bluuebunny/crossref_metadata_2025 huggingface dataset:
Uniaxial Strain Engineering of Anisotropic Phonon in Few‐Layer Violet Phosphorus with High Stretchability for Polarized Sensitive Flexible Photodetector
Authors: Shang Conghui , Wang Weiwei , Zhang Jianbin , Zhao Yi , Li Jiaxuan , Chen Liangqiang , Jia Guohui , Zhou Nan , Liu Ge , Hui Mantang , Huang Hongyang , Zhang Lihui , Dong Guangzhi , Zhang Jinying , Xu Hua , Li Xiaobo , Yang Rusen
Published: August 2024

The manifestation of mechanical phenomena in quantum materials at the macroscopic level is intricately linked to pronounced electron‐electron interactions within their lattices, a relationship that becomes especially evident in low‐dimensional materials. Violet phosphorous (VP), a nascent 2D material distinguished by its unique vertically aligned tubular structures, has garnered considerable attention owing to its layer‐dependent electronic bandgap, exceptional carrier mobility, and robust air stability. Herein, a comprehensive exploration of the phonon modes exhibited by few‐layer VP through an integrated experimental‐theoretical approach, focusing on the modulation of their Raman response under the uniaxial strain along a‐axis, b‐axis, and tube direction, respectively, is undertaken. Density functional theory calculations highlight when strain is applied along the a‐ or b‐axis direction, the strain is predominantly mitigated through tube rotational adaptations instead of the change of bond length and bond angle, culminating in a pronounced anisotropic Raman response. Moreover, the strain engineering can effectively optimize the photoelectric response performance of VP, including increase the responsivity ≈2500% and elevate the anisotropic ratio from 2.26 to 3.38. This investigation not only confirms the superior stretchability and impact resistance properties of cross‐structured VP but also establishes the groundwork for exploring the strain‐induced anisotropic optoelectric properties to VP.
Interface Collaborative Strategy for High Mobility Organic Single‐Crystal Field‐Effect Transistors with Ideal Current–Voltage Curves
Authors: Ren Jianzhou , Rong Bokun , Zheng Lei , Hu Yongxu , Wang Yuchan , Wang Zhongwu , Chen Xiaosong , Zhang Kailiang , Li Liqiang , Hu Wenping
Published: August 2024

The key roles of electrode/semiconductor and semiconductor/dielectric interfaces play in the ideality of organic field‐effect transistors (OFETs) by traditional device preparation technologies are not yet fully understood, which severely limits progress in the design of molecules, the understanding of transport mechanisms, and the circuit applications of OFETs. Herein, at a quantitative level, the origin of nonideal current–voltage (I–V) curves and possibly overestimated mobility in single‐crystal OFETs is revealed, including contact resistance (Rc), charge trapping, and scattering at interfaces of devices. Impressively, an efficient interface collaborative strategy, which consists of transferred “doped” electrodes with tunable contact “doping” localized regions at the source‐drain contacts and polymer‐modified SiO2 with suitable surface polarity (γsp) is further demonstrated that have great advantages in the construction of ideal high mobility devices. Also, an interesting double‐edged sword effect of γsp of dielectric on the ideality of OFETs is observed. The dielectric with a lower γsp can result in higher mobility, while too low γsp would degrade the device ideality due to significant effect of charge scattering. The findings not only provide new perspectives and strategies to construct ideal OFETs but also offer useful guidance to correctly evaluate organic semiconductor materials.
A Robust Phosphonate‐Based Hydrogen‐Bonded Organic Framework Birefringent Crystal
Authors: Sun Yayong , Li Yanqiang , Song Xianyu , Zhao Sangen , Zhou Tianhua , Zhang Jian
Published: August 2024

Birefringent crystals as an important optical anisotropic material play a crucial role in modulating the polarization state of light. To date, most birefringent crystals are purely inorganic compounds with small birefringence. Developing large birefringent crystals remains a great challenge primarily because of the absence of tunable anisotropic structural units for inorganic materials. Herein, a hydrogen‐bonding self‐assembly strategy is reported to construct a robust hydrogen‐bonded organic framework (HOF, namely m‐H3L) birefringent crystal, which consists of π‐conjugated benzene rings and tetrahedral phosphonate groups interconnected via multiple H‐bonding interactions. Interestingly, the birefringence is as large as ∆n = 0.17@550 nm and catches up with those of commercial birefringent crystals. A combination of theoretical calculation and single‐crystal structural analyses reveals that the H‐bonding interactions control the dihedral angle of π‐conjugated benzene rings and the smaller the dihedral angle, the greater the birefringence. This discovery opens the door for the tunable HOFs to be used as a promising new class of birefringence materials.
Construction of Spirocyclic Compounds via Electrochemical Intramolecular Dearomatization of Benzene Derivatives
Authors: Zhang Wen‐Yun , Zhu Long‐Hao , Cheng Yuan‐Zheng , You Shu‐Li
Published: August 2024

The spirocyclic framework is found in many natural products, some of which are biologically active. However, It remains a challenge to develop environmentally friendly and atom‐economic synthetic methods. Herein, we report an intramolecular dearomatization reaction of benzene derivatives enabled by electrochemistry‐mediated two successive single‐electron‐transfer (SET) processes, providing an alternative method for the rapid construction of spirocyclic skeletons without using sacrificial reagents. A series of cyclohexadiene products were obtained in 25–81% yields. Furthermore, a proposed mechanism involving a sequential electron transfer event was supported by cyclic voltammetry experiments. This strategy features transition‐metal‐free conditions and easy handling, which will greatly enhance its practical utility.
Exploring the Optoelectronic and Photovoltaic Characteristics of Lead‐Free Cs2TiBr6 Double Perovskite Solar Cells: A DFT and SCAPS‐1D Investigations
Authors: Hossain M. Khalid , Islam Sahjahan , Sakib M. Najmus , Uddin M. Shihab , Toki Gazi F. I. , Rubel Mirza H. K. , Nasrin Jahanara , Shahatha Sara H. , Mohammad M. R. , Alothman Asma A. , Raorane Chaitany Jayprakash , Haldhar Rajesh , Bencherif Hichem
Published: August 2024

In recent times, the remarkable advancements achieved in the field of perovskite solar cells (PSCs) have sparked significant research efforts aimed at enhancing their overall performance because of their exceptional optoelectronic properties. Due to the toxicity of lead (Pb), the emergence of Ti‐based (Cs2TiBr6) double‐halide PSCs is regarded as a good alternative to Pb‐based PSCs. Here, density functional theory (DFT) calculations are performed to examine the prospect of Cs2TiBr6 perovskite as a layer of absorber for photovoltaic cells (SCs). These computations looked at the material's structural, optical, and electrical characteristics. The density of states (DOS) results demonstrate strong conductivity, principally provided by the 4p states of Br, whilst Ti‐3d and Cs‐5p orbital electrons offer insignificant contributions. The electronic band structure discloses a direct band gap of 1.534 eV. The covalent connections that exist between Ti and Br atoms and the robust electronic charge density around the Ti atom both demonstrate a significant buildup of electronic charge along the 100 planes. The dielectric function and the coefficient of absorption have significance irrespective of lower energies because it is extremely valuable for solar energy applications. The UV absorption peaks of Cs2TiBr6 have a maximum of ≈15.51 eV and are magnified with photon energy up to 2.46 eV, indicating that it may have potential for solar applications. This work also investigated a good combination of the hole transport layer (HTL) and electron transport layer (ETL) with the Cs2TiBr6 absorber layer. AZnO, Nb2O5, LBSO, and Zn2SnO4 are executed as the ETLs, and MoO3, CuAlO2, MEH‐PPV, ZnTe, CNTS, GaAs, MoS2, PTAA, Cu2Te, Zn3P2 are considered as the HTLs to identify the best HTL/Cs2TiBr6/ETL combinations using the SCAPS‐1D numerical simulation. Among all configurations, ITO/LBSO/Cs2TiBr6/CNTS/Au is examined as the best‐optimized structure of Ti‐based PSC, with JSC of 26.63 mA cm−2, a VOC of 1.123 V, FF of 82.94%, and a power conversion efficiency of 24.82%. To validate the findings, PV parameters like the effect of generation rate, recombination rate, J−V, and Q‐E characteristics are evaluated. The effect of series and shunt resistance and structure working temperature are explored to observe the effect of these on PSC devices. The accomplished outcomes suggest that Cs2TiBr6 can be viewed as an optimistic material for PSCs for its higher stability and environment‐friendly characteristics.
Fully Conjugated Anthraquinone‐Quinoxaline Derivative Cathode Enabling a Superior Zn‐Ion Storage at Extremely Low Temperature −50 °C
Authors: Zhai Yunming , Ji Cheng , Wang Rui , Ma Quanwei , Zhang Longhai , Li Hongbao , Zhang Chaofeng , Zhang Qianyu
Published: August 2024

Small molecule organic materials have been considered promising candidates as cathodes in aqueous zinc‐ion batteries (AZIBs) because of their low cost, environmental friendliness, and sustainable production. However, the rapid capacity fading and sluggish kinetics restrict their practical applications, especially under extremely low temperatures (−50 °C). Here, by the condensation of hexaketocyclohexane octahydrate (HKCO) and 1, 2‐diaminoanthraquinone (DQ), a fully conjugated organic molecule, anthraquinone‐quinoxaline derivative (HATAN) is prepared. With the fully conjugated structure, HATAN possesses enhanced π‐electron delocalization and strong intermolecular interaction, which ensure superior electronic conductivity and physicochemical/electrochemical stability. Additionally, the introduction of multiple redox‐active sites (C═O and C═N) can increase the theoretical capacity of HATAN. Consequently, the HATAN cathode for AZIBs exhibits remarkable capacity, long lifespan, and high‐rate capability. Even at −50  C, an exceptional capacity of 75.4 mAh g−1 and 98% capacity retention over 1500 cycles can be preserved. This study presents valuable insights into the structure design of small molecule organic cathodes for advanced AZIBs which can efficiently operate at −50 °C.
Clarifying the Impact of Electrode Material Heterogeneity on the Thermal Runaway Characteristics of Lithium‐Ion Batteries
Authors: Du Chenran , Yan Kun , Shen Xueling , Cui Yi , Li Xiaobing , Li Jingjing , Xu Ran , Ma Xiaoli , Huang Qian , Fang Yanyan , Zhang Hang
Published: August 2024

The safety and efficiency of lithium‐ion batteries (LIBs) suggest a promising future for this technology, particularly in the automobile industry. However, thermal runaway—wherein a LIB undergoes an uncontrollable increase in temperature that may result in smoke, fire, or explosion—represents an important and widely studied failure type. Since the electrodes of LIBs are manufactured from porous composite materials, their heterogeneity can significantly influence the effective material characteristics and microscale behaviors of LIBs during operation. Microstructure geometric and electrochemical–thermal models are typically used to investigate these impacts. Herein, a microstructure geometric model is constructed of LIB's electrodes. A virtual multiphysics model is used to simulate the overcharging thermal runaway condition. The model's accuracy is validated through real‐world experiments. The model shows greater accuracy compared to the result from a conventional homogeneous geometric model and better reflects the heterogeneous internal phenomenon. The model is applied to a variable analysis in order to investigate how the varying heterogeneity of the cathode's porosity impacts the cell during overcharging thermal runaway behavior. Our results indicate that decreasing porosity heterogeneity at the cathode may delay thermal runaway, owing to the heterogeneous impact on particle diffusion behaviors and the side reaction rate.
Electrochemical and mechanical characterization of thermosets as fluorine‐free cathode binders for Li‐ion batteries
Authors: Pan Shihao , Tang Maureen H. , Alvarez Nicolas J.
Published: August 2024

This study demonstrates fluorine‐free cross‐linked (meth)acrylate polymers as alternatives to polyvinylidene fluoride (PVDF) in LiNi0.33Mn0.33Co0.33O2 (NMC111) cathodes. We determine the effects of thermal initiator content, polymer content, and curing environment for two polymer chemistries: a flexible acrylate polymer, and a stiff methacrylate polymer. Electrodes are manufactured and tested for final electrochemical performance and mechanical properties. The results show that the flexible acrylate polymer exhibits higher rate capability compared to the stiff methacrylate polymer because calendering fractures the brittle network of stiff polymer. Electrode adhesion to the current collector and cohesion between particles are found to be a strong function of thermal initiator ratio and oxygen inhibition. Furthermore, there exists an optimal binder concentration that maximizes rate capability performance. Under the right conditions, the two polymers exhibit comparable performance to PVDF electrodes. These results provide important implications for designing cross‐linked polymers as cathode binder alternatives to PVDF.
Tank formation transforms nitrogen metabolism of an epiphytic bromeliad and its phyllosphere bacteria
Authors: Stryker Jade , White Elizabeth , Díaz‐Almeyda Erika , Sidoti Brian , Oberle Brad
Published: August 2024

Premise

Up to half of tropical forest plant species grow on other plants. Lacking access to soils, vascular epiphytes have unique adaptations for mineral nutrition. Among the most distinctive is the tank growth form of certain large bromeliads, which absorb nutrients that are cycled by complex microbial communities in water trapped among their overlapping leaf bases. However, tanks form only after years of growth by juvenile plants, which must acquire nutrients differently. Understanding how nutrient dynamics change during tank bromeliad development can provide key insights into the role of microorganisms in the maintenance of tropical forest biodiversity.

Methods

We evaluated variations in plant morphology, growth, foliar nitrogen physiology, and phyllosphere bacterial communities along a size gradient spanning the transition to tank formation in the threatened species Tillandsia utriculata.

Results

Sequential morphological and growth phases coincided with the transition to tank formation when the longest leaf on plants was between 14 and 19 cm. Before this point, foliar ammonium concentrations were very high, but after, leaf segments absorbed significantly more nitrate. Leaf‐surface bacterial communities tracked ontogenetic changes in plant morphology and nitrogen metabolism, with less‐diverse communities in tankless plants distinguished by a high proportion of taxa implicated in ureolysis, nitrogen fixation, and methanotrophy, whereas nitrate reduction characterized communities on individuals that could form a tank.

Conclusions

Coupled changes in plant morphology, physiology, and microbiome function facilitate the transition between alternative nutritional modes in tank bromeliads. Comparing bromeliads across life stages and habitats may illuminate how nitrogen‐use varies across scales.
Azaacene Diradicals Based on Non‐Kekulé Meta‐Quinodimethane with Large Two‐Photon Cross‐Sections in the Infrared Spectral Region
Authors: Fuchs Kathleen , Oberhof Nils , Sauter Gabriel , Pollien Audrey , Brödner Kerstin , Rominger Frank , Freudenberg Jan , Dreuw Andreas , Tegeder Petra , Bunz Uwe H. F.
Published: August 2024

Non‐Kekulé quinoidal azaacences m‐A (1 a,b) were synthesized and compared to their para‐ and ortho‐quinodimethane analogues. m‐A display high diradical characters (1 b: y0 = 0.88) due to their meta‐quinodimethane (m‐QDM) topology. Electron paramagnetic, nuclear magnetic resonance spectroscopies and supraquantum interference device measurements in combination with quantum‐chemical calculations revealed singlet ground states for m‐A with singlet‐triplet gaps ΔEST (0.13–0.25 kcal mol−1) and thermally populated triplet states. These non‐Kekulé structures are over all void of zwitterionic character and possess record high two‐photon absorption cross sections over a broad spectral range in the near‐infrared.
One‐Pot Biocatalytic Conversion of Chemically Inert Hydrocarbons into Chiral Amino Acids through Internal Cofactor and H2O2 Recycling
Authors: Wang Aiwen , Wang Yongze , You Yuanxiang , Huang Zhiqing , Zhang Xingwang , Li Shengying , Chen Hui
Published: August 2024

Chemically inert hydrocarbons are the primary feedstocks used in the petrochemical industry and can be converted into more intricate and valuable chemicals. However, two major challenges impede this conversion process: selective activation of C−H bonds in hydrocarbons and systematic functionalization required to synthesize complex structures. To address these issues, we developed a multi‐enzyme cascade conversion system based on internal cofactor and H2O2 recycling to achieve the one‐pot deep conversion from heptane to chiral (S)‐2‐aminoheptanoic acid under mild conditions. First, a hydrogen‐borrowing‐cycle‐based NADH regeneration method and H2O2 in situ generation and consumption strategy were applied to realize selective C−H bond oxyfunctionalization, converting heptane into 2‐hydroxyheptanoic acid. Integrating subsequent reductive amination driven by the second hydrogen‐borrowing cycle, (S)‐2‐aminoheptanoic acid was finally accumulated at 4.57 mM with eep>99 %. Hexane, octane, 2‐methylheptane, and butylbenzene were also successfully converted into the corresponding chiral amino acids with eep>99 %. Overall, the conversion system employed internal cofactor and H2O2 recycling, with O2 as the oxidant and ammonium as the amination reagent to fulfill the enzymatic conversion from chemically inert hydrocarbons into chiral amino acids under environmentally friendly conditions, which is a highly challenging transformation in traditional organic synthesis.
One‐Pot Multienzyme Cascades for Stereodivergent Synthesis of Tetrahydroquinolines
Authors: De Arijit , Shukla Ajeet , Masood Husain Syed
Published: August 2024

The tetrahydroquinoline (THQ) framework is commonly found in natural products and pharmaceutically relevant molecules. Apart from using transition metal catalysts and chiral phosphoric acids, the chiral 2‐substituted 1,2,3,4‐THQs are synthesized using amine oxidase biocatalysts. However, the use of imine reductases (IREDs) in their asymmetric synthesis remained unexplored. In the current work, IREDs are employed in telescopic multienzyme cascades to catalyze the intramolecular reductive amination leading to chiral 2‐alkyl and 2‐aryl substituted‐1,2,3,4‐tetrahydroquinolines starting from inexpensive nitroalkenones. The cascades containing NtDBR (an ene reductase), NfsB (a nitro reductase) with either Na2S2O4 or V2O5, various IREDs, and glucose dehydrogenase (for NADPH regeneration) are used to synthesize a broad range of (R)/(S)‐2‐alkyl‐substituted (THQs) (26 examples) with high yield (up to 93 %) and excellent ee (up to 99 %) in one‐pot. The method further facilitates the one‐pot biocatalytic synthesis of chiral 2‐aryl substituted THQs (26 examples) from amino chalcones. Lastly, the asymmetric synthesis of several (R)‐ and (S)‐THQ based intermediates of Hancock alkaloids showed the practical application of the newly developed biocatalytic cascades.
Lanthanide Complexes Based on Rigid Benzimidazole Carboxylic Acid Ligand: Sensing of Nitrobenzene, Fe(III) Ions, and Adsorption of Dyes
Authors: Yao Xiao‐Yan , Yue Tian‐Cai , Xiong Bin‐Bin , Wang Lu‐Lu , Wang Duo‐Zhi
Published: August 2024

Five new lanthanide complexes {[Sm(H2L)(H2O)4(Cl)]⋅H2O⋅Cl}n (1), {[Eu(H2L)(H2O)4Cl]⋅Cl}n (2), {[La(H2L)(H2O)4Cl]⋅Cl}n (3), {[Pr(H2L)(H2O)4Cl]⋅Cl}n (4), {[Ce(H2L)(H2O)4Cl]⋅Cl}n (5) (H3L = 2‐hydroxy‐5‐(5‐(hydroxy‐λ2‐methoxy)‐1H‐benzo[d]imidazole‐5‐carboxylic acid) were successfully synthesized under solvothermal method. 1 exhibits a two‐dimensional (2D) network structure, whereas 2–5 feature one‐dimensional (1D) chain structure. The fluorescence investigations demonstrated that 1–5 could be the fluorescent sensor for nitrobenzene (NB) and Fe(III) ions with high selectivity, sensitivity, and low detection limits. Furthermore, 1–5 displayed the good adsorption to anionic dye Congo red (CR), and the adsorption capacities were 140.5, 206.5, 212.5, 111.5, and 211.5 mg·g−1, respectively.
Guidelines in Practice: Surgical Attire
Authors: Speth Jennifer
Published: August 2024

Perioperative team members wear surgical attire when working in the OR. Wearing clean surgical attire is important to maintain a high level of cleanliness for patient safety. The recently updated AORN “Guideline for surgical attire” provides perioperative nurses with recommendations for wearing surgical attire in the semirestricted and restricted areas of the perioperative setting. This article discusses recommendations for laundering; head coverings; shoes; and identification badges, access cards, and personal items. It also includes a scenario describing compliance monitoring for an updated policy related to cleaning cell phones and performing hand hygiene after cell phone use. Perioperative nurses should review the guideline in its entirety and apply the recommendations for wearing surgical attire in the perioperative environment.
Exploring the role of RNASET2 in the immune response of black soldier fly larvae
Authors: Caramella Sara , Baranzini Nicolò , Bruno Daniele , Orlandi Viviana Teresa , Mohamed Amr , Bolognese Fabrizio , Grimaldi Annalisa , Tettamanti Gianluca
Published: August 2024

T2 RNases are transferase‐type enzymes distributed across phyla, crucial for breaking down single‐stranded RNA molecules. In addition to their canonical function, several T2 enzymes exhibit pleiotropic roles, contributing to various biological processes, such as the immune response in invertebrates and vertebrates. This study aims at characterizing RNASET2 in the larvae of black soldier fly (BSF), Hermetia illucens, which are used for organic waste reduction and the production of valuable insect biomolecules for feed formulation and other applications. Given the exposure of BSF larvae to pathogens present in the feeding substrate, it is likely that the mechanisms of their immune response have undergone significant evolution and increased complexity. After in silico characterization of HiRNASET2, demonstrating the high conservation of this T2 homolog, we investigated the expression pattern of the enzyme in the fat body and hemocytes, two districts mainly involved in the insect immune response, in larvae challenged with bacterial infection. While no variation in HiRNASET2 expression was observed in the fat body following infection, a significant upregulation of HiRNASET2 synthesis occurred in hemocytes shortly after the injection of bacteria in the larva. The intracellular localization of HiRNASET2 in lysosomes of plasmatocytes, its extracellular association with bacteria, and the presence of a putative antimicrobial domain in the molecule, suggest its potential role in RNA clean‐up and as an alarm molecule promoting phagocytosis activation by hemocytes. These insights contribute to the characterization of the immune response of Hermetia illucens larvae and may facilitate the development of animal feedstuff enriched with highly valuable BSF bioactive compounds.
Identification and Functional Analysis of Adipokinetic Hormone Receptor in Ostrinia furnacalis Guenée Larvae Parasitized by Macrocentrus cingulum
Authors: Wang Libao , Han Zhaoyang , Liu Xu , Li Shuzhong , Bi Honglun , Feng Congjing
Published: August 2024

As a typical G protein‐coupled receptor, the adipokinetic hormone receptor (AKHR) has seven transmembrane domains (TMDs), and its structure and function are similar to the gonadotropin‐releasing hormone receptor (GnRHR) in vertebrates. However, there is a dearth of information on other components of the AKHR signaling pathway and how it functions in the interaction between insect hosts and parasitoids. In this study, we cloned and analyzed the multifunctional Ostrinia furnacalis AKHR (OfAKHR) cDNA (GenBank accession number MF797868). OfAKHR has a 2206 bp full‐length cDNA, which includes an open reading frame containing 1194 bp. OfAKHR contains the typical seven TMDs, and a “DRY” motif. OfAKHR has the highest relative expression in the fat body and the fifth instar larvae. The results revealed that ApoLpⅢ, PPO2, GS, TPS, Cecropin, and Moricin decreased the transcription levels from 48 to 72 h after the knockdown of OfAKHR expression by dsOfAKHR injection in the fourth instar O. furnacalis larvae. The parasitization of Macrocentrus cingulum selectively upregulated the expression levels of nutrition metabolism and immune‐related genes in parasitized O. furnacalis larvae, stimulated lysozyme activity, and obviously raised the concentrations of triglyceride and trehalose in the hemolymph of O. furnacalis larvae. However, they inhibited the activities of PO and trehalase. This study is conducive to a deeper cognition of the roles of OfAKHR in nutrition and immune homeostasis, coevolution, and coexistence between parasitic wasps and hosts. It also sheds light on the potential as the target of pest control reagents.
DNA interaction of selected tetrahydropyrimidine and its effects against CCl4‐induced hepatotoxicity in vivo: Part II
Authors: Milović Emilija , Matić Sanja Lj. , Katanić Stanković Jelena S. , Srećković Nikola , Filipović Ignjat , Bradić Jovana , Petrović Anica , Jakovljević Vladimir , Vazquez Natalia Busto , Janković Nenad
Published: August 2024

Tetrahydropyrimidine (compound A = methyl 4‐[4′‐(heptyloxy)‐3′‐methoxyphenyl]‐1,6‐dimethyl‐2‐thioxo‐1,2,3,4‐tetrahydropyrimidine‐5‐carboxylate) was chosen for in vivo studies after exhibiting noteworthy in vitro activity against the K562 and MDA‐MB‐231 cell lines, with IC50 values of 9.20 ± 0.14 µM and 12.76 ± 1.93 µM, respectively. According to experimental (fluorescence titration, viscosity, and differential scanning calorimetry) results, A interacts with DNA via the minor groove. In vivo, acute oral toxicity studies in Wistar albino rats proved no noticeable symptoms of either toxicity or death during the follow‐up period. Genotoxic and antigenotoxic studies at three different concentrations of A (5, 10, and 20 mg/kg of body weight) in Wistar albino rats showed that the dose of 5 mg/kg body weight did not cause DNA damage and had a remarkable DNA protective activity against CCl4‐induced DNA damage, with a percentage reduction of 78.7%. It is also important to note that, under the investigated concentrations of A, liver damage is not observed. Considering all experimental outcomes realized under various in vivo investigations (acute oral toxicity, genotoxicity, antigenotoxicity, and biochemical tests), compound A could be a promising candidate for further clinical testing.
Silver‐Catalyzed Carbamoylation and Carbonylative Cyclization of Alkenes with Oxamic Acids
Authors: A Ru‐Han , Bao Zhi‐Peng , Huo Yong‐Wang , Wu Xiao‐Feng
Published: August 2024

Transition metal‐catalyzed carbonylation functionalization reaction of alkenes is an attractive research area in modern organic chemistry. However, there have been very few reports on silver‐catalyzed reactions in carbonylation reactions. Herein we developed a silver‐catalyzed carbamoylation and carbonylative cyclization of alkenes with oxamic acids to obtain 2‐acetylamino‐1‐tetralone derivatives. Various desired cyclized products were formed in moderate to good yields through radical intermediates.
Extended state observer‐based trajectory tracking control of a wheeled mobile robot with one unpowered trailer
Authors: Yang Hongjiu , Dang Ran , Li Peng
Published: August 2024

In this paper, trajectory tracking control is investigated for a wheeled mobile robot with one unpowered trailer using an extended state observer (ESO). The unpowered trailer is added to improve load capacity, which results in a large impact on trajectory tracking as a slow‐varying and large disturbance. A backstepping controller is proposed to generate desired velocities in an outer loop of a double closed‐loop structure. The ESO is employed in an inner loop to estimate the slow‐varying and large disturbance from the unpowered trailer. An integral sliding mode controller is also designed in the inner loop to track the desired velocities from the outer loop. Stability analysis for the ESO, the backstepping controller and the integral sliding mode controller is conducted via Lyapunov methods. Simulation results are provided to show the effectiveness of the trajectory tracking control for a wheeled mobile robot with one unpowered trailer.
Extracapsular extension risk assessment using an artificial intelligence prostate cancer mapping algorithm
Authors: Priester Alan , Mota Sakina Mohammed , Grunden Kyla P. , Shubert Joshua , Richardson Shannon , Sisk Anthony , Felker Ely R. , Sayre James , Marks Leonard S. , Natarajan Shyam , Brisbane Wayne G.
Published: August 2024

Objective

The objective of this study is to compare detection rates of extracapsular extension (ECE) of prostate cancer (PCa) using artificial intelligence (AI)‐generated cancer maps versus MRI and conventional nomograms.

Materials and methods

We retrospectively analysed data from 147 patients who received MRI‐targeted biopsy and subsequent radical prostatectomy between September 2016 and May 2022. AI‐based software cleared by the United States Food and Drug Administration (Unfold AI, Avenda Health) was used to map 3D cancer probability and estimate ECE risk. Conventional ECE predictors including MRI Likert scores, capsular contact length of MRI‐visible lesions, PSMA T stage, Partin tables, and the “PRedicting ExtraCapsular Extension” nomogram were used for comparison.

Postsurgical specimens were processed using whole‐mount histopathology sectioning, and a genitourinary pathologist assessed each quadrant for ECE presence. ECE predictors were then evaluated on the patient (Unfold AI versus all comparators) and quadrant level (Unfold AI versus MRI Likert score). Receiver operator characteristic curves were generated and compared using DeLong's test.

Results

Unfold AI had a significantly higher area under the curve (AUC = 0.81) than other predictors for patient‐level ECE prediction. Unfold AI achieved 68% sensitivity, 78% specificity, 71% positive predictive value, and 75% negative predictive value. At the quadrant level, Unfold AI exceeded the AUC of MRI Likert scores for posterior (0.89 versus 0.82, p = 0.003), anterior (0.84 versus 0.80, p = 0.34), and all quadrants (0.89 versus 0.82, p = 0.002). The false negative rate of Unfold AI was lower than MRI in both the anterior (−60%) and posterior prostate (−40%).

Conclusions

Unfold AI accurately predicted ECE risk, outperforming conventional methodologies. It notably improved ECE prediction over MRI in posterior quadrants, with the potential to inform nerve‐spare technique and prevent positive margins. By enhancing PCa staging and risk stratification, AI‐based cancer mapping may lead to better oncological and functional outcomes for patients.
Prozessbegleitende Ableitung mechanischer Eigenschaften hochfester Betone bei Schnellfertigung
Authors: Hoppe Jannik , Schwarz Yannik , Stindt Jan , Forman Patrick , Sanio David , Mark Peter
Published: August 2024

Die Vorfertigung von Stahlbetonbauteilen bietet erhebliche Vorteile gegenüber einer konventionellen Ortbetonbauweise. Beispielsweise erlaubt die Integration einer rapiden Wärmebehandlung die Reduktion der Fertigungszeit hin zu einer Schnellfertigung in nur wenigen Stunden. Behandlungsdauern und ‐temperaturen nehmen dabei Einfluss auf die Entwicklung der mechanischen Eigenschaften. Die Kontrolle Letzterer gewährleistet die Qualität der Bauteile. Für Betonbauteile werden dazu in der Regel zerstörende Prüfungen in Begleitversuchen eingesetzt. Im Beitrag wird eine Methode entwickelt, mit der sich Druckfestigkeit, E‐Modul und Verbundfestigkeit anhand einer im Prozess integrierbaren Prüfung ableiten lassen. Untersucht wird dazu die Eignung der Rückprallhammerprüfung, wobei die Randbedingungen der Wärmebehandlung berücksichtigt werden. In experimentellen Untersuchungen werden die aufgeführten Zielgrößen für den hochfesten Nanodur‐Beton bei Herstellung mit variierender Wärmebehandlungsdauer bestimmt. Den experimentellen werden rechnerisch, anhand normativ beschriebener Zusammenhänge, abgeleitete Größen gegenübergestellt. So wird ein Modell gebildet, mit dem sich die Druckfestigkeit und auf Basis dieser der Elastizitätsmodul und die Verbundfestigkeit ableiten lassen. Die Methode wird anhand der gegenübergestellten Werte diskutiert und die Anwendung an einem simplen Beispiel gezeigt sowie Empfehlungen für den Einsatz zur Kontrolle mechanischer Eigenschaften in der Schnellfertigung gegeben.
Dissipation pattern and dietary risk assessment of chlorfenapyr and methomyl in corn under Egyptian field conditions
Authors: Saber El‐Sayed , Malhat Farag , Saber Ayman N. , Heikal Sara , Hussien Mohamed
Published: August 2024

Corn is the second most widely farmed grain for human consumption. Low corn productivity due to damage caused by pests has led to using pesticides to control pest infestations. However, the uncontrolled application of pesticides on corn harms both environmental and human health. Accordingly, field experiments followed good agricultural practices to investigate the dissipation pattern and terminal residues of chlorfenapyr and methomyl in corn and compare the values with established safety limits. Gas chromatography–tandem mass spectrometer coupled with the quick, easy, cheap, effective, rugged, and safe technique was used to analyze residues of chlorfenapyr and methomyl in corn. The average recoveries varied from 94% to 105%, with relative standard deviations (RSDs) of 8%–13% for chlorfenapyr and from 99% to 111%, with RSDs of 10–16% for methomyl. Chlorfenapyr and methomyl residues degraded in corn following a first‐order kinetic model, with an estimated half‐life (t1/2) of 3.9 and 2.8 days, respectively, and significant degradation (91.4%–98.1.5%, respectively) after 14 days. Although the maximum residue limits of chlorfenapyr and methomyl for corn are yet to be formulated in Egypt, the long‐term dietary risk for those pesticides was acceptable, with arisk quotient < 100%, according to the national assessments. These findings are required to guide the correct and safe application of these insecticides in Egypt.
Use of biliary stents for large coronary arteries
Authors: Madanat Luai , Jabri Ahmad , Sankar Parvathy , Safian Robert D.
Published: August 2024

Dedicated coronary artery drug‐eluting stents may be inadequate in coronary arteries >6 mm in diameter, due to the risk of stent undersizing if the stent is not fully expanded or to loss of radial strength or damage to the drug coating if the stent is expanded >6 mm. We present two patients with large coronary arteries who were successfully treated with biliary balloon expandable stents.
Laser ablation for preventing coronary obstruction and maintaining coronary access in redo‐TAVR: A proof of concept
Authors: Brlansky John , Qiu Dong , Azadani Ali N.
Published: August 2024

Background

Redo‐transcatheter aortic valve replacement (TAVR) is a promising treatment for transcatheter aortic valve degeneration, becoming increasingly relevant with an aging population. In redo‐TAVR, the leaflets of the initial (index) transcatheter aortic valve (TAV) are displaced vertically when the second TAV is implanted, creating a cylindrical cage that can impair coronary cannulation and flow. Preventing coronary obstruction and maintaining coronary access is essential, especially in young and low‐risk patients undergoing TAVR. This study aimed to develop a new leaflet modification strategy using laser ablation to prevent coronary obstruction and facilitate coronary access after repeat TAVR.

Methods

To evaluate the feasibility of the leaflet modification technique using laser ablation, the initial phase of this study involved applying a medical‐grade ultraviolet laser for ablation through pericardial tissue. Following this intervention, computational fluid dynamics simulations were utilized to assess the efficacy of the resulting perforations in promoting coronary flow. These simulations played a crucial role in understanding the impact of the modifications on blood flow patterns, ensuring these changes would facilitate the restoration of coronary circulation.

Results

Laser ablation of pericardium leaflets was successful, demonstrating the feasibility of creating openings in the TAV leaflets. Flow simulation results show that ablation of index valve leaflets can effectively mitigate the flow obstruction caused by sinus sequestration in redo‐TAVR, with the extent of restoration dependent on the number and location of the ablated openings.

Conclusions

Laser ablation could be a viable method for leaflet modification in redo‐TAVR, serving as a new tool in interventional procedures.
Prevention and treatment of coronary catheter kinking
Authors: Elrayes Mahmoud M. , Al‐Ogaili Ahmed , Jalli Sandeep , Brilakis Emmanouil S.
Published: August 2024

Coronary catheter kinking is an uncommon but potentially catastrophic complication of cardiac catheterization. Although simple maneuvers can often result in resolution of a kink, tighter knots may not respond to such measures. We provide a systematic, stepwise approach to the prevention and treatment of catheter kinking.
Cr2O3 Clusters on ZnO as Hydrogen Pools for Efficient Syngas‐To‐Light Olefins
Authors: Ding Beikai , Yang Chengsheng , Chen Yue , Shao Wei‐Peng , Yang Fan , Zhang Chi , Wang Zheng , Liu Yongmei , Cao Yong , Zhu Yifeng , Bao Xinhe
Published: August 2024

Interfaces of mixed oxide are often considered the primary catalytic sites, yet the functionalities of the surrounding environments are less understood. Composite oxides, particularly ZnO‐Cr2O3, show high activity and selectivity for syngas conversion, with ZnO dissociating H2 to hydrides and Cr2O3 activating CO. However, hydrides on ZnO cannot remain stable at temperatures above room temperature. Focusing on the puzzlingly high performance despite ZnO's inability to stabilize active hydrides at reaction temperatures (300–400 °C), we clarified the roles of each phase using models of Cr2O3/ZnO and ZnO/Cr2O3. Cr2O3 clusters on ZnO effectively stabilize and store hydrides, significantly enhancing syngas conversion compared to individual oxides or ZnO/Cr2O3. An acetate/ketene pathway on Cr2O3/ZnO was identified, driven by the unique role of Cr2O3 clusters in regulating local hydride and CO coverages, unlike other routes observed on ZnO/Cr2O3. These insights advance the understanding of the active structures and functionalities of mixed oxides in catalysis.
Development of Natural‐Product‐Inspired ABCB1 Inhibitors Through Regioselective Tryptophan C3‐Benzylation
Authors: Mariya Vincent Dona , Mostafa Habib , Suneer Anza , Radha Krishnan Sabhashina , Ong Mingmin , Itahana Yoko , Itahana Koji , Viswanathan Rajesh
Published: August 2024

The emergence of drug resistance in cancer cells eventually causing relapse is a serious threat that demands new advances. Upregulation of the ATP‐dependent binding cassette (ABC) transporters, such as ABCB1, significantly contributes to the emergence of drug resistance in cancer. Despite more than 30 years of therapeutic discovery, and several generations of inhibitors against P‐gp, the search for effective agents that minimize toxicity to human cells, while maintaining efflux pump inhibition is still underway. Leads derived from natural product scaffolds are well‐known to be effective in various therapeutic approaches. Inspired by the biosynthetic pathway to Nocardioazine A, a marine alkaloid known to inhibit the P‐gp efflux pump in cancer cells, we devised a regioselective pathway to create structurally unique indole‐C3‐benzyl cyclo‐L‐Trp‐L‐Trp diketopiperazines (DKPs). Using bat cells as a model to derive effective ABCB1 inhibitors for targeting human P‐gp efflux pumps, we have recently identified exo‐C3‐N‐Dbn‐Trp2 (13) as a lead ABCB1 inhibitor. This C3‐benzylated lead inhibited ABCB1 better than Verapamil.[21] Additionally, C3‐N‐Dbn‐Trp2 restored chemotherapy sensitivity in drug‐resistant human cancer cells and had no adverse effect on cell proliferation in cell cultures. For a clearer structure‐activity relationship, we developed a broader screen to test C3‐functionalized pyrroloindolines as ABCB1 inhibitors and observed that C3‐benzylation is outperforming respective isoprenylated derivatives. Results arising from the molecular docking studies indicate that the interactions at the access tunnel between ABCB1 and the inhibitor result in a powerful predictor for the efficacy of the inhibitor. Based on fluorescence‐based assays, we conclude that the most efficacious inhibitor is the p‐cyano‐derived exo‐C3‐N‐Dbn‐Trp2 (33 a), closely followed by the p‐nitro substituted analogue. By combining assay results with molecular docking studies, we further correlate that the predictions based on the inhibitor interactions at the access tunnel provide clues about the design of improved ABCB1 inhibitors. As it has been well documented that ABCB1 itself is powerfully engaged in multi‐drug resistance, this work lays the foundation for the design of a new class of inhibitors based on the endogenous amino acid‐derived cyclo‐L‐Trp‐L‐Trp DKP scaffold.
Dirhodium(II)/XantPhos Catalyzed Synthesis of β‐(E)‐Vinylsilanes via Hydrosilylation and Isomerization from Alkynes
Authors: Yang Liqun , Yi Mingjun , Wu Xiaoyu , Lu Yan , Zhang Zhaoguo
Published: August 2024

A concise hydrosilylation of alkynes for synthesizing β‐(E)‐vinylsilanes catalyzed by dirhodium(II)/XantPhos has been developed. In this reaction, β‐(E)‐vinylsilanes were generated from the isomerization of β‐(Z)‐vinylsilanes catalyzed by dirhodium(II) hydride species rather than the direct insertion of triple bond into M−H or M−Si bond (traditional Chalk‐Harrod mechanism or modified Chalk‐Harrod mechanism). The hydrosilylation displayed a broad substrate scope for alkynes and tertiary silanes, tolerating diverse functional groups including halides, nitriles, amines, esters, and heterocycles.
Columnar Organization of Nonalternant Fluorinated Dehydrobenzannulenes
Authors: Karki Sumitra , Jalife Said , Wang Xiqu , Lin Yun‐Hsien , Wu Judy I. , Miljanić Ognjen Š.
Published: August 2024

Two new partially fluorinated dehydrobenzannulenes have been prepared by inter‐ and intramolecular oxidative homocoupling of diyne precursors. These systems contain fluorinated and nonfluorinated arene rings in a desymmetrized non‐alternant arrangement. Both macrocycles are roughly planar and organize into extended columns in the solid state. The assembly of these columns is mediated by the combination of dispersion interactions, slipped [π⋅⋅⋅π] stacking interactions of the perfluorinated rings with each other, and their association with the nonfluorinated rings in the molecules of the neighboring macrocycles. These results suggest that partial fluorination of dehydrobenzannulenes can serve as a versatile motif for their assembly into columnar superstructures.
Cation Enrichment Promotes High‐rate CO Electroreduction to C2+ Liquid Products
Authors: Cui Chunyu , Xu Liang , Yu Peiping , Wang Nan , Ni Fenglou , Guo Wen , Yang Hao , Cheng Tao , Zhang Bo
Published: August 2024

Electrochemical reduction of CO into valuable multicarbon (C2+) liquids is crucial for reducing CO2 emissions and advancing clean energy, yet mastering efficiency and selectivity in this process remains a tough challenge. Herein, we employ a surface‐modification strategy using electrochemically active polymeric 1,4,5,8‐naphthalenete‐tracarboxylic dianhydride (PNTCDA)‐modified copper nanosheets (PM−Cu) to rearrange reactive species in the electric double layer, where the PNTCDA triggers a distinctive enolization that anchor potassium ions (K+) onto the cathode surface under reduction condition. Electrochemical analysis and computational simulations revealed that this approach fine‐tunes K+ distribution in the double layer, making the dehydration of hydrated K+ more efficient and reducing active water molecules at the interface, thus inhibiting the hydrogen evolution reaction while concurrently promoting CO reduction via enhanced C−C coupling. For the first time, the PM−Cu catalyst demonstrates ampere‐scale current densities with the exclusive selectivity of a C2+ liquid product yield exceeding 90 %. Thus, by tailoring the local microenvironment with electrochemically active organics, it is possible to modulate CO reduction, improve sustainable energy storage, and increase industrial carbon utilization.
Enhancing Oxygen Reduction Reaction of Single‐Atom Catalysts by Structure Tuning
Authors: Song Kexin , Jing Haifeng , Yang Binbin , Shao Jing , Tao Youkun , Zhang Wei
Published: August 2024

Deciphering the fine structure has always been a crucial approach to unlocking the distinct advantages of high activity, selectivity, and stability in single‐atom catalysts (SACs). However, the complex system and unclear catalytic mechanism have obscured the significance of exploring the fine structure. Therefore, we endeavored to develop a three‐component strategy to enhance oxygen reduction reaction (ORR), delving deep into the profound implications of the fine structure, focusing on central atoms, coordinating atoms, and environmental atoms. Firstly, the mechanism by which the chemical state and element type of central atoms influence catalytic performance is discussed. Secondly, the significance of coordinating atoms in SACs is analyzed, considering both the number and type. Lastly, the impact of environmental atoms in SACs is reviewed, encompassing existence state and atomic structure. Thorough analysis and summarization of how the fine structure of SACs influences the ORR have the potential to offer valuable insights for the accurate design and construction of SACs.
A severe asthma phenotype of excessive airway Haemophilus influenzae relative abundance associated with sputum neutrophilia
Authors: Versi Ali , Azim Adnan , Ivan Fransiskus Xaverius , Abdel‐Aziz Mahmoud I , Bates Stewart , Riley John , Uddin Mohib , Zounemat Kermani Nazanin , Maitland‐Van Der Zee Anke‐H , Dahlen Sven‐Eric , Djukanovic Ratko , Chotirmall Sanjay H , Howarth Peter , Adcock Ian M , Chung Kian Fan ,   the U‐BIOPRED study group
Published: August 2024

Background

Severe asthma (SA) encompasses several clinical phenotypes with a heterogeneous airway microbiome. We determined the phenotypes associated with a low α‐diversity microbiome.

Methods

Metagenomic sequencing was performed on sputum samples from SA participants. A threshold of 2 standard deviations below the mean of α‐diversity of mild‐moderate asthma and healthy control subjects was used to define those with an abnormal abundance threshold as relative dominant species (RDS).

Findings

Fifty‐one out of 97 SA samples were classified as RDSs with Haemophilus influenzae RDS being most common (n = 16), followed by Actinobacillus unclassified (n = 10), Veillonella unclassified (n = 9), Haemophilus aegyptius (n = 9), Streptococcus pseudopneumoniae (n = 7), Propionibacterium acnes (n = 5), Moraxella catarrhalis (n = 5) and Tropheryma whipplei (n = 5). Haemophilus influenzae RDS had the highest duration of disease, more exacerbations in previous year and greatest number on daily oral corticosteroids. Hierarchical clustering of RDSs revealed a C2 cluster (n = 9) of highest relative abundance of exclusively Haemophilus influenzae RDSs with longer duration of disease and higher sputum neutrophil counts associated with enrichment pathways of MAPK, NF‐κB, TNF, mTOR and necroptosis, compared to the only other cluster, C1, which consisted of 7 Haemophilus influenzae RDSs out of 42. Sputum transcriptomics of C2 cluster compared to C1 RDSs revealed higher expression of neutrophil extracellular trap pathway (NETosis), IL6‐transignalling signature and neutrophil activation.

Conclusion

We describe a Haemophilus influenzae cluster of the highest relative abundance associated with neutrophilic inflammation and NETosis indicating a host response to the bacteria. This phenotype of severe asthma may respond to specific antibiotics.