bluuebunny/crossref_metadata_2025 huggingface dataset:
Time Transients with Inductive Loop Traces in Metal Halide Perovskites
Authors: Hernández‐Balaguera Enrique , Bisquert Juan
Published: October 2023

Metal halide perovskites are archetypal ionic‐electronic materials with great prospects for optoelectronic applications. Among the rich variety of physics exhibited by ionic‐electronic conduction, here, those most relevant to optoelectronic devices in which ionic mechanisms introduce a kinetic delay in the electronic phenomena are analyzed. The attention is focused on the inductive loop features and a dynamical model is developed to describe the corresponding complex multiscale dynamics in the time domain under experimental conditions, finally explaining the fundamental structure of the current transient responses in halide perovskite semiconductors. Based on complex capacitive and inductive patterns extensively studied in impedance measurements, an adequate interpretation of time domain methods capable of monitoring charge‐carrier dynamics is produced. Therefore, this methodology identifies the characteristic parameters of all types of transient dynamics in metal halide perovskites, providing a suitable connection of correlated techniques, including impedance and chronoamperometric experiments, toward a robust interpretation of the device response. The scope of the method is fairly general, since these counterintuitive transient effects are observable not only in metal halide perovskites, but also in multiple materials and processes, mainly in different research fields pertaining to electrochemistry and electronics.
High‐Performing Acid‐Free PEDOT:PSS‐Based Organic Photodiodes for Cardiovascular Disease Diagnosis
Authors: Yang Zhao , Kim Byung Gi , Jang Woongsik , Park Jong Hyeok , Wang Dong Hwan
Published: October 2023

Photodetectors made from low‐toxicity organic materials are considered a promising alternative to conventional inorganic photodetectors. However, the performance of current organic photodetectors (OPD) needs to be further enhanced. This study aims to introduce acid‐free poly(3,4‐ethylenedioxythiophene)‐(polystyrene sulfonate) (PEDOT‐(PSS)) films in order to improve the performance of OPDs in practical applications. Utilization of heterocyclic 1,3‐diazole (HDZ) in PEDOT‐(PSS) improves the polymerization degree, carrier mobility, and other physicochemical properties. These enhanced properties also improve the comprehensive performance of OPD. In this flow, the enhanced noise suppression is also confirmed by elucidating the device's performance limitations. Consequently, the presented OPD‐based photoplethysmography sensor has the ability to diagnose blood circulation status and cardiovascular diseases. This accomplishment marks the first in single pixel‐based organic photodiode research.
Graphdiyne as an Electron Modifier for Boosting Electrochemical Production of Adipic Acid
Authors: Liu Fulai , Gao Xutao , Shi Rui , Xiong Jinfan , Guo Zhengxiao , Tse Edmund C. M. , Chen Yong
Published: October 2023

Adipic acid (AA) is a crucial feedstock for nylon polymers, and is industrially produced by thermal oxidation of cyclohexanone/cyclohexanol mixture (KA oil). However, this process consumes large quantities of corrosive nitric acid as oxidants, while emits ozone‐depleting greenhouse gas N2O. Here, an electrocatalytic strategy for selective oxidation of KA oil to AA coupled with H2 evolution over a Co3O4/graphdiyne cooperative catalyst (Co3O4/GDY) is reported. The Co3O4/GDY displays high electrooxidation activity of KA oil to AA (100 mA cm−2 at ≈1.5 V vs RHE), outperforming all the reported findings. Detailed ex situ and in situ experimental studies, theoretical calculations, and molecular dynamic simulations reveal that GDY not only facilitates the enrichment of cyclohexanone on the catalyst surface in aqueous medium, but also upshifts the d‐band center of Co sites, strengthening the adsorption/activation of cyclohexanone. This study offers a green route for AA synthesis and proposes a GDY interface engineering strategy for efficient electrooxidation.
PCTS‐Controlled Synthesis of L10/L12‐Typed Pt‐Mn Intermetallics for Electrocatalytic Oxygen Reduction
Authors: Yan Wei , Wang Xuan , Liu Manman , Ma Kaiyue , Wang Liqi , Liu Qicheng , Wang Caikang , Jiang Xian , Li Hao , Tang Yawen , Fu Gengtao
Published: October 2023

Pt‐based intermetallics are recognized as effective catalysts for oxygen reduction reaction (ORR) in fuel cells. However, the synthesis of intermetallics often requires prolonged annealing and the effect of different crystal structures on ORR still need to be investigated. Herein, L12‐Pt3Mn and L10‐PtMn intermetallics with Pt‐skin are rapidly synthesized through an emerging periodic carbothermal shock method to investigate their ORR‐activity difference. The formation of L12‐Pt3Mn and L10‐PtMn can be well‐controlled by the Pt/Mn feeding ratio, pulse cycles, and temperature. Electrocatalytic investigations show that L12‐Pt3Mn presents a more positive half‐wave potential (0.91 V vs RHE) and onset potential (1.02 V vs RHE) than those of L10‐PtMn. The mass activity and specific activity of L12‐Pt3Mn are respectively fourfold and threefold greater than those of L10‐PtMn. Theoretical calculations indicate that the L12‐Pt3Mn has a more substantial work function than L10‐PtMn, thereby conferring L12‐Pt3Mn with an increased electron density allocation for catalytic involvement. This electron confinement imparts L12‐Pt3Mn with a Pt d‐band center lower than that of L10‐PtMn, consequently attenuating the adsorption of strongly bonded *O intermediates during the rate‐determining step. This study not only employs a straightforward method for intermetallic preparation but also elucidates the discrepancies in ORR activity across intermetallics with distinct structures.
Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites
Authors: Batool Samar , Langer Marcel , Myakala Stephen Nagaraju , Heiland Magdalena , Eder Dominik , Streb Carsten , Cherevan Alexey
Published: October 2023

Thiomolybdates are molecular molybdenum‐sulfide clusters formed from Mo centers and sulfur‐based ligands. For decades, they have attracted the interest of synthetic chemists due to their unique structures and their relevance in biological systems, e.g., as reactive sites in enzymes. More recently, thiomolybdates are explored from the catalytic point of view and applied as homogeneous and molecular mimics of heterogeneous molybdenum sulfide catalysts. This review summarizes prominent examples of thiomolybdate‐based electro‐ and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. Active sites of thiomolybdates relevant for the hydrogen evolution reaction are examined, aiming to shed light on the link between cluster structure and performance. The shift from solution‐phase to surface‐supported thiomolybdates is discussed with a focus on applications in electrocatalysis and photocatalysis. The outlook highlights current trends and emerging areas of thiomolybdate research, ending with a summary of challenges and key takeaway messages based on the state‐of‐the‐art research.
Pseudopolymorphic Phase Engineering for Improved Thermoelectric Performance in Copper Sulfides
Authors: Yang Tian‐Yu , Gu Shi‐Wei , Zhang Yi‐Xin , Zheng Fengshan , Kong Deli , Dunin‐Borkowski Rafal E. , Wu Di , Ge Zhen‐Hua , Feng Jing , Jin Lei
Published: October 2023

Polymorphism (and its extended form – pseudopolymorphism) in solids is ubiquitous in mineralogy, crystallography, chemistry/biochemistry, materials science, and the pharmaceutical industries. Despite the difficulty of controlling (pseudo‐)polymorphism, the realization of specific (pseudo‐)polymorphic phases and associated boundary structures is an efficient route to enhance material performance for energy conversion and electromechanical applications. Here, this work applies the pseudopolymorphic phase (PP) concept to a thermoelectric copper sulfide, Cu2‐xS (x ≤ 0.25), via CuBr2 doping. A peak ZT value of 1.25 is obtained at 773 K in Cu1.8S + 3 wt% CuBr2, which is 2.3 times higher than that of a pristine Cu1.8S sample. Atomic‐resolution scanning transmission electron microscopy confirms the transformation of pristine Cu1.8S low digenite into PP‐engineered high digenite, as well as the formation of (semi‐)coherent interfaces between different PPs, which is expected to enhance phonon scattering. The results demonstrate that PP engineering is an effective approach for achieving improved thermoelectric performance in Cu‐S compounds. It is also expected to be useful in other materials.
Enhanced CO2 Electrolysis Through Mn Substitution Coupled with Ni Exsolution in Lanthanum Calcium Titanate Electrodes
Authors: Zhang Nuoxi , Naden Aaron , Zhang Lihong , Yang Xiaoxia , Connor Paul , Irvine John
Published: October 2023

In this study, perovskite oxides La0.3Ca0.6Ni0.05MnxTi0.95−xO3−γ (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 – 3% H2O. The performance of La0.3Ca0.6Ni0.05Ti0.95O3−γ is notably improved by co‐doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO3) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133 h of high‐temperature operation, suggesting a reliable cathode material for CO2 electrolysis.
Molecular Masking of Synthetic Immunomodulator Evokes Antitumor Immunity With Reduced Immune Tolerance and Systemic Toxicity by Temporal Activity Recovery and Sustained Stimulation
Authors: Shin Hong Sik , Kim Sohyun , Jin Seung Mo , Yoo Yeon Jeong , Heo Jang Hun , Lim Yong Taik
Published: October 2023

Activation of the innate immune system counteracts tumor‐induced immunosuppression. Hence, small molecule‐based toll‐like receptor 7/8 agonists (TLR7/8a), which can modulate immunosuppression in the tumor microenvironment along with the activation of innate immunity, are emerging as essential components of cancer immunotherapy. However, the clinical application of synthetic TLR7/8a therapies is limited by systemic immune‐associated toxicity and immune tolerance induced by uncontrolled stimulatory activities and repeated treatments. To address these limitations, a dynamic immunomodulation strategy incorporating masking and temporal recovery of the activity of TLR7/8a through prodrug‐like TLR7/8a (pro‐TLR7/8a) at the molecular level and a sustained and controlled release of active TLR7/8a from nanoliposome (pro‐TLR7/8a) (NL(pro‐TLR7/8)) in a macroscale depot are designed. Immunization with cationic NL(pro‐TLR7/8) and anionic antigens triggers robust activation of innate immune cells as well as antigen‐specific T cell responses, eliciting reprogramming of immunosuppressive cells into tumor‐suppressive cells, with decreased systemic adverse effects and immune tolerance. Combination treatment with NL(pro‐TLR7/8a) and immune checkpoint inhibitors (anti‐CTLA‐4 plus anti‐PD‐L1) or nanoliposomes (Doxorubicin) has synergistic effects on antitumor immunity in various tumor models. The concept of pro‐TLR7/8a suggested herein may facilitate the advancement of small‐molecule‐based immunomodulators for clinical translation and safe and effective cancer immunotherapy.
Polymer‐Entangled Spontaneous Pseudo‐Planar Heterojunction for Constructing Efficient Flexible Organic Solar Cells
Authors: Zhang Jiayou , Mao Houdong , Zhou Kangkang , Zhang Lifu , Luo Dou , Wang Pei , Ye Long , Chen Yiwang
Published: October 2023

Flexible organic solar cells (FOSCs) have attracted considerable attention from researchers as promising portable power sources for wearable electronic devices. However, insufficient power conversion efficiency (PCE), intrinsic stretchability, and mechanical stability of FOSCs remain severe obstacles to their application. Herein, an entangled strategy is proposed for the synergistic optimization of PCE and mechanical properties of FOSCs through green sequential printing combined with polymer‐induced spontaneous gradient heterojunction phase separation morphology. Impressively, the toughened‐pseudo‐planar heterojunction (Toughened‐PPHJ) film exhibits excellent tensile properties with a crack onset strain (COS) of 11.0%, twice that of the reference bulk heterojunction (BHJ) film (5.5%), which is among the highest values reported for the state‐of‐the‐art polymer/small molecule‐based systems. Finite element simulation of stress distribution during film bending confirms that Toughened‐PPHJ film can release residual stress well. Therefore, this optimal device shows a high PCE (18.16%) with enhanced (short‐circuit current density) JSC and suppressed energy loss, which is a significant improvement over the conventional BHJ device (16.99%). Finally, the 1 cm2 flexible Toughened‐PPHJ device retains more than 92% of its initial PCE (13.3%) after 1000 bending cycles. This work provides a feasible guiding idea for future flexible portable power supplies.
Optical Read‐Out of the Electrical Switching of Cobalt‐Terpyridine‐BODIPY Molecules Immobilized as Single Layer on ITO
Authors: Magra Kévin , Audibert Jean‐Frédéric , Dragoe Diana , Mallah Talal , Miomandre Fabien , Boillot Marie‐Laure
Published: October 2023

A single layer of a dyad made of a cobalt(II) bis‐terpyridine complex functionalized with a Boron‐dipyrromethene (BODIPY) fluorophore on transparent Indium Tin Oxide (ITO) electrode is prepared. A modulation of the photoluminescence intensity of the fluorophore upon the application of an electric stimulus on the ITO electrode that supports 10 picomoles of molecules is demonstrated. The intensity of the fluorescence intensity decreases when the cobalt is at the oxidation state +III, due to CoIII oxidative quenching of BODIPY emission that has a higher driving force than the CoII reductive quenching initially responsible for the low fluorescence intensity of the chemisorbed dyad.
Improving Performance of Organic Photodetectors by Using TCNQ Doped Copper Thiocyanate as the Anode Interfacial Layer
Authors: Luo Xuanang , Huang Zhenqiang , Zhong Zhiming , Quan Huilei , Peng Feng , An Kang , Li Ning , Ying Lei
Published: October 2023

The responsivity and specific detectivity are critical figures of merits for organic photodetectors; however, it remains challenging to simultaneously enhance two such parameters, since enhancing external quantum efficiency corresponding to responsivities will inevitably increase leakage current and noises, resulting in decreased specific detectivity. To address such a trade‐off, an effective anode interfacial layer of 7,7,8,8‐tetracyanoquinodimethane (TCNQ) doped copper thiocyanate (CuSCN) is developed herein, which can enhance shunt resistance, increase depletion width, enhance hole extraction efficiency, as well as reduce trap density of states of organic photodetectors. The organic photodetectors based on doped CuSCN present a very low dark current density of 4.4 × 10−11 A cm−2 and an impressively high specific detectivity of 1.1 × 1014 Jones. As evidenced by X‐ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy measurements, the energy levels of the doped CuSCN:TCNQ film are deepened, associated with the occurrence of dopant bonding and charge transfer. In addition, it is found that increasing the delay time can suppress the hysteresis effects of current density–voltage characteristics of organic photodetectors and make the minimum dark current density obtainable at 0 V. These findings demonstrate the great potential of using molecular doping to adjust the anode interfacial layer for developing high‐performance organic photodetectors.
Low rates of sugarcane bagasse‐derived biochar have limited effects on soil properties and sugarcane crop yield
Authors: White Paul M. , Ellsworth Patrick Z. , Lima Isabel
Published: October 2023

Sugarcane (Saccharumspp.) represents the most valuable row crop in Louisiana. High levels of biomass production and extensive tillage have degraded portions of the state's alluvial soils used to grow sugarcane. In addition to sucrose, processing the crop generates excess bagasse each year, which can represent a disposal problem for sugar factories. However, converting the bagasse to biochar at nearby pyrolysis facilities may prove to be an economical means of improving degraded soils. The objective was to determine the impacts of low rates of biochar (<3.2 mt ha−1) on soil physical, chemical, and biological properties. Plant available nutrient levels were marginally impacted by biochar additions as the biochar exhibited a relatively low surface area and neutral pH. Bagasse‐derived biochar did not affect soil nitrate retention or leaching, and overall recovery was >86%. Biochar did not increase soil CO2evolution, indicating its stability as a soil carbon amendment. However, adding biochar with mineral nitrogen decreased CO2evolution, compared to biochar alone, indicating a negative priming effect. Soil moisture retention was minimally impacted by biochar. Cane yield, sucrose content, and sucrose yield were not statistically affected by applying biochar with or without starter fertilizer at planting. Overall, the results indicate that lower levels of bagasse‐derived biochar minimally impacted soil properties and crop yield; however, the biochar was stable in soil and may find utility as a carbon‐rich amendment should carbon credits prove to be an additional source of grower or land‐owner revenue.
Synthesis of Heptagon‐Containing Polyarenes by Catalytic C−H Activation
Authors: Yamada Keigo E. , Stepek Iain A. , Matsuoka Wataru , Ito Hideto , Itami Kenichiro
Published: October 2023

Nanocarbons incorporating non‐hexagonal aromatic rings ‐ such as five‐, seven‐, and eight‐membered rings ‐ have various intriguing physical properties such as curved structures, unique one‐dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficient synthetic approach to polycyclic aromatics containing seven‐membered rings via a palladium‐catalyzed intramolecular Ar−H/Ar−Br coupling. In addition to all‐hydrocarbon scaffolds, heteroatom‐embedded heptagon‐containing polyarenes can be efficiently constructed with this method. Rhodium‐ and palladium‐catalyzed sequential six‐ and seven‐membered ring formations also afford complex heptagon‐containing molecular nanocarbons from readily available arylacetylenes and biphenyl boronic acids. Detailed mechanistic analysis by DFT calculations showed the feasibility of seven‐membered ring formation by a concerted metalation‐deprotonation mechanism. This reaction can serve as a template for the synthesis of a wide range of seven‐membered ring‐containing molecular nanocarbons.
Neutral and Anionic Square Planar Palladium(0) Complexes Stabilized by a Silicon Z‐Type Ligand
Authors: Ansmann Nils , Münch Joshua , Schorpp Marcel , Greb Lutz
Published: October 2023

Anionic [Pd(0)−X]− ate complex were proposed as key intermediates in Pd‐catalyzed cross‐coupling for decades, but their isolation remained elusive. Herein, a chelating Lewis acidic bis(amidophenolato)silane is introduced as a strong Z‐type ligand which enables the characterization of the first anionic [Pd(0)−X]− ate complex. Intriguingly, these compounds and the neutral L−Pd(0) analogs exhibit a square planar coordination that is highly unusual for a d10 metal. Theoretical methods scrutinize the interaction between the Lewis acidic Si(IV) center and the late transition metal, while reactivity studies shed light on the potential role of anionic additives in oxidative addition reactions.
Non‐Interacting Ni and Fe Dual‐Atom Pair Sites in N‐Doped Carbon Catalysts for Efficient Concentrating Solar‐Driven Photothermal CO2 Reduction
Authors: Mo Shengpeng , Zhao Xinya , Li Shuangde , Huang Lili , Zhao Xin , Ren Quanming , Zhang Mingyuan , Peng Ruosi , Zhang Yanan , Zhou Xiaobin , Fan Yinming , Xie Qinglin , Guo Yanbing , Ye Daiqi , Chen Yunfa
Published: October 2023

Solar‐to‐chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar‐driven photothermal system coupling a dual‐metal single‐atom catalyst (DSAC) with adjacent Ni−N4 and Fe−N4 pair sites is designed for boosting gas‐solid CO2 reduction with H2O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16 μmol g−1 h−1), CH4 (135.35 μmol g−1 h−1) and CH3OH (59.81 μmol g−1 h−1), which are equivalent to 1.70‐fold, 1.27‐fold and 1.23‐fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d‐band center of Fe atom is efficiently regulated in non‐interacting Ni and Fe dual‐atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar‐driven photothermal CO2 reduction to initial CO production.
Photoenzymatic Enantioselective Synthesis of Oxygen‐Containing Benzo‐Fused Heterocycles
Authors: Zhu Changtong , Yuan Zhenbo , Deng Zhiwei , Yin Dejing , Zhang Yan , Zhou Jingwen , Rao Yijian
Published: October 2023

New‐to‐nature biocatalysis in organic synthesis has recently emerged as a green and powerful strategy for the preparation of valuable chiral products, among which chiral oxygen‐containing benzo‐fused heterocycles are important structural motifs in pharmaceutical industry. However, the asymmetric synthesis of these compounds through radical‐mediated methods is challenging. Herein, a novel asymmetric radical‐mediated photoenzymatic synthesis strategy is developed to realize the efficient enantioselective synthesis of oxygen‐containing benzo‐fused heterocycles through structure‐guided engineering of a flavin‐dependent ‘ene’‐reductase GluER. It shows that variant GluER‐W100H could efficiently produce various benzoxepinones, chromanone and indanone with different benzo‐fused rings in high yields with great stereoselectivities under visible light. Moreover, these results are well supported by mechanistic experiments, revealing that this photoenzymatic process involves electron donor‐acceptor complex formation, single electron transfer and hydrogen atom transfer. Therefore, we provide an alternative green approach for efficient chemoenzymatic synthesis of important chiral skeletons of bioactive pharmaceuticals.
High‐Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All‐Solid‐State Batteries
Authors: Li Shenghao , Lin Jing , Schaller Mareen , Indris Sylvio , Zhang Xin , Brezesinski Torsten , Nan Ce‐Wen , Wang Shuo , Strauss Florian
Published: October 2023

Superionic solid electrolytes (SEs) are essential for bulk‐type solid‐state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge‐transport properties, however a thorough understanding of how configurational entropy (ΔSconf) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen‐rich lithium argyrodites with the general formula Li5.5PS4.5ClxBr1.5‐x (0≤x≤1.5). Using neutron powder diffraction and 31P magic‐angle spinning nuclear magnetic resonance spectroscopy, the S2−/Cl−/Br− occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li‐ion dynamics, leading to a room‐temperature ionic conductivity of 22.7 mS cm−1 (9.6 mS cm−1 in cold‐pressed state) for Li5.5PS4.5Cl0.8Br0.7 (ΔSconf=1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li5.5PS4.5Cl0.8Br0.7 SE allowed for stable cycling of single‐crystal LiNi0.9Co0.06Mn0.04O2 (s‐NCM90) composite cathodes in SSB cells, emphasizing that dual‐substituted lithium argyrodites hold great promise in enabling high‐performance electrochemical energy storage.
Heterogeneous Copper‐Catalyzed Cross‐Coupling for Sustainable Synthesis of Chiral Allenes: Application to the Synthesis of Allenic Natural Products
Authors: Wu Haibo , Zheng Zhiyao , Zhang Kaiheng , Kajanus Johan , Johansson Magnus J. , Córdova Armando , Bäckvall Jan‐E.
Published: October 2023

Classical Crabbé type SN2' substitutions of propargylic substrates has served as one of the standard methods for the synthesis of allenes. However, the stereospecific version of this transformation often requires either stoichiometric amounts of organocopper reagents or special functional groups on the substrates, and the chirality transfer efficiency is also capricious. Herein, we report a sustainable methodology for the synthesis of diverse 1,3‐di and tri‐substituted allenes by using a simple and cheap cellulose supported heterogeneous nanocopper catalyst (MCC‐Amp‐Cu(I/II)). This approach represents the first example of heterogeneous catalysis for the synthesis of chiral allenes. High yields and excellent enantiospecificity (up to 97 % yield, 99 % ee) were achieved for a wide range of di‐ and tri‐substituted allenes bearing various functional groups. It is worth noting that the applied heterogeneous catalyst could be recycled at least 5 times without any reduced reactivity. To demonstrate the synthetic utility of the developed protocol, we have applied it to the total synthesis of several chiral allenic natural products.
Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis
Authors: Rogova Tatiana , Ahrweiler Eric , Schoetz Markus D. , Schoenebeck Franziska
Published: October 2023

Within the sphere of traditional Pd0/PdII cross coupling reactions, organogermanes have been historically outperformed both in terms of scope and reactivity by more conventional transmetalating reagents. Subsequently, this class of compounds has been largely underutilized as a coupling partner in bond‐forming strategies. Most recent studies, however, have shown that alternative modes of activation of these notoriously robust building blocks transform organogermanes into the most reactive site of the molecule—capable of outcompeting other functional groups (such as boronic acids, esters and silanes) for both C−C and C–heteroatom bond formation. As a result, over the past few years, the literature has increasingly featured methodologies that explore the potential of organogermanes as chemoselective and orthogonal coupling partners. Herein we highlight some of these recent advances in the field of organogermane chemistry both with respect to their synthesis and applications in synthetic and catalytic transformations.
A Single‐Enantiomer Emitter Enabled Superstructural Helix Inversion for Upconverting and Downshifting Luminescence with Bidirectional Circular Polarization
Authors: Ren Chao , Sun Wenjing , Zhao Tonghan , Li Chengxi , Jiang Chengyu , Duan Pengfei
Published: October 2023

The helical twisting tendency of liquid crystals (LCs) is generally governed by the inherent configuration of the chiral emitter. Here, we introduce the multistage inversion of supramolecular chirality as well as circularly polarized luminescence (CPL) by manipulating the ratio of single enantiomeric emitters (R‐PCP) to LC monomers (5CB). Increasing the content of R‐PCP from 1 wt % to 3 wt % inverted the helix of LCs from left‐handed to right‐handed, accompanying a CPL sign changed from positive to negative. The biaxiality of chiral emitters, as well as the steric effect of chiral‐chiral and chiral‐achiral interaction, were identified as the reasons for helical sense inversion. Due to the strong helical twisting power, 4 wt % R‐PCP drove the photonic band gap (PBG) of chiral LCs to match up with their emission range, leading to an inversion of the CPL again with a high dissymmetry factor (≈1.2). Directly adjusting the PBG using chiral emitters is seldom achieved in cholesteric LCs. On this basis, an achiral sensitizer PtTPBP was assembled into the helical superstructure. The generation of triplet‐triplet annihilation‐induced upconverted CPL from R‐PCP and the downshifting CPL from PtTPBP with opposite rotation was achieved in a single chiral LC system by tuning the position of the PBG.
Doctor Versus Artificial Intelligence: Patient and Physician Evaluation of Large Language Model Responses to Rheumatology Patient Questions in a Cross‐Sectional Study
Authors: Ye Carrie , Zweck Elric , Ma Zechen , Smith Justin , Katz Steven
Published: October 2023

Objective

The objective of the current study was to assess the quality of large language model (LLM) chatbot versus physician‐generated responses to patient‐generated rheumatology questions.

Methods

We conducted a single‐center cross‐sectional survey of rheumatology patients (n = 17) in Edmonton, Alberta, Canada. Patients evaluated LLM chatbot versus physician‐generated responses for comprehensiveness and readability, with four rheumatologists also evaluating accuracy by using a Likert scale from 1 to 10 (1 being poor, 10 being excellent).

Results

Patients rated no significant difference between artificial intelligence (AI) and physician‐generated responses in comprehensiveness (mean 7.12 ± SD 0.99 vs 7.52 ± 1.16; P = 0.1962) or readability (7.90 ± 0.90 vs 7.80 ± 0.75; P = 0.5905). Rheumatologists rated AI responses significantly poorer than physician responses on comprehensiveness (AI 5.52 ± 2.13 vs physician 8.76 ± 1.07; P < 0.0001), readability (AI 7.85 ± 0.92 vs physician 8.75 ± 0.57; P = 0.0003), and accuracy (AI 6.48 ± 2.07 vs physician 9.08 ± 0.64; P < 0.0001). The proportion of preference to AI‐ versus physician‐generated responses by patients and physicians was 0.45 ± 0.18 and 0.15 ± 0.08, respectively (P = 0.0106). After learning that one answer for each question was AI generated, patients were able to correctly identify AI‐generated answers at a lower proportion compared to physicians (0.49 ± 0.26 vs 0.97 ± 0.04; P = 0.0183). The average word count of AI answers was 69.10 ± 25.35 words, as compared to 98.83 ± 34.58 words for physician‐generated responses (P = 0.0008).

Conclusion

Rheumatology patients rated AI‐generated responses to patient questions similarly to physician‐generated responses in terms of comprehensiveness, readability, and overall preference. However, rheumatologists rated AI responses significantly poorer than physician‐generated responses, suggesting that LLM chatbot responses are inferior to physician responses, a difference that patients may not be aware of.

image
Do we have to rethink inclusive pedagogies for secondary schools? A critical systematic review of the international literature
Authors: Koutsouris George , Bremner Nicholas , Stentiford Lauren
Published: October 2023

This article builds on the findings of a critical systematic review that aimed to explore understandings and applications of inclusive pedagogies in the secondary school. Inclusive pedagogies are often conceptualised as both a set of strategies that aim to ensure access to learning for all students, and as value principles that reflect particular views on inclusion; this is why they tend to be approached in diverse ways. We were particularly interested in secondary school as the focus on particular curricular areas and subjects, additional pressures for teachers and students derived from assessment and exams, and fewer opportunities for collaboration between teachers as a result of the compartmentalisation of the curriculum can make the implementation of inclusive pedagogies more challenging than at primary level. Six databases were searched for literature published exploring inclusive pedagogies in the context of secondary school. We found that inclusive pedagogies were often filtered through the lenses of particular subjects and were associated with other approaches with similar philosophies, such as differentiation and student‐centred learning; that student perceptions of inclusive pedagogies are still little explored; and that tensions associated with inclusion were only acknowledged to some extent. Based on the findings, we argue for a refined way of understanding inclusive pedagogies in the secondary school context, one that acknowledges the unique characteristics, challenges and tensions at this school level. The review findings also affirm the ‘messiness’ of the inclusion literature and raise questions as to the relevance and usefulness of systematic reviews in exploring this fragmented topic.
Over 104‐fold amplified upconversion luminescence of lanthanide nanocrystals through optical oscillator‐like system
Authors: Zhu Xinyan , Yang Mingzhu , Zhang Hongxin
Published: October 2023

Recently, lanthanide (Ln) luminescent nanocrystals have attracted increasing attention in various fields such as biomedical imaging, lasers, and anticounterfeiting. However, due to the forbidden 4f–4f transition of lanthanide ions, the absorption cross‐section and luminescence brightness of lanthanide nanocrystals are limited. To address the challenge, we constructed an optical oscillator‐like system to repeatedly simulate lanthanide nanocrystals to enhance the absorption efficiency of lanthanide ions on excitation photons. In this optical system, the upconversion luminescence (UCL) of Tm3+ emission of ~450 nm excited by a 980 nm laser can be amplified by a factor beyond 104. The corresponding downshifting luminescence of Tm3+ at 1460 nm was enhanced by three orders of magnitude. We also demonstrated that the significant luminescence enhancement in the designed optical oscillator‐like system was general for various lanthanide nanocrystals including NaYF4:Yb3+/Ln3+, NaErF4@NaYF4 and NaYF4:Yb3+/Ln3+@NaYF4:Yb3+@NaYF4 (Ln = Er, Tm, Ho) regardless of the wavelengths of excitation sources (808 and 980 nm). The mechanism study revealed that both elevated laser power in the optical system and multiple excitations on lanthanide nanocrystals were the main reason for the luminescence amplification. Our findings may benefit the future development of low‐threshold upconversion and downshifting luminescence of lanthanide nanocrystals and expand their applications.
Detection and elimination of trace d‐lactic acid in lignocellulose biorefining chain: Generation, flow, and impact on chiral lactide synthesis
Authors: Guo Xiaomeng , Li Zhibin , He Niling , Zhang Bin , Liu Xiucai , Bao Jie
Published: October 2023

High chiral purity of lactic acid is a crucial indicator for the synthesis of chiral lactide as the primary intermediate chemical for ring‐open polymerization of high molecular weight polylactic acid (PLA). Lignocellulose biomass is the most promising carbohydrate feedstock for commercial production of PLA, but the presence of trace d‐lactic acid in the biorefinery chain adversely affects the synthesis and quality of chiral lactide. This study analyzed the fingerprint of trace 
d‐lactic acid in the biorefinery chain and found that the major source of 
d‐lactic acid comes from lignocellulose feedstock. The naturally occurring lactic acid bacteria and water‐soluble carbohydrates in lignocellulose feedstock provide the necessary conditions for 
d‐lactic acid generation. Three strategies were proposed to eliminate the generation pathway of 
d‐lactic acid, including reduction of moisture content, conversion of water‐soluble carbohydrates to furan aldehydes in pretreatment, and conversion to 
l‐lactic acid by inoculating engineered 
l‐lactic acid bacteria. The natural reduction of lactic acid content in lignocellulose feedstock during storage was observed due to the lactate oxidase‐catalyzed oxidation of 
l‐ and 
d‐lactic acids. This study provided an important support for the production of cellulosic 
l‐lactic acid with high chiral purity.
The effect of body mass index on quality of life in modified single stoma cutaneous ureterostomy or ileal conduit after radical cystectomy
Authors: Zhang Wan‐Jin , Huang Xu‐Yun , Lin Bin , Zheng Wen‐Cai , Ke Zhi‐Bin , Lin Xiao‐Dan , Chen Jia‐Yin , Cai Hai , Lin Yun‐Zhi , Chen Ye‐Hui , Zheng Qing‐Shui , Wei Yong , Xue Xue‐Yi , Li Xiao‐Dong , Xu Ning
Published: October 2023

Objective

To explore the influence of postoperative body mass index (BMI) change on postoperative quality of life (QOL) in patients undergoing radical cystectomy (RC) plus modified single stoma cutaneous ureterostomy (MSSCU) or ileal conduit (IC).

Methods

Patients were divided into two groups according to different BMI change patterns: patients experiencing an elevated postoperative BMI level, along with a clinically significant increase in their BMI (an increase of more than 10%) were categorized as Group 1, while patients experiencing a decrease postoperative BMI level, along with a clinically significant reduction in their BMI (a decrease of more than 5%) were categorized as Group 2. Spearman correlation analysis was used to examine the correlations between quality‐of‐life scores and postoperative clinical parameters.

Results

Spearman correlation analysis showed that postoperative BMI, late complications and catheter‐free state were significantly associated with postoperative global QoL and symptom scale in MSSCU and postoperative global QoL and physical scale in IC patients. Additionally, postoperative BMI, catheter‐free state and the use of adjuvant therapy were associated with bad performance in many scales of QoL like body image, future perspective, social scale, future perspective (MSSCU), and abdominal bloating (IC) (Table 2, p<0.05). Patients in Group 2 with significant weight loss had a better Global QoL, a lower rate of stomal stricture and a higher catheter‐free state compared with those in Group 1 in both IC and MSSCU patients. MSSCU patients in Group 2 could achieve a comparable Global QoL as to IC patients in Group 1.

Conclusion

Controlling the substantial increase in body weight after surgery contributes to improving QoL, reducing the occurrence of stomal stricture, and ensuring a postoperative catheter‐free state in BCa patients undergoing MSSCU.
Comparative analysis of clinicopathologic characteristics and prognosis between nasal and nonnasal extranodal NK/T‐cell lymphoma
Authors: Shen Ziyuan , Chen Xicheng , Sun Cai , Lu Tianyi , Shi Yuye , Zhang Hao , Ye Jingjing , Wang Ling , Zhu Taigang , Miao Yuqing , Zhang Xudong , Wang Liang , Cai Guoqi , Sang Wei
Published: October 2023

Background

The clinicopathologic characteristics and prognosis of nasal and nonnasal extranodal natural killer T‐cell lymphoma (ENKTL) are considered to be different. However, the underlying features responsible for these differences are not well clarified especially in the era of asparaginase therapy.

Methods

In total, 1007 newly diagnosed ENKTL patients from 11 medical centers were included in this study. Clinicopathologic characteristics and survival data were collected. The chi‐squared test and Kruskal–Wallis test were utilized for the comparison of different groups. Univariable and multivariable Cox proportional hazards models were used to screen prognostic factors.

Results

Overall, 869 (86.3%) patients were nasal forms. Compared to patients with nasal ENKTL, nonnasal patients were at more advanced stages and had poor performance status, bone marrow involvement, elevated serum lactate dehydrogenase (LDH), and CD56‐negative status (p < 0.05). The 5‐year overall survival (OS) for nasal and nonnasal patients were 65.6% and 45.0%, respectively. The OS of nasal forms patients were superior to nonnasal patients, especially in Eastern Cooperative Oncology Group performance status (ECOG PS) (≥2), advanced stage, KPI (HIR/HR), IPI (HIR/HR), PINK (HR), and high EBV DNA load groups. In patients treated with pegaspargase/L‐asparaginase‐based regimens, the OS of nasal patients was better than that of nonnasal patients. After adjusting the covariates of age, stage, ECOG PS score, LDH, B symptoms, and BM involvement, results showed that the nonnasal site was associated with poor survival of ENKTL.

Conclusions

The clinicopathologic characteristics and prognosis of nasal and nonnasal ENKTL patients are different. Nasal forms patients had superior OS than nonnasal patients, especially in the era of asparaginase.
Easy to Use DFT Approach for Computational pKa Determination of Carboxylic Acids
Authors: Pezzola Silvia , Venanzi Mariano , Galloni Pierluca , Conte Valeria , Sabuzi Federica
Published: October 2023

In pKa computational determination, the challenge in exploring and fostering new methodologies and approaches goes in parallel with the amelioration of computational performances. In this paper a “ready to use methodology” has been compared to other strategies, such as the re‐shaping in solvation cavity (Bondi radius re‐shaping), wanting to assess its reliability in predicting the pKa of a broad list of carboxylic acids. Thus, the functionals B3LYP and CAM‐B3LYP have been selected, using SMD as continuum solvation model. Exploiting our previous results, two water molecules were made explicit on the reaction centre. Data show that our model (CAM‐B3LYP/2H2O) is capable to accurately predict pKa, leading to mean absolute error (MAE) values lower than 0.5. Noteworthy, good results were achieved in computing the pKa of substituents bearing nitro and cyano groups. Focusing on B3LYP, eventually remarkable outputs were obtained only when Bondi correction was applied to the complex with two water molecules. Hence, massive outcomes were obtained in foreseeing the trichloro and trifluoro acetic acid pKa. These findings demonstrated that no complex level of theory nor external factor is required to accurately predict carboxylic acids pKa, with MAE well below 0.5 units.
Luminescent Chiral Furanol‐PAHs via Straightforward Ni‐Catalysed Csp2−F Functionalization: Mechanistic Insights into the Scholl Reaction
Authors: Sala Judith , Capdevila Lorena , Berga Cristina , de Aquino Araceli , Rodríguez Laura , Simon Sílvia , Ribas Xavi
Published: October 2023

Here we report the stepwise synthesis of new nanographenes (NGs) and polycyclic aromatic hydrocarbons (PAHs) obtained via Scholl ring fusion applied at aromatic homologation compounds, which are obtained through one‐step Ni‐catalysed Csp2−F functionalization. The latter are rapidly accessed valid precursors for the Scholl reaction, and screening of experimental conditions allowed us to describe for the first time furanol‐bearing PAHs. Mechanistic insights are obtained by DFT to rationalize the formation of the furanol PAHs under moderately acidic conditions. All PAHs and NGs synthesized show moderate/weak fluorescent properties, and all PAHs crystallized show some degree of curvature and are obtained as racemic mixtures. Enantiomeric separation by chiral HPLC of one furanol‐bearing PAH allowed the study of their chiroptical CD properties.
Direct Synthesis of N‐formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO2 Fixation in a Metal‐Organic Framework
Authors: Huang Wenyuan , Mei Qingqing , Xu Shaojun , An Bing , He Meng , Li Jiangnan , Chen Yinlin , Han Xue , Luo Tian , Guo Lixia , Hurd Joseph , Lee Daniel , Tillotson Evan , Haigh Sarah J. , Walton Alex , Day Sarah J. , Natrajan Louise S. , Schröder Martin , Yang Sihai
Published: October 2023

Formamides are important feedstocks for the manufacture of many fine chemicals. State‐of‐the‐art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom‐economy. Here, we report the first example of direct synthesis of N‐formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass‐derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal‐organic framework supported ruthenium catalyst, Ru/MFM‐300(Cr). Highly selective production of N‐formamides has been observed for a wide range of carbonyl compounds. Synchrotron X‐ray powder diffraction reveals the presence of strong host‐guest binding interactions via hydrogen bonding and parallel‐displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.
New Methyl Methacrylate Derived Adsorbents – Synthesis, Characterization and Adsorptive Removal of Toxic Organic Compounds
Authors: Wawrzkiewicz Monika , Podkościelna Beata , Podkościelny Przemysław , Gilev Jadranka Blazhevska
Published: October 2023

This study aimed to synthesize polymeric adsorbents by suspension polymerization using methyl methacrylate (MMA) with different crosslinking monomers. Divinylbenzene (DVB) and aliphatic monomers: ethylene glycol dimethacrylate (EGDMA) or N,N′‐methylenebisacrylamide (NN) containing additional amide groups were used. The possibility of using the prepared copolymers (MMA‐NN, MMA‐EGDMA, MMA‐DVB) as adsorbents for the removal of toxic compounds such as dyes (C.I. Acid Red 18 (AR18), C.I. Acid Green 16 (AG16), C.I. Acid Violet 1 (AV1), C.I. Basic Yellow 2 (BY2), C.I. Basic Blue 3 (BB3) and C.I. Basic Red 46 (BR46)) and phenol (PhOH) from dye baths and effluents was evaluated. Preferential adsorption of basic‐type dyes compared to acid‐type dyes or phenol was observed by the polymers. Adsorbent based on MMA‐EGDMA exhibited the highest capacity for investigated dyes and phenol. The pseudo‐second order kinetic model as well as the intraparticle diffusion model can find application in predicting sorption kinetics. Based on the equilibrium sorption data fitted to the Langmuir, Freundlich, Temkin and Dubinin‐Radushkevich model, uptake of BB3, AV1 and PhOH is rather physisorption than chemisorption. The regeneration yield of MMA‐EGDMA does not exceed 60 % using 1 M HCl, 1 M NaCl, and 1 M NaOH in 50 %v/v methanol.
Crystal Structure, Quantum Chemical, Hirshfeld Surface and Molecular Docking of Organic Molecular Salt: 2‐Amino‐5‐Chloropyridinium‐2,4‐Dihydroxybenzoate
Authors: Ponnusamy Kavitha , Madhu Rajkumar , Athianna Muthusamy
Published: October 2023

An organic molecular salt, 2‐amino‐5‐chloropyridinium‐2,4‐dihydroxybenzoate (ACP‐DHB) is synthesized by the slurry method followed by crystallization from methanol. The formation of molecular salt is initially confirmed by1H and13C nuclear magnetic resonance (NMR) spectral data. Single crystal X‐ray diffraction (XRD) analysis shows that the crystal belongs to the monoclinic crystal system with space group, P21/n. Further, the supramolecular assembly involved the extensive network of N+−H···O−and N−H···O hydrogen bonds as well as C‐Cl···O halogen bond. Using UV‐Visible spectral data, the optical band gap is calculated and found to be 4.21 eV. Photoluminescence studies indicate the crystal has blue light emission properties. TG/DTA analysis shows that ACP‐DHB is thermally stable up to 162 °C. The quantum chemical calculations and natural bond analysis (NBO) are performed at B3LYP/6‐311G++ (d,p) basis set using Gaussian 09 software. The relative contributions of various intermolecular connections are discussed using Hirshfeld surface analysis and fingerprint plot illustration. The antibacterial and antifungal activity exhibits better inhibitory capacity against pathogens. Molecular docking revealed that ACP‐DHB efficiently binds with the 1UAG and 5KEE targets and has strong binding ability to the proteins. ADMET factors and Lipinski's rule of five are used to predict drug likeness property.