bluuebunny/crossref_metadata_2025 huggingface dataset:
Bioinspired Self‐Propelled Micromotors with Improved Transport Efficiency in the Subsurface Environment for Soil Decontamination
Authors: Wang Ke , Ma Enhui , Cui Haohao , Hu Zhenqi , Wang Hong
Published: September 2023

Limited transport efficiency of remediation reagents in the subsurface environment is regarded as a key challenge facing in situ soil remediation. Herein, taking advantage of natural hollow fibers, tubular micromotors capable of autonomous movement to facilitate the migration of remediation reagents and achieve efficient degradation of organic pollutants in soil are developed. Widely‐used nanocatalysts in soil treatment, Fe3O4 and MnO2, are integrated on the fiber surface to enable self‐propulsion via recoil of micro/nanobubbles and activation of hydrogen peroxide (H2O2) and peroxymonosulfate. Featured with tiny sizes and wireless motion, the micromotors navigate in microchannels and microenvironments with complex terrain. The dependence of transport efficiency in heterogeneous and porous environments on H2O2 concentration is revealed based on column studies. With fluorescent g‐C3N4 decorated on the surface to enable visualization, the horizontal/vertical migration of prepared micromotors in soil is proved to be greatly enhanced due to self‐propulsion and bubble generation. The micromotors exhibit excellent catalytic performances toward the degradation of a wide spectrum of water‐soluble antibiotics and water‐insoluble polycyclic aromatic hydrocarbons. Overall, the bioinspired micromotors unveil a new strategy to improve the transport of remediation reagents in the subsurface environment, which holds great potential for efficient in situ soil treatment.
Construction of 2D/3D/2D‐Structured Perovskite for High‐Performance and Stable Solar Cells
Authors: Zhang Yiqing , Zhang Yingzhu , Niu Benfang , Huang Yanchun , Wu Haotian , Fu Weifei , Chen Hongzheng
Published: September 2023

2D/3D‐structured perovskites are promising for high‐performance and stable solar cells due to the passivation ability and hydrophobic character of the large organic cations. However, most of the 2D/3D‐structured perovskites prepared by adding ammonium halides into the precursors or depositing ammonium halides on top of a 3D perovskite film ignore the buried interface which is crucial for the device efficiency and stability. Here, 2D/3D/2D‐structured perovskite films with optimized buried interface are constructed by depositing phenethylammonium bromide (PEABr) on top and 2D perovskite PEA2FA2Pb3Br10 at the bottom of 3D Cs0.07FA0.85MA0.08Pb(I0.95Br0.05)3 perovskite. Thus, a power conversion efficiency (PCE) of 24.2% is achieved due to the minimal nonradiative recombination. The encapsulated device also shows an improved stability, maintaining 93.5% of the initial value after 1000 h under 1 sun equivalent illumination at the maximum power point. This strategy may provide important insights into designing perovskite film structures to achieve high‐performance solar cells with high stability.
Achieving 17.46% Efficiency CsPbI2Br Perovskite Solar Cells via Multifunction Lead Chloride‐Modified ZnO Electron Transporting Layer
Authors: Li Yaru , Zhang Yong , Zhu Peide , Li Jingbai , Wu Jiawen , Zhang Jiyao , Zhou Xianyong , Jiang Zhengyan , Wang Xingzhu , Xu Baomin
Published: September 2023

CsPbI2Br perovskite solar cells (PSCs) have garnered significant attention owing to their remarkable thermal stability and desirable bandgap. However, CsPbI2Br‐based devices still face critical challenges, particularly at the interfaces between the active layer and adjacent components. In this study, a multifunctional ZnO composition has developed as the electron transporting layer (ETL) for CsPbI2Br PSCs, enabling simultaneous efficient charge extraction and passivation of buried interface defects in CsPbI2Br. The nanocomposite, composed of PbCl2‐modified ZnO (PbCl2‐ZnO), facilitates the regulation of bandgap and conduction band to align the energy level of ETL and CsPbI2Br. Additionally, the residual PbCl2 at the buried interface of the perovskite incorporates into the perovskite lattice, reducing I defect and thus improving film quality. The improved energy level alignment at the ETL/CsPbI2Br interface and the suppressed I defect‐induced carrier nonradiative recombination result in a remarkable reduction in energy loss from 0.73 to 0.52 eV. Finally, the PbCl2‐ZnO hybrid nanocomposite ETL significantly enhances the efficiency of CsPbI2Br PSCs, increasing it from 14.15% to 17.46%, representing one of the highest reported power conversion efficiency (PCE) values for CsPbI2Br PSCs. These findings demonstrate the potential of PbCl2‐ZnO hybrid nanocomposite as an effective ETL for CsPbI2Br PSCs.
Catalyzing Generation and Stabilization of Oxygen Vacancies on CeO2−x Nanorods by Pt Nanoclusters as Nanozymes for Catalytic Therapy
Authors: Zhang Jiankang , Yang Yu , Qin Fengmin , Hu Tingting , Zhao Xinshuo , Zhao Shichao , Cao Yueqiang , Gao Zhe , Zhou Zhan , Liang Ruizheng , Tan Chaoliang , Qin Yong
Published: September 2023

Although CeO2 nanomaterials have been widely explored as nanozymes for catalytic therapy, they still suffer from relatively low activities. Herein, the catalyzing generation and stabilization of oxygen vacancies on CeO2 nanorods by Pt nanoclusters via H2 gas reduction under mild temperature (350 °C) to obtain Pt/CeO2−x, which can serve as a highly efficient nanozyme for catalytic cancer therapy, is reported. The deposited Pt on CeO2 by the atomic layer deposition technique not only can serve as the catalyst to generate oxygen vacancies under mild temperature reduction through the hydrogen spillover effect, but also can stabilize the generated oxygen vacancies. Meanwhile, the oxygen vacancies also provide anchoring sites for Pt forming strong metal‐support interactions and thus preventing their agglomerations. Importantly, the Pt/CeO2−x reduced at 350 °C (Pt/CeO2−x‐350R) exhibits excellent enzyme‐mimicking catalytic activity for generation of reactive oxygen species (e.g., ·OH) as compared to other control samples, including CeO2, Pt/CeO2, and Pt/CeO2−x reduced at other temperatures, thus achieving excellent performance for tumor‐specific catalytic therapy to efficiently eliminate cancer cells in vitro and ablate tumors in vivo. The excellent enzyme‐mimicking catalytic activity of Pt/CeO2−x‐350R originates from the good catalytic activities of oxygen vacancy‐rich CeO2−x and Pt nanoclusters.
Suppressing Rampant and Vertical Deposition of Cathode Intermediate Product via PH Regulation Toward Large‐Capacity and High‐Durability Zn//MnO2 Batteries
Authors: Chen Minfeng , Yang Ming , Han Xiang , Chen Jizhang , Zhang Peixin , Wong Ching‐Ping
Published: September 2023

Despite great prospects, Zn//MnO2 batteries suffer from rampant and vertical deposition of zinc sulfate hydroxide (ZSH) at the cathode surface, which leads to a significant impact on their electrochemical performance. This phenomenon is primarily due to the drastic increase in the electrolyte pH value upon discharging, which is closely associated with the electrodissolution of Mn‐based active materials. Herein, the pH value change is effectively inhibited by employing an electrolyte additive with excellent pH buffering capability. As such, the formation of ZSH at the cathode is postponed, resulting in the deposition of ZSH in a horizontal arrangement. This strategy can significantly enhance the utilization efficiency of cathode active material, while also enabling a solid electrolyte interphase layer at the Zn anode to address low Zn stripping/plating reversibility. With the optimal electrolyte, the Zn//MnO2 battery realizes a 25.6% increase in the specific capacity at 0.2 A g−1 compared to that with the baseline electrolyte, great rate capability (161.6 mAh g−1 at 5 A g−1), and superior capacity retention (90.2% over 5,000 cycles). In addition, the pH buffering strategy is highly applicable in hydrogel electrolytes. This work underscores the importance of pH regulation for Zn//MnO2 batteries and provides enlightening insights.
Aramid Nanodielectrics for Ultraconformal Transparent Electronic Skins
Authors: Zhao Sanchuan , Zhao Yingtao , Li Chenning , Wang Wei , Liu Hai‐Yang , Cui Lei , Li Xiang , Yang Zhenhua , Zhang Anni , Wang Yurou , Lin Yuxuan , Hao Tailang , Yin Jun , Kang Joohoon , Zhu Jian
Published: September 2023

On‐skin electronics require minimal thicknesses and decent transparency for conformal contact, imperceptible wearing, and visual aesthetics. It is challenging to search for advanced ultrathin dielectrics capable of supporting the active components while maintaining bending softness, easy handling, and wafer‐scale processability. Here, self‐delaminated aramid nanodielectrics (ANDs) are demonstrated, enabling any skin‐like electronics easily exfoliated from the processing substrates after complicated nanofabrication. In addition, ANDs are mechanically strong, chemically and thermally stable, transparent and breathable, therefore are ideal substrates for soft electronics. As demonstrated, compliant epidermal electrodes comprising silver nanowires and ANDs can successfully record high‐quality electromyogram signals with low motion artifacts and satisfying sweat and water resistance. Furthermore, ANDs can serve as both substrates and dielectrics in single‐walled carbon nanotube field‐effect transistors (FETs) with a merely 160‐nm thickness, which can be operated within 4 V with on/off ratios of 1.4 ± 0.5 × 105, mobilities of 39.9 ± 2.2 cm2 V−1 s−1, and negligible hysteresis. The ultraconformal FETs can function properly when wrapped around human hair without any degradation in performance.
Boron and Nitrogen Isotope Effects on Hexagonal Boron Nitride Properties
Authors: Janzen Eli , Schutte Hannah , Plo Juliette , Rousseau Adrien , Michel Thierry , Desrat Wilfried , Valvin Pierre , Jacques Vincent , Cassabois Guillaume , Gil Bernard , Edgar James H.
Published: September 2023

The unique physical, mechanical, chemical, optical, and electronic properties of hexagonal boron nitride (hBN) make it a promising 2D material for electronic, optoelectronic, nanophotonic, and quantum devices. Here, the changes in hBN's properties induced by isotopic purification in both boron and nitrogen are reported. Previous studies on isotopically pure hBN have focused on purifying the boron isotope concentration in hBN from its natural concentration (≈20 at% 10B, 80 at% 11B) while using naturally abundant nitrogen (99.6 at% 14N, 0.4 at% 15N), that is, almost pure 14N. In this study, the class of isotopically purified hBN crystals to 15N is extended. Crystals in the four configurations, namely h10B14N, h11B14N, h10B15N, and h11B15N, are grown by the metal flux method using boron and nitrogen single isotope (> 99%) enriched sources, with nickel plus chromium as the solvent. In‐depth Raman and photoluminescence spectroscopies demonstrate the high quality of the monoisotopic hBN crystals with vibrational and optical properties of the 15N‐purified crystals at the state‐of‐the‐art of currently available 14N‐purified hBN. The growth of high‐quality h10B14N, h11B14N, h10B15N, and h11B15N opens exciting perspectives for thermal conductivity control in heat management, as well as for advanced functionalities in quantum technologies.
Thermochromic Printable and Multicolor Polymeric Composite Based on Hybrid Organic–Inorganic Perovskite
Authors: Cinquino Marco , Prontera Carmela Tania , Giuri Antonella , Pugliese Marco , Giannuzzi Roberto , Maggiore Antonio , Altamura Davide , Mariano Fabrizio , Gigli Giuseppe , Esposito Corcione Carola , Giannini Cinzia , Rizzo Aurora , De Marco Luisa , Maiorano Vincenzo
Published: September 2023

Hybrid organic–inorganic perovskites (PVKs) are among the most promising materials for optoelectronic applications thanks to their outstanding photophysical properties and easy synthesis. Herein, a new PVK‐based thermochromic composite is demonstrated. It can reversibly switch from a transparent state (transmittance > 80%) at room temperature to a colored state (transmittance < 10%) at high temperature, with very fast kinetics, taking only a few seconds to go from the bleached to the colored state (and vice versa). X‐ray diffraction, Fourier‐transform infrared spectroscopy, differential scanning calometry, rheological, and optical measurements carried out during heating/cooling cycles reveal that thermochromism in the material is based on a reversible process of PVK disassembly/assembly mediated by intercalating polymeric chains, through the formation and breaking of hydrogen bonds between polymer and perovskite. Therefore, differently from other thermochromic perovskites, that generally work with the adsorption/desorption of volatile molecules, the system is able to perform several heating/cooling cycles regardless of environmental conditions. The color and transition temperature (from 70 to 120 °C) can be tuned depending on the type of perovskite. Moreover, this thermochromic material is printable and can be deposited by cheap techniques, paving the way for a new class of smart coatings with an unprecedented range of colors.
Lab‐in‐a‐Bead: Magnetic Janus Bead Probe for the Detection of Biomarkers in Blood
Authors: Gunatilake Udara Bimendra , Caballe‐Abalos Adriana , Garcia‐Rey Sandra , Mercader‐Ruiz Jon , Basabe‐Desmonts Lourdes , Benito‐Lopez Fernando
Published: September 2023

Remotely handled miniaturized colorimetric sensor platforms with multiple functionalities are able to mimic conventional laboratory operations with reduced assets. The integration of a magnetic phase in a miniaturized hydrogel sensor system allows the manipulation of the sensor, under a magnetic field, in a programmable manner. However, dark color interferences from conventional magnetic phases (Fe3O4, Fe2O3, and Fe micro/nanoparticles) affect the signal readout, hindering the colorimetric response. Therefore, a novel Janus bead configuration is introduced and tested by the localized incorporation of ferromagnetic iron microparticles into a TiO2 nanotubes/alginate hydrogel bead biosystem, under an applied magnetic field. The so‐called hydrogel Janus bead shows both, magnetic translocation and biosensing properties in the same bead. These beads are used for the direct colorimetric analysis of biomarkers in blood. The surface of the Janus bead prevents the biofouling of red blood cells, keeping the sensor surface clean for accurate optical colorimetric analysis. Moreover, the external magnetic manipulation of the bead permits precise control of the time and position of the bead in the sample. Therefore, multiple functionalities are presented by a single magnetic TiO2 nanotubes/alginate Janus bead such as actuation, low biofouling, and sensing, positioning this technology as a truly Lab‐in‐a‐Bead System.
Anti Stokes Thermometry of Plasmonic Nanoparticle Arrays
Authors: Ezendam Simone , Nan Lin , Violi Ianina L. , Maier Stefan A. , Cortés Emiliano , Baffou Guillaume , Gargiulo Julian
Published: September 2023

Metallic nanoparticles possess strong photothermal responses, especially when illuminated as ensembles due to collective effects. However, accurately quantifying the temperature increase remains a significant challenge, impeding progress in several applications. Anti Stokes thermometry offers a promising solution by enabling direct and non‐invasive temperature measurements of the metal without the need for labeling or prior calibration. While Anti Stokes thermometry is successfully applied to individual nanoparticles, its potential to study light‐to‐heat conversion with plasmonic ensembles remains unexplored. In this study, the theoretical framework and the conditions that must be fulfilled for applying Anti Stokes thermometry to ensembles of nanoparticles are discussed. Then, this technique is implemented to measure the light‐induced heating of square arrays of Au nanodisks. The obtained temperature measurements are validated using wavefront microscopy, demonstrating excellent agreement between the two thermometry methods. These results showcase the extension of Anti Stokes thermometry to plasmonic ensembles, highlighting its potential for implementation in the diverse photothermal applications involving these systems.
Early Endosomes Undergo Calcium‐Triggered Exocytosis and Enable Repair of Diffuse and Focal Plasma Membrane Injury
Authors: Bittel Daniel C. , Jaiswal Jyoti K.
Published: September 2023

Cells are routinely exposed to agents that cause plasma membrane (PM) injury. While pore‐forming toxins (PFTs), and chemicals cause nanoscale holes dispersed throughout the PM, mechanical trauma causes focal lesions in the PM. To examine if these distinct injuries share common repair mechanism, membrane trafficking is monitored as the PM repairs from such injuries. During the course of repair, dispersed PM injury by the PFT Streptolysin O activates endocytosis, while focal mechanical injury to the PM inhibits endocytosis. Consequently, acute block of endocytosis prevents repair of diffuse, but not of focal injury. In contrast, a chronic block in endocytosis depletes cells of early endosomes and inhibits repair of focal injury. This study finds that both focal and diffuse PM injury activate Ca2+‐triggered exocytosis of early endosomes. The use of markers including endocytosed cargo, Rab5, Rab11, and VAMP3, all reveal injury‐triggered exocytosis of early endosomes. Inhibiting Rab5 prevents injury‐triggered early endosome exocytosis and phenocopies the failed PM repair of cells chronically depleted of early endosomes. These results identify early endosomes as a Ca2+‐regulated exocytic compartment, and uncover the requirement of their dual functions – endocytosis and regulated exocytosis, to differentially support PM repair based on the nature of the injury.
TAOK3 Facilitates Esophageal Squamous Cell Carcinoma Progression and Cisplatin Resistance Through Augmenting Autophagy Mediated by IRGM
Authors: Sun Mingchuang , Li Zhaoxing , Wang Xiaoyuan , Zhao Meirong , Chu Yuan , Zhang Zehua , Fang Kang , Zhao Ziying , Feng Anqi , Leng Zhuyun , Shi Jianing , Zhang Li , Chen Tao , Xu Meidong
Published: September 2023

Esophageal squamous cell carcinoma (ESCC) is one of the deadliest cancers because of its robust aggressive phenotype and chemoresistance. TAO kinase belongs to mitogen‐activated protein kinases, which mediate drug resistance in multiple cancers. However, the role of TAO kinase in ESCC progression and chemoresistance has never been explored. Here, it is reported that TAOK3 augments cell autophagy and further promotes ESCC progression and chemoresistance. Mechanistically, TAOK3 phosphorylates KMT2C at S4588 and strengthens the interaction between KMT2C and ETV5. Consequently, the nuclear translocation of KMT2C is increased, and the transcription of autophagy‐relevant gene IRGM is further upregulated. Additionally, the inhibitor SBI‐581 can significantly suppress cell autophagy mediated by TAOK3 and synergizes with cisplatin to treat ESCC in vitro and in vivo.
PGAM1 Inhibition Promotes HCC Ferroptosis and Synergizes with Anti‐PD‐1 Immunotherapy
Authors: Zheng Yimin , Wang Yining , Lu Zhou , Wan Jinkai , Jiang Lulu , Song Danjun , Wei Chuanyuan , Gao Chao , Shi Guoming , Zhou Jian , Fan Jia , Ke Aiwu , Zhou Lu , Cai Jiabin
Published: September 2023

The combination of immunotherapy and molecular targeted therapy exhibits promising therapeutic efficacy in hepatocellular carcinoma (HCC), but the underlying mechanism is still unclear. Here, phosphoglycerate mutase 1 (PGAM1) is identified as a novel immunometabolic target by using a bioinformatic algorithm based on multiple HCC datasets. PGAM1 is highly expressed in HCC and associated with a poor prognosis and a poor response to immunotherapy. In vitro and in vivo experiments indicate that targeting PGAM1 inhibited HCC cell growth and promoted the infiltration of CD8+ T‐cells due to decreased enzymatic activity. Mechanistically, inhibition of PGAM1 promotes HCC cell ferroptosis by downregulating Lipocalin (LCN2) by inducing energy stress and ROS‐dependent AKT inhibition, which can also downregulate Programmed death 1‐ligand 1 (PD‐L1). Moreover, an allosteric PGAM1 inhibitor (KH3) exhibits good antitumor effects in patient‐derived xenograft (PDX) models and enhanced the efficacy of anti‐PD‐1 immunotherapy in subcutaneous and orthotopic HCC models. Taken together, the findings demonstrate that PGAM1 inhibition exerts an antitumor effect by promoting ferroptosis and CD8+ T‐cell infiltration and can synergize with anti‐PD‐1 immunotherapy in HCC. Targeting PGAM1 can be a promising new strategy of “killing two birds with one stone” for HCC treatment.
A follow‐up survey to assess stakeholders’ perspectives on weed management challenges and current practices in Nebraska, USA
Authors: McDonald Shawn T. , Sarangi Debalin , Rees Jennifer M. , Jhala Amit J.
Published: September 2023

Stakeholders across the state of Nebraska, USA, were surveyed in 2019–2020 to assess problem weeds and weed management practices in agronomic crops. A total of 420 complete responses were obtained across four Nebraska districts (Northeast, Panhandle, Southeast, and West Central). Accumulated across the state, 65.5% of farmed or scouted crop ground in Nebraska was under no‐till production, with the major crops being corn and soybean representing 39.3% and 30.7% of agronomic crop production area, respectively. Palmer amaranth, horseweed, waterhemp, kochia, and giant ragweed were ranked the most problematic weeds. In a 2014–2015 survey, Palmer amaranth was the sixth most problematic weed. The most used preplant herbicides were 2,4‐D, glyphosate, and dicamba in the 2019–2020 survey. Atrazine applied alone or in mixture with acetochlor, bicyclopyrone, clopyralid, mesotrione, or S‐metolachlor were the most applied pre‐emergence (PRE) herbicides in corn, whereas the most applied PRE herbicides in soybean were metribuzin/sulfentrazone, flumioxazin/pyroxasulfone, and chloransulam‐methyl/sulfentrazone. Like the previous survey, glyphosate was the most frequent choice of survey respondents as a post‐emergence (POST) herbicide in glyphosate‐resistant corn and soybean, while 2,4‐D was the most applied POST herbicide in grain sorghum and wheat. Most of the respondents (77%) were aware of the new multiple herbicide‐resistant crops, and 86% listed physical drift and volatility of dicamba/2,4‐D as a primary concern. Twenty‐three percent of survey respondents identified integrated pest management as a primary research and extension priority for profitable agronomic crop production in Nebraska.
Targeted dosing of anti‐thymocyte globulin in adult unmanipulated haploidentical peripheral blood stem cell transplantation: A single‐arm, phase 2 trial
Authors: Wang Haitao , Wang Nan , Wang Lili , Du Jishan , Li Fei , Shao Yangliu , Peng Bo , Luan Songhua , Wang Lu , Jin Xiangshu , Gao Chunji , Dou Liping , Liu Daihong
Published: September 2023

Anti‐thymocyte globulin (ATG) is widely used in allogeneic hematopoietic stem cell transplantation to prevent severe graft‐versus‐host disease (GVHD) and graft failure. However, overexposure to ATG may increase cytomegalovirus (CMV), Epstein‐Barr virus (EBV) reactivation, non‐relapse mortality, and disease recurrence. To investigate the optimal dosing of ATG, we established a targeted dosing strategy based on ATG concentration monitoring for haploidentical peripheral blood stem cell transplantation (haplo‐PBSCT). The aim of this phase 2 trial is to evaluate the safety and efficacy of the ATG‐targeted dosing strategy in adult unmanipulated haplo‐PBSCT. ATG was administered for 4 days (−5 days to −2 days) during conditioning. The ATG doses on −3 days and −2 days were adjusted by our dosing strategy to achieve the optimal ATG exposure. The primary endpoint was CMV reactivation on +180 days. Between December 2020 and January 2022, 66 haplo‐PBSCT patients were enrolled and 63 of them were evaluable with a median follow‐up of 632 days. The cumulative incidence of CMV reactivation was 36.7% and that of EBV was 58.7%. The 1‐year disease‐free survival was 82.5%, overall survival was 92.1%, and CD4+ T‐cell reconstruction on +100 days was 76.8%. The most common severe regimen‐associated toxicities (> grade 3) were infections (51.5%) and gastrointestinal toxicity (25.5%). A total of 102 haplo‐PBSCT patients who received the conventional fixed ATG dose (cumulative 10 mg/kg) comprised historical control. The outcomes in historical control were inferior to those of phase 2 trial cohort (CMV reactivation: 70.8%, p < .001; EBV reactivation: 76.0%, p = .024; CD4 + T‐cell reconstruction: 54.1%, p = .040). In conclusion, ATG‐targeted dosing strategy reduced CMV/EBV reactivation and improved survival without increasing GVHD after haplo‐PBSCT. These advantages may be associated with accelerated immune reconstitution.
Woodhouse–Sakati syndrome in an Indian patient with a novel pathogenic variant
Authors: Amalnath S. Deepak , Jothivanan  , Oshima Junko , Buchan Jillian G. , Paolucci Sarah
Published: September 2023

Woodhouse–Sakati syndrome consists of hypogonadism, diabetes mellitus, alopecia, ECG abnormalities, and dystonia. This condition is caused by the loss of function of the DCAF17 gene. Most of the patients have been reported from Greater Middle Eastern countries. We report a 38 male from southern India who presented with syncope and massive hemoptysis due to ruptured bronchopulmonary collaterals. He also had alopecia, cataracts, recently diagnosed diabetes and hypogonadism. Whole exome sequencing showed a novel homozygous truncating variant in the DCAF17 gene. Despite embolization of the aortopulmonary collaterals, the patient died of recurrent hemoptysis.
Chemoselective Three‐Component Geminal Cross Couplings of Dihaloalkanes with Cr Catalysis: Rapid Access to Tertiary and Quaternary Alkanes via a Metal–Carbene Intermediate
Authors: Wang Sha , Long Linhong , Zhang Xiaoyu , Ling Liang , Chen Hui , Zeng Xiaoming
Published: September 2023

Geminal cross couplings using multiple components enable the formation of several different bonds at one site in the building of tertiary and quaternary alkanes. Nevertheless, there are remaining issues of concern—cleavage of two geminal bonds and control of selectivity present challenges. We report here the geminal cross couplings of three components by reactions of dihaloalkanes with organomagnesium and chlorosilanes or alkyl tosylates by Cr catalysis, affording the formation of geminal C−C/C−Si or C−C/C−C bonds in the creation of tertiary and quaternary alkanes. The geminal couplings are catalyzed by low‐cost CrCl2, enabling the sluggishness of competitive Kumada‐type side couplings and homocouplings of Grignard reagents, in achieving high chemoselectivity. Experimental and theoretical studies indicate that two geminal C‐halide bonds are continuously cleaved by Cr to afford a metal carbene intermediate, which couples with a Grignard reagent, followed by silylation, in the formation of geminal C−C and C−Si bonds via a novel inner‐sphere radical coupling mechanism. These three‐component geminal cross couplings are value‐addition to the synthesis of commercial drugs and bioactive molecules in medicinal chemistry.
Shape Control of Carbon Nanoparticles via a Simple Anion‐Directed Strategy for Precise Endoplasmic Reticulum‐Targeted Imaging
Authors: E Shuang , Xing Yan Zhi , Du Sang , Liu An Min , Gao Zhao , Zhou Quan , Xuan Yang , Zhao Yi Nan , Chen Xu Wei , Zhang Shu Biao
Published: September 2023

Herein, small‐sized fluorescent carbon nanoparticles (CNs) with tunable shapes ranging from spheres to various rods with aspect ratios (ARs) of 1.00, 1.51, 1.89, and 2.85 are prepared using a simple anion‐directed strategy for the first time. Based on comprehensive morphological and structural characteristics of CNs, along with theoretical calculations of density functional theory and molecular dynamics simulations, their shape‐control mechanism is attributed to interionic interactions‐induced self‐assembly, followed by carbonization. The endoplasmic reticulum‐targeting accuracy of CNs is gradually enhanced as their shape changes from spherical to higher‐AR rods, accompanied by a Pearson's correlation coefficient up to 0.90. This work presents a facile approach to control the shape of CNs and reveals the relationship between the shape and organelle‐targeting abilities of CNs, thereby providing a novel idea to synthesize CNs that serve as precise organelle‐targeted fluorescent probes.
Anatomical variations in the cerebral arterial circle of the Saimaa (Pusa hispida saimensis) and Baltic ringed seals (Pusa hispida botnica)
Authors: Laakkonen Juha , Nihtilä Heini , Jernvall Jukka
Published: September 2023

The intracranial arterial vascularization of the Saimaa ringed seals (Pusa hispida saimensis; Nordquist, 1899) and Baltic ringed seals (Pusa hispida botnica; Gmelin, 1788) disclosed patterns of anatomical architecture comparable to that of other pinniped species. Arterial silicone casts on skull scaffolds, and magnetic resonance imaging (MRI) showed that the besides joining the caudal communicating arteries upon entering the cerebral arterial circle, the bilateral internal carotid arteries bifurcated as laterally oriented rostral choroidal arteries and rostral cerebral arteries. The latter arteries almost immediately gave off the laterally oriented middle cerebral arteries. Numerous individual variations were evident in differences in the exact branching sites of bilateral vessels or the size or number of arterial branches. Two Saimaa ringed seals had only a tiny foramen for the left internal carotid artery to enter the intracranial space, and the intracranial part of this vessel was short. It did not reach the cerebral arterial circle. The intracranial part of the right internal carotid artery is bifurcated and also supplied the left side of the cerebral arterial circle. Both specimens had aplasia of the left rostral cerebral artery. The intracranial arterial arrangement of Saimaa and Baltic ringed seals reflects the arterial architecture of this body region in terrestrial mammals with little evidence for aquatic adaptations or changes related to thermoregulation.
Remote training of educators in Taiwan to disseminate discrete trial training for students with developmental disabilities
Authors: Chen Ning , Lerman Dorothea C.
Published: September 2023

Educators in many areas of the world lack the necessary resources and training to serve students with developmental disabilities effectively. Telehealth technologies and a train‐the‐trainer approach may help disseminate evidence‐based instructional strategies to teachers in underserved areas. In this study, experimenters combined synchronous and asynchronous remote training to prepare six teachers in Taiwan to implement discrete trial training (DTT) with students. First, the experimenter taught three teachers from a private school to implement DTT with their students. Then, they trained these participants to teach another educator at their school. Finally, the three teachers trained those additional educators. Results indicated that the training was effective for all participants and that the DTT skills of the three trainers maintained over time and transferred to their in‐classroom instruction. These findings replicate and extend the current literature suggesting that the use of telehealth and a train‐the‐trainer model is a promising and socially valid method for disseminating ABA to countries with limited resources.
Dietary lithium stimulates female fecundity in Drosophila melanogaster
Authors: Jans Katharina , Lüersen Kai , von Frieling Jakob , Roeder Thomas , Rimbach Gerald
Published: September 2023

The trace element lithium exerts a versatile bioactivity in humans, to some extend overlapping with in vivo findings in the model organism Drosophila melanogaster. A potentially essential function of lithium in reproduction has been suggested since the 1980s and multiple studies have since been published postulating a regulatory role of lithium in female gametogenesis. However, the impact of lithium on fruit fly egg production has not been at the center of attention to date. In the present study, we report that dietary lithium (0.1–5.0 mM LiCl) substantially improved life time egg production in D. melanogaster w1118 females, with a maximum increase of plus 45% when supplementing 1.0 mM LiCl. This phenomenon was not observed in the insulin receptor mutant InRE19, indicating a potential involvement of insulin‐like signaling in the lithium‐mediated fecundity boost. Analysis of the whole‐body and ovarian transcriptome revealed that dietary lithium affects the mRNA levels of genes encoding proteins related to processes of follicular maturation. To the best of our knowledge, this is the first report on dietary lithium acting as an in vivo fecundity stimulant in D. melanogaster, further supporting the suggested benefit of the trace element in female reproduction.
Enhancing the thermostability and catalytic activity of Bacillus subtilis chitosanase by saturation mutagenesis of Lys242
Authors: Guo Jing , Gao Wenjun , Zhang Xuan , Pan Wenxin , Zhang Xin , Man Zaiwei , Cai Zhiqiang
Published: September 2023

Catalysis activity and thermostability are some of the fundamental characteristic of enzymes, which are of great significance to their industrial applications. Bacillus subtilis chitosanase BsCsn46A is a kind of enzyme with good catalytic activity and stability, which can hydrolyze chitosan to produce chitobiose and chitotriose. In order to further improve the catalytic activity and stability of BsCsn46A, saturation mutagenesis of the C‐terminal K242 of BsCsn46A was performed. The results showed that the six mutants (K242A, K242D, K242E, K242F, K242P, and K242T) showed increased catalytic activity on chitosan. The catalytic activity of K242P increased from 12971 ± 597 U mg−1 of wild type to 17820 ± 344 U mg−1, and the thermostability of K242P increased by 2.27%. In order to elucidate the reason for the change of enzymatic properties, hydrogen network, molecular docking, and molecular dynamics simulation were carried out. The hydrogen network results showed that all the mutants lose their interaction with Asp6 at 242 site, thereby increasing the flexibility of Glu19 at the junction sites of α1 and loop1. Molecular dynamics results showed that the RMSD of K242P was lower at both 313 and 323 K than that of other mutants, which supported that K242P had better thermostability. The catalytic activity of mutant K242P reached 17820.27 U mg−1, the highest level reported so far, which could be a robust candidate for the industrial application of chitooligosaccharide (COS) production.
Perioperative opioids and survival outcomes in resectable head and neck cancer: A systematic review
Authors: Mastrolonardo Eric V. , Mann Derek S. , Sethi Harleen K. , Yun Bo H. , Sina Elliott M. , Armache Maria , Worster Brooke , Fundakowski Christopher E. , Mady Leila J.
Published: September 2023

Background

Opioids are a mainstay in pain control for oncologic surgery. The objective of this systematic review is to evaluate the associations of perioperative opioid use with overall survival (OS) and disease‐free survival (DFS) in patients with resectable head and neck cancer (HNC).

Methods

A systematic review of PubMed, SCOPUS, and CINAHL between 2000 and 2022 was conducted following the Preferred Reporting Items for Systematic Reviews and Meta‐Analyses guidelines. Studies investigating perioperative opioid use for patients with HNC undergoing surgical resection and its association with OS and DFS were included.

Results

Three thousand three hundred seventy‐eight studies met initial inclusion criteria, and three studies representing 562 patients (intraoperative opioids, n = 463; postoperative opioids, n = 99) met final exclusion criteria. One study identified that high intraoperative opioid requirement in oral cancer surgery was associated with decreased OS (HR = 1.77, 95% CI 0.995–3.149) but was not an independent predictor of decreased DFS. Another study found that increased intraoperative opioid requirements in treating laryngeal cancer was demonstrated to have a weak but statistically significant inverse relationship with DFS (HR = 1.001, p = 0.02) and OS (HR = 1.001, p = 0.02). The last study identified that patients with chronic opioid after resection of oral cavity cancer had decreased DFS (HR = 2.7, 95% CI 1.1–6.6) compared to those who were not chronically using opioids postoperatively.

Conclusion

An association may exist between perioperative opioid use and OS and DFS in patients with resectable HNC. Additional investigation is required to further delineate this relationship and promote appropriate stewardship of opioid use with adjunctive nonopioid analgesic regimens.
Differences in mutational signature of diffuse large B‐cell lymphomas according to the primary organ
Authors: Koh Hyun‐Hee , Yoon Sang Eun , Kim Seok Jin , Kim Won Seog , Cho Junhun
Published: September 2023

Background

Comprehensive molecular subtyping of diffuse large B‐cell lymphoma (DLBCL) through genetic profiling has broadened our understanding of DLBCL biology. In this study, we investigated whether DLBCL, not otherwise specified (NOS) shows differences in mutational patterns depending on the primary organ.

Patients and Methods

Panel‐based next‐generation sequencing was performed on 345 DLBCL from various primary organs, and patterns of mutations according to primary organs were analyzed.

Results

DLBCL showed a characteristic mutational signature in several primary organs. Among them, the mutational pattern of DLBCL in the breast and ileocecal area was particularly different from that of other DLBCL NOS. In breast DLBCL, MYD88L265P (57.1%), CD79B mutation (42.9%), and CDKN2A/B loss (71.4%) were found at high frequencies, which were similar to the mutation patterns of DLBCL of immune‐privileged sites compared with DLBCL NOS. DLBCL in the ileocecal area showed a characteristic mutation pattern with the most frequent TP53 mutation (52.6%) and 18q21 gain (42.1%). This was also different from the mutational pattern observed in the stomach or other intestines. In discriminant analysis, DLBCL of the breast and ileocecal area tended to form separate genetic constellations from other DLBCL NOS.

Conclusion

DLBCL NOS has a characteristic mutational profile that depends on the primary organ. In particular, the mutational signature of DLBCL in the breast and ileocecal area was heterogeneous compared with that of other DLBCL NOS. Further research is needed to determine whether primary DLBCL in the breast and ileocecal area can be classified as an independent subtype.
Biomass Separators as a “Lifesaver” for Safe and Long‐Life Lithium Metal Batteries
Authors: Bao Jinxi , Song Xiaohui , Tian Feng , Shi Haiting , Liang Shuaitong , Wang Shuo , Zeng Ming , Xue Yanling , Hong Chunxia , Xu Zhiwei
Published: September 2023

The growth of lithium dendrites and the shuttle of polysulfides in lithium metal batteries (LMBs) have hindered their development. In LMBs, the cathode and anode are separated by a separator, although this does not solve the battery‘s issues. The use of biomass materials is widespread for modifying the separator due to their porous structure and abundant functional groups. LMBs perform more electrochemically when lithium ions are deposited uniformly and polysulfide shuttling is reduced using biomass separators. In this review, we analyze the growth of lithium dendrite and the shuttle of polysulfide in LMBs, summarize the types of biomass separator materials and the mechanisms of action (providing mechanical barriers, promoting uniform deposition of metal ions, capturing polysulfides, shielding polysulfide). The prospect of developing new separator materials from the perspective of regulating ion transport and physical sieving efficiency as well as the application of advanced technologies such as synchrotron radiation to characterize the mechanism of action of biomass separators is also proposed.
Porphyrin‐based Bi‐MOFs with Enriched Surface Bi Active Sites for Boosting Photocatalytic CO2 Reduction
Authors: Cheng Mingjie , Yan Pengfei , Zheng Xiaoli , Gao Bo , Yan Xinying , Zhang Gaoxiang , Cui Xiaomin , Xu Qun
Published: September 2023

The inherent challenges in using metal‐organic frameworks (MOFs) for photocatalytic CO2 reduction are the combination of wide‐range light harvesting, efficient charge separation and transfer as well as highly exposed catalytic active sites for CO2 activation and reduction. We present here a promising solution to satisfy these requirements together by modulating the crystal facet and surface atomic structure of a porphyrin‐based bismuth‐MOF (Bi‐PMOF). The series of structural and photo‐electronic characterizations together with photocatalytic CO2 reduction experiment collectively establish that the enriched Bi active sites on the (010) surface prefer to promote efficient charge separation and transfer as well as the activation and reduction of CO2. Specifically, the Bi‐PMOFs‐120‐F with enriched surface Bi active sites exhibits optimal photocatalytic CO2 reduction performance to CO (28.61 μmol h−1g−1) and CH4 (8.81 μmol h−1g−1). This work provides new insights to synthesize highly efficient main group p‐block metal Bi‐MOF photocatalysts for CO2 reduction through a facet‐regulation strategy and sheds light on the surface structure‐activity relationships of the MOFs.
Nassmechanische Aufbereitung von Bauschutt‐Brechsand mit der Setztechnik – ein Schritt auf dem Weg zum Ersatzbaustoff
Authors: Pienkoß Fabian , Kalbe Ute , Simon Franz-Georg
Published: September 2023

Das Recycling von gemischten Baustoffen führt neben der Herstellung von Gesteinskörnungen parallel zu einem stärker schadstoffbelasteten Stoffstrom, der circa ein Drittel der ursprünglichen Masse ausmacht. Dieser sogenannte Brechsand endet derzeit in der Deponierung und wird somit der Kreislaufwirtschaft entzogen. Der vorliegende Beitrag untersucht nun die Aufbereitung dieses Materials unter Verwendung einer Setzmaschine im Pilotmaßstab. Hierbei wird die Eignung dieser Technik evaluiert und das Aufbereitungsprodukt als möglicher Ersatzbaustoff untersucht.
5‐Substituted Uridines with Activity against Gram‐Positive Bacteria
Authors: Makarov Dmitry A. , Negrya Sergey D. , Jasko Maxim V. , Karpenko Inna L. , Solyev Pavel N. , Chekhov Vladimir O. , Kaluzhny Dmitry N. , Efremenkova Olga V. , Vasilyeva Byazilya F. , Chizhov Alexander O. , Avdanina Darya A. , Zhgun Alexander A. , Kochetkov Sergey N. , Alexandrova Liudmila A.
Published: September 2023

The emergence of drug‐resistant strains of pathogenic microorganisms necessitates the creation of new drugs. A series of uridine derivatives containing an extended substituent at the C‐5 position as well as C‐5 alkyloxymethyl, alkylthiomethyl, alkyltriazolylmethyl, alkylsulfinylmethyl and alkylsulfonylmethyl uridines were obtained in order to explore their antimicrobial properties and solubility. It has been shown that new ribonucleoside derivatives have an order of magnitude better solubility in water compared to their 2′‐deoxy analogues and effectively inhibit the growth of a number of Gram‐positive bacteria, including resistant strains of Mycobacterium smegmatis (MIC=15–200 μg/mL) and Staphylococcus aureus (MIC=25–100 μg/mL). Their activity is comparable to that of some antibiotics used in medicine.
Landscape complexity beyond invariance and the elastic manifold
Authors: Ben Arous Gérard , Bourgade Paul , McKenna Benjamin
Published: September 2023

This paper characterizes the annealed, topological complexity (both of total critical points and of local minima) of the elastic manifold. This classical model of a disordered elastic system captures point configurations with self‐interactions in a random medium. We establish the simple versus glassy phase diagram in the model parameters, with these phases separated by a physical boundary known as the Larkin mass, confirming formulas of Fyodorov and Le Doussal. One essential, dynamical, step of the proof also applies to a general signal‐to‐noise model of soft spins in an anisotropic well, for which we prove a negative‐second‐moment threshold distinguishing positive from zero complexity. A universal near‐critical behavior appears within this phase portrait, namely quadratic near‐critical vanishing of the complexity of total critical points, and cubic near‐critical vanishing of the complexity of local minima. These two models serve as a paradigm of complexity calculations for Gaussian landscapes exhibiting few distributional symmetries, that is, beyond the invariant setting. The two main inputs for the proof are determinant asymptotics for non‐invariant random matrices from our companion paper (Ben Arous, Bourgade, McKenna 2022), and the atypical convexity and integrability of the limiting variational problems.
α‐Synuclein Drives Tau's Cytotoxic Aggregates Formation through Hydrophobic Interactions
Authors: Ojeda Ana , Cofré Valentina , Melo Francisco , Caballero Leonardo , Fuentealba Denis , Cornejo Alberto
Published: September 2023

Tau and α‐synuclein are proteins involved in pathologies known as tauopathies and synucleinopathies, respectively. Moreover, evidence shows that there is a crosstalk between them as is seen in the brains of individuals with sporadic neurodegenerative disorders. Based on that, we present data showing that the hydrophobic α‐peptide 71VTGVTAVAQKTV82 induces the aggregation of the full‐length tau fragment in the absence of heparin assessed by ThT. Moreover, AFM images reveal the presence of straight filaments and amorphous aggregates of full‐length tau in the presence of the α‐peptide. Additionally, ITC experiments showed the interaction of the α‐peptide with tau full‐length (441 amino acids),4R (amino acids from 244 to 369), and both hexapeptides 275VQIINK280 and 306VQIVYK311 through hydrophobic interactions. The Raman spectroscopy spectra showed conformational changes in the Amide region in the aggregates formed with full‐length tau and α‐syn peptide. Furthermore, the incubation of extracellular aggregates with N2a cells showed morphological differences in the cellular body and the nucleus suggesting cell death. Moreover,, the incubation of different types of aggregates in cell culture provokes the release of Lactate dehydrogenase (LDH). Altogether, we found that α‐synuclein peptide can drive the aggregation of full‐length tau‐provoking morphological and structural changes evoking cytotoxic effects.
Integration of Isothermal Enzyme‐Free Nucleic Acid Circuits for High‐Performance Biosensing Applications
Authors: Wang Siyuan , Shang Jinhua , Zhao Bingyue , Wang Huimin , Yang Changying , Liu Xiaoqing , Wang Fuan
Published: September 2023

The isothermal enzyme‐free nucleic acid amplification method plays an indispensable role in biosensing by virtue of its simple, robust, and highly efficient properties without the assistance of temperature cycling or/and enzymatic biocatalysis. Up to now, enzyme‐free nucleic acid amplification has been extensively utilized for biological assays and has achieved the highly sensitive detection of various biological targets, including DNAs, RNAs, small molecules, proteins, and even cells. In this Review, the mechanisms of entropy‐driven reaction, hybridization chain reaction, catalytic hairpin assembly and DNAzyme are concisely described and their recent application as biosensors is comprehensively summarized. Furthermore, the current problems and the developments of these DNA circuits are also discussed.