bluuebunny/crossref_metadata_2025_split huggingface dataset:
Quantitative Dynamic Structural Color: Dual‐Band Hyperchromatic Sensing with Mesoporous Metamaterials
Authors: Kumar Nithesh , Dos Santos Estevao Marques , Talukdar Tahmid H. , Ryckman Judson D. 
Published: July 2024

AbstractDynamic and responsive structural color devices present promising opportunities for sensing and display technologies, with applications including point‐of‐care diagnostics, portable/wearable sensors, and low‐power full‐color displays. However, it is often difficult to generate a large and quantitatively meaningful colorimetric response especially toward weak stimuli. Here, dual‐band hyperchromatic structural color (HSC) is presented as an approach to overcome these challenges. Within this framework, a dual‐band mesoporous silicon rugate filter metamaterial co‐designed is experimentally realized for use with a dichromatic (red/green) illuminant. This is shown to enable an amplified red‐to‐green color transition with a substantially smaller wavelength shift than conventional structural color devices, Δλ ≪ |λG – λR|, as well as a direct quantitative mapping between the observed chromaticity and the input stimulus. This approach is experimentally demonstrated for the spatiotemporally resolved sensing of refractometric stimuli including small‐molecules and volatile organic compounds (VOCs) with a ≈0.08 nm equivalent spectral resolution. This approach is entirely scanning‐free, enabled by simple color imaging, and does not require advanced spectroscopic (hyperspectral) imaging or interferometric imaging to obtain meaningful quantitative and spatiotemporally resolved information pertaining to the sensor's attributes. These results demonstrate dual‐band HSC as a promising approach for realizing low‐cost and high performance dynamic structural color devices and sensors.
Ferroelasticity in Halide Perovskites Affects Electro‐Optical Properties through Facet Stability
Authors: Veber Noam , Shamaev Betty , Shaek Saar , Massasa Emma H. , Zimmerman Jonathan , Be'er Orr , Levy Shai , Bekenstein Yehonadav 
Published: July 2024

AbstractAdvancements in ferroic materials center upon understanding domain structures and their boundaries. This study innovates by directing the growth of lead halide perovskite microcrystals from the gas phase onto pre‐chosen substrates, thereby inducing an interfacial strain that prompts ferroelasticity‐driven structural transformation. A method of ferroelastic engineering in vapor‐grown perovskite heterostructures is thus unveiled, revealing ordered domain patterns of bright crystals with contrasting electro‐optical properties. In the case of the frustrated halide perovskite crystals, the strain is relaxed by the formation of alternating crystallographic twin domains. In the demonstrated orthorhombic system, these domains alternate between (110) and (002) orientation, with a (112) domain boundary. Perovskite ferroelastic effect with facet stability is correlated, attributed to the exposure of lower surface energy terminations, promoting the material's stability and efficiency. This findings result from direct electrical measurements, which pave the way for the tailored design of ferroic materials, optimizing their optoelectronic characteristics for enhanced device performance.
Three Component Cascade Processes Involving Palladium Catalyzed Transformations/Dipolar Cycloadditions for the Synthesis of Angular Heterotriquinane Derivatives
Authors: Jovanovic Predrag , Jovanovic Milos , Petkovic Milos , Simic Milena , Tasic Gordana , Rodic Marko , Rakic Srdjan , Vlahovic Filip , Savic Vladimir 
Published: July 2024

AbstractCombining chemical reactivities of allenes and oximes created a methodology for the preparation of heterocyclic triquinane‐type skeletons via a cascade process constructing four bonds in a single step. The initial reaction of allene moiety promoted by Pd‐catalysis, affording π‐allyl Pd‐species, was followed by two additional transformations ‐ nucleophilic displacement and dipolar cycloaddition ‐ to furnish the product highly stereoselectively in moderate to good yields. For the process to be efficient, it was necessary to use a dipolarophilic component as a solvent. Intriguingly, while the reaction with cyclopentanone derived oxime progressed through the whole cascade, with cyclohexanone analogue it stopped at the nitrone stage, requiring an additional step to yield similar type of products. Some aspects of the studied cascade were examined by DFT.
Influence of Rhenium Concentration on Charge Doping and Defect Formation in MoS2
Authors: Munson Kyle T. , Torsi Riccardo , Habis Fatimah , Huberich Lysander , Lin Yu‐Chuan , Yuan Yue , Wang Ke , Schuler Bruno , Wang Yuanxi , Asbury John B. , Robinson Joshua A. 
Published: July 2024

AbstractSubstitutionally doped transition metal dichalcogenides (TMDs) are essential for advancing TMD‐based field effect transistors, sensors, and quantum photonic devices. However, the impact of local dopant concentrations and dopant–dopant interactions on charge doping and defect formation within TMDs remains underexplored. Here, a breakthrough understanding of the influence of rhenium (Re) concentration is presented on charge doping and defect formation in MoS2 monolayers grown by metal–organic chemical vapor deposition (MOCVD). It is shown that Re‐MoS2 films exhibit reduced sulfur‐site defects, consistent with prior reports. However, as the Re concentration approaches ⪆2 atom%, significant clustering of Re in the MoS2 is observed. Ab Initio calculations indicate that the transition from isolated Re atoms to Re clusters increases the ionization energy of Re dopants, thereby reducing Re‐doping efficacy. Using photoluminescence (PL) spectroscopy, it is shown that Re dopant clustering creates defect states that trap photogenerated excitons within the MoS2 lattice, resulting in broad sub‐gap emission. These results provide critical insights into how the local concentration of metal dopants influences carrier density, defect formation, and exciton recombination in TMDs, offering a novel framework for designing future TMD‐based devices with improved electronic and photonic properties.
Phosphonium Iodide Featuring Blue Thermally Activated Delayed Fluorescence for Highly Efficient X‐Ray Scintillator
Authors: Wei Jun‐Hua , Luo Jian‐Bin , He Zi‐Lin , Peng Qing‐Peng , Chen Jing‐Hua , Zhang Zhi‐Zhong , Guo Xiu‐Xian , Kuang Dai‐Bin 
Published: July 2024

AbstractOrganic scintillators are praised for their abundant element reserves, facile preparation procedures, and rich structures. However, the weak X‐ray attenuation ability and low exciton utilization efficiency result in unsatisfactory scintillation performance. Herein, a new family of highly efficient organic phosphonium halide salts with thermally activated delayed fluorescence (TADF) are designed by innovatively adopting quaternary phosphonium as the electron acceptor, while dimethylamine group and halide anions (I−) serve as the electron donor. The prepared butyl(2‐[2‐(dimethylamino)phenyl]phenyl)diphenylphosphonium iodide (C4‐I) exhibits bright blue emission and an ultra‐high photoluminescence quantum yield (PLQY) of 100 %. Efficient charge transfer is realized through the unique n‐π and anion‐π stacking in solid‐state C4‐I. Photophysical studies of C4‐I suggest that the incorporation of I accounts for high intersystem crossing rate (kISC) and reverse intersystem crossing rate (kRISC), suppressing the intrinsic prompt fluorescence and enabling near‐pure TADF emission at room temperature. Benefitting from the large Stokes shift, high PLQY, efficient exciton utilization, and remarkable X‐ray attenuation ability endowed by I, C4‐I delivers an outstanding light yield of 80721 photons/MeV and a low limit of detection (LoD) of 22.79 nGy ⋅ s−1. This work would provide a rational design concept and open up an appealing road for developing efficient organic scintillators with tunable emission, strong X‐ray attenuation ability, and excellent scintillator performance.
5,18‐Dimesitylorangarin: a Stable Antiaromatic [20]Pentaphyrin(1.0.1.0.0) Displaying Remarkable Oxidative Self‐Coupling Reactions
Authors: Rao Yutao , Lee Jiyeon , Chen Jinchao , Xu Ling , Zhou Mingbo , Yin Bangshao , Kim Jiwon , Osuka Atsuhiro , Song Jianxin 
Published: July 2024

Abstract5,18‐Dimesitylorangarin and its BF2 complex were synthesized by double SNAr reaction of 3,5‐dibromo‐BODIPY with 2‐pyrrolydipyrrin as the first examples of meso‐aryl‐substituted orangarin. These orangarins, delineated as [20]pentaphyrin(1.0.1.0.0), are strongly antiaromatic but rather stable. The free base orangarin was coupled by oxidation with MnO2 to give a 11,11′‐linked dimer, a cyclooctatetraene(COT)‐centered trimer, and a spiro‐trimer. Fused COT‐centered 3H‐orangarin dimer was oxidized to the corresponding 2H‐orangarin dimer, which was further coupled to give a triply COT‐centered 2H‐orangarin tetramer. 3H‐Orangarin oligomers are all antiaromatic as evinced by extremely low‐field‐shifted 1H NMR signals of the inner NH and ill‐defined absorption spectra with broad tails. In contrast, COT‐centered 2H‐orangarin dimer and tetramer show moderately low‐field‐shifted NH signals and intense NIR absorbance over 900 nm, suggesting effective π‐conjugation through the COT bridge and almost non‐antiaromatic character. These orangarin oligomers exhibit many reversible redox potentials owing to the intramolecular electronic interactions. Regardless of the different aromatic characters, all the orangarin monomers and oligomers exhibit very rapid excited‐state decays.
The skull of the semi‐aquatic neotropical lizard Echinosaura horrida (Gymnophthalmidae: Cercosaurinae) reveals new synapomorphies within Gymnophthalmoidea
Authors: Hernández‐Morales Cristian , Ngo Alison , Abdelhadi Leila , Schargel Walter E. , Daza Juan D. , Yánez‐Muñoz Mario H. , Smith Eric N. 
Published: July 2024

AbstractThe rough teiid or water cork lizard (Echinosaura horrida) is a small reptile from Colombia and Ecuador placed in a genus that contains eight species and well‐known phylogenetic relationships. Here we provide a detailed description and illustrations, bone by bone, of its skull, while we discussed its intraspecific variation by comparing high‐resolution computed tomography data from two specimens and the variation within the genus by including previously published data from Echinosaura fischerorum. This allowed to propose putative diagnostic character states for Echinosaura horrida and synapomorphies for Echinosaura. In addition, our discussion includes broader comparisons of new character transformations of the jugal, vomer, orbitosphenoid, and hyoid. These characters are important for diagnosing clades at different levels of the Gymnophthalmoidea phylogeny.
Design, synthesis, biological evaluation, and molecular modeling simulations of new phthalazine‐1,4‐dione derivatives as anti‐Alzheimer's agents
Authors: Nuha Demokrat , Evren Asaf Evrim , Özkan Begüm Nurpelin Sağlık , Gundogdu‐Karaburun Nalan , Karaburun Ahmet Çagri 
Published: July 2024

AbstractThe development of targeted phthalazine‐1,4‐dione acetylcholinesterase (AChE) inhibitors for treating Alzheimer's disease involved the synthesis of 32 compounds via a multistage process. Various analytical techniques confirmed the compounds' identities. Thirteen compounds were found to inhibit AChE by more than 50% without affecting butyrylcholinesterase (BChE). Among these, three compounds, 8m, 8n, and 8p, exhibited extraordinary activity similar to donepezil, a reference AChE inhibitor. During enzyme kinetic studies, compound 8n, displaying the highest AChE inhibitory activity, underwent evaluation at three concentrations (2 × IC50, IC50, and IC50/2). Lineweaver–Burk plots indicated mixed inhibition activity for compound 8n against AChE, suggesting a combination of competitive and noncompetitive characteristics. Additionally, effective derivatives 8m, 8n, and 8p exhibited high blood–brain barrier (BBB) permeability in in vitro parallel artificial membrane permeability assay tests. Molecular docking studies revealed that these compounds bind to the enzyme's active site residues in a position similar to donepezil. Molecular dynamic simulations confirmed the stability of the protein–ligand system, and the chemical reactivity characteristics of the compounds were investigated using density functional theory. The compounds' wide energy gaps suggest stability and therapeutic potential. This research represents a significant step toward finding a potential cure for Alzheimer's disease. However, further research and testing are required to determine the compounds' safety and efficacy. The unique structure of phthalazine derivatives makes them suitable for various biological activities, and these compounds show promise for developing effective drugs for treating Alzheimer's disease. Overall, the development of these targeted compounds is a crucial advancement in the search for an effective treatment for Alzheimer's disease.
Characterization of a Novel Pathogenic PLCG2 Variant Leading to APLAID Syndrome Responsive to a TNF Inhibitor
Authors: Yang Zhaohui , Tao Panfeng , Han Xu , Kozlova Anna , He Tingyan , Volchkov Egor , Nesterenko Zoya , Pershin Dmitryi , Raykina Elena , Fatkhudinov Timur , Korobeynikova Anastasia , Aksentijevich Ivona , Yang Jun , Shcherbina Anna , Zhou Qing , Yu Xiaomin 
Published: July 2024

ObjectiveAutoinflammation and phospholipase C (PLC) γ2–associated antibody deficiency and immune dysregulation (APLAID) syndrome is an autoinflammatory disease caused by gain‐of‐function variants in PLCG2. This study investigates the pathogenic mechanism of a novel variant of PLCG2 in a patient with APLAID syndrome.MethodsWhole‐exome sequencing and Sanger sequencing were used to identify the pathogenic variant in the patient. Single‐cell RNA sequencing, immunoblotting, luciferase assay, inositol monophosphate enzyme‐linked immunosorbent assay, calcium flux assay, quantitative PCR, and immunoprecipitation were used to define inflammatory signatures and evaluate the effects of the PLCG2 variant on protein functionality and immune signaling.ResultsWe identified a novel de novo variant, PLCG2 p.D993Y, in a patient with colitis, pansinusitis, skin rash, edema, recurrent respiratory infections, B‐cell deficiencies, and hypogammaglobulinemia. The single‐cell transcriptome revealed exacerbated inflammatory responses in the patient's peripheral blood mononuclear cells. Expression of the D993Y variant in HEK293T, COS‐7, and PLCG2 knock‐out THP‐1 cell lines showed heightened PLCγ2 phosphorylation; elevated inositol‐1,4,5‐trisphosphate production and intracellular Ca2+ release; and activation of the MAPK, NF‐κB, and NFAT signaling pathways compared with control‐transfected cells. In vitro experiments indicated that the D993Y variant altered amino acid properties, disrupting the interaction between the catalytic and autoinhibitory domains of PLCγ2, resulting in PLCγ2 autoactivation.ConclusionOur findings demonstrated that the PLCG2 D993Y variant is a gain‐of‐function mutation via impairing its autoinhibition, activating multiple inflammatory signaling pathways, thus leading to APLAID syndrome. This study further broadens the molecular underpinnings and phenotypic spectrum of PLCγ2‐related disorders.
Patient‐reported physical well‐being predicts good long‐term survival of hematopoietic stem cell transplantation
Authors: Lu Yin , You Tao , Ma Qin , Wang Weijuan , Qi Jiaqian , Yang Pan , Song Yaya , Chen Jia , Fu Jianhong , Ge Yongqin , Zhu Xiaming , Wu Depei 
Published: July 2024

AbstractAimThis study aimed to explore the association between patient‐reported items at different time points after hematopoietic stem cell transplantation (HSCT) and long‐term survival.MethodsWe conducted a study with 144 allogeneic HSCT patients, following them for 5 years post‐transplantation. Data from the Functional Assessment of Cancer Therapy‐Bone Marrow Transplant (FACT‐BMT) questionnaire were collected before transplantation and at 1, 3, 6, 12, 18, 36, and 60 months after transplantation. Demographic characteristics and survival status were also assessed.ResultsAmong the 144 cases, the 5‐year overall survival (OS), progression‐free survival (PFS), non‐relapse mortality (NRM), and graft‐versus‐host disease‐free (GRFS) rates were 65%, 48%, 17%, and 36% respectively. Health‐related quality of life (HRQOL) showed a fluctuating pattern over 5 years. Using a latent class mixed model, patients were classified into two groups based on their physical well‐being (PWB) scores during the 60‐month follow‐up. Class 1 had initially lower PWB scores, which gradually increased over time. In contrast, Class 2 maintained higher PWB scores with slight increases over time. Kaplan–Meier survival analysis revealed that Class 1 had better OS (70.9% vs. 52.9%, p = 0.021), PFS (60.5% vs. 41.2%, p = 0.039), and GRFS (35.1% vs. 29.3%, p = 0.035) compared to Class 2.ConclusionsPatients who had higher initial PWB scores after HSCT demonstrated improved long‐term survival outcomes. The PWB score could serve as a valuable predictor for the prognosis of HSCT.
Promoting Effect of Pd Nanoparticles on SrTi0.8Mn0.2O3 in the Reverse Water‐Gas Shift Reaction via the Mars–Van Krevelen Mechanism
Authors: Kobayashi Minori , Naniwa Shimpei , Goto Keita , Matsuo Hiroki , Iguchi Shoji , Tanaka Tsunehiro , Teramura Kentaro 
Published: July 2024

AbstractThe reverse water‐gas shift (RWGS) reaction serves as a critical pathway for converting CO2 into diverse chemicals. The Mars–van Krevelen (MvK) mechanism, which leverages lattice oxygen as the oxidant and oxygen vacancies as reductants, offers an alternative catalytic strategy for the selective RWGS reaction. While Mn‐substituted SrTiO3 (i. e., SrTi0.8Mn0.2O3) has been shown to promote the RWGS reaction selectively via the MvK mechanism, achieving a sufficient conversion of CO2 necessitates elevated temperatures. This study investigated the effect of Pd‐loaded SrTi0.8Mn0.2O3 on the activation of adsorbed H2 molecules, which generated oxygen vacancies and enhanced CO2 conversion. Notably, 1.0 wt % Pd‐loaded SrTi0.8Mn0.2O3 yielded 13.4 % of CO at 673 K, whereas pristine SrTi0.8Mn0.2O3 and Pd‐loaded SrTiO3 yielded negligible or minimal amount of CO. Hydrogen temperature‐programmed reduction and X‐ray absorption spectroscopy measurements revealed that Pd promoted the formation of oxygen vacancies via both thermodynamic and kinetic mechanisms. Fourier transform infrared spectroscopy and kinetic studies revealed that the RWGS reaction over Pd‐loaded SrTi0.8Mn0.2O3 proceeded primarily via the MvK mechanism with a partial contribution from the Langmuir–Hinshelwood mechanism. This study underscores the effectiveness of combining metal and MvK‐type catalysts to enhance the efficiency of the RWGS reaction.
Arc plasma‐deposited Co single‐atom catalysts supported on an aligned carbon nanofiber for hydrogen peroxide electrosynthesis and an electro‐Fenton process
Authors: Hwang Chang‐Kyu , Kim Sooyeon , Yoon Ki Ro , Le Thao Thi , Hoang Chinh V. , Choi Jae Won , Zhang Wenjun , Paek Sae Yane , Lee Chung Hyeon , Lee Ji Hyun , Chae Keun Hwa , Jeong Sohee , Lee Seung Yong , Ju Byeong‐Kwon , Kim Sang Hoon , Han Sang Soo , Kim Jong Min 
Published: July 2024

AbstractAtomically dispersed single‐atom catalysts (SACs) on carbon supports show great promise for H2O2 electrosynthesis, but conventional wet chemistry methods using particulate carbon blacks in powder form have limited their potential as two‐electron (2e−) oxygen reduction reaction (ORR) catalysts. Here, we demonstrate high‐performance Co SACs supported on a free‐standing aligned carbon nanofiber (CNF) using electrospinning and arc plasma deposition (APD). Based on the surface oxidation treatment of aligned CNF and precise control of the deposition amount in a dry‐based APD process, we successfully form densely populated Co SACs on aligned CNF. Through experimental analyses and density functional theory calculations, we reveal that Co SAC has a Co–N2–O2 moiety with one epoxy group, leading to excellent 2e− ORR activity. Furthermore, the aligned CNF significantly improves mass transfer in flow cells compared to randomly oriented CNF, showing an overpotential reduction of 30 mV and a 1.3‐fold improvement (84.5%) in Faradaic efficiency, and finally achieves an outstanding production rate of 15.75 mol gcat−1 h−1 at 300 mA cm−2. The high‐performance Co SAC supported on well‐aligned CNF is also applied in an electro‐Fenton process, demonstrating rapid removal of methylene blue and bisphenol F due to its exceptional 2e− ORR activity.
Biocatalysis in Non‐Conventional Media: Unlocking the Potential for Sustainable Chiral Amine Synthesis
Authors: Cananà Stefania , De Nardi Federica , Blangetti Marco , Parisotto Stefano , Prandi Cristina 
Published: July 2024

AbstractThe application of biocatalysis has become essential in both academic and industrial domains for the asymmetric synthesis of chiral amines, and it serves as an alternative tool to transition‐metal catalysis and complements traditional chemical methods. It relies on the swift expansion of available processes, primarily as a result of advanced tools for enzyme discovery, combined with high‐throughput laboratory evolution techniques for optimizing biocatalysts. This concept paper explores the utilization of non‐conventional media such as ether‐type solvents, deep eutectic solvents, and micellar catalysis to enhance biocatalytic reactions for chiral amine synthesis. Each section focuses on the unique properties of these media, including their ability to stabilize enzymes, alter substrate solubility, and modulate enzyme selectivity. The paper aims to provide insights into how these innovative media can overcome traditional limitations, offering new avenues for sustainable and efficient chiral amine production through biocatalytic processes.
Heterogenization of Ionic Liquid on Multiwalled Carbon Nanotubes for Lead(II) Ion Detection
Authors: Soni Abhishek , Singh Dilbag , Gupta Neeraj 
Published: July 2024

AbstractThe presence of lead(II) ion poses a significant threat to water systems due to their toxicity and potential health hazards. The detection of Pb2+ ions in contaminated water is very crucial. The ionic liquid functionalized multiwalled carbon nanotubes (IL@MWCNT) nanocomposite was fabricated using ionic liquid (IL) 1‐methyl‐3‐(4‐sulfobutyl)‐imidazolium chloride and multiwalled carbon nanotubes (MWCNTs) for detection of lead(II) ions. It is a novel method to heterogenize the layer of IL on the surface of MWCNTs. The XPS and FTIR analyses confirm that the ionic liquid is not decomposed during annealing process. Moreover, the XRD analysis shows the presence of MWCNTs and carbon quantum dots (CQDs). The HRTEM results exhibit the aggregation of MWCNTs with IL, and formation of small distorted round shaped flakes of CQDs. Further, the successful heterogenization of IL on the surface of MWCNTs is also confirmed by TGA‐DSC analysis. The quenching phenomenon of nanocomposite was observed by UV‐Visible spectroscopy. The nanocomposite exhibits high performance for the selective detection of lead(II) ions in comparison to other metal ions. The presence of lead(II) ions eventually reduced the intensity of absorption. A limit of detection (LOD) of 9.16 nM was attained for Pb2+ ions in a concentration range of 0–20 nM.