bluuebunny/crossref_metadata_2025 huggingface dataset:
Posttreatment Surveillance Imaging After Radiation for Head and Neck Cancer
Authors: Chen Allen M. , Harris Jeremy P. , Gan Meng , Nabar Rupali , Tjoa Tjoson , Haidar Yarah M. , Truong Annie , Chow Daniel S. , Armstrong William B.
Published: November 2023

Importance

The role of surveillance imaging after treatment for head and neck cancer is controversial and evidence to support decision-making is limited.

Objective

To determine the use of surveillance imaging in asymptomatic patients with head and neck cancer in remission after completion of chemoradiation.

Design, Setting, and Participants

This was a retrospective, comparative effectiveness research review of adult patients who had achieved a complete metabolic response to initial treatment for head and neck cancer as defined by having an unequivocally negative positron emission tomography (PET) scan using the PET response criteria in solid tumors (PERCIST) scale within the first 6 months of completing therapy. The medical records of 501 consecutive patients who completed definitive radiation therapy (with or without chemotherapy) for newly diagnosed squamous cell carcinoma of the head and neck between January 2014 and June 2022 were reviewed.

Exposure

Surveillance imaging was defined as the acquisition of a PET with computed tomography (CT), magnetic resonance imaging (MRI), or CT of the head and neck region in the absence of any clinically suspicious symptoms and/or examination findings. For remaining patients, subsequent surveillance after the achievement of a complete metabolic response to initial therapy was performed on an observational basis in the setting of routine follow-up using history-taking and physical examination, including endoscopy. This expectant approach led to imaging only in the presence of clinically suspicious symptoms and/or physical examination findings.

Main Outcome and Measures

Local-regional control, overall survival, and progression-free survival based on assignment to either the surveillance imaging or expectant management cohort.

Results

This study included 340 patients (mean [SD] age, 59 [10] years; 201 males [59%]; 88 Latino patients [26%]; 145 White patients [43%]) who achieved a complete metabolic response during this period. There was no difference in 3-year local-regional control, overall survival, progression-free survival, or freedom from distant metastasis between patients treated with surveillance imaging vs those treated expectantly.

Conclusions and Relevance

In this comparative effectiveness research, imaging-based surveillance failed to improve outcomes compared with expectant management for patients who were seemingly in remission after completion of primary radiation therapy for head and neck cancer.
School Closures and ED Visits for Suicidality in Youths Before and During the COVID-19 Pandemic
Authors: Dvir Yael , Ryan Clare , Lee JungAe
Published: November 2023

This cohort study investigates the association of COVID-19–related school closures with rates of emergency department suicidality visits among youths ages 12 to 25 years.
Microglia heterogeneity in health and disease
Authors: Dadwal Shilauni , Heneka Michael T.
Published: November 2023

Microglia, the resident immune cells of the central nervous system (CNS), have received significant attention due to their critical roles in maintaining brain homeostasis and mediating cerebral immune responses. Understanding the origin of microglia has been a subject of great interest, and emerging evidence suggests that microglia consist of multiple subpopulations with unique molecular and functional characteristics. These subpopulations of microglia may exhibit specialized roles in response to different environmental cues as in disease conditions. The newfound understanding of microglial heterogeneity has significant implications for elucidating their roles in both physiological and pathological conditions. In the context of disease, microglia have been studied rigorously as they play a very important role in neuroinflammation. Dysregulated microglial activation and function contribute to chronic inflammation. Further exploration of microglial heterogeneity and their interactions with other cell types in the CNS will undoubtedly pave the way to novel therapeutic strategies targeting microglia‐mediated pathologies. In this review, we discuss the latest advances in the field of microglia research, focusing specifically on the origin and subpopulations of microglia, the populations of microglia types in the brains of patients with neurodegenerative diseases, and how microglia are regulated in the healthy CNS.
High‐Temperature Creep Behavior of Selective‐Laser‐Melting‐Fabricated Lattice Structures Inspired from Euplectella Aspergillum
Authors: Sharma Deepak , Hiremath Somashekhar S.
Published: November 2023

In this study, the lattice‐like arrangement of Euplectella aspergillum is used to derive bionic grid‐stiffened structures in the form of thin tubes. The bionic tubes are 3D printed with AlSi10Mg alloy using a selective laser melting process. High‐temperature creep behavior at 250 °C and stress (0.3–0.7) times yield strength of the tubes is studied under uniaxial constant compressive load. The effect of the stress level, temperature, and tube design on the creep performance and deformation behavior is studied. The creep performance of bioinspired tubes is compared with honeycomb lattice tubes. In the results, the dependence of creep life and creep rate on the design of the bionic tubes is shown. E. aspergillum–based thin tubes show higher creep life and lower creep rate as compared to honeycomb‐based tubes at all stress levels. Also, the creep curves of lattice structures based thin tubes are different than the solid material, especially in the primary and tertiary regions. The fractography analysis shows higher creep life in E. aspergillum–inspired thin tubes is due to the improvement in ductility at high temperature. The stress exponent value in the Mukherjee–Bird–Dorn equation shows that the mechanism of creep is diffusion. Herein, in the results, it is shown that the bioinspiration and additive manufacturing provide an opportunity to design and fabricate advanced iso‐grids structures.
A Biomimetic Structural Material with Adjustable Mechanical Property for Bone Tissue Engineering
Authors: Kong Deyin , Wang Qing , Huang Jiangeng , Zhang Zhihui , Wang Xiebin , Han Qing , Shi Yanbin
Published: November 2023

The development of cellular materials with adjustable mechanical properties, total porosity (Tp), and elastic modulus (E) similar to those of natural bone are eternal pursuits in the field of bone implants. Designing and manufacturing an implant that fulfills all these requirements is a challenging task. In this study, inspired by the trabecular structure of natural bone and developed a biomimetic structural material. Laser powder bed fusion (L‐PBF) is utilized to create the biomimetic structural material. Comprehensive valuations of both the natural trabecular bone and biomimetic structural material are conducted using micro‐CT scanning, nanoindentation testing, finite element (FE) analysis, and compression testing. The results demonstrate that the mechanical properties of the developed biomimetic structural material have excellent controllability. The rod‐plate‐like trabecular (RPT) biomimetic structural material exhibited significantly superior mechanical load‐bearing performance compared to the natural bone trabeculae while maintaining the natural bone's Tp (83.1%) and E (798.1 MPa). The biomimetic structural material effectively balances the combination of strength and E, providing a design template for the next generation of medical implants. It has great potential as a bone repair material for clinical applications, and its adjustable mechanical properties also make it highly promising in the field of tissue engineering.
Strain as a Global Factor in Stabilizing the Ferroelectric Properties of ZrO2
Authors: Xu Bohan , Lomenzo Patrick D. , Kersch Alfred , Schenk Tony , Richter Claudia , Fancher Chris M. , Starschich Sergej , Berg Fenja , Reinig Peter , Holsgrove Kristina M. , Kiguchi Takanori , Mikolajick Thomas , Boettger Ulrich , Schroeder Uwe
Published: November 2023

Since the discovery of ferroelectricity in doped HfO2and ZrO2thin films over a decade ago, fluorite‐structured ferroelectric thin films have attracted much research attention due to their excellent scalability and complementary metal‐oxide semiconductor compatibility compared to conventional perovskite ferroelectric materials. Although various factors influencing the formation of the ferroelectric properties are identified, a clear understanding of the causes of the phase formation have been difficult to determine. In this work, ZrO2films deposited by atomic layer deposition and chemical solution deposition have resulted in films with completely different structural properties. Regardless of these differences, a general relationship between strain and phase formation is established, leading to a more unified understanding of ferroelectric phase formation in undoped ZrO2films, which can be applied to other fluorite‐structured films.
Stem Cells Expansion Vector via Bioadhesive Porous Microspheres for Accelerating Articular Cartilage Regeneration
Authors: Bai Lang , Han Qibin , Han Zeyu , Zhang Xiaoyu , Zhao Jingwen , Ruan Huitong , Wang Junliang , Lin Feng , Cui Wenguo , Yang Xing , Hao Yuefeng
Published: November 2023

Stem cell tissue engineering is a potential treatment for osteoarthritis. However, the number of stem cells that can be delivered, loss of stem cells during injection, and migration ability of stem cells limit applications of traditional stem cell tissue engineering. Herein, kartogenin (KGN)‐loaded poly(lactic‐co‐glycolic acid) (PLGA) porous microspheres is first engineered via emulsification, and then anchored with chitosan through the amidation reaction to develop a new porous microsphere (PLGA‐CS@KGN) as a stem cell expansion vector. Following 3D co‐culture of the PLGA‐CS@KGN carrier with mesenchymal stem cells (MSCs), the delivery system is injected into the capsule cavity in situ. In vivo and in vitro experiments show that PLGA‐CS microspheres have a high cell‐carrying capacity up to 1 × 104 mm−3 and provide effective protection of MSCs to promote their controlled release in the osteoarthritis microenvironment. Simultaneously, KGN loaded inside the microspheres effectively cooperated with PLGA‐CS to induce MSCs to differentiate into chondrocytes. Overall, these findings indicate that PLGA‐CS@KGN microspheres held high cell‐loading ability, adapt to the migration and expansion of cells, and promote MSCs to express markers associated with cartilage repair. Thus, PLGA‐CS@KGN can be used as a potential stem cell carrier for enhancing stem cell therapy in osteoarthritis treatment.
Sprayable Multifunctional Black Phosphorus Hydrogel with On‐Demand Removability for Joint Skin Wound Healing
Authors: Ding Xiaoya , Yu Yunru , Fan Lu , Li Wenzhao , Bian Feika , Wang Jinglin , Zhao Yuanjin
Published: November 2023

Wound healing remains a critical challenge in regenerative engineering. Great efforts are devoted to develop functional patches for wound healing. Herein, a novel sprayable black phosphorus (BP)‐based multifunctional hydrogel with on‐demand removability is presented as a joints’ skin wound dressing. The hydrogel is facilely prepared by mixing dopamine‐modified oxidized hyaluronic acid, cyanoacetategroup‐functionalized dextran containing black phosphorus, and the catalyst histidine. The catechol‐containing dopamine can not only enhance tissue adhesiveness, but also endow the hydrogel with antioxidant capacity. In addition, benefiting from the photothermal conversion ability of the BP and thermally reversible performance of the formed C═C double bonds between aldehyde groups and cyanoacetate groups, the resulting hydrogel displays excellent antibacterial performance and on‐demand dissolving ability under NIR irradiation. Moreover, by loading vascular endothelial growth factor into the hydrogel, the promoted migration and angiogenesis effects of endothelial cells can also be achieved. Based on these features, it is demonstrated that such sprayable BP hydrogels can effectively facilitate joint wounds healing by accelerating angiogenesis, alleviating inflammation, and improving wound microenvironment. Thus, it is believed that this NIR‐responsive removable BP hydrogel dressing will put forward an innovative concept in designing wound dressings.
An Efficient and Stable Lithium‐Oxygen Battery Based on Metal‐Organic Framework Separator Operating at 160 °C
Authors: Qiu Qianyuan , Yuan Jiashu , Li Gen , Pan Zheng‐ze , Yao Penghui , Zhao Yicheng , Zhang Cuijuan , Li Yongdan
Published: November 2023

A lithium oxygen battery (LOB) with molten salt electrolyte operating at elevated temperature has aroused great interest because it enables fast reaction kinetics. However, there is still a lack of open literature on the separator (membrane) of this kind of LOB. Metal‐organic framework (MOF) materials are widely used as components of separators in many kinds of energy storage devices, due to their regular crystalline and well‐defined pore structures. In this work, a MOF material, zirconium (II) 1,4‐benzenedicarboxylate after lithiation (UiO‐66‐SO3Li) with a narrow pore size (6 Å), is used as a key component of the separator for LOB operating at elevated temperature. A “rolling dough” method is adopted to prepare the separator, which achieves 100% material utilization. The LOB with this membrane operates at 160 °C and delivers a specific capacity of 5.1 mAh cm−2 with an overpotential as low as 40 mV at 0.1 mA cm−2 and a prolonged cycle life, 180 cycles with a high coulombic efficiency of 99.9% at 0.5 mA cm−2. This MOF‐based membrane provides efficient Li+ transfer and restricts discharge product migration during battery operation, which is promising for the development of LOB in large‐scale practical applications.
Fabrication and Characterization of a Thermoelectric Generator with High Aspect Ratio Thermolegs for Electrically Active Implants
Authors: Rao Yongchen , Xu Chu , Voss Matthias , Ying Pingjun , Reith Heiko , Nielsch Kornelius , Bechtold Tamara , Hohlfeld Dennis
Published: November 2023

Implantable thermoelectric generators hold significant promise as an alternative or supplementary energy source for implantable medical devices, but their performance is constrained by spatial limitations within implants and relies heavily on design optimization. In this study, an optimized thermoelectric generator featuring high aspect ratio thermolegs (0.5 × 0.5 × 4 mm3) is presented, which achieves a remarkable power output of 110 µW with a simulated temperature difference (3 K) in an implantation scenario. This achievement is realized through the use of a removable assembly rig during the soldering process, streamlining the fabrication process. Furthermore, the integration of a boost converter within the thermoelectric generator results in a voltage output of 2.5 V, addressing the voltage requirements of active implants. These findings highlight the potential that implantable thermoelectric generators can be used as a reliable, quiet and self‐sufficient power source for implantable medical devices.
Fabrication of Plastic Optics from Chalcogenide Hybrid Inorganic/Organic Polymers for Infrared Thermal Imaging
Authors: Molineux Jake , Lee Taeheon , Kim Kyung Jo , Kang Kyung‐Seok , Lyons Nicholas P. , Nishant Abhinav , Kleine Tristan S. , Durfee Sam W. , Pyun Jeffrey , Norwood Robert A.
Published: November 2023

The development of infrared (IR) plastic optics for infrared thermal imaging, particularly, in the long‐wave IR (LWIR) spectrum (7–14 µm) is an area of growing technological interest due to the potential advantages associated with plastic optics (e.g., moldability and low cost). The development of a new class of optical polymers, chalcogenide‐based inorganic/organic hybrid polymers (CHIPs) derived from the inverse vulcanization of elemental sulfur, has enabled significant improvements in IR transparency due to reduction of IR absorbing organic comonomer units. The vast majority of effort has focused on new chalcogenide hybrid polymer synthesis and optical property improvements (e.g., refractive index, Abbe number, and LWIR transmission); however, fabrication and IR imaging methodology to prepare optical components has not been demonstrated, which remains critical to develop viable IR plastic optics. A new methodology is reported to fabricate optical components and evaluate LWIR imaging performance of this emerging class of optical polymers. New diffractive flat optics with a Fresnel lens design for these materials have been developed, along with a basic LWIR imaging system to evaluate CHIPs for LWIR imaging. This system‐based approach enables correspondence of copolymer structure‐property correlations with LWIR imaging performance, along with demonstration of room temperature LWIR imaging.
Magnetic Mesoporous Janus Microrollers for Combined Chemo‐ and Photothermal Ablation Therapy
Authors: Aybar Tural Gulsen , Bozuyuk Ugur , Dogan Nihal Olcay , Alapan Yunus , Akolpoglu Mukrime Birgul , Aghakhani Amirreza , Lazovic Jelena , Ozer Ozgen , Sitti Metin
Published: November 2023

Mobile microrobots have been proposed as a promising approach to overcome the limitations of traditional drug/gene delivery systems. Magnetically actuated surface rolling microrobots, or magnetic surface microrollers, have shown potential for navigation in physiologically relevant environments due to their robust locomotion characteristics. Although much is known about their locomotion abilities in various environments, the full extent of their potential in medical applications has yet to be fully explored. Here, the potential of surface microrollers for combined chemo‐ and photothermal ablation therapy under medical imaging modalities is demonstrated. The surface microrollers are half‐coated with magnetic material, allowing for photothermal heating and magnetic locomotion, and loaded with a biopharmaceutics classification system (BCS) class IV anti‐cancer drug, Docetaxel (DTX), for combined therapy. Synergistic action of on‐demand photothermal ablation and the controlled release of DTX result in the efficient elimination of cancer cells. Furthermore, microrollers can be detected ex vivo with magnetic resonance imaging (MRI) and photoacoustic imaging (PA), highlighting the potential of surface microrollers for future targeted medical applications.
Inhibition of CARM1‐Mediated Methylation of ACSL4 Promotes Ferroptosis in Colorectal Cancer
Authors: Feng Shengjie , Rao Zejun , Zhang Jiakun , She Xiaowei , Chen Yaqi , Wan Kairui , Li Haijie , Zhao Chongchong , Feng Yongdong , Wang Guihua , Hu Junbo , Luo Xuelai
Published: November 2023

Ferroptosis, which is caused by iron‐dependent accumulation of lipid peroxides, is an emerging form of regulated cell death and is considered a potential target for cancer therapy. However, the regulatory mechanisms underlying ferroptosis remain unclear. This study defines a distinctive role of ferroptosis. Inhibition of CARM1 can increase the sensitivity of tumor cells to ferroptosis inducers in vitro and in vivo. Mechanistically, it is found that ACSL4 is methylated by CARM1 at arginine 339 (R339). Furthermore, ACSL4 R339 methylation promotes RNF25 binding to ACSL4, which contributes to the ubiquitylation of ACSL4. The blockade of CARM1 facilitates ferroptosis and effectively enhances ferroptosis‐associated cancer immunotherapy. Overall, this study demonstrates that CARM1 is a critical contributor to ferroptosis resistance and highlights CARM1 as a candidate therapeutic target for improving the effects of ferroptosis‐based antitumor therapy.
Engineering Heterogeneous Tumor Models for Biomedical Applications
Authors: Wu Zhuhao , Huang Danqing , Wang Jinglin , Zhao Yuanjin , Sun Weijian , Shen Xian
Published: November 2023

Tumor tissue engineering holds great promise for replicating the physiological and behavioral characteristics of tumors in vitro. Advances in this field have led to new opportunities for studying the tumor microenvironment and exploring potential anti‐cancer therapeutics. However, the main obstacle to the widespread adoption of tumor models is the poor understanding and insufficient reconstruction of tumor heterogeneity. In this review, the current progress of engineering heterogeneous tumor models is discussed. First, the major components of tumor heterogeneity are summarized, which encompasses various signaling pathways, cell proliferations, and spatial configurations. Then, contemporary approaches are elucidated in tumor engineering that are guided by fundamental principles of tumor biology, and the potential of a bottom‐up approach in tumor engineering is highlighted. Additionally, the characterization approaches and biomedical applications of tumor models are discussed, emphasizing the significant role of engineered tumor models in scientific research and clinical trials. Lastly, the challenges of heterogeneous tumor models in promoting oncology research and tumor therapy are described and key directions for future research are provided.
Nongenetic Optical Modulation of Pluripotent Stem Cells Derived Cardiomyocytes Function in the Red Spectral Range
Authors: Ronchi Carlotta , Galli Camilla , Tullii Gabriele , Marzuoli Camilla , Mazzola Marta , Malferrari Marco , Crasto Silvia , Rapino Stefania , Di Pasquale Elisa , Antognazza Maria Rosa
Published: November 2023

Optical stimulation in the red/near infrared range recently gained increasing interest, as a not‐invasive tool to control cardiac cell activity and repair in disease conditions. Translation of this approach to therapy is hampered by scarce efficacy and selectivity. The use of smart biocompatible materials, capable to act as local, NIR‐sensitive interfaces with cardiac cells, may represent a valuable solution, capable to overcome these limitations. In this work, a far red‐responsive conjugated polymer, namely poly[2,1,3‐benzothiadiazole‐4,7‐diyl[4,4‐bis(2‐ethylhexyl)−4H‐cyclopenta[2,1‐b:3,4‐b’]dithiophene‐2,6‐diyl]] (PCPDTBT) is proposed for the realization of photoactive interfaces with cardiomyocytes derived from pluripotent stem cells (hPSC‐CMs). Optical excitation of the polymer turns into effective ionic and electrical modulation of hPSC‐CMs, in particular by fastening Ca2+dynamics, inducing action potential shortening, accelerating the spontaneous beating frequency. The involvement in the phototransduction pathway of Sarco‐Endoplasmic Reticulum Calcium ATPase (SERCA) and Na+/Ca2+exchanger (NCX) is proven by pharmacological assays and is correlated with physical/chemical processes occurring at the polymer surface upon photoexcitation. Very interestingly, an antiarrhythmogenic effect, unequivocally triggered by polymer photoexcitation, is also observed. Overall, red‐light excitation of conjugated polymers may represent an unprecedented opportunity for fine control of hPSC‐CMs functionality and can be considered as a perspective, noninvasive approach to treat arrhythmias.
Metal–Organic Frameworks for the Enhancement of Lithium‐Based Batteries: A Mini Review on Emerging Functional Designs
Authors: Mu Anthony U. , Cai Guorui , Chen Zheng
Published: November 2023

Metal–organic frameworks (MOFs) have played a crucial role in recent advancements in developing lithium‐based battery electrolytes, electrodes, and separators. Although many MOF‐based battery components rely on their well‐defined porosity and controllable functionality, they also boast a myriad of other significant properties relevant to battery applications. In this mini‐review, the distinct advantages of MOFs in battery applications are discussed, including using MOFs to 1) scavenge impurities to increase cycling stability, 2) widen the operation temperature range of conventional electrolytes, 3) widen the operation voltage range of common electrolytes, and 4) employ as artificial solid‐electrolyte interphases to prevent lithium dendrite growth. Furthermore, subsisting challenges of developing these emerging MOF‐based battery technologies are discussed and guidance for shaping the future of this field is given.
Control of Properties through Hydrogen Bonding Interactions in Conjugated Polymers
Authors: Wan Qingpei , Thompson Barry C.
Published: November 2023

Molecular design is crucial for endowing conjugated polymers (CPs) with unique properties and enhanced electronic performance. Introducing Hydrogen‐bonding (H‐bonding) into CPs has been a broadly exploited, yet still emerging strategy capable of tuning a range of properties encompassing solubility, crystallinity, electronic properties, solid‐state morphology, and stability, as well as mechanical properties and self‐healing properties. Different H‐bonding groups can be utilized to tailor CPs properties based on the applications of interest. This review provides an overview of classes of H‐bonding CPs (assorted by the different H‐bond functional groups), the synthetic methods to introduce the corresponding H‐bond functional groups and the impact of H‐bonding in CPs on corresponding electronic and materials properties. Recent advances in addressing the trade‐off between electronic performance and mechanical durability are also highlighted. Furthermore, insights into future directions and prospects for H‐bonded CPs are discussed.
The farmer and the fates: Locus of control and investment in rainfed agriculture
Authors: Malacarne J. G.
Published: November 2023

Vulnerable households, often the target for efforts to increase resilience, likely hold beliefs about their ability to control outcomes that make them less likely to invest in new technologies. Locus of control provides one way to elicit these beliefs and can help identify populations requiring additional support prior to widespread adoption of new technologies. This paper presents evidence from a large sample of maize‐producing households in Mozambique and Tanzania. A more external locus of control is strongly associated with lower expected returns to improved maize varieties and a reduced probability of their adoption.
Mobility‐Modulated Sequential Dissociation Analysis Enables Structural Lipidomics in Mass Spectrometry Imaging
Authors: Qian Yao , Guo Xiangyu , Wang Yunfang , Ouyang Zheng , Ma Xiaoxiao
Published: November 2023

Spatial lipidomics based on mass spectrometry imaging (MSI) is a powerful tool for fundamental biology studies and biomarker discovery. But the structure‐resolving capability of MSI is limited because of the lack of multiplexed tandem mass spectrometry (MS/MS) method, primarily due to the small sample amount available from each pixel and the poor ion usage in MS/MS analysis. Here, we report a mobility‐modulated sequential dissociation (MMSD) strategy for multiplex MS/MS imaging of distinct lipids from biological tissues. With ion mobility‐enabled data‐independent acquisition and automated spectrum deconvolution, MS/MS spectra of a large number of lipid species from each tissue pixel are acquired, at no expense of imaging speed. MMSD imaging is highlighted by MS/MS imaging of 24 structurally distinct lipids in the mouse brain and the revealing of the correlation of a structurally distinct phosphatidylethanolamine isomer (PE 18 : 1_18 : 1) from a human hepatocellular carcinoma (HCC) tissue. Mapping of structurally distinct lipid isomers is now enabled and spatial lipidomics becomes feasible for MSI.
Herstellung von biobasiertem Ethylbenzol durch Kaskaden‐Biokatalyse mit einer speziell entwickelten Photodecarboxylase
Authors: Qin Zhaoyang , Zhou Yi , Li Zhi , Höhne Matthias , Bornscheuer Uwe T. , Wu Shuke
Published: November 2023

Die Herstellung von chemischen Grundstoffen wie Benzol, Toluol, Ethylbenzol und Xylol (BTEX) aus erneuerbaren Ressourcen ist der Schlüssel zu einer nachhaltigen Gesellschaft. Die Biokatalyse ermöglicht die Ein‐Topf‐Mehrschritt‐Transformation von Bioressourcen unter milden Bedingungen, ist jedoch oft auf Biochemikalien beschränkt. Wir haben eine nicht‐natürliche Drei‐Enzym‐Kaskade für die Ein‐Topf‐Umwandlung von biobasiertem l‐Phenylalanin in Ethylbenzol entwickelt. Die geschwindigkeitsbestimmende Photodecarboxylase als Schlüsselenzym wurde einem strukturbasierten semi‐rationalem Engineering unterzogen und es wurde eine Dreifachmutante CvFAP(Y466T/P460A/G462I) mit einer 6.3‐fach höheren Produktivität erhalten. Mit dieser verbesserten Photodecarboxylase wurde ein optimiertes sequentielles E. coli Zwei‐Zellsystem‐Verfahren zur Umwandlung von l‐Phenylalanin in Ethylbenzol mit 82 % Umsatz entwickelt. Die Kaskadenreaktion wurde in die Fermentation integriert, um eine Ein‐Topf‐Bioproduktion von Ethylbenzol aus biobasiertem Glycerin zu erreichen. Dies zeigt das Potenzial der Kaskaden‐Biokatalyse in Kombination mit einem Enzym‐Engineering für die Produktion von biobasierten chemischen Grundstoffen auf.
Photoredox Nickel‐Catalysed Stille Cross‐Coupling Reactions
Authors: Zhou Zhenghong , Yang Jimin , Yang Bo , Han Yang , Zhu Lijuan , Xue Xiao‐Song , Zhu Feng
Published: November 2023

The Stille cross‐coupling reaction is one of the most common strategies for the construction of C−C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium‐catalysed Stille reactions, cost‐effective nickel‐catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped. Herein, we present a pioneering instance of nickel‐catalysed enantioconvergent Stille cross‐coupling reactions of racemic stannane reagents, resulting in the formation of C−C bonds in good to high yields with excellent stereoselectivity. This strategy provides a practical, scalable, and operationally straightforward method for the synthesis of C(sp3)−C(sp3), C(sp3)−C(sp2), and C(sp3)−C(sp) bonds under exceptionally mild conditions (without additives and bases, ambient temperature). The innovative use of synergistic photoredox/nickel catalysis enables a novel single‐electron transmetalation process of stannane reagents, providing a new research paradigm of Stille reactions.
Dual‐katalysierte intermolekulare reduktive Kopplung von Dienen und Ketonen**
Authors: Mayerhofer Victor J. , Lippolis Martina , Teskey Christopher J.
Published: November 2023

Wir berichten über eine milde, katalytische Methode für die intermolekulare reduktive Kopplung von Dienen und Styrolen mit Ketonen. Unsere Bedingungen ermöglichen die gleichzeitige Bildung einer Cobalthydrid‐Spezies und die Ein‐Elektronen‐Reduktion von Ketonen. Der anschließende selektive Wasserstoff‐Atom‐Transfer vom Cobalthydrid erzeugt ein allylisches Radikal, das sich selektiv mit dem persistenten Radikal‐Anion des Ketons verbinden kann. Diese Radikal‐Radikal‐Kopplung hebt die ungünstigen sterischen Wechselwirkungen der Ionenwege auf und vermeidet das instabile Alkoxy‐Radikal früherer radikalischer Olefin‐Carbonyl‐Kopplungen, die infolgedessen auf Aldehyde beschränkt waren. Zu den Anwendungen dieser neuen Methode gehören die effiziente Synthese von Arzneimittelmolekülen, wichtige Zwischenprodukte in der Arzneimittelsynthese und die ortselektive Late‐Stage‐Funktionalisierung.
Particle Engineering via Supramolecular Assembly of Macroscopic Hydrophobic Building Blocks
Authors: Kim Chan‐Jin , Goudeli Eirini , Ercole Francesca , Ju Yi , Gu Yuang , Xu Wanjun , Quinn John F. , Caruso Frank
Published: November 2023

Tailoring the hydrophobicity of supramolecular assembly building blocks enables the fabrication of well‐defined functional materials. However, the selection of building blocks used in the assembly of metal–phenolic networks (MPNs), an emerging supramolecular assembly platform for particle engineering, has been essentially limited to hydrophilic molecules. Herein, we synthesized and applied biscatechol‐functionalized hydrophobic polymers (poly(methyl acrylate) (PMA) and poly(butyl acrylate) (PBA)) as building blocks to engineer MPN particle systems (particles and capsules). Our method allowed control over the shell thickness (e.g., between 10 and 21 nm), stiffness (e.g., from 10 to 126 mN m−1), and permeability (e.g., 28–72 % capsules were permeable to 500 kDa fluorescein isothiocyanate‐dextran) of the MPN capsules by selection of the hydrophobic polymer building blocks (PMA or PBA) and by controlling the polymer concentration in the MPN assembly solution (0.25–2.0 mM) without additional/engineered assembly processes. Molecular dynamics simulations provided insights into the structural states of the hydrophobic building blocks during assembly and mechanism of film formation. Furthermore, the hydrophobic MPNs facilitated the preparation of fluorescent‐labeled and bioactive capsules through postfunctionalization and also particle–cell association engineering by controlling the hydrophobicity of the building blocks. Engineering MPN particle systems via building block hydrophobicity is expected to expand their use.
Tetraphenylethylene‐Based Hydrogen‐Bonded Organic Frameworks (HOFs) with Brilliant Fluorescence
Authors: Wang Shi‐Cheng , Zhang Qiang‐Sheng , Wang Zheng , Guan Shao‐Qi , Zhang Xiao‐Dong , Xiong Xiao‐Hong , Pan Mei
Published: November 2023

By synergistically employing four key strategies: (I) introducing tetraphenylethylene groups as the central core unit with aggregation‐induced emission (AIE) properties, (II) optimizing the π‐conjugated length by extending the building block branches, (III) incorporating flexible groups containing ethylenic bonds, and (IV) applying crystal engineering to attain dense stacking mode and highly twisty conformation, we successfully synthesized a series of hydrogen‐bonded organic frameworks (HOFs) exhibiting exceptional one/two‐photon excited fluorescence. Notably, when utilizing the fluorescently superior building block L2, HOF‐LIFM‐7 and HOF‐LIFM‐8 exhibiting high quantum yields (QY) of 82.1 % and 77.1 %, and ultrahigh two‐photon absorption (TPA) cross‐sections of 148959.5 GM and 123901.1 GM were achieved. These materials were successfully employed in one and two‐photon excited lysosome‐targeting cellular imaging. It is believed that this strategy, combining building block optimization and crystal engineering, holds significant potential for guiding the development of outstanding fluorescent HOF materials.
Macrocyclic Encapsulation in a Non‐fused Tetrathiophene Acceptor for Efficient Organic Solar Cells with High Short‐Circuit Current Density
Authors: Shen Shuaishuai , Mi Yu , Ouyang Yanni , Lin Yi , Deng Jingjing , Zhang Wenjun , Zhang Jianqi , Ma Zaifei , Zhang Chunfeng , Song Jinsheng , Bo Zhishan
Published: November 2023

Non‐fullerene acceptors have shown great promise for organic solar cells (OSCs). However, challenges in achieving high efficiency molecular system with conformational unicity and effective molecular stacking remain. In this study, we present a new design of non‐fused tetrathiophene acceptor R4T‐1 via employing the encapsulation of tetrathiophene with macrocyclic ring. The single crystal structure analysis reveals that cyclic alkyl side chains can perfectly encapsulate the central part of molecule and generate a conformational stable and planar molecular backbone. Whereas, the control 4T‐5 without the encapsulation restriction displays cis‐ and twisted conformation. As a result, R4T‐1 based OSCs achieved an outstanding power conversion efficiency (PCE) exceeding 15.10 % with a high short‐circuit current density (Jsc) of 25.48 mA/cm2, which is significantly improved by ≈30 % in relative to that of the control. Our findings demonstrate that the macrocyclic encapsulation strategy could assist fully non‐fused electron acceptors (FNEAs) to achieve a high photovoltaic performance and pave a new way for FNEAs design.
High‐Performance Near‐Infrared Chlorinated Rylenecarboximide Fluorophores via Consecutive C−N and C−C Bond Formation
Authors: Wu Ze‐Hua , Skabeev Artem , Zagranyarski Yulian , Duan Ruomeng , Jin Jun‐O , Kwak Minseok , Basché Thomas , Müllen Klaus , Li Chen
Published: November 2023

A new class of near‐infrared (NIR) fluorophores, PAI, is obtained by consecutive C−N/C−C bond formation between diphenylamines and 9,10‐dibromoperylenecarboximide. Owing to the rigid structure, extended π‐conjugation and pronounced push‐pull substitution, these fluorophores show emission maxima up to 804 nm and large Stokes shifts. The extraordinarily high fluorescence quantum yields from 47 % to 70 % are attributed to chloro substitution in the bay positions of the perylene core. These characteristics, together with high photostability, qualify them as useful NIR emitters for applications as biomarkers and security inks.
Synthesis of new Cu (II) and Zn (II) complexes derived from isatin‐3‐thiosemicarbazone: X‐ray, anticancer activity, molecular docking, ADMET study, and quantum chemical calculations
Authors: Mohamad Rodzi Ummi Liyana , Mohd Tajuddin Amalina , Sirat Siti Syaida , Kamaruzaman Nur Azzalia , Meroshine Nageswara Rao , Anouar El Hassane , Kassim Karimah
Published: November 2023

The current work aimed to synthesize new mononuclear Cu (II) and Zn (II) complexes derived from isatin‐based thiosemicarbazide, (Z)‐N‐methyl‐2‐(2‐oxoindolin‐3‐ylidene)hydrazinecarbothioamide ligand (L1) using the reflux conventional method. Structural characterization for the synthesized compounds was achieved via elemental analyses, spectroscopic analysis, magnetic susceptibility, molar conductivity, and thermal analysis. The compounds were further explored for their prospective anticancer properties with the aid of in silico methodology. Complexation of metal centers with L1 was observed using the shifting of the v(C=N) peak to lower frequencies and the emergence of new peaks in the range of 454–512 cm−1 assigned to v(M‐N) and v(M‐O). The non‐electrolytic character of Cu2+ and Zn2+ compounds was displayed by their low molar conductivities. Quantum chemical calculations were employed to investigate the electronic and molecular properties of the complexes. The frontier molecular orbitals were performed by density functional theory (DFT) calculations to provide valuable information regarding their molecular orbitals, reactivity indices, and electronic structures, assisting in understanding their structure–activity relationships and potential mechanisms of action. Additionally, molecular docking was carried out to comprehend the interaction of the compounds with the selected enzyme and determine their potential binding mode and energy. Meanwhile, the ADMET study exhibited that all of the compounds possess good oral bioavailability suggesting potent and suitable anticancer drug candidates. All the compounds were tested against human leukemia K562 cancer cell line and human fibroblasts Hs27 cell line. Overall, this comprehensive study highlights the synthesis, characterization, anticancer activity, molecular docking, ADMET evaluation, and quantum chemical calculations of new Cu (II) and Zn (II) complexes derived from isatin‐3‐thiosemicarbazone.
Monitored indentation for the detection of inclusions in elastomer material
Authors: Caro Anne‐Sophie , Iaquinta Sarah , Chhean Sarah , Guérandelle Léa , Mewa Singh Yohann , Léger Romain , Barés Jonathan , Regazzi Arnaud , Corn Stéphane , Ienny Patrick
Published: November 2023

The detection of inclusions in soft material is of great interest, especially in the medical field. Traditionally, a biopsy exam is performed after palpation, when necessary. In the present work, a potentially quantitative method, via monitored indentation, is used to mimic palpation. This method consists in investigating the relaxation and stress‐free relaxation responses to an indentation test performed on a silicone block with an inclusion. The aim of the study is to evaluate how a difference in position, size and adhesion of the inclusion can influence the response of the samples to monitored indentation. A finite element model is constructed to conduct comparative studies. The hyper‐viscoelastic parameters of the silicone have been identified experimentally. Results from the simulations showed that the indicators measured during monitored indentation, especially during the stress‐free relaxation phase, are sensitive to adhesive inclusions, while they provide little information regarding their non‐adhesive counterparts. Depths and sizes for which adhesive inclusions are more likely to be detected have been identified. These results are encouraging but are conducted on polymer material and a rigid inclusion; nevertheless, they suggest that the non‐destructive measure of the stress‐free relaxation response of a tissue may help practicians to quantitatively characterize the nature of a nodule.
Exploration of antiproliferative potential of modified triazole–benzohydrazone scaffold: Multitarget approach
Authors: Ali Alaa M. , Khalaf Mohamed A. , Bhongade Bhoomendra A. , Selim Khalid B. , Mostafa Amany S.
Published: November 2023

A novel series of triazole–benzohydrazone hybrids was efficiently designed and synthesized as antiproliferative agents, targeting different kinases. All compounds were screened via the National Cancer Institute (NCI) against 60 cancer cell lines, where compounds 16, 17, and 18 exhibited growth inhibition percent (GI%) of various leukemia subpanels with values of 70.33%, 64.13%, and 76.03%, respectively. Compound 18 showed broad‐spectrum antiproliferative efficacy toward most cancer cells, with outstanding potency regarding melanoma (MALME‐3M GI% = 101.82%) and breast cancer cell lines (MCF7 GI% = 85.87%), while proving safe toward the WI‐38 normal cell line, compared to doxorubicin. Multikinase investigation including vascular endothelial growth factor receptor 2 (VEGFR‐2), mesenchymal epithelial transition factor (c‐Met), proto‐oncogene B‐Raf, mitogen‐activated protein kinase kinase, extracellular signal‐regulated kinase, and phosphoinositide 3‐kinase was accomplished to reveal its plausible mechanism of action, giving the ultimate potency against both VEGFR‐2 and c‐Met with IC50 values of 0.055 and 0.042 μM, respectively, while displaying moderate to good inhibition concerning the remaining kinases. DNA binding capability was excluded using the methyl green colorimetric assay. Further, it exhibited both early and late apoptotic induction by about 16‐ and 9.4‐fold over the control, respectively, triggering cell cycle arrest in the G2/M phase. Physicochemical properties and bioavailability radar plot inferred drug‐likeness characteristics for compound 18. The molecular docking study assessed the binding pattern with the active sites of c‐Met and VEGFR‐2.
Design and synthesis of benzo[b]thiophene‐based hybrids as novel antitubercular agents against MDR/XDR Mycobacterium tuberculosis
Authors: Al‐Warhi Tarfah , Rashad Nermeen M. , Almahli Hadia , Abdel‐Aziz Marwa M. , Elsayed Zainab M. , Shahin Mai I. , Eldehna Wagdy M.
Published: November 2023

In an effort to support the global fight against tuberculosis (TB), which is widely recognized as the most lethal infectious disease worldwide, we present the design and synthesis of new benzo[b]thiophene‐based hybrids as promising candidates for the management of multidrug‐resistant (MDR)/extensively drug‐resistant (XDR) Mycobacterium tuberculosis. The isatin motif was incorporated into the target hybrids as it represents a privileged scaffold in antitubercular drug discovery. Since lipophilicity plays a pivotal role in the anti‐TB agents' activity, the lipophilicity of the target hybrids was manipulated via the development of two series of N‐1 methyl and N‐1 benzyl substituted isatins (6a–h and 9a–h, respectively). Screening of the target hybrids was first performed against drug‐sensitive M. tuberculosis (ATCC 25177). The structure–activity relationship outputs highlighted that incorporation of 3‐unsubstituted benzo[b]thiophene and 5‐methoxy isatin moieties was favorable for the antimycobacterial activity. Thereafter, the most potent molecules (6b–h, 9c–e, and 9h) were evaluated against the resistant strains MDR‐TB (ATCC 35822) as well as against XDR‐TB (RCMB 2674) where they displayed promising activity. To evaluate the safety of the target hybrids, an sulforhodamine B assay was conducted to determine their possible cytotoxic effects on VERO cells.
Prospective Evaluation of High Titer Autoantibodies and Fetal Home Monitoring in the Detection of Atrioventricular Block Among Anti‐SSA/Ro Pregnancies
Authors: Buyon Jill. P. , Masson Mala , Izmirly Caroline G. , Phoon Colin , Acherman Ruben , Sinkovskaya Elena , Abuhamad Alfred , Makhoul Majd , Satou Gary , Hogan Whitnee , Pinto Nelangi , Moon‐Grady Anita , Howley Lisa , Donofrio Mary , Krishnan Anita , Ahmadzia Homa , Levasseur Stephanie , Paul Erin , Owens Sonal , Cumbermack Kristopher , Matta Jyothi , Joffe Gary , Lindblade Christopher , Haxel Caitlin , Kohari Katherine , Copel Joshua , Strainic James , Doan Tam , Bermudez‐Wagner Karla , Holloman Conisha , Sheth Shreya S. , Killen Stacy , Tacy Theresa , Kaplinski Michelle , Hornberger Lisa , Carlucci Philip M. , Izmirly Peter , Fraser Nicola , Clancy Robert M. , Cuneo Bettina F.
Published: November 2023

Objective

This prospective study of pregnant patients, Surveillance To Prevent AV Block Likely to Occur Quickly (STOP BLOQ), addresses the impact of anti‐SSA/Ro titers and utility of ambulatory monitoring in the detection of fetal second‐degree atrioventricular block (AVB).

Methods

Women with anti‐SSA/Ro autoantibodies by commercial testing were stratified into high and low anti–52‐kD and/or 60‐kD SSA/Ro titers applying at‐risk thresholds defined by previous evaluation of AVB pregnancies. The high‐titer group performed fetal heart rate and rhythm monitoring (FHRM) thrice daily and weekly/biweekly echocardiography from 17–26 weeks. Abnormal FHRM prompted urgent echocardiography to identify AVB.

Results

Anti–52‐kD and/or 60‐kD SSA/Ro met thresholds for monitoring in 261 of 413 participants (63%); for those, AVB frequency was 3.8%. No cases occurred with low titers. The incidence of AVB increased with higher levels, reaching 7.7% for those in the top quartile for anti–60‐kD SSA/Ro, which increased to 27.3% in those with a previous child who had AVB. Based on levels from 15 participants with paired samples from both an AVB and a non‐AVB pregnancy, healthy pregnancies were not explained by decreased titers. FHRM was considered abnormal in 45 of 30,920 recordings, 10 confirmed AVB by urgent echocardiogram, 7 being second‐degree AVB, all <12 hours from normal FHRM and within another 0.75 to 4 hours to echocardiogram. The one participant with second/third‐degree and two participants with third‐degree AVB were diagnosed by urgent echocardiogram >17 to 72 hours from an FHRM. Surveillance echocardiograms detected no AVB when the preceding interval FHRM recordings were normal.

Conclusion

High‐titer antibodies are associated with an increased incidence of AVB. Anti‐SSA/Ro titers remain stable over time and do not explain the discordant recurrence rates, suggesting that other factors are required. Fetal heart rate and rhythm (FHRM) with results confirmed by a pediatric cardiologist reliably detects conduction abnormalities, which may reduce the need for serial echocardiograms.

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