bluuebunny/crossref_metadata_2025 huggingface dataset:
Chiral Van Der Waals Superlattices for Enhanced Spin‐Selective Transport and Spin‐Dependent Electrocatalytic Performance
Authors: Bian Zhiyun , Nakano Yuki , Miyata Keisuke , Oya Ichiro , Nobuoka Masaki , Tsutsui Yusuke , Seki Shu , Suda Masayuki
Published: September 2023

The emergence of the chiral‐induced spin‐selectivity (CISS) effect offers a new avenue for chiral organic molecules to autonomously manipulate spin configurations, thereby opening up possibilities in spintronics and spin‐dependent electrochemical applications. Despite extensive exploration of various chiral systems as spin filters, one often encounters challenges in achieving simultaneously high conductivity and high spin polarization (SP). In this study, a promising chiral van der Waals superlattice, specifically the chiral TiS2 crystal, is synthesized via electrochemical intercalation of chiral molecules into a metallic TiS2 single crystal. Multiple tunneling processes within the highly ordered chiral layered structure of chiral TiS2 superlattices result in an exceptionally high SP exceeding 90%. This remarkable observation of significantly high SP within the linear transport regime is unprecedented. Furthermore, the chiral TiS2 electrode exhibits enhanced catalytic activity for oxygen evolution reaction (OER) due to its remarkable spin‐selectivity for triplet oxygen evolution. The OER performance of chiral TiS2 superlattice crystals presented here exhibits superior characteristics to previously reported chiral MoS2 catalysts, with an approximately tenfold increase in current density. The combination of metallic conductivity and high SP sets the stage for the development of a new generation of CISS materials, enabling a wide range of electron spin‐based applications.
Regulating Lithium Transfer Pathway to Avoid Capacity Fading of Nano Si Through Sub‐Nano Scale Interfused SiOx/C Coating
Authors: Yu Ruohan , Pan Yexin , Jiang Yuqian , Zhou Liang , Zhao Dongyuan , Van Tendeloo Gustaaf , Wu Jinsong , Mai Liqiang
Published: September 2023

Si nanoparticles (NPs) are considered as a promising high‐capacity anode material owing to their ability to prevent mechanical failure from drastic volume change during (de)lithiation. However, upon cycling, a quick capacity fading is still observed for Si NPs, and the underlying mechanism remains elusive. In this contribution, it is demonstrated that the quick capacity fading is mainly caused by the generation of dead (electrochemically inert) Si with blocked electron conductivity in a densely composited Si/SEI (solid electrolyte interface) hybrid. This is due to the combined influence of electrolyte‐related side reactions and the accompanied agglomeration of Si NPs. A compact, sub‐nano scale interfused SiOx/C composite coating onto the Si NPs is constructed, and a highly stabilized electrochemistry is achieved upon long cycling. The SiOx/C coating with electron/ion dual transport paths and robust mechanical flexibility enables a fast and stable lithium ion/electron dual diffusion pathway towards the encapsulated Si. With fast reaction kinetics, stable SEI, and an antiagglomeration feature, the obtained Si@SiOx/C composite demonstrates a stable high capacity. This work unravels new perspectives on the capacity fading of Si NPs and provides an effective encapsulating method to remedy the structure degradation and capacity fading of nano Si.
Photoluminescence Mechanism of Dual‐State Emission Materials Based on the Sulfone Bridged Distyrylbenzene Derivative
Authors: Li Yexi , Dai Jianan , Yang Song , Sui Ning , Wang Chenguang , Meng Xiangdong , Wang Kai , Zhang Hanzhuang , Liu Xiaomin , Lu Geyu , Wang Yinghui
Published: September 2023

Herein, a novel molecular SO2‐Bri‐DSB based on the sulfone‐bridged distyrylbenzene derivative is synthesized, and its organic crystal is fabricated. It has a very high photoluminescence (PL) quantum efficiency in the solution and crystalline state, i.e., dual‐state emission (DSE), and the corresponding PL mechanism is clarified in detail using the transient absorption and transient PL test. The PL behaviors in the monomolecular state and organic crystal are compared. In addition, the optical anisotropy of the SO2‐Bri‐DSB crystal is thoroughly investigated using various polarization‐dependent spectroscopy techniques. The time evolution of anisotropy is composed of a step behavior caused by the anisotropy of the electronic transition and a slow enhancing process with a lifetime of 4.86 ns, which is governed by the change in emission lifetime due to the anisotropy. The space‐resolved evolution of the optical anisotropy is investigated using the polarization‐dependent light wave‐guiding test and exhibits that the emission anisotropy gradually decreases with length, and it has a longer effective propagation length than the polarization emission signal. The findings provide insight into the intrinsic optical anisotropy of single‐molecular crystals and indicate that these materials have enormous potential in the domains of polarization lighting and display.
Symmetry‐Induced Selective Excitation of Topological States in Su–Schrieffer–Heeger Waveguide Arrays
Authors: Tang Min , Wang Jiawei , Valligatla Sreeramulu , Saggau Christian N. , Dong Haiyun , Saei Ghareh Naz Ehsan , Klembt Sebastian , Lee Ching Hua , Thomale Ronny , van den Brink Jeroen , Fulga Ion Cosma , Schmidt Oliver G. , Ma Libo
Published: September 2023

The investigation of topological state transition in carefully designed photonic lattices is of high interest for fundamental research, as well as for applied studies such as manipulating light flow in on‐chip photonic systems. Herein, the topological phase transition between symmetric topological zero modes (TZM) and antisymmetric TZMs in Su–Schrieffer–Heeger mirror symmetric waveguides is reported. The transition of TZMs is realized by adjusting the coupling ratio between neighboring waveguide pairs, which is enabled by selective modulation of the refractive index in the waveguide gaps. Bidirectional topological transitions between symmetric and antisymmetric TZMs can be achieved with proposed switching strategy. Selective excitation of topological edge mode is demonstrated owing to the symmetry characteristics of the TZMs. The flexible manipulation of topological states is promising for on‐chip light flow control and may spark further investigations on symmetric/antisymmetric TZM transitions in other photonic topological frameworks.
Cross‐Correlated Quantum Thermometry Using Diamond Containing Dual‐Defect Centers
Authors: Gupta Madhav , Zhang Tongtong , Yeung Lambert , Zhang Jiahua , Tan Yayin , Yiu Yau Chuen , Zhang Shuxiang , Wang Qi , Wang Zhongqiang , Chu Zhiqin
Published: September 2023

The contactless temperature measurement at micro/nanoscale is vital to a broad range of fields in modern science and technology. The nitrogen‐vacancy (NV) center, a kind of diamond defect with unique spin‐dependent photoluminescence, is recognized as one of the most promising nanothermometers. However, this quantum thermometry technique is prone to a number of possible perturbations, which will unavoidably degrade its actual temperature sensitivity. Here, for the first time, a cross‐validated optical thermometry method is developed using a bulk diamond sample containing both NV centers and silicon‐vacancy (SiV) centers, achieving a sensitivity of 22 and 86 mK (√Hz)−1 respectively. Particularly, the latter has been intrinsically immune to those influencing perturbations for the NV‐based quantum thermometry, hence serving as a real‐time cross‐validation system. As a proof‐of‐concept demonstration, a trustworthy temperature measurement is shown under the influence of varying magnetic fields, which is a common artefact present in practical systems. This multi‐modality approach allows synchronized cross‐validation of the measured temperature, which is required for micro/nanoscale quantum thermometry in complicated environments such as a living cell.
Multilayer C and BN δ‐Graphyne Sheets: An Exploration of Electronic and Optical Characteristics
Authors: Majidi Roya
Published: September 2023

The structural, electronic, and optical characteristics of multilayer C δ‐graphyne and δ‐graphyne‐like BN sheets are discussed by first‐principles study. The calculations approved that the sheets are energetically favorable and thermally stable. The layers are held together by van der Waals forces. The mono‐ and tri‐layer C δ‐graphyne exhibit semimetallic behavior, while bi‐ and tetra‐layer C δ‐graphyne are semiconductors with negligible bandgap. All multilayer BN δ‐graphyne sheets are insulators with indirect bandgap. The bandgap increases with increasing number of layers. The optical behavior of the structures is anisotropic under electric fields polarized parallel and perpendicular to the sheets. The sheets exhibit high static dielectric constants, optical absorption, and optical conductivity. The electronic and optical characteristics of C and BN δ‐graphyne sheets promise their progress and application in the world of optoelectronics.
Full‐Control and Switching of Optical Fano Resonance by Continuum State Engineering
Authors: Ko Joo Hwan , Park Jin‐Hwi , Yoo Young Jin , Chang Sehui , Kang Jiwon , Wu Aiguo , Yang Fang , Kim Sejeong , Jeon Hae‐Gon , Song Young Min
Published: September 2023

Fano resonance, known for its unique asymmetric line shape, has gained significant attention in photonics, particularly in sensing applications. However, it remains difficult to achieve controllable Fano parameters with a simple geometric structure. Here, a novel approach of using a thin‐film optical Fano resonator with a porous layer to generate entire spectral shapes from quasi‐Lorentzian to Lorentzian to Fano is proposed and experimentally demonstrated. The glancing angle deposition technique is utilized to create a polarization‐dependent Fano resonator. By altering the linear polarization between s‐ and p‐polarization, a switchable Fano device between quasi‐Lorentz state and negative Fano state is demonstrated. This change in spectral shape is advantageous for detecting materials with a low‐refractive index. A bio‐particle sensing experiment is conducted that demonstrates an enhanced signal‐to‐noise ratio and prediction accuracy. Finally, the challenge of optimizing the film‐based Fano resonator due to intricate interplay among numerous parameters, including layer thicknesses, porosity, and materials selection, is addressed. The inverse design tool is developed based on a multilayer perceptron model that allows fast computation for all ranges of Fano parameters. The method provides improved accuracy of the mean validation factor (MVF = 0.07, q‐q') compared to the conventional exhaustive enumeration method (MVF = 0.37).
Second Harmonic Generation Studies of Interfacial Strain Engineering in BaZr0.2Ti0.8O3
Authors: Ren Yuhang , Maity Piyali , Ascienzo David , Kurt Onur , Cheng H. , Ouyang Jun
Published: September 2023

Film ferroelectrics demonstrate large breakdown strength, high energy density, and many unique phenomena not found in bulk materials. In this investigation, a rhombohedral BaZr0.2Ti0.8O3 (BZT) solid solution and various film‐substrate misfit strains are utilized to optimize the energy storage performance of ferroelectric thick films. Optical second harmonic generation is applied in both reflection and transmission geometries to reveal the renovation of entangled rhombohedral and tetragonal phases in the BZT films under compressive misfit strains. It is shown that the interfacial strain between the BZT film and substrate introduces the tetragonal domains. The competition between the tetragonal and rhombohedral phases creates the self‐assembled, anisotropically strained morphotropic structures to effectively accommodate the elastic and electrical stress fields through inside the thick BZT film. The BZT films demonstrate exceptional energy storage performance because of the adaptable nano‐domain structure within the bulk of the BZT films and may be engineered to optimize the superior performance of BZT films in energy storage.
Bright dual‐color electrochemiluminescence of a structurally determined Pt1Ag18 nanocluster
Authors: Yin Bing , Jiang Lirong , Wang Xiaojian , Liu Ying , Kuang Kaiyang , Jing Mengmeng , Fang Chunmin , Zhou Chuanjun , Chen Shuang , Zhu Manzhou
Published: September 2023

Metal nanoclusters possess excellent electrochemical, optical, and catalytic properties, but correlating these properties remains challenging, which is the foundation to generate electrochemiluminescence (ECL). Herein, we report for the first time that a structurally determined Pt1Ag18 nanocluster generates intense ECL and simultaneously enhances the ECL of carbon dots (CDs) via an electrocatalytic effect. Pt1Ag18 nanocluster show aggregation‐induced emission enhancement and aggregation‐induced ECL enhancement under light and electrochemical stimulation, respectively. In the presence of tripropylamine (TPrA) as a coreactant, solid Pt1Ag18 shows unprecedented ECL efficiency, which is more than nine times higher than that of 1 mM Ru(bpy)32+ with the same TPrA concentration. Potential‐resolved ECL spectra reveal two ECL emission bands in the presence of TPrA. The ECL emission centered at 650 nm is assigned to the solid Pt1Ag18 nanocluster, consistent with the peak wavelength in self‐annihilation ECL and photoluminescence of the solid state. The ECL emission centered at 820 nm is assigned to the CDs on the glassy carbon electrode. The electrocatalytic effect of the nanoclusters enhanced the ECL of the CDs by a factor of more than 180 in comparison to that without nanoclusters. Based on the combined optical and electrochemical results, the ECL generation pathways and mechanisms of Pt1Ag18 and CDs are proposed. These findings are extremely promising for designing multifunctional nanocluster luminophores with strong emissions and developing ratiometric sensing devices.
Recent progress in polymerization‐induced self‐assembly: From the perspective of driving forces
Authors: Zhao Zizhuo , Lei Shujing , Zeng Min , Huo Meng
Published: September 2023

Polymerization‐induced self‐assembly (PISA) enables the simultaneous growth and self‐assembly of block copolymers in one pot and therefore has developed into a high‐efficiency platform for the preparation of polymer assemblies with high concentration and excellent reproducibility. During the past decade, the driving force of PISA has extended from hydrophobic interactions to other supramolecular interactions, which has greatly innovated the design of PISA, enlarged the monomer/solvent toolkit, and endowed the polymer assemblies with intrinsic dynamicity and responsiveness. To unravel the important role of driving forces in the formation of polymeric assemblies, this review summarized the recent development of PISA from the perspective of driving forces. Motivated by this goal, here we give a brief overview of the basic principles of PISA and systematically discuss the various driving forces in the PISA system, including hydrophobic interactions, hydrogen bonding, electrostatic interactions, and π‐π interactions. Furthermore, PISA systems that are driven and regulated by crystallization or liquid crystalline ordering were also highlighted.
The normal relationship between fat and lean mass for mature (21–30 year old) physically fit men and women
Authors: Potter Adam W. , Tharion William J. , Nindl Lyndsey J. , McEttrick David M. , Looney David P. , Friedl Karl E.
Published: September 2023

Objective

Determine if relative body fat (%BF) remains a biological norm in physically active, non‐obese American men and women and determine reference values for other components of body composition.

Methods

Participants (n = 174 men, 70 women) were physically fit U.S. Marine 2nd Lieutenants, in their third decade of physical maturity (age 21–30). Body composition was assessed by dual‐energy x‐ray absorptiometry (DXA) and bioelectrical impedance analysis (BIA); and body images were obtained by 3D body scans.

Results

For men and women, respectively, %BF averaged 16.2 ± 4.1 (median 15.3), 24.3 ± 4.5 (median 23.8); fat‐free mass (FFM): 67.7 ± 7.2, 49.4 ± 5.3 kg; FFM index: 21.5 ± 1.8, 18.3 ± 1.6 kg/m2; and body mass index (BMI): 25.5 ± 1.9, 24.1 ± 2.2 kg/m2. Bone mineral content (BMC) was 5% of FFM; total body water (TBW) was 70%–72% of FFM. Physique remained similar between median and higher percentiles of %BF. Only small changes in key measures were noted across the six‐month training program.

Conclusions

Mean %BF of healthy active men and women in 2021 remains very similar to the 15% and 25% posited in 1980, suggesting that relative body fat has a normal fat‐lean relationship in physically mature humans. These data may bring new attention to sex‐appropriate %BF.
Hypervalent Iodine‐Mediated Alkyne Functionalization: Facile Access to Trifluoromethyl‐ and Pentafluoroethyl‐Substituted Thiazoles
Authors: Kwak Yoonna , Choi Ye Rin , Yu Jaeni , Choi Sungwook , Hong Ki Bum
Published: September 2023

The use of hypervalent iodine with Lewis acid provided alkyne trifluoromethylation and pentafluoroethylation to access trifluoro‐and pentafluoro‐substituted thiazoles. This simple and efficient method is compatible with a broad range of aryl‐ and alkyl‐substituted thiourea starting materials. Additionally, a gram‐scale reaction proves the practicality of this transformation.
Organocatalytic Enantioselective One‐pot Synthesis of Dihydrocoumarins via C−H Oxidation and Cyclization Cascade
Authors: Kim Kyeong Seop , Kim Dae Young
Published: September 2023

Chiral 3,4‐dihydrocoumarin derivatives were obtained from 2‐benzyl phenols and oxazolones in moderate to high yields with excellent enantioselectivitie (up to 96 % ee) through one‐pot cascade via C−H oxidation and cyclization cascade using a binaphthyl‐modified squaramide bifunctional organocatalyst under mild reaction conditions.
Fine‐Tuning Electrolyte Concentration and Metal–Organic Framework Surface toward Actuating Fast Zn2+ Dehydration for Aqueous Zn‐Ion Batteries
Authors: Jiang Yizhi , Wan Zheng , He Xiao , Yang Jinrong
Published: September 2023

Functional porous coating on zinc electrode is emerging as a powerful ionic sieve to suppress dendrite growth and side reactions, thereby improving highly reversible aqueous zinc ion batteries. However, the ultrafast charge rate is limited by the substantial cation transmission strongly associated with dehydration efficiency. Here, we unveil the entire dynamic process of solvated Zn2+ ions’ continuous dehydration from electrolyte across the MOF‐electrolyte interface into channels with the aid of molecular simulations, taking zeolitic imidazolate framework ZIF‐7 as proof‐of‐concept. The moderate concentration of 2 M ZnSO4 electrolyte being advantageous over other concentrations possesses the homogeneous water‐mediated ion pairing distribution, resulting in the lowest dehydration energy, which elucidates the molecular mechanism underlying such concentration adopted by numerous experimental studies. Furthermore, we show that modifying linkers on the ZIF‐7 surface with hydrophilic groups such as −OH or −NH2 can weaken the solvation shell of Zn2+ ions to lower the dehydration free energy by approximately 1 eV, and may improve the electrical conductivity of MOF. These results shed light on the ions delivery mechanism and pave way to achieve long‐term stable zinc anodes at high capacities through atomic‐scale modification of functional porous materials.
Programmable and Self‐Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding
Authors: Guo Hongshuang , Liang Chen , Ruoko Tero‐Petri , Meteling Henning , Peng Bo , Zeng Hao , Priimagi Arri
Published: September 2023

Shape‐changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape‐morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self‐healing ability. Here, we report halogen‐bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape‐programmed and that self‐heal under mild thermal or photothermal stimulation. We incorporate halogen‐bond‐donating diiodotetrafluorobenzene molecules as dynamic supramolecular crosslinks into the LCEs and show that these relatively weak crosslinks are pertinent for their mechanical programming and self‐healing. Utilizing the halogen‐bonded LCEs, we demonstrate proof‐of‐concept soft robotic motions such as crawling and rolling with programmed velocities. Our results showcase halogen bonding as a promising, yet unexplored tool for the preparation of smart supramolecular constructs for the development of advanced soft actuators.
Atomically Dispersed Cobalt/Copper Dual‐Metal Catalysts for Synergistically Boosting Hydrogen Generation from Formic Acid
Authors: Shi Yanzhe , Luo Bingcheng , Liu Runqi , Sang Rui , Cui Dandan , Junge Henrik , Du Yi , Zhu Tianle , Beller Matthias , Li Xiang
Published: September 2023

The development of practical materials for (de)hydrogenation reactions is a prerequisite for the launch of a sustainable hydrogen economy. Herein, we present the design and construction of an atomically dispersed dual‐metal site Co/Cu−N−C catalyst allowing significantly improved dehydrogenation of formic acid, which is available from carbon dioxide and green hydrogen. The active catalyst centers consist of specific CoCuN6 moieties with double‐N‐bridged adjacent metal‐N4 clusters decorated on a nitrogen‐doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L ⋅ gmetal−1 ⋅ h−1) is up to 40 times higher compared to commercial 5 % Pd/C. In situ spectroscopic and kinetic isotope effect experiments indicate that Co/Cu−N−C promoted formic acid dehydrogenation follows the so‐called formate pathway with the C−H dissociation of HCOO* as the rate‐determining step. Theoretical calculations reveal that Cu in the CoCuN6 moiety synergistically contributes to the adsorption of intermediate HCOO* and raises the d‐band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier.
Copper chlorophyllin immobilized on ZrO2 nanoparticle as an effective and green catalyst in the one‐pot thioetherification reaction
Authors: Rostamizadeh Hossein , Rahmati Abbas
Published: September 2023

The synthesis of organosulfur compounds gained specific interest in the interference of organic chemistry and chemical biology. Copper chlorophyllin (CC) is a bio‐based copper complex that facilitates the synthesis of organosulfur compounds through the thioetherification reaction. The current paper deals with the immobilization of CC on the ZrO2 nanoparticles (CC@ZrO2) and its application in the one‐pot thioetherification of alkyl and aryl halides using thiourea, an alternative to the bad‐smelling thiols. After the characterization of CC@ZrO2 with different analytical techniques such as FT‐IR, TGA, XPS, N2 adsorption/desorption, XRD, ICP, and FESEM, the catalytic activity of the prepared CC@ZrO2 was evaluated in the synthesis of different types of thioether derivatives. Good to excellent yields, high reusability, and reproducibility made this cost‐effective approach a benchmark in C–S cross‐coupling reactions.
Current advances in Candida tropicalis: Yeast overview and biotechnological applications
Authors: Queiroz Sarah de Souza , Jofre Fanny Machado , Bianchini Italo de Andrade , Boaes Tatiane da Silva , Bordini Fernanda Weber , Chandel Anuj Kumar , Felipe Maria das Graças de Almeida
Published: September 2023

Candida tropicalis is a nonconventional yeast with medical and industrial significance, belonging to the CTG clade. Recent advancements in whole‐genome sequencing and genetic analysis revealed its close relation to other unconventional yeasts of biotechnological importance. C. tropicalis is known for its immense potential in synthesizing various valuable biomolecules such as ethanol, xylitol, biosurfactants, lipids, enzymes, α,ω‐dicarboxylic acids, single‐cell proteins, and more, making it an attractive target for biotechnological applications. This review provides an update on C. tropicalis biological characteristics and its efficiency in producing a diverse range of biomolecules with industrial significance from various feedstocks. The information presented in this review contributes to a better understanding of C. tropicalis and highlights its potential for biotechnological applications and market viability.
A fiducial‐based confidence interval for the linear combination of multinomial probabilities
Authors: Batterton Katherine A. , Schubert Christine M. , Warr Richard L.
Published: September 2023

Across a broad set of applications, system outcomes may be summarized as probabilities in confusion or contingency tables. In settings with more than two outcomes (e.g., stages of cancer), these outcomes represent multinomial experiments. Measures to summarize system performance have been presented as linear combinations of the resulting multinomial probabilities. Statistical inference on the linear combination of multinomial probabilities has been focused on large‐sample and parametric settings and not small‐sample settings. Such inference is valuable, however, especially in settings such as those resulting from pilot or low‐cost studies. To address this gap, we leverage the fiducial approach to derive confidence intervals around the linear combination of multinomial parameters with desirable frequentist properties. One of the original arguments against the fiducial approach was its inability to extend to multiparameter settings. Therefore, the great novelty of this work is both the derived interval and the logical framework for applying the fiducial approach in multiparameter settings. Through simulation, we demonstrate that the proposed method maintains a minimum coverage of , unlike the bootstrap and large‐sample methods, at comparable interval lengths. Finally, we illustrate its use in a medical problem of selecting classifiers for diagnosing chronic allograph nephropathy in postkidney transplant patients.
Multiparametric MRI‐based model for prediction of local progression of hepatocellular carcinoma after thermal ablation
Authors: Chen Chao , Han Qiuying , Ren He , Wu Siyi , Li Yangyang , Guo Jiandong , Li Xinghai , Liu Xiang , Li Chengzhi , Tian Yunfei
Published: September 2023

Purpose

To develop a deep learning radiomics of multiparametric magnetic resonance imaging (DLRMM)‐based model that incorporates preoperative and postoperative signatures for prediction of local tumor progression (LTP) after thermal ablation (TA) in hepatocellular carcinoma (HCC).

Methods

From May 2017 to October 2021, 417 eligible patients with HCC were retrospectively enrolled from three hospitals (one primary cohort [PC, n = 189] and two external test cohorts [ETCs][n = 135, 93]). DLRMM features were extracted from T1WI + C, T2WI, and DWI using ResNet18 model. An integrative model incorporating the DLRMM signature with clinicopathologic variables were further built to LTP risk stratification. The performance of these models were compared by areas under receiver operating characteristic curve (AUC) using DeLong test.

Results

A total of 1668 subsequences and 31,536 multiparametric MRI slice including T1WI, T2WI, and DWI were collected simultaneously. The DLRMM signatures were extracted from tumor and ablation zone, respectively. Ablative margin, multiple tumors, and tumor abutting major vessels were regarded as risk factors for LTP in clinical model. The AUC of DLRMM model were 0.864 in PC, 0.843 in ETC1, and 0.858 in ETC2, which was higher significantly than those in clinical model (p < 0.001). After integrating clinical variable, DLRMM model obtained significant improvement with AUC of 0.870–0.869 in three cohorts (all, p < 0.001), which can provide the risk stratification for overall survival of HCC patients.

Conclusions

The DLRMM model is essential to identify LTP risk of HCC patients who underwent TA and may potentially benefit personalized decision‐making.
Advancing precision oncology through systematic germline and tumor genetic analysis: The oncogenetic point of view on findings from a prospective multicenter clinical trial of 666 patients
Authors: Mazel Benoit , Bertolone Geoffrey , Baurand Amandine , Cosset Elodie , Sawka Caroline , Robert Marion , Gautier Elodie , Lançon Allan , Réda Manon , Favier Laure , Dérangère Valentin , Richard Corentin , Binquet Christine , Boidot Romain , Goussot Vincent , Albuisson Juliette , Ghiringhelli François , Faivre Laurence , Nambot Sophie
Published: September 2023

Introduction

With the emergence of targeted therapies, there is a need to accurately identify more tumor biomarkers. The EXOMA trial was designed to offer tumor and germline exome sequencing (ES) to patients with solid malignant tumors and facing therapeutic failure. As hereditary cancer predispositions could be identified, with genetic counseling and health management implications, a genetic consultation was systematically established. This design needs to be discussed as genetic human resources are limited and indication of theranostic tests will increase.

Methods

Genetic counseling was conducted within 15 days following inclusion in the study for patients recruited between December 2015 and July 2019. In silico analyses from theranostic ES were limited to 317 genes involved in oncogenesis, from both tumor and blood DNA.

Results

Six hundred and sixty six patients had a genetic consultation before ES. In 65/666 patients, 66 germline pathogenic or likely pathogenic (P/LP) variants were identified in 16 actionable genes and seven non‐actionable genes according to French guidelines. 24/65 patients had previously received genetic analysis for diagnostic purposes, and for 17 of them, a P/LP variant had already been identified. Among the 48/65 remaining cases for which the EXOMA protocol revealed a previously unknown P/LP variant, only 19 met the criteria for genetic testing for inherited cancer risk after familial survey. These criteria had not been identified by the oncologist in 10 cases. In 21/65 cases, the variant was considered incidental.

Discussion

In 7.4% of patients, an undiagnosed hereditary genetic predisposition was identified, whether or not related to the clinical presentation, and germline analysis impacted oncological management for only 6.3% of the cohort. This low percentage should be weighed against the burden of systematic genetic consultation and urgent circuits. Information or training tools to form oncologists to the prescription of germline genetic analyses should be explored, as well as information supports and patient preferences.
Design, Synthesis, Anticancer Evaluation and Molecular Modeling Studies of New Thiazolidinone‐Benzoate Scaffold as EGFR Inhibitors, Cell Cycle Interruption and Apoptosis Inducers in HepG2
Authors: Magdy Eldaly Salwa , Salama Zakaria Dalia , Hanafy Metwally Nadia
Published: September 2023

Synthesis of new anticancer candidates with protein kinases inhibitory potency is a major goal of pharmaceutical science and synthetic research. This current work represents the synthesis of a series of substituted benzoate‐thiazolidinones. Most prepared thiazolidinones were evaluated in vitro for their potential anticancer activity against three cell lines by MTT assay, and they found to be more effective against cancer cell lines with no harm toward normal cells. Thiazolidinones 5 c and 5 h were further evaluated to be kinase inhibitors against EGFR showing effective inhibitory impact (with IC50 value; 0.2±0.009 and 0.098±0.004 μM, for 5 c and 5 h, respectively). Furthermore, 5 c and 5 h have effects on cell cycle and apoptosis induction capability in HepG2 cell lines by DNA‐flow cytometry analysis and annexin V‐FITC apoptosis assay, respectively. The results showed that they have effect of disrupting the cell cycle and causing cell mortality by apoptosis in the treated cells. Moreover, molecular docking studies showed better binding patterns for 5 c and 5 h with the active site of the epidermal growth factor receptor (EGFR) protein kinase (PDB code 1M17). Finally, toxicity risk and physicochemical characterization by Osiris method was performed on most of the compounds, revealing excellent properties as possible drugs.
Antifungal Activity of Cadinane‐Type Sesquiterpenes from Eupatorium adenophorum against Wood‐Decaying Fungi
Authors: Liu Yang , Wang Deyan , Hu Shijun , Wu Jianrong , Luo Jianmei , Cao Mingming , Yan Xiaohui
Published: September 2023

The present study aimed to evaluate the antifungal activities of Eupatorium adenophorum against four strains of wood‐decaying fungi, including Inonotus hispida, Inonotus obliquus, and Inonotus cuticularis. Bioguided isolation of the methanol extract of E. adenophorum by silica gel column chromatography and high‐performance liquid chromatography afforded six cadinane‐type sesquiterpenes. Their structures were identified by nuclear magnetic resonance and MS analyses. According to the antifungal results, the inhibition rate of the compound was between 59.85 % and 77.98 % at a concentration of 200 μg/mL. The EC50 values ranged from 74.5 to 187.4 μg/mL.
Preparation of Some New Pyrazolo[1,5‐a]pyrimidines and Evaluation of Their Antioxidant, Antibacterial (MIC and ZOI) Activities, and Cytotoxic Effect on MCF‐7 Cell Lines
Authors: Vahedi Mohammad Mehdi , Asghari Sakineh , Tajbakhsh Mahmood , Mohseni Mojtaba
Published: September 2023

This study aims to synthesize some novel pyrazolo[1,5‐a]pyrimidine derivatives, and investigate their biological activities. These compounds exhibited good to high antioxidant activities [2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical scavenging capabilities]. Among them, Ethyl 5‐(2‐ethoxy‐2‐oxoethyl)‐7‐hydroxy‐2‐methylpyrazolo[1,5‐a]pyrimidine‐3‐carboxylate (3h) showed the highest antioxidant activity [Half‐maximal Inhibitory Concentration (IC50)=15.34 μM] compared to ascorbic acid (IC50=13.53 μM) as a standard compound. Their antibacterial activities were investigated against two Gram‐positive bacteria (Bacillus subtilis, and Staphylococcus aureus) and two Gram‐negative bacteria (Pseudomonas aeruginosa, and Escherichia coli). The results showed that Ethyl 7‐hydroxy‐5‐phenylpyrazolo[1,5‐a]pyrimidine‐3‐carboxylate (3i) has the best antibacterial activity against Gram‐positive B. subtilis [Zone of Inhibition (ZOI)=23.0±1.4 mm, Minimum Inhibitory Concentration (MIC)=312 μM]. Also, the cytotoxicity of these compounds was assessed against breast cancer cell lines [human breast adenocarcinoma (MCF‐7)], which 7‐Hydroxy‐2‐methyl‐5‐phenylpyrazolo[1,5‐a]pyrimidine‐3‐carbonitrile (3f) displayed the most cytotoxicity (IC50=55.97 μg/mL), in contrast with Lapatinib (IC50=79.38 μg/mL) as a known drug.
Rapid On‐Resin N‐Formylation of Peptides as One‐Pot Reaction
Authors: Kokollari Agon , Werner Marius , Lindner Christina , Pham Truc Lam , Thomas Franziska
Published: September 2023

N‐formylation is a common pre‐ and post‐translational modification of the N‐terminus or the lysine side chain of peptides and proteins that plays a role in the initiation of immune responses, gene expression, or epigenetics. Despite its high biological relevance, protocols for the chemical N‐formylation of synthetic peptides are scarce. The few available methods are elaborate in their execution and the yields are highly sequence‐dependent. We present a rapid, easy‐to‐use one‐pot procedure that runs at room temperature and can be used to formylate protected peptides at both the N‐terminus and the lysine side chain on the resin in near‐quantitative yields. Only insensitive, storage‐stable standard chemicals – formic acid, acetic anhydride, pyridine and DMF – are used. Formylation works for both short and long peptides of up to 34 amino acids and over the spectrum of canonical amino acids.
Heart surgery in a pediatric patient with congenital heart disease and hemophilia B: A case report from Sudan
Authors: Mohmmedahmed Mohmmed A. , Eltahir Esra M. , Mohammedali Amna M. , Yousef Bashir A.
Published: September 2023

Key Clinical Message

A multidisciplinary team approach, careful hemostasis, and factor replacement therapy are important in the perioperative management of hemophiliac patients undergoing pediatric cardiac surgery.

The combination of congenital heart diseases (CHD) and hemophilia is rare; furthermore, heart surgery and perioperative management of such cases is challenging. This report illustrates the challenges of pediatric cardiac surgery in an infant with both hemophilia B and CHD. Multidisciplinary team approach, careful hemostasis, and factor replacement therapy were key to success without hemorrhagic complications before, during and after surgery.
Management and saving a traumatized poor prognosis maxillary central incisor for 18 years: A patient‐centered treatment
Authors: Aminsobhani Mohsen , HafeziMotlagh Kimia , MahjourianQomi Reza
Published: September 2023

Key clinical message

With today's increasing desire to preserve natural teeth, managing teeth with a poor prognosis is a new challenge for clinicians. A dentist's attention to patient‐centered care is essential, which improves dental outcomes.

Nowadays, patients' interest in preserving their natural teeth has increased. In the patient‐centered care model, the clinician should consider the patient's preferences and values in the treatment plan. This strengthens the patient's responsibility toward his own body, resulting in more patient satisfaction and effective cooperation. Therefore, the skill of saving teeth with a poor prognosis, in which there was no other choice but to extract them, becomes essential in patients who want to preserve their natural teeth. This case report presents the successful 18‐year treatment and management of a maxillary central incisor of a 17‐year‐old male with a horizontal root fracture, who was incompletely treated in another medical center when the trauma occurred. The patient presented to us after 6 months. Due to the short length of the root, the patient underwent regenerative endodontic treatment first, but he did not attend follow‐ups. Finally, after 8 years, the patient returned with symptoms of infection and periapical radiolucency. The apical part of the root was resorbed during this time. Finally, it was decided to place an apical plug with MTA. MTA was extruded from the apical part of the root canal during the placement of the apical plug. In the 1‐, 2‐, 4‐, and 10‐year follow‐ups, the patient was completely asymptomatic, and the radiolucent periradicular lesion had healed. However, the extruded MTA was still present in the radiographic images without interfering with the healing process. Finally, the tooth has remained functional for 18 years.
Persistently high serum aspartate aminotransferase level in an asymptomatic young patient
Authors: Pei Xiong , Zhao Yanhua , Jiang Wei , Zeng Qingmin , Liu Changhai , Wang Ming , Wang Hui , Liang Shanshan , Gan Wei , Wu Dongbo , Tang Hong
Published: September 2023

Key Clinical Message

We report a young man with isolated elevated AST. He had no other evidence of liver or other related diseases. All the tests and examination reports were negative. The final diagnosis of macro‐AST was confirmed by PEG precipitation tests.

Elevated liver enzymes, such as alanine aminotransferase (ALT) and aspartate aminotransferase (AST), may commonly indicate liver injury. However, macro‐AST is generally a benign condition that may be considered as pathologic by clinicians. A young man with isolated elevated AST for more than 10 years who have taken extensive tests and examinations was diagnosed with macro‐AST in our article. Thus, in patients with isolated AST‐elevation, polyethylene glycol (PEG) precipitation test was recommended to test whether macro‐AST could be diagnosed.
Defluorinative 1,3‐Dienylation of Fluoroalkyl N‐Triftosylhydrazones with Homoallenols
Authors: Zhang Xiaolong , Deng Jiahua , Ji Yong , Li Rong , Sivaguru Paramasivam , Song Qingmin , Karmakar Swastik , Bi Xihe
Published: September 2023

A silver‐catalyzed regioselective defluorinative 1,3‐dienylation of trifluoromethyl phenyl N‐triftosylhydrazones using homoallenols as 1,3‐dienyl sources provides a variety of α‐(di)fluoro‐β‐vinyl allyl ketones with excellent functional group tolerance in moderate to good yields. The reaction proceeds through a silver carbene‐initiated sequential etherification and Claisen type [3,3]‐sigmatropic rearrangement cascade. The synthetic utility of this protocol was demonstrated through the downstream synthetic elaboration toward diverse synthetically useful building blocks.
Dipolarophile‐Steered Formal Stereodivergent Synthesis of 2,5‐cis/trans‐Pyrrolidines Based on Asymmetric 1,3‐Dipolar Cycloaddition of Imino Lactones
Authors: Furuya Shohei , Muroi Kenji , Kanemoto Kazuya , Fukuzawa Shin‐ichi
Published: September 2023

The stereodivergent asymmetric synthesis of 2,5‐trans/cis pyrrolidines by 1,3‐dipolar cycloaddition using two different types of activated alkenes is described. When ylidene‐isoxazolones were employed as dipolarophiles, the Ag/(S,Sp)‐iPr‐FcPHOX‐catalyzed asymmetric [3+2] cycloaddition of imino lactones proceeded with 2,5‐trans selectivity. Subsequent decarboxylation of the isoxazolone rings produced pyrrolidines with 2,5‐trans stereoretention. In the reaction using acyclic enones as activated alkenes, the Ag/(R,Sp)‐ThioClickFerrophos complex‐catalyzed asymmetric [3+2] cycloaddition afforded 2,5‐cis substituted pyrrolidines in high yields and enantioselectivities. Therefore, these methods can be considered as a formal stereodivergent synthesis of 2,5‐cis/trans pyrrolidines.
Synthesis and Characterization of Quinone Compounds Derived from Doubly and Triply Linked Diporphyrins and Tuning of Their Absorption Properties**
Authors: Yamashita Ken‐ichi , Hirano Daisuke , Sugiura Ken‐ichi
Published: September 2023

Porphyrins are attracting increasing attention in materials science and photochemistry owing to their unique properties and diverse applications. This study focuses on modifying and tuning the absorption properties of porphyrins, specifically those of quinoidal porphyrins, to extend their spectral range into the near‐infrared (NIR) region. We report the synthesis and structural and physical properties of quinone compounds derived from doubly and triply linked diporphyrins and their metal complexes. Doubly linked diporphyrinquinone exhibits broad panchromatic absorption properties in solution owing to its low symmetry. Metal complexation markedly extends its absorption range into the near‐infrared region. In contrast, the metal complexes of the triply linked diporphyrinquinones exhibit sharp and strong absorption bands in the visible to near‐infrared region owing to their higher symmetry. The longest absorption wavelength of the triply linked diporphyrinquinones was approximately 1500 nm, which was significantly more red‐shifted than that of the doubly linked ones.
Planar Hexacoordinate Beryllium: Covalent Bonding Between s–block Metals
Authors: Jin Bo , Guan Xiao‐Ling , Yan Miao , Wang Ying‐Jin , Wu Yan‐Bo
Published: September 2023

Achieving a planar hypercoordinate arrangement of s‐block metals through covalent bonding with ligands is challenging due to the strong ionicity involved. Herein, we report the first case of a neutral binary global minimum containing a planar hexacoordinate beryllium atom. The central Be atom is coordinated by six active Be atoms, the latter in turn are enclosed by an equal number of more electronegative chlorine atoms in the periphery, forming a star‐like phBe cluster (Be©Be6Cl6). Importantly, the cluster exhibits dynamically stabilized stemming geometrically from the appropriate matching of metal‐ligand size and electronically from adherence to the octet rule as well as possessing a 6σ/2π double aromaticity. Remarkably, energy decomposition analysis‐natural orbitals for chemical valence (EDA‐NOCV) analysis reveals a significant covalent interaction between the ligand and the central metal beryllium atoms, a fact further supported by a large Wiberg bond index. This cluster is a promising synthetic as its excellent electronic, dynamic and thermodynamic stability.
Mechanism of CO2 Reduction to Methanol with H2 on an Iron(II)‐scorpionate Catalyst
Authors: Zhu Chengxu , D'Agostino Carmine , de Visser Sam P.
Published: September 2023

CO2 utilization is an important process in the chemical industry with great environmental power. In this work we show how CO2 and H2 can be reacted to form methanol on an iron(II) center and highlight the bottlenecks for the reaction and what structural features of the catalyst are essential for efficient turnover. The calculations predict the reactions to proceed through three successive reaction cycles that start with heterolytic cleavage of H2 followed by sequential hydride and proton transfer processes. The H2 splitting process is an endergonic process and hence high pressures will be needed to overcome this step and trigger the hydrogenation reaction. Moreover, H2 cleavage into a hydride and proton requires a metal to bind hydride and a nearby source to bind the proton, such as an amide or pyrazolyl group, which the scorpionate ligand used here facilitates. As such the computations highlight the non‐innocence of the ligand scaffold through proton shuttle from H2 to substrate as an important step in the reaction mechanism.
Yellow‐Fluorescence Carbon Dots Employed for pH Sensing and Detection of Tigecycline†
Authors: Zhao Jingwen , Wang Junchen , Zeng Linggao , Zhou Sen , Yang Xiaoming
Published: September 2023

Comprehensive Summary

Long‐wavelength fluorescence carbon dots (CDs) show great importance in multiple fields, especially for the biochemical sensing. Here, we proposed one type of CDs doped with nitrogen and sulfur through the hydrothermal method, which exhibited obvious yellow‐fluorescence in aqueous solution. Importantly, the fluorescence intensity of CDs decreased with pH decreasing in the acidic range, thus a linear relationship between pH and fluorescence intensity was established, exhibiting the potential of pH sensing. Additionally, introducing tigecycline into CDs resulted in their decreased fluorescence, thus, we further established a strategy of detecting tigecycline with the concentration range of 200 μM to 7 nM. Meanwhile, we elucidated the static quenching as the major mechanism for CDs responding tigecycline, which was induced by the formed new complex between CDs and tigecycline. Furthermore, the practicality of the method was verified by examining the recovery of tigecycline in the actual lake‐water samples.
Cationic Conjugated Oligomers for Efficient and Rapid Antibacterial Photodynamic Therapy via Both Type I and Type II Pathways
Authors: Wang Huan , Guo Shuwen , Yuan Qiong , Li Meiqi , Tang Yanli
Published: September 2023

Comprehensive Summary

Recently, photodynamic therapy (PDT) has attracted wide attention due to its less susceptibility to drug resistance, broad‐spectrum biocidal activity and biosafety in normal tissues. However, the traditional photosensitizers (PSs) face the disadvantage of poor therapeutic efficacy due to the requirement of an aerobic environment to generate 1O2 through Type ІI pathway. Herein, we designed and synthesized a novel cationic conjugated oligomer oligo(phenylene vinylene) (OPV) and studied its antibacterial photodynamic activity against both Gram‐negative Escherichia coli (E. coli) and Gram‐positive bacteria methicillin‐resistant Staphylococcus aureus (MRSA). Importantly, the OPV can rapidly produce reactive oxygen species (ROS) through double pathways, Type I and II mechanism under white light irradiation, and efficiently kill E. coli and MRSA at a nanomolar level. The dual type photosensitizing capability makes OPV promising for enhanced PDT to treat pathogens and tumors in complex environments.