bluuebunny/crossref_metadata_2025 huggingface dataset:
High Performance Shortwave Infrared Organic Photodetectors Adopting Thiadiazole Quinoxaline‐Based Copolymers
Authors: Park Insun , Kim Changki , Kim Raesung , Li Ning , Lee Jaejun , Kwon Oh Kyu , Choi Byoungki , Ng Tse Nga , Leem Dong‐Seok
Published: July 2022

Detection of light in the near‐infrared (NIR) and shortwave infrared (SWIR) spectral range is essential for the wide practical applications of biometrics, surveillance, machine vision, etc., in which organic molecules have gained growing interest as the potential sensing materials. In this study, the newly synthesized donor–acceptor type copolymers consisting of [1,2,5]thiadiazolo[3,4‐g]quinoxaline core unit with phenyl pendant groups as the acceptor and thiophene unit as the donor for achieving high‐efficiency organic SWIR photodetectors are presented. A further variation of the alkoxy chain lengths in the core unit allows the optimized device to exhibit a high external quantum efficiency of 19.5%–21.7% at 1200 nm under the low reverse bias of −1 V, leading to a high detectivity up to 2.96 × 1010Jones for the spectral range beyond 1 µm. This further suggests the possible origin of the molecular structure‐dependent device performance in terms of the molecular stacking, morphological changes, and charge‐transporting properties in the bulk heterojunction blends.
Cytochrome P450 Monooxygenases Catalyse Steroid Nucleus Hydroxylation with Regio‐ and Stereo‐Selectivity
Authors: Zhu Rui , Liu Yang , Yang Yueying , Min Qing , Li Hua , Chen Lixia
Published: July 2022

Steroids are the second largest class of drugs with a wide range of pharmacological properties. Hydroxylation of steroids seriously affects their biological activities and other properties. However, steroids are mostlysp3hybridized carbons with numerous C−H bonds far from the functional group that can activate them, and achieving regio‐ and stereo‐selective hydroxylation on steroids is a highly challenging task that is almost impossible to achieve using modern organic synthesis techniques. Interestingly, cytochrome P450 monooxygenases possess the ability to catalyse regio‐ and stereo‐selective oxidations of nonactivated C−H bonds in complex organic molecules under mild conditions. This review summarizes the P450s identified and engineered in recent years that can catalyse steroid nucleus hydroxylation stereo‐ and regio‐selectively.

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Strain Engineering by Local Chemistry Manipulation of Triphase Heterostructured Oxide Cathodes to Facilitate Phase Transitions for High‐Performance Sodium‐Ion Batteries
Authors: Hu Hai‐Yan , Zhu Yan‐Fang , Xiao Yao , Li Shi , Li Jia‐Yang , Hao Zhi‐Qiang , Zhao Jia‐Hua , Chou Shu‐Lei
Published: July 2022

Sodium‐ion oxide cathodes with triphase heterostructures have attracted intensive attention, since the sodium‐storage performance can be enhanced by utilizing the synergistic effect of different phases. However, the composite structures generally suffer from multiple irreversible phase transitions and high lattice strain because of interlayer‐gliding during the charge/discharge process. Here, the concept of strain engineering via manipulating the local chemistry of heterostructured oxide cathode is proposed to regulate the relevant physical and chemical properties, resulting in highly reversible structural evolution (P2/P3/spinel → P2/P3″/spinel) and low intrinsic stress in the potential window of 1.5–4.0 V. Also, the simple structural evolution at a relatively high cut‐off potential of 4.3 V can be detected by in situ X‐ray diffraction and other electrochemical characterization techniques during Na+ extraction/insertion. Meanwhile, the electrode exhibits a high reversible capacity (169.4 mAh g−1 at 0.2 C) and excellent rate performance from 1.5 to 4.3 V. Overall, this study reveals the mechanisms of regulating local chemistry to realize strain engineering of the cathode materials and paves the way for the further improvement of high‐performance sodium‐ion batteries.
Surface Reconstruction of Water Splitting Electrocatalysts
Authors: Zeng Ye , Zhao Mengting , Huang Zihao , Zhu Weijie , Zheng Jiaxian , Jiang Qiu , Wang Zhoucheng , Liang Hanfeng
Published: July 2022

Water electrolysis is regarded as an efficient and green method to produce hydrogen gas, a clean energy carrier that holds the key to solving global energy problems. So far, the efficiency and large‐scale application of water electrolysis are restricted by the electrocatalytic activity of applied catalysts. Recently, the reconstruction phenomenon of electrocatalysts during a catalytic reaction has been discovered, which could form reactive sites for both the oxygen evolution and hydrogen evolution reactions. Regulation of the reconstruction process to generate a large number of reactive species with high activity has since been demonstrated as an effective strategy to enhance the catalytic performance of electrocatalysts. This review summarizes recent progress in the regulation strategies for reconstruction reactions. First, the mechanism of water electrolysis is briefly introduced, and the critical factors regarding the reconstruction process are systematically discussed, followed by a brief introduction of advanced characterization for reconstruction. Moreover, the modulation strategies are summarized with reported examples highlighting the promoted effects on the reconstruction process. Finally, the challenges facing surface‐reconstructed catalysts for water electrolysis in the future are discussed.
Dimethyl Sulfoxide as Methyl Source for the Synthesis of Quinazolinones under Metal‐Free Conditions
Authors: Wu Jiwei , Yu Xiaoxiao , Zhong Liangchen , Jin Kejun , Zhao Guoxu , Zhu Jianye , Shi Haowen , Wei Yuanyuan
Published: July 2022

An efficient synthesis of biologically important quinazolinones via using dimethyl sulfoxide as a synthon has been developed. This reaction proceeds smoothly to obtain the corresponding quinazolinones products in good yield under metal free conditions and shows an excellent functional group tolerance. A preliminary mechanistic study indicates that the C2 hydrogen of the synthesized heterocycles come from the dimethyl sulfoxide.
Low‐Pt NiNC‐Supported PtNi Nanoalloy Oxygen Reduction Reaction Electrocatalysts—In Situ Tracking of the Atomic Alloying Process
Authors: Feng Quanchen , Wang Xingli , Klingenhof Malte , Heggen Marc , Strasser Peter
Published: July 2022

We report and analyze a synthetic strategy toward low‐Pt platinum‐nickel (Pt‐Ni) alloy nanoparticle (NP) cathode catalysts for the catalytic electroreduction of molecular oxygen to water. The synthesis involves the pyrolysis and leaching of Ni‐organic polymers, subsequent Pt NP deposition, followed by thermal alloying, resulting in single Ni atom site (NiNC)‐supported PtNi alloy NPs at low Pt weight loadings of only 3–5 wt %. Despite low Pt weight loading, the catalysts exhibit more favorable Pt‐mass activities compared to conventional 20–30 wt % benchmark PtNi catalysts. Using in situ microscopic techniques, we track and unravel the key stages of the PtNi alloy formation process directly at the atomic scale. Surprisingly, we find that carbon‐encapsulated metallic Ni@C structures, rather than NiNx sites, act as the Ni source during alloy formation. Our materials concepts offer a pathway to further decrease the overall Pt content in hydrogen fuel cell cathodes.
Drug Repurposing by Siderophore Conjugation: Synthesis and Biological Evaluation of Siderophore‐Methotrexate Conjugates as Antibiotics
Authors: Zhao Sheng , Wang Zhi‐Peng , Lin Zihua , Wei Guoxing , Wen Xumei , Li Siyu , Yang Xiaohong , Zhang Qun , Jing Chunmei , Dai Yuanwei , Guo Jian , He Yun
Published: July 2022

Drug repurposing is considered a promising strategy to fight antimicrobial resistance (AMR). Methotrexate (Mtx), a classical anticancer drug, could strongly inhibit bacterial dihydrofolate reductase (DHFR). However, its poor permeability into bacteria and potent human cytotoxicity make it unsuitable as an antibacterial. Herein, we reported the conjugation of Mtx with a siderophore to construct “Trojan horse” antibacterials. The most potent conjugate 8 with nanomolar minimum inhibitory concentration (MIC) values exhibited over 1.00×103‐fold improved activity against Gram‐positive Streptococcus pneumoniae (S. pneumoniae) and Gram‐negative Yersinia enterocolitica (Y. enterocolitica) compared with Mtx, while possessing 2.31×103‐fold reduced human cytotoxicity, resulting in 2.08×106‐fold improvements in the therapeutic index. This proof‐of‐principle study verifies that siderophore conjugation is an effective strategy for developing new antibacterials from anticancer drugs.
Unterdrückung der SARS‐CoV‐2‐Replikation mit stabilisierten und durch Klick‐Chemie modifizierten siRNAs
Authors: Traube Franziska R. , Stern Marcel , Tölke Annika J. , Rudelius Martina , Mejías‐Pérez Ernesto , Raddaoui Nada , Kümmerer Beate M. , Douat Céline , Streshnev Filipp , Albanese Manuel , Wratil Paul R. , Gärtner Yasmin V. , Nainytė Milda , Giorgio Grazia , Michalakis Stylianos , Schneider Sabine , Streeck Hendrik , Müller Markus , Keppler Oliver T. , Carell Thomas
Published: July 2022

Die Entstehung von leichter übertragbaren oder aggressiveren Varianten von SARS‐CoV‐2 erfordert die Entwicklung von antiviralen Medikamenten, die schnell an sich entwickelnde virale Escape‐Mutationen anpassbar sind. Hier berichten wir über die Synthese von chemisch stabilisierter small interfering RNA (siRNA) gegen SARS‐CoV‐2. Die siRNA kann mit Hilfe von CuI‐katalysierter Klick‐Chemie mit Rezeptorliganden wie Peptiden zusätzlich modifiziert werden. Wir zeigen, dass optimierte siRNAs die Viruslast und die virus‐induzierte Zytotoxizität in Zelllinien, die mit SARS‐CoV‐2 infiziert sind, um bis zu fünf Größenordnungen reduzieren können. Darüber hinaus zeigen wir, dass eine mit einem ACE2‐bindenden Peptid‐konjugierte siRNA in der Lage ist, die Virusreplikation und die virus‐induzierte Apoptose in mukoziliären 3D‐Lungenmikrogeweben zu reduzieren. Eine Änderung der siRNA‐Sequenz ermöglicht eine schnelle Anpassung ihrer antiviralen Aktivität gegen verschiedene Virusvarianten. Die Möglichkeit, die siRNA mittels Klick‐Chemie an Rezeptorliganden zu konjugieren, erleichtert die Entwicklung zielgerichteter siRNAs für eine flexible antivirale Abwehrstrategie.
Double‐Cavity Nor‐Seco‐Cucurbit[10]uril Enables Efficient and Rapid Separation of Pyridine from Mixtures of Toluene, Benzene, and Pyridine
Authors: Liu Ming , Cen Ran , Li Jisen , Li Qing , Tao Zhu , Xiao Xin , Isaacs Lyle
Published: July 2022

Benzene, toluene and pyridine are widely used as essential raw materials in industry and laboratory research, with stringent purity requirements. Herein, we show that solid double‐cavity host nor‐seco‐cucurbit[10]uril (ns‐Q[10]) functions as an efficient adsorption separator for pyridine; benzene and toluene can be obtained in >99.9 % purity by this method. Thermal removal of pyridine from ns‐Q[10]⋅Py2 allows 10 separation cycles without erosion of performance. The geometry of the ns‐Q[10]⋅Py2 ternary complex was established by single‐crystal X‐ray diffraction methods. The ns‐Q[10] cage facilitates the removal of pyridine from toluene and benzene, with >99.9 % purity for the separated compounds.
Phosphorus Tailors thed‐Band Center of Copper Atomic Sites for Efficient CO2Photoreduction under Visible‐Light Irradiation
Authors: Sun Xiaohui , Sun Lian , Li Guanna , Tuo Yongxiao , Ye Chenliang , Yang Jiarui , Low Jingxiang , Yu Xiang , Bitter Johannes H. , Lei Yongpeng , Wang Dingsheng , Li Yadong
Published: July 2022

Photoreduction of CO2into solar fuels has received great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, two single‐Cu‐atom catalysts with unique Cu configurations in phosphorus‐doped carbon nitride (PCN), namely, Cu1N3@PCN and Cu1P3@PCN were fabricated via selective phosphidation, and tested in visible light‐driven CO2reduction by H2O without sacrificial agents. Cu1N3@PCN was exclusively active for CO production with a rate of 49.8 μmolCO gcat−1 h−1, outperforming most polymeric carbon nitride (C3N4) based catalysts, while Cu1P3@PCN preferably yielded H2. Experimental and theoretical analysis suggested that doping P in C3N4by replacing a corner C atom upshifted thed‐band center of Cu in Cu1N3@PCN close to the Fermi level, which boosted the adsorption and activation of CO2on Cu1N3, making Cu1N3@PCN efficiently convert CO2to CO. In contrast, Cu1P3@PCN with a much lower Cu3delectron energy exhibited negligible CO2adsorption, thereby preferring H2formation via photocatalytic H2O splitting.
Dearomative Ring Expansion of Polycyclic Arenes
Authors: Piacentini Paolo , Bingham Tanner W. , Sarlah David
Published: July 2022

Benzocycloheptenes constitute a common structural motif embedded in many natural products and biologically active compounds. Herein, we report their concise preparation from non‐activated polycyclic arenes using a two‐step sequence involving dearomative [4+2]‐cycloaddition with arenophile in combination with palladium‐catalyzed cyclopropanation, followed by cycloreversion‐initiated ring expansion. The described strategy provides a working alternative to the Buchner reaction, which is limited to monocyclic arenes. Overall, this methylene‐insertion molecular editing approach enables rapid and direct conversion of simple (hetero)arenes into a range of substituted (aza)benzocycloheptatrienes, which can undergo a myriad of downstream functionalizations.
Glycidyl ester and 3‐MCPD ester content in esters of monoglyceride and polyglycerol esters
Authors: Keller Erik , Miller Rasmus Leth
Published: July 2022

It is a well‐established fact that 3‐MCPD esters and glycidyl esters (GE) are groups of food‐processing contaminants, which presents several health issues and that their presence should be reduced to the lowest possible level. The public focus has been on edible oils and fats, but in this work the 3‐MCPDE and GE formation or reduction effect of the esterification is investigated in the synthesis of the food emulsifiers ACETEM, CITREM, LACTEM, PGE, and PGPR. It is shown through factory productions that the content of glycidol, 3‐MCPD and their esters as a sum is most often below 5 mg/kg MCPD equivalents. This is even the case when the raw material contains considerable amounts and in cases up to 75 mg/kg. It is also indicated that the content of glycidol + GE changes much more than 3‐MCPD +3‐MCPD ester, and that the total sum is always reduced through the esterification process. Lab‐scale results on CITREM suggest that 3‐MCPD +3‐MCPD ester comprise a significant part of the total content of 3‐MCPD equivalents in the end‐product. That is, it is likely that the glycidol + GE content in the end‐product is most often well below 1 mg/kg (quantified as free glycidol). The emulsifier ester production processes are characterized by acidic conditions, and this fits nicely with other reports that e.g. acid activated bleaching earth is effective for glycidol/GE reduction in edible oils.
Gaia search for stellar companions of TESS Objects of Interest III
Authors: Mugrauer Markus , Zander Jule , Michel Kai‐Uwe
Published: July 2022

The latest results from our ongoing multiplicity study of (Community) TESS Objects of Interest are presented, using astro‐ and photometric data from the ESA‐Gaia mission, to detect stellar companions of these stars and characterize their properties. A total of 124 binary and 7 hierarchical triple star systems were detected among 2175 targets, whose multiplicity was investigated in the course of our survey, which are located at distances closer than about 500 pc around the Sun. The detected companions and the targets are located at the same distance and share a common proper motion, as expected for components of gravitationally bound stellar systems, as proven with their accurate Gaia EDR3 astrometry. The companions have masses in the range between about 0.09 and 2.5 and are most frequently found in the mass range between 0.15 and 0.8 . The companions exhibit projected separations to the targets between about 50 to 9700 au and their frequency is the highest and constant up to about 500 au, while it decreases for larger projected separations. In addition to mainly mid M to early K dwarfs, 4 white dwarf companions were also detected in this survey, whose true nature could be identified with their photometric properties.
All Redox‐Active 2D MXene and 0D Phosphomolybdic Acid Nanoclusters‐Anchored Polypyrrole Nanotubes for High‐Performance Aqueous Hybrid Supercapacitors
Authors: Stephanie Ruth , Patil Swati J. , Chodankar Nilesh R , Suk Huh Yun , Han Young‐Kyu , Park Tae Jung
Published: July 2022

Invited for this month's cover picture is the work of a collaboration group led by Professor Tae Jung Park, Dept. of Chemistry, Chung‐Ang University, Republic of Korea. The work depicted in the cover picture is a high‐performance aqueous hybrid supercapacitor based on all redox‐active 2D MXenes and 0D phosphomolybdic acid nanocluster‐anchored polypyrrole nanotubes. The resulting device showed a specific energy of 36.1 Wh kg−1 and a specific power of 6.66 kW kg−1, with good stability over 5000 charge‐discharge cycles. Read the full text of the Research Article at 10.1002/batt.202200108.
Vestibular Extremely Low‐Frequency Magnetic and Electric Stimulation Effects on Human Subjective Visual Vertical Perception
Authors: Bouisset Nicolas , Villard Sébastien , Legros Alexandre
Published: July 2022

Electric fields from both extremely low‐frequency magnetic fields (ELF‐MF) and alternating current (AC) stimulations impact human neurophysiology. As the retinal photoreceptors, vestibular hair cells are graded potential cells and are sensitive to electric fields. Electrophosphene and magnetophosphene literature suggests different impacts of AC and ELF‐MF on the vestibular hair cells. Furthermore, while AC modulates the vestibular system more globally, lateral ELF‐MF stimulations could be more utricular specific. Therefore, to further address the impact of ELF‐MF‐induced electric fields on the human vestibular system and the potential differences with AC stimulations, we investigated the effects of both stimulation modalities on the perception of verticality using a subjective visual vertical (SVV) paradigm. For similar levels of SVV precision, the ELF‐MF condition required more time to adjust SVV, and SVV variability was higher with ELF‐MF than with AC vestibular‐specific stimulations. Yet, the differences between AC and ELF‐MF stimulations were small. Overall, this study highlights small differences between AC and ELF‐MF vestibular stimulations, underlines a potential utricular contribution, and has implications for international exposure guidelines and standards. © 2022 Bioelectromagnetics Society.
Structural and optical properties of a new Milarite type Na3Mg4LiSi12O30:Eu3+ phosphor
Authors: Giri Varadarajan Kanmani , Velladurai Ponnusamy , Govindan Rajkumar , Mundiyanikal Thomas Jose
Published: July 2022

A new red‐emitting Eu3+ (1−17 mol%)‐doped Na3Mg4LiSi12O30 (NMLS) phosphor was prepared using a conventional solid‐state reaction method at low temperature. The prepared samples belong to a hexagonal structure with a good match to JCPDS card no. 73–0934. The photoluminescence (PL) emission spectrum showed an intense peak at 612 nm when excited at 393 nm. The variation of electric dipole transition (5D0–7F2) emission intensity with increasing Eu3+ ion concentration was investigated. The concentration quenching at 11 mol% is due to the dipole–dipole interaction mechanism in the NMLS host. The optimized NMLS:Eu3+phosphor shows 2.18 times higher luminescence intensity than the (Y,Gd)BO3 (YGB) commercial phosphor. The NMLS:Eu3+showed an intense red emission, having Commission Internationale de l'éclairage (CIE) coordinates (0.6280, 0.3691) and colour purity of 99.2%. The resulting phosphor exhibits good thermal stability of 80% at 423 K. The magnified images of fingerprint showed various minute features such as bridges, sweat pores, ridge end, bifurcation, island and core with better visualization under 393 nm excitation. Furthermore, the optimized NMLS:Eu3+ was used for pc‐LED, latent fingerprints, and anticounterfeit applications as a promising red phosphor.
Coupling riboflavin de novo biosynthesis and cytochrome expression for improving extracellular electron transfer efficiency in Shewanella oneidensis
Authors: Li Yan , Li Yuanyuan , Chen Yaru , Cheng Meijie , Yu Huan , Song Hao , Cao Yingxiu
Published: July 2022

Shewanella oneidensis MR‐1, as a model exoelectrogen with divergent extracellular electron transfer (EET) pathways, has been widely used in microbial fuel cells (MFCs). The electron transfer rate is largely determined by riboflavin (RF) and c‐type cytochromes (c‐Cyts). However, relatively low RF production and inappropriate amount of c‐Cyts substantially impede the capacity of improving the EET rate. In this study, coupling of riboflavin de novo biosynthesis and c‐Cyts expression was implemented to enhance the efficiency of EET in S. oneidensis. First, the upstream pathway of RF de novo biosynthesis was divided into four modules, and the expression level of 22 genes in above four modules was fine‐tuned by employing promoters with different strengths. Among them, genes zwf*, glyA, and ybjU which exhibited optimal RF production were combinatorially overexpressed, leading to the enhancement of maximum output power density by 166%. Second, the diverse c‐Cyts genes were overexpressed to match high RF production, and omcA was selected for further combination. Third, RF de novo biosynthesis and c‐Cyts expression were combined, resulting in 2.34‐fold higher power output than the parent strain. This modular and combinatorial manipulation strategy provides a generalized reference to advance versatile practical applications of electroactive microorganisms.
The landscape of enhancer RNA identify prognosis‐related molecular subtypes in gastric cancer
Authors: Yan Aiting , Chen Ying , Bian Rongrong , Wang Cuizhu , Que Haitao , Shen Yucheng , Lu Xiaomin
Published: July 2022

Background

Enhancer RNAs (eRNAs), the transcriptional products of active enhancers, are of great significance in the initial progression of cancers. However, the biological function and bioinformatics profiles of eRNA in gastric cancer remains largely enigmatic.

Methods

Firstly, STAD were clustered into three subtypes with the data of eRNA expression from TCeA. Then we explored the difference of the tumor immune microenvironment, transcription levels, and transcription regulation among the three clusters. Finally, samples collected from 12 patients diagnosed with STAD were used to conduct qRT‐PCR, verifying the conclusion based on network database.

Results

The three clusters were detected to have different tumor microenvironments: Cluster A has an immune “cold” microenvironment. While cluster B features as more infiltration of immune cells, accompanied with higher expression of immune checkpoints such as PDCD1, LAG3, and TIGIT. Besides, Cluster C shows a higher stromal feature with B lineage, neutrophils, and fibroblasts. Further analyses indicated that CpG island methylation level of Cluster B is different from the other two clusters. Meanwhile, Cluster A and B showed significant enrichment of TP53 and KRAS mutation respectively while Cluster C has higher tumor mutation burden (TMB) and microsatellite instability (MSI). With the elaboration of transcriptional regulation of epigenetic clustering, we detected that Cluster A enriched in epithelial phenotype pathways. Cluster B enriched in cell–cell adhesion. Cluster C enriched in fibroblast proliferation. The clinical cohort show that Cluster B patients have lower interstitial cell characteristics and CAF infiltration.

Conclusion

We identified three unique epigenetic clusters of STAD through the differential activation of super‐enhancers, and identified Cluster B with a higher immune infiltrating and a better prognosis, which provides a novel understanding of eRNAs and potential clinical applicability of eRNA‐based molecular subtypes in gastric cancer.
Applications and Limitations of Oxime‐Linked “Split PROTACs”
Authors: Gui Weijun , Kodadek Thomas
Published: July 2022

Proteolysis targeting chimeras are of keen interest as probe molecules and drug leads. Their activity is highly sensitive to the length and nature of the linker connecting the E3 Ubiquitin Ligase (E3 Ubl) and target protein (TP) ligands, which therefore requires tedious optimization. The creation of “split PROTACs” from E3 Ubl and TP ligands modified with residues suitable for them to couple when simply mixed together would allow various combinations to be assessed in a combinatorial fashion, thus greatly easing the workload relative to a one‐by‐one synthesis of many different PROTACs (proteolysis targeting chimeras). We explore oxime chemistry here for this purpose. We show that PROTAC assembly occurs efficiently when the components are mixed at a high concentration, then added to cells. However, in situ coupling of the TP and E3 Ubl ligands is inefficient when these units are added to cells at lower concentrations.
Intramolecular Covalent Bonds in Gram‐Positive Bacterial Surface Proteins
Authors: Ma Quan , Lei Hai , Cao Yi
Published: July 2022

Gram‐positive bacteria experience considerable mechanical perturbation when adhering to host surfaces during colonization and infection. They have evolved various adhesion proteins that are mechanically robust to ensure strong surface adhesion. Recently, it was discovered that these adhesion proteins contain rare, extra intramolecular covalent bonds that stabilize protein structures and participate in surface bonding. These intramolecular covalent bonds include isopeptides, thioesters, and ester bonds, which often form spontaneously without the need for additional enzymes. With the development of single‐molecule force spectroscopy techniques, the detailed mechanical roles of these intramolecular covalent bonds have been revealed. In this review, we summarize the recent advances in this area of research, focusing on the link between the mechanical stability and function of these covalent bonds in Gram‐positive bacterial surface proteins. We also highlight the potential impact of these discoveries on the development of novel antibiotics and chemical biology tools.
VA‐ECMO‐assisted aspiration thrombectomy in a patient presenting with acute massive PE with absolute contraindications to thrombolytics
Authors: Patel Mit , Mujer Mark , John Alan , Darki Amir
Published: July 2022

Massive pulmonary embolism (PE) is a life‐threatening complication of major surgery with a mortality rate up to 50%. First‐line therapy for massive PE is systemic thrombolytics, but surgical patients are at high bleeding risk with absolute contraindications. As surgical thrombectomy carries a high burden of morbidity and mortality, endovascular interventions are becoming more common in these clinical scenarios. We report a case of a neurosurgical patient whose postoperative course was complicated by massive PE and subsequent cardiac arrest that required emergent venoarterial extracorporeal membrane oxygenation, followed by aspiration thrombectomy with the Inari FlowTriever Device (Inari Medical). The patient had immediate hemodynamic improvement with eventual recovery to baseline functional status.
Mo−N Bonds Effect Between MoSx Coupling With CoN For Efficient Photocatalytic Hydrogen Production
Authors: Liu Hai , Zhang Yueyang , Li Youji , Yang Mengxue , Li Yanbin , Jin Zhiliang
Published: July 2022

The facet‐engineered surface and interface design has attracted much attention in the preparation of efficient photocatalysts. Polyvinylpyrrolidone (PVP) is used as the morphological modifier to prepare 3D MoSx in this work. Benefit by its suitable conduction band position and good conductivity, CoN accepts photo‐induced electrons from MoSx as an excellent electron acceptor in the form of active sites. With the addition of CoN, hydrogen evolution performance of MoSx has been greatly improved by building the Mo−N bond since the form of Mo−N bond successfully shorten electron transport routes. The reason for the improved hydrogen precipitation efficiency is demonstrated by PL, XPS, and electrochemical characterization. The H2 production activity of MoSx@CoN with the best mass ratio of MoSx to CoN is up to 7617.5 μmol/g/h, and the hydrogen production stability of MoSx@CoN is also considerable. These findings provide new insights for the preparation of highly efficient photocatalytic hydrogen evolution materials.
ZrO2/C Nanosphere Enables High‐Efficiency Nitrogen Reduction to Ammonia at Ambient Conditions
Authors: Dong Shuyue , Xia Jiaojiao , Zhu Hexin , Du Xiangning , Gu Yang , Liu Qian , Luo Yonglan , Kong Qingquan , Guo Haoran , Li Tingshuai , Traversa Enrico
Published: July 2022

Electrochemical synthesis of ammonia via nitrogen reduction reaction is a rational route to save energy and relieve pollution compared to the traditional Haber‐Bosch process. In this report, ZrO2 nanosphere derived from thermolysis of Zr‐based biphenyl‐4,4′‐dicarboxylic acid MOFs (ZrO2/C) as a non‐noble metal catalyst with large specific surface area and porous structure is proposed to fix nitrogen to ammonia at ambient conditions. Such catalyst achieves Faradaic efficiency of 11.86 % and a NH3 yield rate of 10.72 μg h−1 mg−1cat. at −0.6 V vs. the reversible hydrogen electrode in 0.1 M Na2SO4. First‐principles calculations confirm the alternating reaction at the catalyst surface.
Temperature Driven Transformation of the Flexible Metal–Organic Framework DUT‐8(Ni)
Authors: Ehrling Sebastian , Senkovska Irena , Efimova Anastasia , Bon Volodymyr , Abylgazina Leila , Petkov Petko , Evans Jack D. , Gamal Attallah Ahmed , Wharmby Michael Thomas , Roslova Maria , Huang Zhehao , Tanaka Hideki , Wagner Andreas , Schmidt Peer , Kaskel Stefan
Published: July 2022

DUT‐8(Ni) metal–organic framework (MOF) belongs to the family of flexible pillared layer materials. The desolvated framework can be obtained in the open pore form (op) or in the closed pore form (cp), depending on the crystal size regime. In the present work, we report on the behaviour of desolvated DUT‐8(Ni) at elevated temperatures. For both, op and cp variants, heating causes a structural transition, leading to a new, crystalline compound, containing two interpenetrated networks. The state of the framework before transition (op vs. cp) influences the transition temperature: the small particles of the op phase transform at significantly lower temperature in comparison to the macroparticles of the cp phase, transforming close to the decomposition temperature. The new compound, confined closed pore phase (ccp), was characterized by powder X‐ray diffraction and spectroscopic techniques, such as IR, EXAFS, and positron annihilation lifetime spectroscopy (PALS). Thermal effects of structural transitions were studied using differential scanning calorimetry (DSC), showing an overall exothermic effect of the process, involving bond breaking and reformation. Theoretical calculations reveal the energetics, driving the observed temperature induced phase transition.
Bottom‐up Synthesis of Water‐Soluble Gold Nanoparticles Stabilized by N‐Heterocyclic Carbenes: From Structural Characterization to Applications
Authors: Thomas Sophie R. , Yang Wenjie , Morgan David J. , Davies Thomas E. , Li Jiao Jiao , Fischer Roland A. , Huang Jun , Dimitratos Nikolaos , Casini Angela
Published: July 2022

N‐heterocyclic carbenes (NHCs) have become attractive ligands for functionalizing gold nanoparticle surfaces with applications ranging from catalysis to biomedicine. Despite their great potential, NHC stabilized gold colloids (NHC@AuNPs) are still scarcely explored and further efforts should be conducted to improve their design and functionalization. Here, the ‘bottom‐up’ synthesis of two water‐soluble gold nanoparticles (AuNP‐1 and AuNP‐2) stabilized by hydrophilic mono‐ and bidentate NHC ligands is reported together with their characterization by various spectroscopic and analytical methods. The NPs showed key differences likely to be due to the selected NHC ligand systems. Transmission electron microscopy (TEM) images showed small quasi‐spherical and faceted NHC@AuNPs of similar particle size (ca. 2.3–2.6 nm) and narrow particle size distribution, but the colloids featured different ratios of Au(I)/Au(0) by X‐ray photoelectron spectroscopy (XPS). Furthermore, the NHC@AuNPs were supported on titania and fully characterized. The new NPs were studied for their catalytic activity towards the reduction of nitrophenol substrates, the reduction of resazurin and for their photothermal efficiency. Initial results on their application in photothermal therapy (PTT) were obtained in human cancer cells in vitro. The aforementioned reactions represent important model reactions towards wastewater remediation, bioorthogonal transformations and cancer treatment.
What constrains firms from divesting their legacy business?
Authors: Ding Yang
Published: July 2022

This study focuses on a unique business phenomenon, legacy divestitures, which refers to the sale or spinoff of a firm's original business. I argue that firms may be prevented from engaging in legacy divestiture by organizational inertia, which become increasingly stronger as the legacy business gets older. I also examine factors that help firms overcome the constraints of inertial forces on firms' legacy divestitures. Hypotheses are tested using a sample of 108 diversified American companies, 27 of which divested legacy businesses between 1980 and 2017. Firms are less likely to divest their legacy businesses as the legacy units get older. The negative relationship is weakened by two factors, performance–aspiration gaps and R&D intensity.
Synthesis of (E)‐β‐Iodovinyl Sulfones via Photoredox Catalyzed Difunctionalization of Terminal Alkynes
Authors: Kumar Sourav , Kumar Jaswant , Naqvi Tahira , Raheem Shabnam , Rizvi Masood Ahmad , Shah Bhahwal Ali
Published: July 2022

A photoredox mediated approach enabling the synthesis of (E)‐β‐iodovinyl sulfones at room temperature using simple alkynes and thiols as the coupling partners in the presence of TBAI as iodine source is reported. The direct conversion of thiols into sulfones following the tandem introduction of C−I and C−S bonds is achieved using SeO2 as an oxidizing agent. The method is viable with a wide range of alkynes and thiols at room temperature, employs mild conditions, and has good yields. Besides, we could also use β‐iodovinyl sulfones as the starting material to access different β‐functionalized sulfone derivatives.
Tolerance to mid‐season drought in peanut can be achieved by high water use efficiency or high efficient use of water
Authors: Zhang Qiong , Dang Phat , Chen Charles , Feng Yucheng , Batchelor William , Lamb Marshall , Sanz‐Saez Alvaro
Published: July 2022

Peanut (Arachis Hypogaea L) is an economic cash crop mainly planted in arid and semi‐arid regions where drought causes approximately 20% yield losses every year. It has been demonstrated that drought tolerance can be achieved by two different mechanisms in plants: either by saving water or by extracting more water from the soil (water spender genotypes). The objective of this research was to screen for these two mechanisms of drought tolerance in peanut. Plants were grown in rainout shelters under irrigated conditions until mid‐pod filling, then drought was induced using rain‐out shelters. Gas exchange parameters were measured regularly during the drought period and recovery. Genotypes PI 502120 and AU‐NPL 17 were classified as water spender genotypes as they showed high yield, Δ13C, photosynthesis, and stomatal conductance under drought. This is the first time that water spender genotypes have been identified in peanut. On the other hand, genotypes Line‐8 and AU16‐28 were classified as water savers as they showed equally high yields but with low Δ13C and stomatal conductance and moderate photosynthesis under drought stress. In this study, water spender genotypes did not show a yield advantage in comparison with water savers.
Identification and characterization of novel CD274 (PD‐L1) regulating microRNAs and their functional relevance in melanoma
Authors: Vaxevanis Christoforos K. , Friedrich Michael , Tretbar Sandy Uta , Handke Diana , Wang Yuan , Blümke Juliane , Dummer Reinhard , Massa Chiara , Seliger Barbara
Published: July 2022

Background

Immune checkpoint inhibitors directed against programmed cell death 1 (PDCD1/PD1) receptor and programmed cell death‐ligand 1 (CD274/PD‐L1) have been recently successfully implemented for the treatment of many cancers, but the response rate of tumour patients is still limited due to intrinsic and acquired resistances. However, the underlying molecular mechanisms of this limited response have still to be defined in detail. The aim of this study is to uncover processes inhibiting PDCD1/CD274 expression thereby enhancing anti‐tumour immune responses. The identification and characterization of microRNAs (miRNAs) targeting the 3′‐untranslated region (3′‐UTR) as well as the coding sequence (CDS) of CD274 will provide the basis for a new drug development.

Methods

Human melanoma cell lines and tissue samples were subjected to mRNA and/or protein expression analysis using qPCR, Western blot, flow cytometry, and/or immunohistochemistry. The data were correlated to clinical parameters. MiRNA trapping by RNA in vitro affinity purification (miTRAP) technology in combination with small RNA sequencing and different bioinformatics tools were employed to identify CD274‐regulating miRNAs.

Results

Screening based on miTRAP in combination with RNAseq identified a large number of novel CD274‐regulating candidate miRNAs, from which eight selected miRNAs were functionally validated. Five out of eight miRNAs were able to significantly reduce CD274 surface expression indicating that these miRNAs directly bind to the 3′‐UTR or CDS of the CD274 gene. The miRNA‐mediated inhibition of CD274 expression was accompanied by an increased T cell recognition. Furthermore, an inverse expression of three CD274‐regulating miRNAs and CD274 was demonstrated in melanoma lesions. A CD274 miRNA score was generated, which was associated with disease progression and reduced survival of melanoma patients.

Conclusions

These data revealed a novel mechanism that miRNAs targeting the CDS of immune checkpoint genes are functional, have prognostic relevance, and also the potential for the development of novel miRNA‐based therapies.
Hybrid grasshopper and differential evolution algorithm for prolonging network life expectancy in wireless sensor networks (WSNs)
Authors: Manoharan Mathankumar , Ponnusamy Thirumoorthi
Published: July 2022

In wireless sensor networks (WSNs), restricted battery power, balanced energy consumption, and collaborative data processing are considered as key challenges that need to be handled with utmost care. Clustering in WSNs is an optimal methodology for conserving energy of sensor nodes and attaining efficient data processing that attributes toward the maximization of network lifetime. An efficient cluster head (CH) selection scheme is essential for achieving superior collaborative data processing in WSNs. Swarm intelligent metaheuristic algorithm‐based CH selection approaches are identified to be better for designing energy‐efficient schemes that select optimal CHs from nodes in a fair way. In this paper, Hybrid Grasshopper and Differential Evolution‐based Optimization Algorithm (HGDEOA) is proposed for targeting on the objective of attaining energy stability and prolonging network lifetime. This HGDEOA incorporates an adaptive strategy into differential evolution (DE) for improving the global searching capability during the process of optimization. It is proposed for improving the convergence efficiency and maintaining population diversity. It also possesses the capability of enhancing the degree of convergence speed and precision in calculation. This integration of GOA into DE prevents the premature convergence of the algorithm, since the deviation amid the scaling individuals induces the population to be more randomly distributed, targeting at the retention of population diversity. The simulation results confirm that the proposed HGDEOA sustains residual energy by 19.32%, improves throughput by 16.21%, prolongs network lifetime by 18.76%, and maintains stability by18.94% when compared to the benchmarked approaches used for investigation.
Raised circulating soluble growth differentiation factor 15 is negatively associated with testosterone level in hypogonadic men with type 2 diabetes
Authors: Mei Yufeng , Lyu Yongnan , Le Juan , Li Di , Liu Hang , Zhao Zhiming , Li Yan
Published: July 2022

Aims

Epidemiological studies consistently show that decreases in serum testosterone level are observed more frequently in men with type 2 diabetes mellitus (T2DM), while clinical investigations have demonstrated that an increased level of circulating growth differentiation factor‐15 (GDF‐15) are also related closely to T2DM. The aim of this study was to examine the potential relationship between serum GDF‐15 levels and hypogonadism in Chinese male patients with T2DM.

Materials and Methods

A total of 305 T2DM men were recruited between July 2020 and August 2021. GDF‐15 and total testosterone concentrations were quantified by an enzyme‐linked immunosorbent assay and LC/MS mass spectrometry, respectively. Multiple linear regression analysis, logistic regression, and restricted cubic splined models were used to examine the correlation between GDF‐15 levels and hypogonadism in these patients.

Results

When compared with T2DM patients without hypogonadism circulating GDF‐15 levels were significantly higher in the hypogonadism group [1081.83 (746.79,1539.94) versus 779.49 (548.46,1001.27), p < 0.001] and were associated positively with hypogonadism in unadjusted and fully adjusted multivariate regression models (p < 0.01). The fully adjusted regression coefficients with 95% confidence intervals for circulating GDF‐15 and testosterone deficiency were −1.795 (−2.929, −0.661). Serum GDF‐15 levels were also associated positively with testosterone deficiency in each logistic regression model (p < 0.05), while after adjustment for all risk factors, the same findings were obtained in the restricted cubic splined models (p < 0.01).

Conclusions

In hypogonadal men with T2DM, an elevated serum GDF‐15 level is associated negatively with serum testosterone concentration. GDF‐15 may be a novel cytokine related to T2DM men with hypogonadism.
Big Health Data Research and Group Harm: The Scope of IRB Review
Authors: Doerr Megan , Meeder Sara
Published: July 2022

Much of precision medicine is driven by big health data research—the analysis of massive datasets representing the complex web of genetic, behavioral, environmental, and other factors that impact human well‐being. There are some who point to the Common Rule, the regulation governing federally funded human subjects research, as a regulatory panacea for all types of big health data research. But how well does the Common Rule fit the regulatory needs of this type of research? This article suggests that harms that may arise from artificial intelligence and machine‐learning technologies used in big health data research—and the increased likelihood that this research will affect public policy—mean it is time to consider whether the current human research regulations prohibit comprehensive, ethical review of big health data research that may result in group harm.
Developing and Implementing Electronic Consent Procedures in Response to Covid‐19 Restrictions
Authors: Bromberg Julie R. , Nimaja Evelyn , Kiragu Andrew W. , Lawson Karla A. , Lee Lois , Nasr Isam W. , Pruitt Charles , Ruest Stephanie M. , Mello Michael J.
Published: July 2022

The Covid‐19 pandemic resulted in unprecedented restrictions on many public, private, and workplace activities throughout the United States and elsewhere. When restrictions were imposed, we were conducting a type III hybrid effectiveness‐implementation trial in 10 pediatric trauma centers. In response to several pandemic‐based restrictions, we had to develop procedures for engaging with potential research participants while limiting nonclinical, in‐person interactions. This manuscript describes the procedures and challenges of obtaining electronic informed consent and assent in a multisite trauma center‐based research study. We developed, tested, and trained staff to implement three options for obtaining informed consent. Twenty‐five participants were enrolled in the effectiveness‐implementation multisite trial during the first six months of utilization of the consent options, with eleven of these individuals enrolled using hybrid or electronic consent procedures. The challenges we identified involving electronic consent procedures included confusion over who would complete the electronic consent process and difficulties reconnecting with families. Lessons learned can strengthen electronic consent and assent procedures for future studies. More research is needed to further strengthen this process and increase its utilization.
How intensive revegetation affects runoff in semiarid watersheds: A case study based on an integrated modelling framework
Authors: Chang Yiming , Lei Huimin
Published: July 2022

Revegetation projects are beneficial measures used to control soil erosion, though they can adversely affect the water yield of semiarid watersheds. In this study, Dali River basin that is a semiarid basin with intensive ecological restoration strategies on the Loess Plateau of China was selected as an extreme condition to examine how revegetation projects affect watershed runoff. In the study watershed, the vegetation indicator Normalized Difference Vegetation Index (NDVI) and Soil Adjusted Total Vegetation Index (SATVI) increased by 6.9% and 189.1% after 2000, respectively. Human activities contributed most to vegetation increase (77.1% for NDVI and 98.6% for SATVI). We quantified the response of runoff change to revegetation within a physically based modelling framework that incorporated the effects of check‐dam construction and was constrained by the observed runoff data. The results showed that revegetation explained 29.2% of the runoff decrease in the impact period 2 (2000–2010), but its contribution was lower than that of check‐dam construction (75.2%). Compared with climatic factors, implementation of the two ecological restoration projects was the dominant driver of runoff reduction after 2000. This study demonstrates the importance of attribution analysis in an integrated modelling framework with revegetation and other ecological restoration projects and constrained by the observed runoff data.