bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modulating Emission of Boric Acid into Highly Efficient and Color‐Tunable Afterglow via Dehydration‐Induced Through‐Space Conjugation
Authors: Zhang Zhen , Wang Zhenguang , Liu Xiao , Shi Yu‐e , Li Zhiqiang , Zhao Yanli 
Published: March 2023

AbstractInorganic boric acid (BA) is generally not considered an efficient afterglow material, and several groups have reported its extremely weak room‐temperature phosphorescence (RTP) in the blue spectral region. It is discovered that heat treatment of BA results in increased afterglow intensity (27‐fold increase) and prolonged emission lifetime (from 0.83 to 1.59 s), attributed to enhanced through‐space conjugation (TSC) of BA. The afterglow intensity of BA can be increased further (≈415 folds) by introducing p‐hydroxybenzoic acid (PHA), which contains a conjugated molecular motif, to further promote the TSC of the BA system. This combination results in the production of afterglow materials with a photoluminescence quantum yield of 83.8% and an emission lifetime of 2.01 s. In addition, a tunable multicolor afterglow in the 420–490 nm range is achieved owing to the enhancement of the RTP and thermally activated delayed fluorescence of PHA, where BA exerts a confinement effect on the guest molecules. Thus, this study demonstrates promising afterglow materials produced from extremely abundant and simple precursor materials for various applications.
Electronic Coupling of Metal‐to‐Insulator Transitions in Nickelate‐Based Heterostructures
Authors: Varbaro Lucia , Mundet Bernat , Domínguez Claribel , Fowlie Jennifer , Georgescu Alexandru B. , Korosec Lukas , Alexander Duncan T.L. , Triscone Jean‐Marc 
Published: March 2023

AbstractIn rare earth nickelates, the metal‐to‐insulator transition observed as a function of temperature can be described using an electronic and a structural order parameter. The electronic one is linked to the electronic disproportionation observed below the transition temperature and the structural one characterizes the breathing mode that develops in the low temperature phase. Here SmNiO3/NdNiO3 superlattices are grown with insulating LaAlO3 spacer layers to study the unusual coupling of metal‐to‐ insulator transitions observed at SmNiO3/NdNiO3 interfaces and determine the role of the two order parameters. Temperature‐dependent transport measurements reveal that a single unit cell of LaAlO3 inserted between SmNiO3 and NdNiO3 leads to a complete decoupling of the metal‐to‐insulator transitions suggesting that the order parameter controlling the coupling is the electronic one.
Development of a Triboelectric Nanogenerator for Joining of Silver Nanorods
Authors: Jalili Mohammad Amin , Karimzadeh Fathallah , Enayati Mohammad Hossein , Kalali Ehsan Naderi , Kheirabadi Noushin Raeisi 
Published: March 2023

AbstractOn account of their excellent properties, 2D nanostructures beyond graphene, such as MoS2, have extensive applications. Given their quantum confinement effects, MoS2 monolayers could efficiently trap electrons as an intermediate layer between friction and electrode in triboelectric nanogenerators (TENGs) and successfully hinder their recombination and air breakdown, increasing their output. With the help of this phenomenon, a TENG called PS+PS/MoS2‐AHSG (PPMA) TENG is fabricated with an open‐circuit voltage of ≈1200 V and a short‐circuit current of 0.74 mA, and a maximum power of 11.27 mW. PPMA TENG consists of transparent polystyrene (PS) and PS/MoS2 as negative contact and storage layers. Also, the positive layer is a novel Alyssum homolocarpum seed gum (AHSG) layer, which is a natural polymer. This TENG could successfully light up 115 commercial light‐emitting diodes. PPMA TENG exhibits exceptional mechanical robustness so that after a decrease in its outputs, heating would activate the self‐healing mechanism, and the surface charge density could reach from 0.428 to 0.874 µC m−2, which is 82% of the initial value. To demonstrate the practical applications of PPMA TENG as a high‐voltage sustainable power source, it is successfully employed to perform a dielectrophoretic assisted welding of silver nanorods.
Tailoring Active Cu2O/Copper Interface Sites for N‐Formylation of Aliphatic Primary Amines with CO2/H2
Authors: Dai Xingchao , Li Teng , Wang Bin , Kreyenschulte Carsten , Bartling Stephan , Liu Shujuan , He Dongcheng , Yuan Hangkong , Brückner Angelika , Shi Feng , Rabeah Jabor , Cui Xinjiang 
Published: March 2023

AbstractHeterogeneously catalyzed N‐formylation of amines to formamide with CO2/H2 is highly attractive for the valorization of CO2. However, the relationship of the catalytic performance with the catalyst structure is still elusive. Herein, mixed valence catalysts containing Cu2O/Cu interface sites were constructed for this transformation. Both aliphatic primary and secondary amines with diverse structures were efficiently converted into the desired formamides with good to excellent yields. Combined ex and in situ catalyst characterization revealed that the presence of Cu2O/Cu interface sites was vital for the excellent catalytic activity. Density functional theory (DFT) calculations demonstrated that better catalytic activity of Cu2O/Cu(111) than Cu(111) is attributed to the assistance of oxygen at the Cu2O/Cu interface (Ointer) in formation of Ointer‐H moieties, which not only reduce the apparent barrier of HCOOH formation but also benefit the desorption of the desired N‐formylated amine, leading to high activity and selectivity.
A Dissipative Reaction Network Drives Transient Solid–Liquid and Liquid–Liquid Phase Cycling of Nanoparticles
Authors: Roy Soumendu , Gravener Laura , Philp Douglas , Kay Euan R. 
Published: March 2023

AbstractTransient states maintained by energy dissipation are an essential feature of dynamic systems where structures and functions are regulated by fluxes of energy and matter through chemical reaction networks. Perfected in biology, chemically fueled dissipative networks incorporating nanoscale components allow the unique properties of nanomaterials to be bestowed with spatiotemporal adaptability and chemical responsiveness. We report the transient dispersion of gold nanoparticles in water, powered by dissipation of a chemical fuel. A dispersed state that is generated under non‐equilibrium conditions permits fully reversible solid–liquid or liquid–liquid phase transfer. The molecular basis of the out‐of‐equilibrium process is reversible covalent modification of nanoparticle‐bound ligands by a simple inorganic activator. Activator consumption by a coupled dissipative reaction network leads to autonomous cycling between phases. The out‐of‐equilibrium lifetime is tunable by adjusting the pH value, and reversible phase cycling is reproducible over several cycles.
Enhanced Carrier Diffusion Enables Efficient Back‐Contact Perovskite Photovoltaics
Authors: Zhao Boya , Gillan Lara V. , Scully Andrew D. , Chesman Anthony S. R. , Tan Boer , Lin Xiongfeng , Liu Jingying , Rietwyk Kevin J. , Deng Siqi , Bailey Christopher , Cheng Yi‐Bing , McCamey Dane R. , Bach Udo 
Published: March 2023

AbstractBack‐contact architectures offer a promising route to improve the record efficiencies of perovskite solar cells (PSCs) by eliminating parasitic light absorption. However, the performance of back‐contact PSCs is limited by inadequate carrier diffusion in perovskite. Here, we report that perovskite films with a preferred out‐of‐plane orientation show improved carrier dynamic properties. With the addition of guanidine thiocyanate, the films exhibit carrier lifetimes and mobilities increased by 3–5 times, leading to diffusion lengths exceeding 7 μm. The enhanced carrier diffusion results from substantial suppression of nonradiative recombination and improves charge collection. Devices using such films achieve reproducible efficiencies reaching 11.2 %, among the best performances for back‐contact PSCs. Our findings demonstrate the impact of carrier dynamics on back‐contact PSCs and provide the basis for a new route to high‐performance back‐contact perovskite optoelectronic devices at low cost.
Influence of Composition of Nickel‐Iron Nanoparticles for Abiotic CO2 Conversion to Early Prebiotic Organics
Authors: Beyazay Tuğçe , Ochoa‐Hernández Cristina , Song Youngdong , Belthle Kendra S. , Martin William F. , Tüysüz Harun 
Published: March 2023

AbstractAbiotic synthesis of formate and short hydrocarbons takes place in serpentinizing vents where some members of vent microbial communities live on abiotic formate as their main carbon source. To better understand the catalytic properties of Ni−Fe minerals that naturally exist in hydrothermal vents, we have investigated the ability of synthetic Ni−Fe based nanoparticular solids to catalyze the H2‐dependent reduction of CO2, the first step required for the beginning of pre‐biotic chemistry. Mono and bimetallic Ni−Fe nanoparticles with varied Ni‐to‐Fe ratios transform CO2 and H2 into intermediates and products of the acetyl‐coenzyme A pathway—formate, acetate, and pyruvate—in mM range under mild hydrothermal conditions. Furthermore, Ni−Fe catalysts converted CO2 to similar products without molecular H2 by using water as a hydrogen source. Both CO2 chemisorption analysis and post‐reaction characterization of materials indicate that Ni and Fe metals play complementary roles for CO2 fixation.
Small Data Can Play a Big Role in Chemical Discovery
Authors: Shalit Peleg Hadas , Milo Anat 
Published: March 2023

AbstractThe chemistry community is currently witnessing a surge of scientific discoveries in organic chemistry supported by machine learning (ML) techniques. Whereas many of these techniques were developed forbig dataapplications, the nature of experimental organic chemistry often confines practitioners to small datasets. Herein, we touch upon the limitations associated withsmall datain ML and emphasize the impact of bias and variance on constructing reliable predictive models. We aim to raise awareness to these possible pitfalls, and thus, provide an introductory guideline for good practice. Ultimately, we stress the great value associated with statistical analysis ofsmall data, which can be further boosted by adopting a holistic data‐centric approach in chemistry.
A Facile Strategy for the Development of Recyclable Multifunctional Liquid Crystal Polymers via Post‐Polymerization Modification and Ring‐Opening Metathesis Polymerization
Authors: Zhao Xin , Chen Yan , Peng Bo , Wei Jia , Yu Yanlei 
Published: March 2023

AbstractPost‐polymerization modification (PPM) offers a versatile approach for engineering multifunctional polymers, but this advantage has not been fully exploited to fabricate multifunctional liquid crystal polymers (LCPs). Here, we design a facile synthetic approach towards multifunctional LCP by combining the ring‐opening metathesis polymerization (ROMP) with PPM, in which ROMP helps to prepare a reactive LCP precursor with high molecular weight, and PPM provides a facilitation to introduce functional groups into the precursor. Consequently, a photo‐ and humidity‐responsive linear LCP (LLCP) is demonstrated to show the potential of this synthetic strategy to diversify functions of the LCPs. Under light irradiation and humidity changes, the deformation modes of the LLCP films are converted to complex shapes (bending, twisting, and curling). The obtained dual‐responsive LLCP with high molecular weight possesses excellent processability and recyclability, making it possible to construct 3D shape actuators with programmable deformation behaviors under light/humidity.
Cyclopentylmethyl Ether, a Non‐Fluorinated, Weakly Solvating and Wide Temperature Solvent for High‐Performance Lithium Metal Battery
Authors: Zhang Han , Zeng Ziqi , Ma Fenfen , Wu Qiang , Wang Xinlan , Cheng Shijie , Xie Jia 
Published: March 2023

AbstractWhile recent work demonstrates the advantages of weakly solvating solvents in enhancing the cyclability of LMBs, both new designs and design strategies for high performance weakly solvating solvent, especially physicochemical properties, are still lacking. Here, we propose a molecular design to tune the solvating power and physicochemical properties of non‐fluorinated ether solvent. The resulting cyclopentylmethyl ether (CPME) have a weak solvating power and wide liquid‐phase temperature range. By optimizing the salt concentration, the CE is further promoted to 99.4 %. Besides, the improved electrochemical performance of Li−S battery in CPME‐based electrolytes is obtained at −20 °C. The Li||LFP (17.6 mg cm−2) battery with developed electrolyte maintains >90 % of the original capacity over 400 cycles. Our design concept for solvent molecule provides a promising pathway to non‐fluorinated electrolytes with weakly solvating power and wide temperature window for high‐energy‐density LMBs.
Carbazole‐Dendronized Luminescent Radicals
Authors: Xiaotian Rui , Ota Wataru , Sato Tohru , Furukori Minori , Nakayama Yasuo , Hosokai Takuya , Hisamura Eri , Nakamura Kazuhiro , Matsuda Kenshiro , Nakao Kohei , Monkman Andrew P. , Albrecht Ken 
Published: March 2023

AbstractA series of carbazole‐dendronized tris(2,4,6‐trichlorophenyl)methyl (TTM) radicals have been synthesized. The photophysical properties of dendronized radicals up to the fourth generation were compared systematically to understand how structure–property relationships evolve with generation. The photoluminescence quantum yield (PLQY) was found to increase with the increasing generation, and the fourth generation (G4TTM) in cyclohexane solution showed a PLQY as high as 63 % at a wavelength of 627 nm (in the deep‐red region) from the doublet state. The dendron modification strategy also showed a blue‐shift of the emission on increasing the generation number, and the photostability was also increased compared to the bare TTM radical.
Organic pH Buffer for Dendrite‐Free and Shuttle‐Free Zn‐I2 Batteries
Authors: Lyu Yanqiu , Yuwono Jodie A. , Wang Pengtang , Wang Yanyan , Yang Fuhua , Liu Sailin , Zhang Shilin , Wang Baofeng , Davey Kenneth , Mao Jianfeng , Guo Zaiping 
Published: March 2023

AbstractAqueous Zn‐Iodine (I2) batteries are attractive for large‐scale energy storage. However, drawbacks include, Zn dendrites, hydrogen evolution reaction (HER), corrosion and, cathode “shuttle” of polyiodines. Here we report a class of N‐containing heterocyclic compounds as organic pH buffers to obviate these. We evidence that addition of pyridine /imidazole regulates electrolyte pH, and inhibits HER and anode corrosion. In addition, pyridine and imidazole preferentially absorb on Zn metal, regulating non‐dendritic Zn plating /stripping, and achieving a high Coulombic efficiency of 99.6 % and long‐term cycling stability of 3200 h at 2 mA cm−2, 2 mAh cm−2. It is also confirmed that pyridine inhibits polyiodines shuttling and boosts conversion kinetics for I−/I2. As a result, the Zn‐I2 full battery exhibits long cycle stability of >25 000 cycles and high specific capacity of 105.5 mAh g−1 at 10 A g−1. We conclude organic pH buffer engineering is practical for dendrite‐free and shuttle‐free Zn‐I2 batteries.
Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)2
Authors: Judge Neil R. , Hevia Eva 
Published: March 2023

AbstractReminiscent of Lochmann‐Schlosser superbase recipes, the addition of two molar equivalents of KOtBu to Zn(TMP)2 (TMP=2,2,6,6‐tetramethylpiperidide) transforms this mild zinc bis‐amide base to a powerful metalating agent able to perform facile regioselective zincation of a wide range of sensitive fluoroarenes. Structural authentication of the intermediates post Zn−H exchange demonstrates activation of both TMP groups to form a range of higher order bis‐aryl potassium zincates, isolable as solids and further functionalized in electrophilic interception reactions. Studies assessing the role of KOtBu reveal that the first equivalent undergoes co‐complexation with Zn(TMP)2, enabling kinetic activation of the amide groups; whereas the second equivalent stabilizes the metalated intermediate preventing ligand redistribution. Showcasing its metalating power, this bimetallic KOtBu/Zn(TMP)2 partnership, can effect zincation of toluene and benzene at room temperature.
Hydrogen‐Atom‐Transfer‐Initiated Radical/Polar Crossover Annulation Cascade for Expedient Access to Complex Tetralins
Authors: Johnson Lucas K. , Barnes Griffin L. , Fernandez Sebastian A. , Vanderwal Christopher D. 
Published: March 2023

AbstractA radical/polar crossover annulation between allyl‐substituted arenes and electron‐deficient alkenes is described. Cobalt‐catalyzed hydrogen atom transfer (HAT) facilitates tandem radical C−C bond formation that generates functionalized tetralin products in the face of potentially problematic hydrofluorination, hydroalkoxylation, hydrogenation, alkene isomerization, and radical polymerization reactions. The reactions proceed under mild conditions that tolerate many functional groups, leading to a broad substrate scope. This powerful ring‐forming reaction very quickly assembles complex tetralins that are the formal products of the largely infeasible Diels–Alder cycloadditions of styrenes.
Identification of Turkish extra virgin olive oils produced in different regions by using NMR (1H and 13C) and IRMS (13C/12C)
Authors: Sevim Didar , Köseoğlu Oya , Ertaş Hasan , Özdemir Durmuş , Ulaş Mehmet , Günnaz Salih , Çelenk Veysel Umut 
Published: March 2023

AbstractIsotope ratio mass spectroscopy (IRMS) and nuclear magnetic resonance (NMR) spectroscopy techniques are two of the analytical methods that are used to characterize food products. The aim of this study is to classify extra virgin olive oil (EVOO) samples collected from different regions of Turkey based on 1H and 13C NMR spectra along with IRMS δ13C carbon isotope ratio data by using chemometrics multivariate data analysis methods. A total of 175 EVOO samples were analyzed in 2014/15 and 2015/16 harvest seasons. Multivariate classification and clustering models were used to identify geographical and botanical origins of the EVOOs. IRMS results showed that there was no significant difference in terms of δ13C values between the years in terms of harvest year (p > 0.05), only extraction phase and variety were statistically significant factors (p < 0.05). The interactions of the factors showed that the harvest year × variety interaction is important. The outcomes of this research clearly indicated that considering the partial least squares discriminant analysis result with NMR spectra, the percent success of the model in the South Marmara, North Aegean, and South Aegean region samples were 95%, 95.7%, and 96.4% in the model set, respectively. The results showed that by using classification and clustering models, geographic marking and labeling of these oils can be carried out regardless of differences in year and production systems (2 and 3 phase extraction system) according the NMR analysis.
Why are coauthored academic articles more cited: Higher quality or larger audience?
Authors: Thelwall Mike , Kousha Kayvan , Abdoli Mahshid , Stuart Emma , Makita Meiko , Wilson Paul , Levitt Jonathan 
Published: March 2023

AbstractCollaboration is encouraged because it is believed to improve academic research, supported by indirect evidence in the form of more coauthored articles being more cited. Nevertheless, this might not reflect quality but increased self‐citations or the “audience effect”: citations from increased awareness through multiple author networks. We address this with the first science wide investigation into whether author numbers associate with journal article quality, using expert peer quality judgments for 122,331 articles from the 2014–20 UK national assessment. Spearman correlations between author numbers and quality scores show moderately strong positive associations (0.2–0.4) in the health, life, and physical sciences, but weak or no positive associations in engineering and social sciences, with weak negative/positive or no associations in various arts and humanities, and a possible negative association for decision sciences. This gives the first systematic evidence that greater numbers of authors associates with higher quality journal articles in the majority of academia outside the arts and humanities, at least for the UK. Positive associations between team size and citation counts in areas with little association between team size and quality also show that audience effects or other nonquality factors account for the higher citation rates of coauthored articles in some fields.
Exploring in vitro solubility of lamotrigine in physiologically mimetic conditions to prospect the in vivo dissolution in pediatric population
Authors: Caleffi‐Marchesini Edilainy Rizzieri , Borghi‐Pangoni Fernanda Belincanta , Macente Julia , Chiamulera‐Mantovani Priscila , Mazucheli Josmar , Cristofoletti Rodrigo , Diniz Andréa 
Published: March 2023

AbstractPediatric drugs knowledge still leaves several gaps to be filled, all the while many biopharmaceutic properties applied to adults do not work in pediatrics. The solubility in many cases is extrapolated to pediatrics; however, sometimes it may not represent the real scenario. In this context, the aim of this study was to assess the possibility of the extrapolation of the solubility data assumed for adults to children aged 2–12 years using lamotrigine (LTG) as a model. LTG showed that its solubility is dependent on the pH of the medium, no precipitate formation was seen, and biomimetic media showed a greater capacity to solubilize it. Based on the dose number (D0) in adults, the LTG was soluble in acidic pH media and poorly soluble in neutral to basic. Similar behavior was found in conditions which mimic children aged 10–12 years at a dose of 5 and 15 mg/kg. The D0 for 5‐year‐old children at a dose of 15 mg/kg showed different behaviors between biorelevant and pharmacopeial buffers media. For children aged 2–3 years, LTG appeared to be poorly soluble under both gastric and intestinal conditions. Solubility was dependent on the volume of fluid calculated for each age group, and this may impact the development of better pharmaceutical formulations for this population, better pharmacokinetic predictions in tools as PBPK, and physiologically‐based biopharmaceutics modeling, greater accuracy in the justifications for biowaiver, and many other possibilities.
Mobilization of hematopoietic stem cells with lenograstim in multiple myeloma patients: Prospective multicenter observational study (KMM122)
Authors: Jung Eun Hee , Byun Ja Min , Shin Dong‐Yeop , Do Young Rok , Jo Jae‐Cheol , Lee Sang Min , Yoon Sung‐Soo 
Published: March 2023

AbstractBackgroundCurrent guidelines recommend using filgrastim or tbo‐filgrastim to mobilize hematopoietic progenitor cells in an autologous setting. However, previous studies have suggested other forms of granulocyte colony‐stimulating factor (G‐CSF) are equally efficacious, possibly with fewer leukaphereses required. Thus, we prospectively studied the efficacy of lenograstim, a glycosylated recombinant form of G‐CSF, in multiple myeloma (MM) patients.MethodsFrom November 2011 to January 2020, 98 MM patients undergoing autologous stem cell transplant (ASCT) from five academic centers in Korea were enrolled. Patients were mobilized with subcutaneous lenograstim (Neutrogin®) with fixed doses of 10 μg/kg for 4 days.ResultsMost of the patients ( N = 90, 91.8%) achieved at least the targets of 2 × 106 CD34+ cells/kg body weight, and more than half of MM patients ( N = 57, 58.2%) reached a target of 5 × 106 CD34+ cells/kg body weight. The mobilization failure rate was 8.2% ( N = 8). The median number of CD34 + cell/kg using G‐CSF only was 5.25 × 106/kg (range 0.49–13.47). Adverse events included transfusion (TF, N = 53, 54.1%), bone pain ( N = 6, 6.1%), fever ( N = 2, 2.0%), and gastrointestinal troubles ( N = 2, 2.0%). There were no grade 3 or 4 adverse events during mobilization. Body surface area (BSA) at mobilization and platelet TF were factors associated with CD34+ collection. Most patients achieved neutrophil ( N = 93, 98.9%) and platelet ( N = 89, 95.7%) engraftment.ConclusionLenograstim can safely and effectively mobilize stem cells in MM autologous settings.