bluuebunny/crossref_metadata_2025 huggingface dataset:
Synergistic Anti‐Tumor Effect of Toosendanin and Paclitaxel on Triple‐Negative Breast Cancer via Regulating ADORA2A‐EMT Related Signaling
Authors: Zhang Juan , Xu Hong‐Xi , Wu Yu‐Lin , Cho William Chi Shing , Xian Yan‐Fang , Lin Zhi‐Xiu
Published: July 2023

Triple negative breast cancer (TNBC) is an aggressive cancer with very poor prognosis. Combination therapy has proven to be a promising strategy for enhancing TNBC treatment efficacy. Toosendanin (TSN), a plant‐derived triterpenoid, has shown pleiotropic effects against a variety of tumors. Herein, it is evaluated whether TSN can enhance the efficacy of paclitaxel (PTX), a common chemotherapeutic agent, against TNBC. It is found that TSN and PTX synergistically suppress the proliferation of TNBC cell lines such as MDA‐MB‐231 and BT‐549, and the combined treatment also inhibits the colony formation and induces cell apoptosis. Furthermore, this combination shows more marked migratory inhibition when compared to PTX alone. Mechanistic study shows that the ADORA2A pathway in TNBC is down‐regulated by the combination treatment via mediating epithelial‐to‐mesenchymal transition (EMT) process. In addition, the combined treatment of TSN and PTX significantly attenuates the tumor growth when compared to PTX monotherapy in a mouse model bearing 4T1 tumor. The results suggest that combination of TSN and PTX is superior to PTX alone, suggesting that it may be a promising alternative adjuvant chemotherapy strategy for patients with TNBC, especially those with metastatic TNBC.
Additive Manufacturing of SiOC, SiC, and Si3N4 Ceramic 3D Microstructures
Authors: Merkininkaite Greta , Gailevicius Darius , Staisiunas Laurynas , Ezerskyte Egle , Vargalis Rokas , Malinauskas Mangirdas , Sakirzanovas Simas
Published: July 2023

Herein, the fabrication of hard ceramic SiOC 3D microstructures by precursor synthesis, laser lithography, and pyrolysis combination is proposed. Precursors are hybrid organosilicon materials prepared via sol–gel method using trimethoxymethylsilane and 3‐(trimethoxysilyl)propyl methacrylate, which has an acrylate functional group enabling laser photopolymerization process. Hard 3D ceramic structures (hardness up to ≈15 GPa, reduced elastic modulus ≈105 GPa) from soft organometallic derivatives are obtained after high‐temperature pyrolysis under nitrogen atmosphere. The advantage of the proposed method is the absence of shrinkage defects leading to a uniform repetitive decrease in the volume of printed microstructures. In contrast to slurry‐based printing technology, the proposed method is focused on homogeneous monolithic molecular resins resulting in visual smooth surfaces of prepared microstructures. Moreover, the printing resolution of the proposed method is substantially improved through the absence of predispersed ceramic microparticles in mixtures, which is a necessary element in a slurry‐based technology.
Bioinspired Intervertebral Disc with Multidirectional Stiffness Prepared via Multimaterial Additive Manufacturing
Authors: Song Guangsheng , Qian Zhihui , Liu Xiangyu , Chen Boya , Li Guanghui , Wang Zhenguo , Wang Kunyang , Zou Zhenmin , Galbusera Fabio , Domingos Marco , Ren Lei , Wilke Hans‐Joachim , Ren Luquan
Published: July 2023

Degenerative disc disease (DDD) has become a significant public health issue worldwide. This can result in loss of spinal function affecting patient health and quality of life. Artificial total disc replacement (A‐TDR) is an effective approach for treating symptomatic DDD that compensates for lost functionality and helps patients perform daily activities. However, because current A‐TDR devices lack the unique structure and material characteristics of natural intervertebral discs (IVDs), they fail to replicate the multidirectional stiffness needed to match physiological motions and characterize anisotropic behavior. It is still unclear how the multidirectional stiffness of the disc is affected by structural parameters and material characteristics. Herein, a bioinspired intervertebral disc (BIVD‐L) based on a representative human lumbar segment is developed. The proposed BIVD‐L reproduces the multidirectional stiffness needed for the most common physiological kinematic behaviors. The results demonstrate that the multidirectional stiffness of the BIVD‐L can be regulated by structural and material parameters. The results of this research deepen knowledge of the biomechanical behavior of the human lumbar disc and may provide new inspirations for the design and fabrication of A‐TDR devices for both engineering and functional applications.
Unleashing the Potential of Sodium‐Ion Batteries: Current State and Future Directions for Sustainable Energy Storage
Authors: Singh Aditya Narayan , Islam Mobinul , Meena Abhishek , Faizan Muhammad , Han Daseul , Bathula Chinna , Hajibabaei Amir , Anand Rohit , Nam Kyung‐Wan
Published: July 2023

Rechargeable sodium‐ion batteries (SIBs) are emerging as a viable alternative to lithium‐ion battery (LIB) technology, as their raw materials are economical, geographically abundant (unlike lithium), and less toxic. The matured LIB technology contributes significantly to digital civilization, from mobile electronic devices to zero electric‐vehicle emissions. However, with the increasing reliance on renewable energy sources and the anticipated integration of high‐energy‐density batteries into the grid, concerns have arisen regarding the sustainability of lithium due to its limited availability and consequent price escalations. In this context, SIBs have gained attention as a potential energy storage alternative, benefiting from the abundance of sodium and sharing electrochemical characteristics similar to LIBs. Furthermore, high‐entropy chemistry has emerged as a new paradigm, promising to enhance energy density and accelerate advancements in battery technology to meet the growing energy demands. This review uncovers the fundamentals, current progress, and the views on the future of SIB technologies, with a discussion focused on the design of novel materials. The crucial factors, such as morphology, crystal defects, and doping, that can tune electrochemistry, which should inspire young researchers in battery technology to identify and work on challenging research problems, are also reviewed.
Polyglycerol‐Based Biomedical Matrix for Immunomagnetic Circulating Tumor Cell Isolation and Their Expansion into Tumor Spheroids for Drug Screening
Authors: Tang Peng , Thongrom Boonya , Arora Smriti , Haag Rainer
Published: July 2023

Circulating tumor cells (CTCs) are established as distinct cancer biomarkers for diagnosis, as preclinical models, and therapeutic targets. Their use as preclinical models is limited owing to low purity after isolation and the lack of effective techniques to create 3D cultures that accurately mimic in vivo conditions. Herein, a two‐component system for detecting, isolating, and expanding CTCs to generate multicellular tumor spheroids that mimic the physiology and microenvironment of the diseased organ is proposed. First, an antifouling biointerface on magnetic beads is fabricated by adding a bioinert polymer layer and conjugation of biospecific ligands to isolate cancer cells, dramatically enhancing the selectivity and purity of the isolated cancer cells. Next, the isolated cells are encapsulated into self‐degradable hydrogels synthesized using a thiol‐click approach. The hydrogels are mechanochemically tuned to enable tumor spheroid growth to a size greater than 300 µm and to further release the grown spheroids while retaining their tumor‐like characteristics. In addition, drug treatment highlights the need for 3D culture environments rather than conventional 2D culture. The designed biomedical matrix shows potential as a universal method to ensure mimicry of in vivo tumor characteristics in individual patients and to improve the predictability of preclinical screening of personalized therapeutics.
A Flexible Tough Hydrovoltaic Coating for Wearable Sensing Electronics
Authors: Li Lianhui , Zheng Zhuo , Ge Changlei , Wang Yongfeng , Dai Hao , Li Lili , Wang Shuqi , Gao Qiang , Liu Mengyuan , Sun Fuqin , Zhang Ting
Published: July 2023

The lack of a strong binding mechanism between nanomaterials severely restricts the advantages of the evaporation‐driven hydrovoltaic effect in wearable sensing electronics. It is a challenging task to observably improve the mechanical toughness and flexibility of hydrovoltaic devices to match the wearable demand without abandoning the nanostructures and surface function. Here, a flexible tough polyacrylonitrile/alumina (PAN/Al2O3) hydrovoltaic coating with both good electricity generation (open‐circuit voltage, Voc ≈ 3.18 V) and sensitive ion sensing (2285 V M−1 for NaCl solutions in 10−4 to 10−3 m) capabilities is developed. The porous nanostructure composed of Al2O3 nanoparticles is firmly locked by the strong binding effect of PAN, giving a critical binding force 4 times that of Al2O3 film to easily deal with 9.92 m s−1 strong water‐flow impact. Finally, skin‐tight and non‐contact device structures are proposed to achieve wearable multifunctional self‐powered sensing directly using sweat. The flexible tough PAN/Al2O3 hydrovoltaic coating breaks through the mechanical brittleness limitation and broadens the applications of the evaporation‐induced hydrovoltaic effect in self‐powered wearable sensing electronics.
Unlocking High‐Performance Ammonium‐Ion Batteries: Activation of In‐Layer Channels for Enhanced Ion Storage and Migration
Authors: Zhang Xiangyong , Wei Hua , Ren Baohui , Jiang Jingjing , Qu Guangmeng , Yang Jinlong , Chen Guangming , Li Hongfei , Zhi Chunyi , Liu Zhuoxin
Published: July 2023

Ammonium‐ion batteries, leveraging non‐metallic ammonium ions, have arisen as a promising electrochemical energy storage system; however, their advancement has been hindered by the scarcity of high‐performance ammonium‐ion storage materials. In this study, an electrochemical phase transformation approach is proposed for the in situ synthesis of layered VOPO4·2H2O (E‐VOPO) with predominant growth on the (200) plane, corresponding to the tetragonal channels on the (001) layers. The findings reveal that these tetragonal in‐layer channels not only furnish NH4+ storage sites but also enhance transfer kinetics by providing rapid cross‐layer migration pathways. This crucial aspect has been largely overlooked in previous studies. The E‐VOPO electrode exhibits exceptional ammonium‐ion storage performance, including significantly increased specific capacity, enhanced rate capability, and robust cycling stability. The resulting full cell can be stably operated for 12 500 charge–discharge cycles at 2 A g−1 for over 70 days. The proposed approach offers a new strategy for meticulously engineering electrode materials with facilitated ion storage and migration, thereby paving the way for developing more efficient and sustainable energy storage systems.
Completely Activated and Phase‐Transformed KFeMnHCF for Zn/K Hybrid Batteries with 14 500 Cycles by an OH‐Rich Hydrogel Electrolyte
Authors: Li Chuan , Li Qing , Wu Zhuoxi , Wang Yiqiao , Zhang Rong , Cui Huilin , Hou Yue , Liu Jiahua , Huang Zhaodong , Zhi Chunyi
Published: July 2023

Metal hexacyanoferrates are recognized as superior cathode materials for zinc and zinc hybrid batteries, particularly the Prussian blue analog (PBA). However, PBA development is hindered by several limitations, including small capacities (<70 mAh g−1) and short lifespans (<1000 cycles). These limitations generally arise due to incomplete activation of redox sites and structure collapse during intercalation/deintercalation of metal ions in PBAs. According to this study, the adoption of a hydroxyl‐rich (OH‐rich) hydrogel electrolyte with extended electrochemical stability windows (ESWs) can effectively activate the redox site of low‐spin Fe of the KxFeyMn1−y[Fe(CN)6]w·zH2O (KFeMnHCF) cathode while tuning its structure. Additionally, the strong adhesion of the hydrogel electrolyte inhibits KFeMnHCF particles from falling off the cathode and dissolving. The easy desolvation of metal ions in the developed OH‐rich hydrogel electrolytes can lead to a fast and reversible intercalation/deintercalation of metal ions in the PBA cathode. As a result, the Zn||KFeMnHCF hybrid batteries achieve the unprecedented characteristics of 14 500 cycles, a 1.7 V discharge plateau, and a 100 mAh g−1 discharge capacity. The results of this study provide a new understanding of the development of zinc hybrid batteries with PBA cathode materials and present a promising new electrolyte material for this application.
Unlocking the Stability of Reduced Graphene Oxide Nanosheets in Biological Media via Use of Sodium Ascorbate
Authors: Amato Francesco , Perini Giordano , Friggeri Ginevra , Augello Alberto , Motta Alessandro , Giaccari Leonardo , Zanoni Robertino , De Spirito Marco , Palmieri Valentina , Marrani Andrea Giacomo , Papi Massimiliano
Published: July 2023

Graphene oxide and reduced graphene oxide (RGO) are carbon bidimensional nanomaterials largely exploited in biomedicine. Their unique interactions with eukaryotic and prokaryotic cells are used to obtain precise intracellular delivery, to create device coatings, and to design theranostic materials for both therapeutic and imaging applications, mainly in the cancer research field. It is known, however, that the hydrophobic behavior of RGO limits its stability in biological media. Here, the employment of sodium ascorbate (NaA) as a reducing agent for the preparation of RGO to provide a nanomaterial with remarkable suitability for applications in cell culture media is proposed. It is demonstrated via a combined experimental and theoretical approach that NaA is able to yield a peculiar RGO derivative, exerting a twofold effect, that is, C sp2 network restoration upon epoxide reduction and RGO edge functionalization via H‐bonding, lending RGO a so far unexampled dispersibility in aqueous‐based media. The kinetic stability of the bidimensional layers of RGO obtained from NaA is demonstrated together with its superior biocompatibility for drug delivery, unlocking outstanding potentialities for biological applications.
Facile and Scalable Fabrication of Hydrophilic/Hydrophobic Janus Fabric for Personal Sweat Monitoring and Perspiration Management
Authors: Liu Yingcun , Li Juan , Xu Duo , Su Ziyi , Ge Can , Chen Ze , Xu Weilin , Liu Keshuai
Published: July 2023

Quantifiable monitoring and management of sweat volume have attracted considerable attention because of their role in assessing physiological health and preventing dehydration. However, defective sweat monitoring and poor moisture management limit the performance of most smart textiles under moderate/profuse perspiration scenarios. In this study, a large‐scale fabrication technology is used, including braiding and weaving, to prepare a hydrophilic/hydrophobic Janus fabric (HHJF) with good directional water delivery and sweat‐volume monitoring capabilities. The HHJF consists of polytetrafluoroethylene (PTFE) braided yarns (lower layer) and Tencel braided yarns (upper layer), which comprise a conductive yarn as the core and PTFE/Tencel yarns as the sheath with enhanced water absorption capacity. The unique functional structure design achieves the enhanced unidirectional water transport and high sweat‐sensing response for the HHJF under perspiration conditions. The optimized HHJF facilitates spontaneous droplet penetration from the hydrophobic layer to the hydrophilic layer, while enabling the real‐time detection of sweat volume of up to 2000 mL m−2with excellent durability for over 1000 cycle tests. Thus, the exceptional perspiration management and monitoring capabilities of HHJF are expected to promote the development of practical smart textiles that enable real‐time monitoring of perspiration dynamics.
Highly Sensitive Broadband Bolometric Photodetectors based on 2D PdSe2 Thin Film
Authors: Zhang Rui , Yang Zhuojun , Liu Liwen , Lin Jie , Wen Shaofeng , Meng You , Yin Yi , Lan Changyong , Li Chun , Liu Yong , Ho Johnny C.
Published: July 2023

PdSe2, a semiconductor with a narrow band gap, shows tremendous promise for high‐performance broadband photodetectors. In this study, highly sensitive, broadband, and flexible PdSe2 thin film photodetectors on polyimide (PI) substrates that can detect light from the UV (365 nm) to infrared (2200 nm) regions are reported. The devices with thick (21 nm) PdSe2 films show decent performance with a decent responsivity of 37.6 mA W−1 at 1550 nm and a fast response time. For the thick PdSe2 film, the bolometric effect dominates the positive photoresponse across all wavelength regions, whereas for the thin PdSe2 film (4.5–13 nm), which shows both positive and negative photoresponses, it dominates in the infrared region. The negative photoresponse of thin PdSe2 in the UV to the VIS region is attributed to the charge transfer‐related adsorption‐desorption of gas molecules. Detailed investigations revealed that the temperature coefficient of resistance (TCR) value is closely correlated to film thickness, with the thinnest film exhibiting the highest absolute TCR value of up to 4.3% °C−1. The value is much larger than that of metals, most 2D materials, amorphous Si, and even commercial VOx. These findings suggest that PdSe2 films have a promising future in broadband photodetectors.
Modular Photochemical Flow Synthesis of Structurally Diverse Benzyne and Triazine Precursors
Authors: García‐Lacuna Jorge , Baumann Marcus
Published: July 2023

Benzyne and related arynes are classical high‐energy species with a rich history of widespread applications in synthesis. However, despite several synthetic routes being available to generate arynes and their precursors, none represents an ideal entry to benzyne chemistry in view of safety, scalability, and sustainability. Here we report a new photochemical flow process allowing for the generation of benzyne precursors in high yields, and throughput, with easy isolation of multigram quantities of products. This process leverages a catalyst‐free photochemical rearrangement via a photoexcited nitro arene which involves a cyclic hydroxylamine intermediate that has been fully characterized. The resulting precursors were converted to benzynes via a second photochemical flow process generating heterocyclic targets upon trapping with azide and sydnone partners. Remarkably, when reacting the benzyne precursors with secondary amines, a wide range of aryl triazines is obtained in good yields via a third photo‐flow transformation. This represents a modular approach to synthesize these species, that avoids the use of potentially explosive diazonium salts. Ultimately, three photochemical flow processes using a single high‐power LED light source (365 nm, adjustable in‐put power) are presented with manifest benefits compared to batch processing. Moreover, the functionalization of a pendent carboxyl group to form sets of biologically relevant aryl triazine‐based amides highlights further applications of these unique and industrially relevant triazine entities.
Male‐Biased Gut Microbiome and Metabolites Aggravate Colorectal Cancer Development
Authors: Wang Ling , Tu Yi‐Xuan , Chen Lu , Zhang Yuan , Pan Xue‐Ling , Yang Shu‐Qiao , Zhang Shuai‐Jie , Li Sheng‐Hui , Yu Ke‐Chun , Song Shuo , Xu Hong‐Li , Yin Zhu‐Cheng , Yue Jun‐Qiu , Ni Qian‐Lin , Tang Tang , Zhang Jiu‐Liang , Guo Min , Zhang Shuai , Yao Fan , Liang Xin‐Jun , Chen Zhen‐Xia
Published: July 2023

Men demonstrate higher incidence and mortality rates of colorectal cancer (CRC) than women. This study aims to explain the potential causes of such sexual dimorphism in CRC from the perspective of sex‐biased gut microbiota and metabolites. The results show that sexual dimorphism in colorectal tumorigenesis is observed in both ApcMin/+ mice and azoxymethane (AOM)/dextran sulfate sodium (DSS)‐treated mice with male mice have significantly larger and more tumors, accompanied by more impaired gut barrier function. Moreover, pseudo‐germ mice receiving fecal samples from male mice or patients show more severe intestinal barrier damage and higher level of inflammation. A significant change in gut microbiota composition is found with increased pathogenic bacteria Akkermansia muciniphila and deplets probiotic Parabacteroides goldsteinii in both male mice and pseudo‐germ mice receiving fecal sample from male mice. Sex‐biased gut metabolites in pseudo‐germ mice receiving fecal sample from CRC patients or CRC mice contribute to sex dimorphism in CRC tumorigenesis through glycerophospholipids metabolism pathway. Sexual dimorphism in tumorigenesis of CRC mouse models. In conclusion, the sex‐biased gut microbiome and metabolites contribute to sexual dimorphism in CRC. Modulating sex‐biased gut microbiota and metabolites could be a potential sex‐targeting therapeutic strategy of CRC.
Rescuing Nucleus Pulposus Cells From Senescence via Dual‐Functional Greigite Nanozyme to Alleviate Intervertebral Disc Degeneration
Authors: Shi Yu , Li Hanwen , Chu Dongchuan , Lin Wenzheng , Wang Xinglong , Wu Yin , Li Ke , Wang Huihui , Li Dandan , Xu Zhuobin , Gao Lizeng , Li Bin , Chen Hao
Published: July 2023

High levels of reactive oxygen species (ROS) lead to progressive deterioration of mitochondrial function, resulting in tissue degeneration. In this study, ROS accumulation induced nucleus pulposus cells (NPCs) senescence is observed in degenerative human and rat intervertebral disc, suggesting senescence as a new therapeutic target to reverse intervertebral disc degeneration (IVDD). By targeting this, dual‐functional greigite nanozyme is successfully constructed, which shows the ability to release abundant polysulfides and presents strong superoxide dismutase and catalase activities, both of which function to scavenge ROS and maintain the tissue at physical redox level. By significantly lowering the ROS level, greigite nanozyme rescues damaged mitochondrial function in IVDD models both in vitro and in vivo, rescues NPCs from senescence and alleviated the inflammatory response. Furthermore, RNA‐sequencing reveals ROS‐p53‐p21 axis is responsible for cellular senescence‐induced IVDD. Activation of the axis abolishes greigite nanozyme rescued NPCs senescence phenotype, as well as the alleviated inflammatory response to greigite nanozyme, which confirms the role of ROS‐p53‐p21 axis in greigite nanozyme's function to reverse IVDD. In conclusion, this study demonstrates that ROS‐induced NPCs senescence leads to IVDD and the dual‐functional greigite nanozyme holds strong potential to reverse this process, providing a novel strategy for IVDD management.
Multi‐Omics Analysis Reveals Translational Landscapes and Regulations in Mouse and Human Oocyte Aging
Authors: Huang Jiana , Chen Peigen , Jia Lei , Li Tingting , Yang Xing , Liang Qiqi , Zeng Yanyan , Liu Jiawen , Wu Taibao , Hu Wenqi , Kee Kehkooi , Zeng Haitao , Liang Xiaoyan , Zhou Chuanchuan
Published: July 2023

Abnormal resumption of meiosis and decreased oocyte quality are hallmarks of maternal aging. Transcriptional silencing makes translational control an urgent task during meiosis resumption in maternal aging. However, insights into aging‐related translational characteristics and underlying mechanisms are limited. Here, using multi‐omics analysis of oocytes, it is found that translatomics during aging is related to changes in the proteome and reveals decreased translational efficiency with aging phenotypes in mouse oocytes. Translational efficiency decrease is associated with the N6‐methyladenosine (m6A) modification of transcripts. It is further clarified that m6A reader YTHDF3 is significantly decreased in aged oocytes, inhibiting oocyte meiotic maturation. YTHDF3 intervention perturbs the translatome of oocytes and suppress the translational efficiency of aging‐associated maternal factors, such as Hells, to affect the oocyte maturation. Moreover, the translational landscape is profiled in human oocyte aging, and the similar translational changes of epigenetic modifications regulators between human and mice oocyte aging are observed. In particular, due to the translational silence of YTHDF3 in human oocytes, translation activity is not associated with m6A modification, but alternative splicing factor SRSF6. Together, the findings profile the specific translational landscapes during oocyte aging in mice and humans, and uncover non‐conservative regulators on translation control in meiosis resumption and maternal aging.
Liver‐Inspired Polyetherketoneketone Scaffolds Simulate Regenerative Signals and Mobilize Anti‐Inflammatory Reserves to Reprogram Macrophage Metabolism for Boosted Osteoporotic Osseointegration
Authors: Gu Hao , Zhu Yuhui , Yang Jiawei , Jiang Ruixue , Deng Yuwei , Li Anshuo , Fang Yingjing , Wu Qianju , Tu Honghuan , Chang Haishuang , Wen Jin , Jiang Xinquan
Published: July 2023

Tissue regeneration is regulated by morphological clues of implants in bone defect repair. Engineered morphology can boost regenerative biocascades that conquer challenges such as material bioinertness and pathological microenvironments. Herein, a correlation between the liver extracellular skeleton morphology and the regenerative signaling, namely hepatocyte growth factor receptor (MET), is found to explain the mystery of rapid liver regeneration. Inspired by this unique structure, a biomimetic morphology is prepared on polyetherketoneketone (PEKK) via femtosecond laser etching and sulfonation. The morphology reproduces MET signaling in macrophages, causing positive immunoregulation and optimized osteogenesis. Moreover, the morphological clue activates an anti‐inflammatory reserve (arginase‐2) to translocate retrogradely from mitochondria to the cytoplasm due to the difference in spatial binding of heat shock protein 70. This translocation enhances oxidative respiration and complex II activity, reprogramming the metabolism of energy and arginine. The importance of MET signaling and arginase‐2 in the anti‐inflammatory repair of biomimetic scaffolds is also verified via chemical inhibition and gene knockout. Altogether, this study not only provides a novel biomimetic scaffold for osteoporotic bone defect repair that can simulate regenerative signals, but also reveals the significance and feasibility of strategies to mobilize anti‐inflammatory reserves in bone regeneration.
Record‐High Ultrasound‐Sensitive NO Nanogenerators for Cascade Tumor Pyroptosis and Immunotherapy
Authors: Bao Yuheng , Ge Yanni , Wu Mengjie , Mao Zhengwei , Ye Juan , Tong Weijun
Published: July 2023

Pyroptosis is a pro‐inflammatory cell death that is associated with innate immunity promotion against tumors. Excess nitric oxide (NO)‐triggered nitric stress has potential to induce pyroptosis, but the precise delivery of NO is challenging. Ultrasound (US)‐responsive NO production has dominant priority due to its deep penetration, low side effects, noninvasion, and local activation manner. In this work, US‐sensitive NO donor N‐methyl‐N‐nitrosoaniline (NMA) with thermodynamically favorable structure is selected and loaded into hyaluronic acid (HA)‐modified hollow manganese dioxide nanoparticles (hMnO2 NPs) to fabricate hMnO2@HA@NMA (MHN) nanogenerators (NGs). The obtained NGs have a record‐high NO generation efficiency under US irradiation and can release Mn2+ after targeting the tumor sites. Later on, cascade tumor pyroptosis and cyclic GMP‐AMP synthase‐stimulator of interferon genes (cGAS‐STING)‐based immunotherapy is achieved and tumor growth is effectively inhibited.
Tissue‐Engineered Disease Modeling of Lymphangioleiomyomatosis Exposes a Therapeutic Vulnerability to HDAC Inhibition
Authors: Pietrobon Adam , Yockell‐Lelièvre Julien , Melong Nicole , Smith Laura J. , Delaney Sean P. , Azzam Nadine , Xue Chang , Merwin Nishanth , Lian Eric , Camacho‐Magallanes Alberto , Doré Carole , Musso Gabriel , Julian Lisa M. , Kristof Arnold S. , Tam Roger Y. , Berman Jason N. , Shoichet Molly S. , Stanford William L.
Published: July 2023

Lymphangioleiomyomatosis (LAM) is a rare disease involving cystic lung destruction by invasive LAM cells. These cells harbor loss‐of‐function mutations in TSC2, conferring hyperactive mTORC1 signaling. Here, tissue engineering tools are employed to model LAM and identify new therapeutic candidates. Biomimetic hydrogel culture of LAM cells is found to recapitulate the molecular and phenotypic characteristics of human disease more faithfully than culture on plastic. A 3D drug screen is conducted, identifying histone deacetylase (HDAC) inhibitors as anti‐invasive agents that are also selectively cytotoxic toward TSC2−/− cells. The anti‐invasive effects of HDAC inhibitors are independent of genotype, while selective cell death is mTORC1‐dependent and mediated by apoptosis. Genotype‐selective cytotoxicity is seen exclusively in hydrogel culture due to potentiated differential mTORC1 signaling, a feature that is abrogated in cell culture on plastic. Importantly, HDAC inhibitors block invasion and selectively eradicate LAM cells in vivo in zebrafish xenografts. These findings demonstrate that tissue‐engineered disease modeling exposes a physiologically relevant therapeutic vulnerability that would be otherwise missed by conventional culture on plastic. This work substantiates HDAC inhibitors as possible therapeutic candidates for the treatment of patients with LAM and requires further study.
Early life predictors of body composition trajectories from adolescence to mid‐adulthood
Authors: Poveda Natalia E. , Adair Linda S. , Martorell Reynaldo. , Patel Shivani A. , Ramirez‐Zea Manuel , Stein Aryeh D.
Published: July 2023

Objectives

Guatemala has experienced rapid increases in adult obesity. We characterized body composition trajectories from adolescence to mid‐adulthood and determined the predictive role of parental characteristics, early life factors, and a nutrition intervention.

Methods

One thousand three hundred and sixty‐four individuals who participated as children in a nutrition trial (1969–1977) were followed prospectively. Body composition characterized as body mass index (BMI), fat mass index (FMI), and fat‐free mass indices (FFMI), was available at four ages between 10 and 55 years. We applied latent class growth analysis to derive sex‐specific body composition trajectories. We estimated associations between parental (age, height, schooling) and self‐characteristics (birth order, socioeconomic status, schooling, and exposure to a nutrition supplement) with body composition trajectories.

Results

In women, we identified two latent classes of FMI (low: 79.6%; high: 20.4%) and BMI (low: 73.0%; high: 27.0%), and three of FFMI (low: 20.2%; middle: 55.9%; high: 23.9%). In men, we identified two latent classes of FMI (low: 79.6%; high: 20.4%) and FFMI (low: 62.4%; high: 37.6%), and three of BMI (low: 43.1%; middle: 46.9%; high: 10.0%). Among women, self's schooling attainment inversely predicted FMI (OR [being in a high latent class]: 0.91, 95% CI: 0.85, 0.97), and maternal schooling positively predicted FFMI (OR: 1.16, 95% CI: 0.97, 1.39). Among men, maternal schooling, paternal age, and self's schooling attainment positively predicted FMI. Maternal schooling positively predicted FFMI, whereas maternal age and paternal schooling were inverse predictors. The nutrition intervention did not predict body composition class membership.

Conclusions

Parents' age and schooling, and self's schooling attainment are small but significant predictors of adult body composition trajectories.
A pediatric case of multiple trauma with impending cardiac arrest due to hemorrhagic shock successfully treated with resuscitative thoracotomy: A case report
Authors: Hojo Kento , Abe Tomohiro , Saito Katsutoshi , Sasaki Akira , Ochiai Hidenobu
Published: July 2023

Background

The effectiveness of resuscitative thoracotomy (RT) in pediatric patients with multiple trauma is limited. We present a pediatric case of multiple trauma successfully treated with RT.

Case Presentation

A 9‐year‐old boy was injured after falling down stairs. On arrival, his blood pressure was unmeasurable, and the carotid artery pulse was barely palpable. Sonographic assessment indicated intra‐abdominal hemorrhage. RT and aortic cross‐clamping were performed, and he received a blood transfusion, after which his circulatory status recovered. Laparotomy indicated an inferior mesenteric vein injury that was sutured. Ten hours after arrival, an acute epidural hematoma was observed and treated with an emergency craniotomy. The patient's condition remained stable and he was discharged on the 101st day.

Conclusion

RT may save the life of patients with multiple trauma, even pediatric patients, if performed in a timely manner, based on the diagnosis of hemorrhagic shock, along with rapid transfusion and hemostatic intervention.
What Can a GNOME Do? Search Targets for the Global Network of Optical Magnetometers for Exotic Physics Searches
Authors: Afach Samer , Aybas Tumturk Deniz , Bekker Hendrik , Buchler Ben C. , Budker Dmitry , Cervantes Kaleb , Derevianko Andrei , Eby Joshua , Figueroa Nataniel L. , Folman Ron , Gavilán‐Martín Daniel , Givon Menachem , Grujić Zoran D. , Guo Hong , Hamilton Paul , Hedges Morgan P. , Jackson Kimball Derek F. , Khamis Sami , Kim Dongok , Klinger Emmanuel , Kryemadhi Abaz , Liu Xiyu , Łukasiewicz Grzegorz , Masia‐Roig Hector , Padniuk Mikhail , Palm Christopher A. , Park Sun Yool , Pearson Heather R. , Peng Xiang , Pospelov Maxim , Pustelny Szymon , Rosenzweig Yossi , Ruimi Ophir M. , Scholtes Theo , Segura Perrin C. , Semertzidis Yannis K. , Shin Yun Chang , Smiga Joseph A. , Stadnik Yevgeny V. , Stalnaker Jason E. , Sulai Ibrahim A. , Tandon Dhruv , Vu Kenneth , Weis Antoine , Wickenbrock Arne , Wilson Tatum Z. , Wu Teng , Xiao Wei , Yang Yucheng , Yu Dongrui , Yu Felix , Zhang Jianwei , Zhao Yixin
Published: July 2023

Numerous observations suggest that there exist undiscovered beyond‐the‐standard‐model particles and fields. Because of their unknown nature, these exotic particles and fields could interact with standard model particles in many different ways and assume a variety of possible configurations. Here, an overview of the global network of optical magnetometers for exotic physics searches (GNOME), the ongoing experimental program designed to test a wide range of exotic physics scenarios, is presented. The GNOME experiment utilizes a worldwide network of shielded atomic magnetometers (and, more recently, comagnetometers) to search for spatially and temporally correlated signals due to torques on atomic spins from exotic fields of astrophysical origin. The temporal characteristics of a variety of possible signals currently under investigation such as those from topological defect dark matter (axion‐like particle domain walls), axion‐like particle stars, solitons of complex‐valued scalar fields (Q‐balls), stochastic fluctuations of bosonic dark matter fields, a solar axion‐like particle halo, and bursts of ultralight bosonic fields produced by cataclysmic astrophysical events such as binary black hole mergers are surveyed.
p‐Block Bismuth Nanoclusters Sites Activated by Atomically Dispersed Bismuth for Tandem Boosting Electrocatalytic Hydrogen Peroxide Production
Authors: Zhu Pan , Feng Wuyi , Zhao Di , Song Pengyu , Li Mengwei , Tan Xin , Liu Ting , Liu Shoujie , Zhu Wei , Zhuang Zhongbin , Zhang Jiatao , Chen Chen
Published: July 2023

Constructing electrocatalysts with p‐block elements is generally considered rather challenging owing to their closed d shells. Here for the first time, we present a p‐block‐element bismuth‐based (Bi‐based) catalyst with the co‐existence of single‐atomic Bi sites coordinated with oxygen (O) and sulfur (S) atoms and Bi nanoclusters (Biclu) (collectively denoted as BiOSSA/Biclu) for the highly selective oxygen reduction reaction (ORR) into hydrogen peroxide (H2O2). As a result, BiOSSA/Biclu gives a high H2O2 selectivity of 95 % in rotating ring‐disk electrode, and a large current density of 36 mA cm−2 at 0.15 V vs. RHE, a considerable H2O2 yield of 11.5 mg cm−2 h−1 with high H2O2 Faraday efficiency of ~90 % at 0.3 V vs. RHE and a long‐term durability of ~22 h in H‐cell test. Interestingly, the experimental data on site poisoning and theoretical calculations both revealed that, for BiOSSA/Biclu, the catalytic active sites are on the Bi clusters, which are further activated by the atomically dispersed Bi coordinated with O and S atoms. This work demonstrates a new synergistic tandem strategy for advanced p‐block‐element Bi catalysts featuring atomic‐level catalytic sites, and the great potential of rational material design for constructing highly active electrocatalysts based on p‐block metals.
General Design Concepts for CAPodes as Ionologic Devices
Authors: Zhou Hanfeng , Li Panlong , Zhang En , Kunigkeit Jonas , Zhou Xiongjun , Haase Katherina , Rita Ortega Vega Maria , Wang Shuwen , Xu Xiaosa , Grothe Julia , Mannsfeld Stefan C. B. , Brunner Eike , Kaneko Katsumi , Kaskel Stefan
Published: July 2023

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy‐efficient and nature‐inspired next‐generation computing devices. Here, we disclose the generalized concept for bias‐direction‐adjustable n‐ and p‐CAPodes based on selective ion sieving. Controllable‐unidirectional ion flux is realized by blocking electrolyte ions from entering sub‐nanometer pores. The resulting CAPodes exhibit charge‐storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations (‘OR’, ‘AND’). This work demonstrates CAPodes as a generalized concept to achieve p‐n and n‐p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion‐based diodes in ionologic architectures.
Cleavage of Carbon Dioxide C=O Bond Promoted by Nickel‐Boron Cooperativity in a PBP‐Ni Complex
Authors: Álvarez‐Rodríguez Lucía , Ríos Pablo , Laglera‐Gándara Carlos J. , Jurado Andrea , Fernández‐de‐Córdova Francisco José , Gunnoe T. Brent , Rodríguez Amor
Published: July 2023

The synthesis and characterization of (tBuPBP)Ni(OAc) (5) by insertion of carbon dioxide into the Ni−C bond of (tBuPBP)NiMe (1) is presented. An unexpected CO2 cleavage process involving the formation of new B−O and Ni−CO bonds leads to the generation of a butterfly‐structured tetra‐nickel cluster (tBuPBOP)2Ni4(μ‐CO)2 (6). Mechanistic investigation of this reaction indicates a reductive scission of CO2 by O‐atom transfer to the boron atom via a cooperative nickel‐boron mechanism. The CO2 activation reaction produces a three‐coordinate (tBuP2BO)Ni‐acyl intermediate (A) that leads to a (tBuP2BO)−NiI complex (B) via a likely radical pathway. The NiI species is trapped by treatment with the radical trap (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) to give (tBuP2BO)NiII(η2‐TEMPO) (7). Additionally, 13C and 1H NMR spectroscopy analysis using 13C‐enriched CO2 provides information about the species involved in the CO2 activation process.
Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases
Authors: Lv Weiwei , Dai Yuyang , Guo Rui , Su Yuanting , Ruiz David A. , Liu Liu Leo , Tung Chen‐Ho , Kong Lingbing
Published: July 2023

This report unveils an advancement in the formation of a Lewis superacid (LSA) and an organic superbase by the geometrical deformation of an organoboron species towards a T‐shaped geometry. The boron dication [2]2+ supported by an amido diphosphine pincer ligand features both a large fluoride ion affinity (FIA>SbF5) and hydride ion affinity (HIA>B(C6F5)3), which qualifies it as both a hard and soft LSA. The unusual Lewis acidic properties of [2]2+ are further showcased by its ability to abstract hydride and fluoride from Et3SiH and AgSbF6 respectively, and effectively catalyze the hydrodefluorination, defluorination/arylation, as well as reduction of carbonyl compounds. One and two‐electron reduction of [2]2+ affords stable boron radical cation [2]⋅+ and borylene 2, respectively. The former species has an extremely high spin density of 0.798e at the boron atom, whereas the latter compound has been demonstrated to be a strong organic base (calcd. pKBH+ (MeCN)=47.4) by both theoretical and experimental assessment. Overall, these results demonstrate the strong ability of geometric constraining to empower the central boron atom.
Photosensitized [4+2]‐ and [2+2]‐Cycloaddition Reactions of N‐Sulfonylimines
Authors: Wang Wang , Brown M. Kevin
Published: July 2023

The synthesis of polycyclic compounds is of high interest due to the prevalence of these motifs in drugs and natural products. Herein, we report on the stereoselective construction of 3D bicyclic scaffolds and azetidine derivatives by modulation of N‐sulfonylimines to achieve either [4+2]‐ or [2+2]‐cycloaddition reactions. The utility of the method was established by further modulation of the product. Mechanistic studies are also included, which support reaction via Dexter energy transfer.
Synthesis of Cobalt‐Tin and ‐Lead Tetrylidynes—Reactivity Study of the Triple Bond
Authors: Auer Maximilian , Zwettler Kathrin , Eichele Klaus , Schubert Hartmut , Sindlinger Christian P. , Wesemann Lars
Published: July 2023

Tetrylidynes [TbbSn≡Co(PMe3)3] (1 a) and [TbbPb≡Co(PMe3)3] (2) (Tbb=2,6‐[CH(SiMe3)2]2‐4‐(t‐Bu)C6H2) are accessed for the first time via a substitution reaction between [Na(OEt2)][Co(PMe3)4] and [Li(thf)2][TbbEBr2] (E=Sn, Pb). Following an alternative procedure the stannylidyne [Ar*Sn≡Co(PMe3)3] (1 b) was synthesized by hydrogen atom abstraction using AIBN from the paramagnetic hydride complex [Ar*SnH=Co(PMe3)3] (4) (AIBN=azobis(isobutyronitrile)). The stannylidyne 1 a adds two equivalents of water to yield the dihydroxide [TbbSn(OH)2CoH2(PMe3)3] (5). In reaction of the stannylidyne 1 a with CO2 a product of a redox reaction [TbbSn(CO3)Co(CO)(PMe3)3] (6) was isolated. Protonation of the tetrylidynes occurs at the cobalt atom to give the metalla‐stanna vinyl cation [TbbSn=CoH(PMe3)3][BArF4] (7 a) [ArF=C6H3‐3,5‐(CF3)2]. The analogous germanium and tin cations [Ar*E=CoH(PMe3)3][BArF4] (E=Ge 9, Sn 7 b) (Ar*=C6H3(2,6‐Trip)2, Trip=2,4,6‐C6H2iPr3) were also obtained by oxidation of the paramagnetic complexes [Ar*EH=Co(PMe3)3] (E=Ge 3, Sn 4), which were synthesized by substitution of a PMe3 ligand of [Co(PMe3)4] by a hydridoylene (Ar*EH) unit.
Promoting Photocatalytic H2 Evolution through Retarded Charge Trapping and Recombination by Continuously Distributed Defects in Methylammonium Lead Iodide Perovskite
Authors: Yao Qing , Li Hui , Xue Jiawei , Jiang Shenlong , Zhang Qun , Bao Jun
Published: July 2023

Inspired by its great success in the photovoltaic field, methylammonium lead iodide perovskite (MAPbI3) has recently been actively explored as photocatalysts in H2 evolution reactions. However, the practical application of MAPbI3 photocatalysts remains hampered by the intrinsically fast trapping and recombination of photogenerated charges. Herein, we propose a novel strategy of regulating the distribution of defective areas to promote charge‐transfer dynamics of MAPbI3 photocatalysts. By deliberately designing and synthesizing the MAPbI3 photocatalysts featuring a unique continuation of defective areas, we demonstrate that such a feature enables retardation of charge trapping and recombination via lengthening the charge‐transfer distance. As an outcome, such MAPbI3 photocatalysts turn out to achieve an impressive photocatalytic H2 evolution rate as high as 0.64 mmol ⋅ g−1 ⋅ h−1, one order of magnitude higher than that of the conventional MAPbI3 photocatalysts. This work establishes a new paradigm for controlling charge‐transfer dynamics in photocatalysis.
Measuring and maintaining organ perfusion in a patient with Takayasu's arteritis undergoing cardiac surgery*
Authors: Dan K. , Takahashi K. , Lefor A. K.
Published: July 2023

Takayasu's arteritis is a rare vasculitis affecting the aorta and its branches. Disease progression can result in arterial stenosis and subsequent organ dysfunction. Estimating organ perfusion by measuring the peripheral blood pressure can be challenging because it may be altered by arterial stenosis. We report the case of a 61‐year‐old woman with Takayasu's arteritis with aortic and mitral regurgitation who presented for aortic valve replacement and mitral valvuloplasty. Peripheral arterial pressure was considered a less reliable surrogate for organ perfusion because the patient had diminished blood flow in both the lower and upper extremities. In addition to the bilateral radial arterial pressure, the blood pressure in the ascending aorta was monitored to estimate the patient's organ perfusion pressure during cardiopulmonary bypass. The initial target blood pressure was determined based on the pre‐operative baseline and modified by measurement of the aortic pressure. Cerebral oximetry using near‐infrared spectroscopy and mixed venous saturation was monitored to estimate oxygen supply‐demand balance, which helped evaluate cerebral perfusion and determine the transfusion threshold. The entire procedure was uneventful, and no organ dysfunction was observed postoperatively.
A novel psychotherapy for low‐needs youth on the autism spectrum with emotional regulation challenges
Authors: McGuinty Everett , Carlson Alain , Nelson John , Scott Cailin
Published: July 2023

The externalising of problems and implementation of interactive metaphors may improve emotional regulation of those clients presenting with autism spectrum disorder. This paper describes a new eight‐session treatment protocol in terms of using preferred interest metaphors with the strengths and strategies of client and family across the home, school, and community settings of client life. This exploratory treatment intervention uses externalising metaphors therapy as a brief treatment modality, addressing emotional regulation concerns of youth on the autism spectrum. The treatment model concretises affective states and creatively leverages visual strengths to improve this common presenting concern for this population. A case study on family therapy is presented with the protocol overview and illustrations. Further research is needed to address the testable hypotheses and identify the mediators of change resulting from this current model. This research would help to establish best practices in a clinical population for which there is no broadly accepted treatment paradigm. Mr. McGuinty has indicated that there are no conflicts of interest in this manuscript.
New palladium (II) and platinum (II) complexes with coumarin based O,N,N pincer: Synthesis, structure elucidation, BSA protein binding studies, and anticancer activity
Authors: Bera Biswajit , Mondal Sanchaita , Mandal Subrata , Das Saha Krishna , Mondal Tapan K.
Published: July 2023

New Pd (II) and Pt (II) complexes (C1/C2) with a O,N,N donor pincer ligand, 4‐hydroxy‐3‐((E)‐1‐(((Z)‐phenyl (pyridin‐2‐yl)methylene)hydrazono)ethyl)‐2H‐chromen‐2‐one (HL) were synthesized and methodically characterized by several spectroscopic and XRD techniques. Absorption and fluorescence techniques were used to assess the mechanism of interaction of the complexes with bovine serum albumin protein. MTT assay was executed to investigate the antiproliferative activity of the complexes with several cancer cell lines (MCF‐7, HCT116, A549, and HepG2) along with a normal cell line (PBMC). Both C1 and C2 showed better antiproliferative activity with HepG2 cell line (IC50 value of 15.3 and 5.1 μM, respectively). A cytotoxicity study was performed, and complex C2 exhibited a better antiproliferative activity as compared to C1. The morphological changes were also examined by staining methods, and fragmented DNA unveiled that the cell death took place through apoptosis.