le , Ying Junfeng , Gao Jingyao , Han Meng , Yu Jinhong , Song Chengyi , Gao Jinwei , Sun Rong , Xue Chen , Jiang Nan , Deng Tao , Nishimura Kazuhito , Yang Ronggui , Lin Cheng‐Te , Dai Wen
Published: March 2023

The rapid development of highly integrated microelectronic devices causes urgent demands for advanced thermally conductive adhesives (TCAs) to solve the interfacial heat‐transfer issue. Due to their natural 2D structure and isotropic thermal conductivity, metal nanoflakes are promising fillers blended with polymer to develop high‐performance TCAs. However, achieving corresponding TCAs with thermal conductivity over 10 W m−1K−1at filler content below 30 vol% remains challenging so far. This longstanding bottleneck is mainly attributed to the fact that most current metal nanoflakes are prepared by “bottom‐up” processes (e.g., solution‐based chemical synthesis) and inevitably contain lattice defects or impurities, resulting in lower intrinsic thermal conductivities, only 20–65% of the theoretical value. Here, a “top‐down” strategy by splitting highly purified Ag foil with nanoscale thickness is adopted to prepare 2D Ag nanoflakes with an intrinsic thermal conductivity of 398.2 W m−1K−1, reaching 93% of the theoretical value. After directly blending with epoxy, the resultant Ag/epoxy exhibits a thermal conductivity of 15.1 W m−1K−1at low filler content of 18.6 vol%. Additionally, in practical microelectronic cooling performance evaluations, the interfacial heat‐transfer efficiency of the Ag/epoxy achieves ≈1.4 times that of the state‐of‐the‐art commercial TCA.
A Nitroxide Radical Conjugated Polymer as an Additive to Reduce Nonradiative Energy Loss in Organic Solar Cells
Authors: Shi Furong , Guo Pengzhi , Qiao Xianfeng , Yao Guo , Zhang Tao , Lu Qi , Wang Qian , Wang Xiaofeng , Rikhsibaev Jasurbek , Wang Ergang , Zhang Chunfeng , Kwon Young‐Wan , Woo Han Young , Wu Hongbin , Hou Jianhui , Ma Dongge , Armin Ardalan , Ma Yuguang , Xia Yangjun
Published: March 2023

Nonfullerene‐acceptor‐based organic solar cells (NFA‐OSCs) are now set off to the 20% power conversion efficiency milestone. To achieve this, minimizing all loss channels, including nonradiative photovoltage losses, seems a necessity. Nonradiative recombination, to a great extent, is known to be an inherent material property due to vibrationally induced decay of charge‐transfer (CT) states or their back electron transfer to the triplet excitons. Herein, it is shown that the use of a new conjugated nitroxide radical polymer with 2,2,6,6‐tetramethyl piperidine‐1‐oxyl side groups (GDTA) as an additive results in an improvement of the photovoltaic performance of NFA‐OSCs based on different active layer materials. Upon the addition of GDTA, the open‐circuit voltage (VOC), fill factor (FF), and short‐circuit current density (JSC) improve simultaneously. This approach is applied to several material systems including state‐of‐the‐art donor/acceptor pairs showing improvement from 15.8% to 17.6% (in the case of PM6:Y6) and from 17.5% to 18.3% (for PM6:BTP‐eC9). Then, the possible reasons behind the observed improvements are discussed. The results point toward the suppression of the CT state to triplet excitons loss channel. This work presents a facile, promising, and generic approach to further improve the performance of NFA‐OSCs.
COAP‐Palladium‐Catalyzed Asymmetric Linear Allylic Alkylation of Vinyl Benzoxazinanones for Multifunctional 3,3′‐Disubstituted Oxindole Derivatives
Authors: Shen Jun‐Hao , Zhou Sheng‐Suo , Wang Bai‐Lin , Liu Wen‐Kai , Wang Zheng , Wang Xing‐Wang
Published: March 2023

A Pd‐catalyzed enantioselective linear‐allylic alkylation of vinyl benzoxazinanones with a series of 3‐substituted oxindoles was reported in the presence of a chiral oxamide‐phosphine ligand (COAP−Bn) under mild reaction conditions. A series of optically active multifunctional 3,3′‐disubstituted oxindole derivatives bearing a quaternary stereogenic center and a linear aryl amino side chain were respectively obtained in 55–98% yields with 96–99% ee for 3‐(hetero)aryl substituted oxindoles. The developed protocol demonstrates that the COAP ligands could serve as a privileged chiral ligand to construct diverse chiral 3,3‐disubstituted oxindole compounds with various quaternary stereogenic centers, such as aza‐, thio‐ or all‐carbon quaternary stereogenic centers. The salient features of the method include broad substrate scope, N‐protecting group free, base‐free, and high regio‐ and enantioselectivity.

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AQP4 Aggravates Cognitive Impairment in Sepsis‐Associated Encephalopathy through Inhibiting Nav1.6‐Mediated Astrocyte Autophagy
Authors: Zhu Dan‐Dan , Huang Yue‐Lin , Guo Song‐Yu , Li Na , Yang Xue‐Wei , Sui Ao‐Ran , Wu Qiong , Zhang Yue , Kong Yue , Li Qi‐Fa , Zhang Ting , Zheng Wen‐Fei , Li Ai‐Ping , Yu Jian , Ma Tong‐Hui , Li Shao
Published: March 2023

The pathology of sepsis‐associated encephalopathy (SAE) is related to astrocyte‐inflammation associated with aquaporin‐4 (AQP4). The aim here is to investigate the effects of AQP4 associated with SAE and reveal its underlying mechanism causing cognitive impairment. The in vivo experimental results reveal that AQP4 in peripheral blood of patients with SAE is up‐regulated, also the cortical and hippocampal tissue of cecal ligation and perforation (CLP) mouse brain has significant rise in AQP4. Furthermore, the data suggest that AQP4 deletion could attenuate learning and memory impairment, attributing to activation of astrocytic autophagy, inactivation of astrocyte and downregulate the expression of proinflammatory cytokines induced by CLP or lipopolysaccharide (LPS). Furthermore, the activation effect of AQP4 knockout on CLP or LPS‐induced PPAR‐γ inhibiting in astrocyte is related to intracellular Ca2+ level and sodium channel activity. Learning and memory impairment in SAE mouse model are attenuated by AQP4 knockout through activating autophagy, inhibiting neuroinflammation leading to neuroprotection via down‐regulation of Nav1.6 channels in the astrocytes. This results in the reduction of Ca2+ accumulation in the cell cytosol furthermore activating the inhibition of PPAR‐γ signal transduction pathway in astrocytes.
Ultra‐Low Dosage Lignin Binder for Practical Lithium–Sulfur Batteries
Authors: Chen Zhuzuan , Lu Mingjin , Qian Yong , Yang Yu , Liu Ju , Lin Zhan , Yang Dongjie , Lu Jun , Qiu Xueqing
Published: March 2023

Polymeric binders stabilize lithium–sulfur (Li–S) batteries by suppressing the shuttle of lithium polysulfide (LiPS) and volume variation, but the dosage of state‐of‐the‐art binders in sulfur cathodes (≈20 wt%) hinders the electron/ion transfer and decreases the cell‐specific density. Here, a wood‐inspired lignin binder is developed after modification with amino acids for practical Li–S batteries at ultra‐low low dosage (2 wt%). Benefiting from strong and balanced adhesions with active/conductive/current collector materials, robust mechanical properties, and super LiPS anchoring capability, the Li–S cell delivers an initial discharge capacity of 864 mAh g−1 at 0.5 C and can readily operate 1000 cycles. Moreover, the pouch cell with high mass loading (4.75 mg cm−2) also delivers a high energy density of 484 Wh kg−1. This work provides important guidance in binder design for the sulfur cathode and paves a new way for the practical application of Li–S batteries.
Are people's daily life habits consistent with their preference for food sustainability labels?
Authors: Nian Yefan , Gao Zhifeng , Zhao Ruojin
Published: March 2023

Identifying the factors correlating to consumers' preference for sustainability‐labeled food products is essential for developing policies to promote the consumption of food produced in a socially responsible and environmentally friendly manner. Using a representative US consumer sample, this study systematically examines consumers' preferences for different food sustainability labels and investigates whether consumers' life habits in other domains of life are consistent with their food purchasing decisions. We find that among the four food sustainability labels included in our study, consumers have the highest marginal willingness‐to‐pay (MWTP) for United States Department of Agriculture certified organic labels, followed by the nongenetically modified organism, eco‐friendly, and fair‐trade labels. It is evident that daily activities, such as proenvironmental behaviors away from home and physical exercise in everyday life, are correlated to consumers' MWTP for sustainability‐labeled food products. This study provides implications for designing proper strategies to improve sustainable food consumption, including targeting consumers who adopt a more environmentally sustainable lifestyle, such as conducting proenvironmental activities outside home and physical exercise activities in daily life. [EconLit Citations: Q13, Q18].
A Novel Distal Hybrid Pneumatic/Cable‐Driven Continuum Joint with Variable Stiffness Capacity for Flexible Gastrointestinal Endoscopy
Authors: Luo Xiangyu , Song Dezhi , Zhang Zhiqiang , Wang Shuxin , Shi Chaoyang
Published: March 2023

The robot‐assisted flexible access surgery represented by the emerging robot‐assisted flexible endoscopy (FE) and natural orifice transluminal endoscopic surgery demands flexible and continuum manipulators instead of the rigid and straight instruments in the traditional minimally invasive surgery (MIS). These flexible manipulators are required to advance through the tortuous and narrow anatomic paths via natural orifices for dexterous diagnostic examination and therapeutic operations. Therefore, developing flexible endoscopic manipulators with the capacity of snake‐like movements for flexible access and variable stiffness regulation for operations to address these flexible access surgical difficulties is demanding but remains challenging. To address such challenges, herein, it is proposed that a novel distal continuum joint based on the hybrid pneumatic and cable‐driven approach achieves variable stiffness capacity, excellent bending characteristics in both flexible and rigid states, satisfactory motion consistency and shape‐locking ability during the rigid‐flexible transition, and relatively high loading capacity for flexible gastrointestinal endoscopic robots. Characterization experiments validate these performances, and phantom and ex vivo experiments have been performed to demonstrate the feasibility and effectiveness for FE. The presented method demonstrates an effective and practical approach to enabling continuum robots with both flexible access and tunable stiffness capacity and supports a convenient extension for MIS applications.
Prospective evaluation of plasma phosphorylated tau in a real‐life memory clinic in Thailand
Authors: Thanapornsangsuth Poosanu , Booncharoen Kittithatch , Luechaipanit Watayuth , Supharatpariyakorn Thirawat , Sarutikriangkri Yuthachai , Tangnimitchok Suchart , Likitjaroen Yuttachai , Sukprakun Chanan , Tepmongkol Supatporn , Hemachudha Thiravat
Published: March 2023

Introduction

Despite the substantial accuracy of plasma p‐tau in diagnosing Alzheimer's disease (AD) in research cohorts, data on real‐life memory clinic patients are lacking.

Methods

Memory clinic patients at their early symptomatic stages were prospectively enrolled to undergo routine clinical assessment, plasma p‐tau181 quantification (Simoa), amyloid and tau‐positron emission tomography (PET). The diagnostic performance of plasma p‐tau181, neurocognitive specialists, and regional tau‐PET were compared head‐to‐head using amyloid‐PET as the reference standard.

Results

Plasma p‐tau181 has the area under the curve (AUC), sensitivity, specificity, and accuracy of 0.84 (95% confidence interval [CI] 0.73–0.94), 0.80 (95% CI 0.64–0.90), 0.75 (95% CI 0.51–0.90), and 0.78 (95% CI 0.65–0.88) for detecting amyloid‐PET positivity in early symptomatic patients, respectively. The AUC of clinical diagnosis and tau‐PET were 0.70 (95% CI 0.56–0.85) and 0.88 (95% CI 0.79–0.97), respectively.

Discussion

Plasma p‐tau181 also performed well in real‐life memory clinic settings and its role in clinical practice is supported.
Bio‐inspired Structure‐editing Fluorescent Hydrogel Actuators for Environment‐interactive Information Encryption
Authors: Wang Ruijia , Zhang Yi , Lu Wei , Wu Baoyi , Wei Shuxin , Wu Shuangshuang , Wang Wenqin , Chen Tao
Published: March 2023

Many living organisms have the superb structure‐editing capacity for better adaptation in dynamic environments over the course of their life cycle. However, it's still challenging to replicate such natural structure‐editing capacity into artificial hydrogel actuating systems for enhancing environment‐interactive functions. Herein, we learn from the metamorphosis development of glowing octopus to construct proof‐of‐concept fluorescent hydrogel actuators with life‐like structure‐editing capacity by developing a universal stepwise inside‐out growth strategy. These actuators could perform origami‐like 3D shape deformation and also enable the postnatal growth of new structures to adapt additional actuating states for different visual information delivery by using different environment keys (e.g., temperature, pH). This study opens previously unidentified‐avenues of bio‐inspired hydrogel actuators/robotics and extends the potential uses for environment‐interactive information encryption.
Structural and Morphological Transformations of Covalent Organic Nanotubes
Authors: Koner Kalipada , Karak Suvendu , Ogaeri Yutaro , Nishiyama Yusuke , Banerjee Rahul
Published: March 2023

Covalent organic nanotubes (CONTs) are porous one‐dimensional frameworks connected through imine bonds via Schiff base condensation between aldehydes and amines. The presence of two amine groups at the ortho position in the structurally demanding tetraaminotriptycene (TAT) building block leads to multiple reaction pathways between the ditopic aldehyde and the tetratopic amine. We have synthesized five different monomers of CONT‐1 by the Schiff base condensation reaction between TAT and o‐anisaldehyde. The conversion of imine to imidazole bonding in a monomer is probed using NMR, mass spectrometry, and X‐ray diffraction techniques. Solid‐state NMR provide insights into the CONTs’ structural connectivity. A theoretical investigation suggests that the π‐π stacking could be the driving force for rapid imine to imidazole conversion within the CONT‐1. Microscopic imaging sheds further light on the self‐assembly process of the CONTs, indicating both head‐to‐head and side‐by‐side assembly.
Magnetism in Nonplanar Zigzag Edge Termini of Graphene Nanoribbons
Authors: Xu Xiushang , Sun Kewei , Ishikawa Atsushi , Narita Akimitsu , Kawai Shigeki
Published: March 2023

Graphene nanoribbons (GNRs) and nanographenes synthesized by on‐surface reactions using tailor‐made molecular precursors offer an ideal playground for a study of magnetism towards nano‐spintronics. Although the zigzag edge of GNRs has been known to host magnetism, the underlying metal substrates usually veil the edge‐induced Kondo effect. Here, we report the on‐surface synthesis of unprecedented, π‐extended 7‐armchair GNRs using 7‐bromo‐12‐(10‐bromoanthracen‐9‐yl)tetraphene as the precursor. Characterization by scanning tunneling microscopy/spectroscopy revealed unique rearrangement reactions leading to pentagon‐ or pentagon/heptagon‐incorporated, nonplanar zigzag termini, which demonstrated Kondo resonances even on bare Au(111). Density functional theory calculations indicate that the nonplanar structure significantly reduces the interaction between the zigzag terminus and the Au(111) surface, leading to a recovery of the spin localization of the zigzag edge. Such a distortion of planar GNR structures offers a degree of freedom to control the magnetism on metal substrates.
Spectroscopic Identification of Active Sites of Oxygen‐Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide
Authors: Liu Longxiang , Kang Liqun , Chutia Arunabhiram , Feng Jianrui , Michalska Martyna , Ferrer Pilar , Grinter David C. , Held Georg , Tan Yeshu , Zhao Fangjia , Guo Fei , Hopkinson David G. , Allen Christopher S. , Hou Yanbei , Gu Junwen , Papakonstantinou Ioannis , Shearing Paul R. , Brett Dan J. L. , Parkin Ivan P. , He Guanjie
Published: March 2023

The electrochemical synthesis of hydrogen peroxide (H2O2) via a two‐electron (2 e−) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy‐intensive anthraquinone process. Herein, we develop a facile template‐protected strategy to synthesize a highly active quinone‐rich porous carbon catalyst for H2O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron‐based near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e− ORR performance. The effectiveness of chair‐form quinone groups as the most efficient active sites is highlighted by the molecule‐mimic strategy and theoretical analysis.
Overcoming the Oxygen Dilemma in Photoredox Catalysis: Near‐Infrared (NIR) Light‐Triggered Peroxynitrite Generation for Antibacterial Applications
Authors: Shen Zhiqiang , Zheng Shaoqiu , Fang Yuanmeng , Zhang Guoying , Zhu Chen , Liu Shiyong , Hu Jinming
Published: March 2023

The peroxynitrite anion (ONOO−) is closely associated with many diseases and the creation of ONOO− donors is an essential means of understanding its pathophysiological functions. However, it is challenging to develop ONOO− donors due to the difficulties in simultaneously producing highly reactive and short‐lived nitric oxide (NO) and superoxide anion (O2⋅−). Here, we report a novel strategy for constructing ONOO− donors by combining near‐infrared (NIR)‐mediated type I photosensitization and photoredox catalysis. The key design using a Nile blue analogue that can serve as both a type I photosensitizer and a metal‐free photocatalyst. Intriguingly, the formation of O2⋅− via type I photosensitization avoids oxygen interference and instead activates nitrobenzofurazan‐based NO donors via oxygen‐tolerant NIR photoredox catalysis. The simultaneous release of O2⋅− and NO leads to ONOO− release, showing both antibacterial and antibiofilm activities.
Glucose‐Responsive Charge‐Switchable Lipid Nanoparticles for Insulin Delivery
Authors: Liu Yun , Wang Yanfang , Yao Yuejun , Zhang Juan , Liu Wei , Ji Kangfan , Wei Xinwei , Wang Yuanwu , Liu Xiangsheng , Zhang Shiming , Wang Jinqiang , Gu Zhen
Published: March 2023

Lipid nanoparticle‐based drug delivery systems have a profound clinical impact on nucleic acid‐based therapy and vaccination. Recombinant human insulin, a negatively‐charged biomolecule like mRNA, may also be delivered by rationally‐designed positively‐charged lipid nanoparticles with glucose‐sensing elements and be released in a glucose‐responsive manner. Herein, we have designed phenylboronic acid‐based quaternary amine‐type cationic lipids that can self‐assemble into spherical lipid nanoparticles in an aqueous solution. Upon mixing insulin and the lipid nanoparticles, a heterostructured insulin complex is formed immediately arising from the electrostatic attraction. In a hyperglycemia‐relevant glucose solution, lipid nanoparticles become less positively charged over time, leading to reduced attraction and subsequent insulin release. Compared with native insulin, this lipid nanoparticle‐based glucose‐responsive insulin shows prolonged blood glucose regulation ability and blood glucose‐triggered insulin release in a type 1 diabetic mouse model.
Diastereoselective Synthesis of Monofluorocyclohexenes through Photocatalyzed Cascade Cyclization of gem‐Difluoroalkenes and α,β‐Unsaturated Carbonyl Compounds
Authors: Li Zhengyu , Zhang Yizhi , Zhang Yunxiao , He Xingyi , Shen Xiao
Published: March 2023

Monofluoroalkenes are nonhydrolyzable mimetics of amides. Previous work focused on the synthesis of non‐cyclic monofluoroalkenes. However, diastereoselective synthesis of monofluorocyclohexenes from non‐cyclic substrates is challenging. Herein, we report the first photocatalyzed cascade cyclization reactions of readily available α,β‐unsaturated carbonyl compounds and gem‐difluoroalkenes for the synthesis of highly functionalized monofluorocyclohexenes. The reaction shows broad substrate scope with high diastereoselectivity (>30 examples, up to 86 % yield, >20 : 1 dr). The post‐reaction transformations of the products demonstrate the synthetic potential of this methodology.
Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters**
Authors: Rozsar Daniel , Farley Alistair J. M. , McLauchlan Iain , Shennan Benjamin D. A. , Yamazaki Ken , Dixon Darren J.
Published: March 2023

Herein we describe the enantioselective intermolecular conjugate addition of nitroalkanes to unactivated α,β‐unsaturated esters, catalyzed by a bifunctional iminophosphorane (BIMP) superbase. The transformation provides the most direct access to pharmaceutically relevant enantioenriched γ‐nitroesters, utilizing feedstock chemicals, with unprecedented selectivity. The methodology exhibits a broad substrate scope, including β‐(fluoro)alkyl, aryl and heteroaryl substituted electrophiles, and was successfully applied on a gram scale with reduced catalyst loading, and, additionally, catalyst recovery was carried out. The formal synthesis of a range of drug molecules, and an enantioselective synthesis of (S)‐rolipram were achieved. Additionally, computational studies revealed key reaction intermediates and transition state structures, and provided rationale for high enantioselectivities, in good agreement with experimental results.
Topology optimization of a novel bionic fractal microchannel applied in thermal management of electronic components
Authors: Wang Yuwei , Sun Liang , Qi Cong , Yu Jie , Zhang Wenjie
Published: March 2023

Reducing energy consumption and improving device efficiency are important ways to realize efficient heat dissipation of microdevices, this paper developed a new bionic fractal microchannel heat sink based on fractal theory and topological optimization ideas, which introduced a binary flow stagnation zone optimization based on topological optimization ideas on the basic fractal microchannel. The thermal and hydraulic properties of a nanofluid in a fractal microchannel heat sink (FMCHS) have been numerically simulated with the fractal dimensions (fd = 1, 1.5, and 2) and Reynolds number (Re = 200–1600) as variables, and the comprehensive performance has been analyzed. The results showed that the introduction of the optimization increases the central velocity of the microchannel by 7.14–18.2%. With fractal dimensions of 1.5 and 2, the flow improvement and velocity increase are significant, and a significant Nusselt number improvement is obtained. The best comprehensive performance is obtained for FMCHS with a fractal dimension of 1.5, with an optimization effect of 8.3%.
Preliminary ontogeny of the giraffe neck
Authors: Colalillo Emily , Solounias Nikos
Published: March 2023

The giraffe juvenile has different proportions of head to neck from the adult. The head just about doubles in size from the juvenile to adult, whereas the neck increases almost 4.5× (roughly four times) in length. The T1 posterior dorsal vertebral width of the newborn is clearly wider than in the adult where it is narrow. In the okapi, the dorsal vertebral width is narrow in both juvenile and adult. The giraffe neck changes in ontogeny anisometrically. In the okapi the changes are more isometric. The giraffe juvenile vertebrae are shorter and do not have fused the cranial epiphyseal plates. That facilitates anterior elongation‐growth. The ventral tubercles are undeveloped. The juvenile T1 is wide caudally unlike the adult. This may be a similarity to a gelocid (Gelocidae) ancestor of the giraffe.
Evaluation of clinical assessments of social abilities for use in autism clinical trials by the autism biomarkers consortium for clinical trials
Authors: Faja Susan , Sabatos‐DeVito Maura , Sridhar Aksheya , Kuhn Jocelyn L. , Nikolaeva Julia I. , Sugar Catherine A. , Webb Sara Jane , Bernier Raphael A. , Sikich Linmarie , Hellemann Gerhard , Senturk Damla , Naples Adam J. , Shic Frederick , Levin April R. , Seow Helen A. , Dziura James D. , Jeste Shafali S. , Chawarska Katarzyna , Nelson Charles A. , Dawson Geraldine , McPartland James C. ,   Autism Biomarkers Consortium for Clinical Trials
Published: March 2023

Clinical trials in autism spectrum disorder (ASD) often rely on clinician rating scales and parent surveys to measure autism‐related features and social behaviors. To aid in the selection of these assessments for future clinical trials, the Autism Biomarkers Consortium for Clinical Trials (ABC‐CT) directly compared eight common instruments with respect to acquisition rates, sensitivity to group differences, equivalence across demographic sub‐groups, convergent validity, and stability over a 6‐week period. The sample included 280 children diagnosed with ASD (65 girls) and 119 neurotypical children (36 girls) aged from 6 to 11 years. Full scale IQ for ASD ranged from 60 to 150 and for neurotypical ranged from 86 to 150. Instruments measured clinician global assessment and autism‐related behaviors, social communication abilities, adaptive function, and social withdrawal behavior. For each instrument, we examined only the scales that measured social or communication functioning. Data acquisition rates were at least 97.5% at T1 and 95.7% at T2. All scales distinguished diagnostic groups. Some scales significantly differed by participant and/or family demographic characteristics. Within the ASD group, most clinical instruments exhibited weak (≥ |0.1|) to moderate (≥ |0.4|) intercorrelations. Short‐term stability was moderate (ICC: 0.5–0.75) to excellent (ICC: >0.9) within the ASD group. Variations in the degree of stability may inform viability for different contexts of use, such as identifying clinical subgroups for trials versus serving as a modifiable clinical outcome. All instruments were evaluated in terms of their advantages and potential concerns for use in clinical trials.
Der Gebäuderessourcenpass – ein Steuerungsinstrument für effektiven Ressourcenschutz im Massivbau
Authors: Propach Vanessa , Mrzigod Alexandra , Weidner Stefanie
Published: March 2023

Der Bausektor ist weltweit der Wirtschaftszweig mit dem höchsten Ressourcenverbrauch. Anspruch an die Bauschaffenden ist es daher, die eingesetzten Materialien vollständig im Kreislauf zu halten. Die Dokumentation der in Bauwerken eingesetzten Materialien und deren Verbindungsarten bildet eine essenzielle Grundlage zur Gewährleistung einer Weiter‐ und Wiederverwendbarkeit der Materialien nach dem Rückbau bzw. dem Ende der ersten Nutzungsphase. Der Gebäuderessourcenpass ist ein Dokumentationstool zur Erfassung der detaillierten Material‐ und Konstruktionsparameter von Bauwerken. Mineralische Baustoffe nehmen dabei aufgrund ihres großen Masseanteils einen besonderen Stellenwert ein. Der Beitrag befasst sich damit, wie der Gebäuderessourcenpass als Steuerungsinstrument für mehr Ressourceneffizienz im Bauschaffen wirken kann. Der Fokus der Betrachtung liegt hierbei auf Massivbauten.
Application of gas diffusion electrodes in bioeconomy: An update
Authors: Stöckl Markus , Lange Thomas , Izadi Paniz , Bolat Sera , Teetz Niklas , Harnisch Falk , Holtmann Dirk
Published: March 2023

The transition of today's fossil fuel based chemical industry toward sustainable production requires improvement of established production processes as well as development of new sustainable and bio‐based synthesis routes within a circular economy. Thereby, the combination of electrochemical and biotechnological advantages in such routes represents one important keystone. For the electrochemical generation of reactants from gaseous substrates such as O2 or CO2, gas diffusion electrodes (GDE) represent the electrodes of choice since they overcome solubility‐based mass transport limitations. Within this article, we illustrate the architecture, function principle and fabrication of GDE. We highlight the application of GDE for conversion of CO2 using abiotic catalysts for subsequent biosynthesis as well as the application of microbial catalysts at GDE for CO2 conversion. The reduction of oxygen at GDE is summarized for the application of oxygen depolarized cathodes in microbial fuel cells and generation of H2O2 to drive enzymatic reactions. Finally, engineering aspects such as scale‐up and the modeling of GDE‐based processes are described. This review presents an update on the application of GDE in bio‐based production systems and emphasizes their large potential for sustainable development of new pathways in bioeconomy.
Systematic Investigation of Metabolic Oligosaccharide Engineering Efficiency in Intestinal Cells Using a Dibenzocyclooctyne‐Monosaccharide Conjugate
Authors: Lam Yuen Yi , Tan Angel , Nowell Cameron J. , Kempe Kristian , Boyd Ben J.
Published: March 2023

Metabolic oligosaccharide engineering (MOE) of cells with synthetic monosaccharides can introduce functionality to the glycans of cell membranes. Unnatural sugars (e. g., peracetylated mannose‐azide) can be expressed on the cell surface with the azide group in place. After MOE, the azide group can participate in a copper‐free click reaction with an alkyne (e. g., dibenzocyclooctyne, DBCO) probe. This allows the metabolic fate of monosaccharides in cells to be understood. However, in a drug delivery context it is desirable to have azide groups on the probe (e. g. a drug delivery particle) and the alkyne (e. g. DBCO) on the cell surface. Consequently, the labelling efficiency of intestinal cell lines (Caco‐2 and HT29‐MTX‐E12) treated with N‐dibenzocyclooctyne‐tetra‐acetylmannosamine, and the concentration‐ and time‐dependent labelling were determined. Furthermore, the labelling of mucus in HT29‐MTX‐E12 cells with DBCO was shown. This study highlights the potential for using MOE to target azide‐functionalised probes to intestinal tissues for drug delivery applications.
Effects of delayed hospitalization on the 3‐year clinical outcomes of patients with or without diabetes who had non‐ST‐segment‐elevation myocardial infarction and underwent new‐generation drug‐eluting stent implantation
Authors: Kim Yong Hoon , Her Ae‐Young , Rha Seung‐Woon , Choi Cheol Ung , Choi Byoung Geol , Kim Ji Bak , Kang Dong Oh , Park Ji Young , Park Sang‐Ho , Jeong Myung Ho
Published: March 2023

Clinical outcomes after non‐ST‐segment‐elevation myocardial infarction (NSTEMI) in patients with (symptom‐to‐door time [SDT] ≥ 24 h) or without (SDT < 24 h) delayed hospitalization among patients with or without diabetes were compared. From the Korea Acute Myocardial Infarction Registry‐National Institute of Health, a total of 4517 patients with NSTEMI who underwent new‐generation drug‐eluting stents implantation were recruited and they were classified into the diabetes mellitus (DM) and non‐DM groups. These two groups were subdivided into groups with and without delayed hospitalization. The primary clinical outcome was the occurrence of major adverse cardiac and cerebrovascular events (MACCE), defined as all‐cause death, recurrent myocardial infarction, repeat coronary revascularization, and stroke. The secondary clinical outcome was the occurrence of individual components of MACCE and stent thrombosis. Although after multivariable and propensity score‐adjusted analyses in the DM group, the primary and secondary clinical outcomes between the SDT < 24 h and SDT ≥ 24 h groups were similar; in the non‐DM group, all‐cause (p = 0.003 and p = 0.007, respectively) and cardiac (p = 0.001 and p = 0.008, respectively) death rates were significantly higher in the SDT ≥ 24 h group than in the SDT < 24 h group. Our results suggested that there was no significant difference in prognosis between diabetic patients with and without delayed SDT, but delayed SDT was associated with poor prognosis in nondiabetic patients.
Nodular melanoma in an African American Japanese male
Authors: Gonzalez Sarah , King Andrew D. , Moossavi Meena
Published: March 2023

Nodular melanoma (NM) is the third most common subtype of melanoma among African Americans trailing behind acral lentiginous melanoma and superficial spreading melanoma. This case of NM in an African American Japanese male was selected due to the rare occurrence of NM in people of color.
Antiviral therapy defiant mixed viral retinitis post hematopoietic allogeneic stem cell transplant
Authors: Gabarin Nadia , Dadak Rohan , Roy Mili , Kaplan Alexander J. , Haider Shariq , Khalaf Dina
Published: March 2023

Cytomegalovirus (CMV) retinitis is an uncommon presentation post allogeneic transplant and can be vision‐threatening. Our case demonstrates the occurrence of polymerase chain reaction (PCR) proven mixed viral retinitis (cytomegalovirus and varicella zoster virus) post allogeneic stem cell transplant despite multiple prophylactic antiviral therapies, including letermovir, and in the documented absence of CMV DNAemia. A 21‐year‐old female with acute myeloid leukemia presented with mixed viral retinitis (cytomegalovirus and varicella zoster virus) post allogenic transplant. This presentation occurred despite ongoing standard prophylaxis for both of these viruses, as well as following two courses of treatment for CMV viremia, with a documented negative CMV PCR in the blood prior to the presentation with retinitis. The patient was treated with intravenous ganciclovir and subsequently transitioned to oral valganciclovir with durable resolution of the retinitis. We report a rare case of mixed viral retinitis occurring despite multiple antiviral prophylaxes including letermovir and with PCR‐documented absence of preceding CMV viremia, in a post‐allogeneic stem cell transplant patient, with PCR of the aqueous fluid demonstrating two viral populations. With very little existing literature on either mixed viral retinitis or CMV retinitis during letermovir prophylaxis, this case expands the literature on both topics. CMV retinitis is an uncommon potentially vision threatening presentation post hematopoietic stem cell transplant, and can occur due to early CMV reactivation, low CD4 count, and delayed CD4 lymphocyte recovery. Letermovir has poor CNS and retinal penetration. This case highlights the need for more research on secondary prophylaxis with letermovir.
MCATs: Case report of adnexal adenocarcinoma of not otherwise specified type
Authors: Svyatenko Tetyana , Prokhach Andrii , Antoniuk Stepan , Hurtovyy Vadym , Tereshkov Denys , Prokhach Anna
Published: March 2023

Malignant cutaneous adnexal tumors are rare dermatosis that can have extradermal twins. Diagnosis of adnexal skin tumors is sometimes difficult. Immunohistochemistry has limited value in the diagnosis. Most adnexal skin tumors are localized on the head and neck. Difficulties in their diagnosis associated with absence of strict clinical criteria.
Systemic reduced‐dose alteplase for diffuse pulmonary thrombi in a COVID‐19 patient
Authors: Colkesen Yucel
Published: March 2023

Pulmonary embolism has a high frequency in COVID‐19 patients admitted to the intensive care unit. Low level of fibrinolysis is one of the asserted contributors to a prothrombotic state in COVID‐19. Thrombotic coagulopathy is mostly encountered as diffuse pulmonary thrombi. Diffuse pulmonary microemboli was treated successfully with reduced dose thrombolysis.
Pentafluorophenol (C6F5OH) Catalyzed Pictet‐Spengler Reaction: A Facile and Metal‐Free Approach Towards Tetrahydro‐β‐Carbolines
Authors: Mahato Rina , Hazra Chinmoy Kumar
Published: March 2023

Herein, we have disclosed pentafluorophenol as an operative catalyst for synthesizing (spirocyclic) tetrahydro‐β‐carbolines via the Pictet‐Spengler reaction. This straightforward catalytic protocol works under mild conditions resulting indole alkaloids in excellent yield with remarkable functional group tolerance, including late‐stage modifications. This transformation demonstrates a practical and adaptable approach to produce a highly effective gram‐scale synthesis of the natural alkaloid Komavine and enables the synthesis of the commercial drug Tadalafil.
Transformation of the cyclo‐P5 Middle Deck in [(Cp*Fe)(Cp’’’Co)(μ,η5:η4‐P5)] upon Functionalization – A Comprehensive Study of Reactivity
Authors: Dinauer Sabrina B. , Piesch Martin , Szlosek Robert , Seidl Michael , Balázs Gábor , Scheer Manfred
Published: March 2023

The heterobimetallic triple‐decker complex [(Cp*Fe)(Cp’’’Co)(μ,η5 : η4‐P5)] (1) was functionalized by main group nucleophiles and subsequently electrophilically quenched or oxidized. Reacting 1 with group 14 nucleophiles revealed different organo‐substituted P5R middle‐decks depending on the steric and electronic effects of the used alkali metal organyls (2: R=tBu; 3: R=Me). Further, with group 15 nucleophiles, the first structural characterized monosubstituted complexes with phosphanides could be obtained as P5 ligands containing exocyclic {PR2} units (4: R=Cy, H; 5: R=Ph). These monoanionic complexes 2–5 were isolated and subsequent electrophilic quenching revealed novel types of neutral functionalized polyphosphorus complexes. These complexes bear formal chains of P5R'R’’ (6: R’=tBu, R’=Me) in a 1,3‐disubstitution pattern or P6R'R’’R’’’ units (7: R’=Cy, R’’=H, R’’’=Me; 8: R’=Me, R’’=Ph, R’’’=Me) in a 1,1,3‐substitution as middle‐decks stabilized by one {Cp’’’Co} and one {Cp*Fe} fragment. One‐electron oxidation of 2, 3 or 5 by AgBF4 gave access to paramagnetic triple‐decker complexes bearing P5R middle‐decks in various coordination fashions (R=tBu (10), R=PPh2 (12)). Interestingly, for R=Me (11), a dimerization is observed revealing a diamagnetic tetranuclear cluster containing a unique dihydrofulvalene‐type P10R2 ligand. All complexes were characterized by crystallographic and spectroscopic methods (EPR, multinuclear NMR and mass spectrometry) and their electronic structures were elucidated by DFT calculations.
Simultaneous Hydrogen Bonds with Different Binding Modes: The Acceptor “Rules” but the Donor “Chooses”
Authors: Garcia Marianne Rica , Iribarren Iñigo , Rozas Isabel , Trujillo Cristina
Published: March 2023

Invited for the cover of this issue is the group of Cristina Trujillo at Trinity College Dublin and the University of Manchester. The image depicts a market run by hydrogen bond acceptors in which hydrogen‐bond‐donor “customers” are choosing their preferred binding mode “vegetable”. Read the full text of the article at 10.1002/chem.202203577.