bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multi‐Step Nucleation of a Crystalline Silicate Framework via a Structurally Precise Prenucleation Cluster
Authors: Jin Biao , Chen Ying , Tao Jinhui , Lachowski Kacper J. , Bowden Mark E. , Zhang Zihao , Pozzo Lilo D. , Washton Nancy M. , Mueller Karl T. , De Yoreo James J. 
Published: May 2023

AbstractHierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre‐organized multi‐ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi‐step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small‐angle X‐ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q38 polyanions formed through cross‐linking and polymerization of smaller silicate monomers and other oligomers. These Q38 are stabilized by hydrogen bonds with surrounding H2O and tetramethylammonium ions (TMA+). When Q38 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA)x(Q38)⋅n H2O](x−8) clathrate complexes into step edges on the crystals.
Unlocking the Potential of Bio‐Based Nitrogen‐Rich Furanic Platforms as Biomass Synthons
Authors: Gomes Rafael F. A. , Gonçalves Bruno M. F. , Andrade Késsia H. S. , Sousa Bárbara B. , Maulide Nuno , Bernardes Gonçalo J. L. , Afonso Carlos A. M. 
Published: May 2023

AbstractThe demand for new biomass‐derived fine and commodity chemicals propels the discovery of new methodologies and synthons. Whereas furfural and 5‐hydroxymethylfurfural are cornerstones of sustainable chemistry, 3‐acetamido‐5‐acetyl furan (3A5AF), an N‐rich furan obtained from chitin biomass, remains unexplored, due to the poor reactivity of the acetyl group relative to previous furanic aldehydes. Here we developed a reactive 3‐acetamido‐5‐furfuryl aldehyde (3A5F) and demonstrated the utility of this synthon as a source of bio‐derived nitrogen‐rich heteroaromatics, carbocycles, and as a bioconjugation reagent.
Investigating the Role of Vacancies on the Thermoelectric Properties of EuCuSb‐Eu2ZnSb2 Alloys
Authors: Chanakian Sevan , Peng Wanyue , Meschke Vanessa , Ashiquzzaman Shawon A. K. M. , Adamczyk Jesse , Petkov Valeri , Toberer Eric , Zevalkink Alexandra 
Published: May 2023

AbstractAMX compounds with the ZrBeSi structure tolerate a vacancy concentration of up to 50 % on the M‐site in the planar MX‐layers. Here, we investigate the impact of vacancies on the thermal and electronic properties across the full EuCu1−xZn0.5xSb solid solution. The transition from a fully‐occupied honeycomb layer (EuCuSb) to one with a quarter of the atoms missing (EuZn0.5Sb) leads to non‐linear bond expansion in the honeycomb layer, increasing atomic displacement parameters on the M and Sb‐sites, and significant lattice softening. This, combined with a rapid increase in point defect scattering, causes the lattice thermal conductivity to decrease from 3 to 0.5 W mK−1 at 300 K. The effect of vacancies on the electronic properties is more nuanced; we see a small increase in effective mass, large increase in band gap, and decrease in carrier concentration. Ultimately, the maximum zT increases from 0.09 to 0.7 as we go from EuCuSb to EuZn0.5Sb.
Insight into Iron Leaching from an Ascorbate‐Oxidase‐like Fe−N−C Nanozyme and Oxygen Reduction Selectivity**
Authors: Cao Xuwen , Zhu Caixia , Hong Qing , Chen Xinghua , Wang Kaiyuan , Shen Yanfei , Liu Songqin , Zhang Yuanjian 
Published: May 2023

AbstractAscorbate (H2A) is a well‐known antioxidant to protect cellular components from free radical damage and has also emerged as a pro‐oxidant in cancer therapies. However, such “contradictory” mechanisms underlying H2A oxidation are not well understood. Herein, we report Fe leaching during catalytic H2A oxidation using an Fe−N−C nanozyme as a ferritin mimic and its influence on the selectivity of the oxygen reduction reaction (ORR). Owing to the heterogeneity, the Fe‐Nx sites in Fe−N−C primarily catalyzed H2A oxidation and 4 e− ORR via an iron‐oxo intermediate. Nonetheless, trace O2⋅− produced by marginal N−C sites through 2 e− ORR accumulated and attacked Fe‐Nx sites, leading to the linear leakage of unstable Fe ions up to 420 ppb when the H2A concentration increased to 2 mM. As a result, a substantial fraction (ca. 40 %) of the N−C sites on Fe−N−C were activated, and a new 2+2 e− ORR path was finally enabled, along with Fenton‐type H2A oxidation. Consequently, after Fe ions diffused into the bulk solution, the ORR at the N−C sites stopped at H2O2 production, which was the origin of the pro‐oxidant effect of H2A.
Significant Acceleration of Photocatalytic CO2 Reduction at the Gas‐Liquid Interface of Microdroplets**
Authors: Ge Qiuyue , Liu Yangyang , Li Kejian , Xie Lifang , Ruan Xuejun , Wang Wei , Wang Longqian , Wang Tao , You Wenbo , Zhang Liwu 
Published: May 2023

AbstractSolar‐driven CO2 reduction reaction (CO2RR) is largely constrained by the sluggish mass transfer and fast combination of photogenerated charge carriers. Herein, we find that the photocatalytic CO2RR efficiency at the abundant gas‐liquid interface provided by microdroplets is two orders of magnitude higher than that of the corresponding bulk phase reaction. Even in the absence of sacrificial agents, the production rates of HCOOH over WO3 ⋅ 0.33H2O mediated by microdroplets reaches 2536 μmol h−1 g−1 (vs. 13 μmol h−1 g−1 in bulk phase), which is significantly superior to the previously reported photocatalytic CO2RR in bulk phase reaction condition. Beyond the efficient delivery of CO2 to photocatalyst surfaces within microdroplets, we reveal that the strong electric field at the gas‐liquid interface of microdroplets essentially promotes the separation of photogenerated electron‐hole pairs. This study provides a deep understanding of ultrafast reaction kinetics promoted by the gas‐liquid interface of microdroplets and a novel way of addressing the low efficiency of photocatalytic CO2 reduction to fuel.
Temperature dependent tensile strength modeling and analysis of shape memory polymers with physics‐based energy equivalence principle
Authors: Zhang Xiaoyong , Li Ying , Zuo Mini , Yang Mengqing , Li Weiguo 
Published: May 2023

AbstractThe quantitative characterization of the tensile strength of shape memory polymers (SMPs) at different temperatures has always been an important research topic. In this study, the critical failure energy density of SMPs including the strain energy density, potential energy and kinetic energy of atomic motion per unit volume is first introduced. Then, based on the equivalent contribution of these energies on material failure, a temperature dependent tensile strength (TDTS) model considering the corresponding physical mechanism for SMPs is established. The model provides the quantitative relationship among temperature, Young's modulus, hardening index and the tensile strength of SMPs. Meanwhile, the predicted results of the proposed model are compared with the available TDTS of SMPs, and the agreement between theory and experiment is satisfactory. In addition, the influencing factors of tensile strength and their variation with temperature are analyzed. This work contributes the novel insight for the theoretical predictions on the TDTS of SMPs, which is helpful for the high temperature strength evaluation and property optimization.
Synthesis and properties of biodegradable aliphatic–aromatic polyesters derived from 4‐hydroxybenzaldehyde
Authors: Wang Huan , Cheng Zhengzai , Djouonkep Lesly Dasilva Wandji , Wang Linfeng , Cai Shuanpu , Gauthier Mario 
Published: May 2023

AbstractA novel biphenyl monomer, diethyl 6,6′‐dimethoxy‐[1,1′‐bipheny]‐3,3′‐dicarboxylate (DDBD), was synthesized from 4‐hydroxybenzaldehyde, a phenolic compound derived from lignin. A series of polyesters were prepared by polycondensation of the biphenyl monomer with hydroquinone bis(2‐hydroxyethyl) ether and aliphatic diacids via a two‐step melt polycondensation method. It was shown that the properties of the polyesters can be tuned by varying the length and the structure of the spacer in the aliphatic diacid monomers. Structure–property relations for these materials were investigated by Fourier‐transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. GPC analysis showed that the weight‐average molecular weight (Mw) of the samples varied from 4.2–5.0 × 104 g/mol, while thermal analysis yielded Tg values of 51–120°C, and 5% decomposition temperatures (Td,5%) of 327–389°C. All the samples exhibited a high yield strength (56–87 MPa). After 30 weeks of degradation in soil, the copolyesters had mass losses of up to 4.4%, and an investigation of the ecotoxicity of the copolyesters with Eisenia fetida yielded a survival rate of over 80% after 14 days for the different copolyesters, suggesting low toxicity in the environment. Overall, these copolyesters have good properties and would be suitable to replace petroleum‐based commercial poly(ethylene terephthalate) packaging materials.
Fabrication of Dual‐Stimuli‐Responsive Polymer Vesicles for Regulation of Enzymolysis Efficiency in A Cascade Reaction
Authors: Qiao Juan , Ma Qian , Cheng Cheng , Qi Li 
Published: May 2023

AbstractEnzymatic cascade reactions in confined microenvironments play important roles in cellular chemical transformation. Controlling enzymatic efficiency and eliminating substrate interference in cascade reactions is of great significance. To this end, a vesicle composed of poly(styrene‐maleic anhydride‐N‐isopropylacrylamide)(P(S−M−NIP)) and functionalized with 1,2‐bis(10,12‐ tricosadiynoyl)‐sn‐glycero‐3‐phosphocholine (DC89PC) was designed herein. Based on the thermo‐sensitive property of P(S−M−NIP) and the photo‐responsive property of DC89PC, a serial of dual‐stimuli‐responsive nanoreactors was constructed via enzymes encapsulation to tune their enzymolysis efficiencies. A kinetics study of the glucose oxidase‐encapsulated nanoreactor indicated that its enzymolysis velocity increased 2.1‐ and 1.6‐fold under heating and the ultraviolet (UV)‐light irradiation, respectively. Consequently, an enzymatic cascade reaction in the proposed enzyme reactor encapsulated with β‐galactosidase and glucose oxidase was investigated. The results revealed a 2.9‐fold enhancement in enzymolysis efficiency by changing the ambient temperature under UV irradiation. The dual‐stimuli‐responsive polymer vesicles could also eliminate H2O2 interference during the enzymatic cascade reaction. The vesicles demonstrated potential for switch‐membrane‐permeability, while, the confined microenvironment played a key role in regulating the reactions upon the temperature change and the presence of UV light. Our synthetic multi‐organelle‐like system provides a new way to mimic the control of cascade reaction catalytic processes by programming the “open/close” sates of the nanocapsules.
Phase Engineering of Molybdenum Carbide/Oxide for Highly‐Efficient Electrocatalytic Hydrogen Production
Authors: Na Gao , Chen Xiaojun , Zhao Ruihua , Du Jianping 
Published: May 2023

AbstractMolybdenum carbide is one of non‐precious metal materials and it is a promising electrocatalyst for hydrogen production. Synthesis and improvement of molybdenum carbide's catalytic performance is of great significance. Herein, carbon‐based Mo2C with hybrid phase of MoO2 was fabricated by matching the composition of Mo and C derived from pomelo peel and optimizing raw carbon amount and prolysis temperature. The resulting MoO2/Mo2C@C is composed of loose microspheres with mesoporous microstructure and is self‐assembled from nanoparticles. The results show that MoO2/Mo2C@C2 material exhibits excellent HER performance and only a low overpotentials of 143 mV is needed to drive the current density of 10 mA cm−2 in alkaline solution, and Tafel slopes are only 63.4 mV dec−1, respectively. Notably, it has potential application at low overpotentials to drive large current density and this strategy also provides a universal route to prepare non‐noble metal catalyst with hybrid phase of oxide/carbide.
Drug cross‐linking electrospun fiber for effective infected wound healing
Authors: Luo Yuting , Zheng Sen , Wang Kun , Luo Hangqi , Shi Huiling , Cui Yanna , Li Bingxin , He Huacheng , Wu Jiang 
Published: May 2023

AbstractThe management of infected wounds is still an intractable challenge in clinic. Development of antibacterial wound dressing is of great practical significance for wound management. Herein, a natural‐derived antibacterial drug, tannic acid (TA), was incorporated into the electrospun polyvinyl alcohol (PVA) fiber (TA/PVA fiber, 952 ± 40 nm in diameter). TA worked as a cross‐linker via hydrogen bonding with PVA to improve the physicochemical properties of the fiber and to reach a sustained drug release (88% release of drug at 48 h). Improved mechanical property (0.8–1.2 MPa) and computational simulation validated the formation of the hydrogen bonds between TA and PVA. Moreover, the antibacterial and anti‐inflammatory characteristics of TA laid the foundation for the application of TA/PVA fiber in repairing infected wounds. Meanwhile, in vitro studies proved the high hemocompatibility and cytocompatibility of TA/PVA fiber. Further in vivo animal investigation showed that the TA/PVA fiber promoted the repair of infected wound by inhibiting the bacterial growth, promoting granulation formation, and collagen matrix deposition, accelerating angiogenesis, and inducing M2 macrophage polarization within 14 days. All the data demonstrated that the TA cross‐linked fiber would be a potent dressing for bacteria‐infected wound healing.
The impact of moderate aortic stenosis in acute myocardial infarction: A multicenter retrospective study
Authors: Abraham Bishoy , Farina Juan M. , Fath Ayman , Abdou Merna , Elbanna Mostafa , Suppah Mustafa , Sleem Mohamed , Eldaly Abdullah , Aly Mohamed , Megaly Michael , Agasthi Pradyumna , Chao Chieh‐Ju , Fortuin David , Alsidawi Said , Ayoub Chadi , Alkhouli Mohamad , El Sabbagh Abdallah , Holmes David , Brilakis Emmanouil S. , Arsanjani Reza 
Published: May 2023

AbstractBackgroundAortic stenosis (AS) is associated with myocardial ischemia through different mechanisms and may impair coronary arterial flow. However, data on the impact of moderate AS in patients with acute myocardial infarction (MI) is limited.AimsThis study aimed to investigate the impact of moderate AS in patients presenting with acute myocardial infarction (MI).MethodsWe conducted a retrospective analysis of all patients who presented with acute MI to all Mayo Clinic hospitals, using the Enterprise Mayo PCI Database from 2005 to 2016. Patients were stratified into two groups: moderate AS and mild/no AS. The primary outcome was all cause mortality.ResultsThe moderate AS group included 183 (13.3%) patients, and the mild/no AS group included 1190 (86.7%) patients. During hospitalization, there was no difference between both groups in mortality. Patients with moderate AS had higher in‐hospital congestive heart failure (CHF) (8.2% vs. 4.4%, p = 0.025) compared with mild/no AS patients. At 1‐year follow‐up, patients with moderate AS had higher mortality (23.9% vs. 8.1%, p < 0.001) and higher CHF hospitalization (8.3% vs. 3.7%, p = 0.028). In multivariate analysis, moderate AS was associated with higher mortality at 1‐year (odds ratio 2.4, 95% confidence interval [1.4–4.1], p = 0.002). In subgroup analyses, moderate AS increased all‐cause mortality in STEMI and NSTEMI patients.ConclusionThe presence of moderate AS in acute MI patients was associated with worse clinical outcomes during hospitalization and at 1‐year follow‐up. These unfavorable outcomes highlight the need for a close follow‐up of these patients and for timely therapeutic strategies to best manage these coexisting conditions.
Enantioenriched BoronC,N‐Chelates via Chirality Transfer
Authors: Stöckl Yannick , Tait Ethan J. , Frey Wolfgang , Wegner Sascha , Claasen Birgit , Zens Anna , Laschat Sabine 
Published: May 2023

AbstractMolecules stereogenic only at tetrahedral boron atoms show great promise for applications, for example as chiroptical materials, but are scarcely investigated due to their synthetic challenge. Hence, this study reports a two‐step synthesis of enantioenriched boronC,N‐chelates. First, the diastereoselective complexation of alkyl/aryl borinates with chiral aminoalcohols furnished boron stereogenic heterocycles in up to 86 % yield and d.r. >98 : 2. Treatment of theseO,N‐complexes with chelate nucleophiles was surmised to transfer the stereoinformation via the ate‐complex into theC,N‐products. This chirality transfer succeeded by substitution of theO,N‐chelates with lithiated phenyl pyridine to give boron stereogenicC,N‐chelates in up to 84 % yield and e.r. up to 97 : 3. The chiral aminoalcohol ligands could be recovered after isolation of theC,N‐chelates. The chirality transfer tolerated alkyl, alkynyl and (hetero‐)aryl moieties at boron and could be further extended by post‐modification: transformations such as catalytic hydrogenations or sequential deprotonation/electrophilic trapping were feasible while maintaining the stereochemical integrity of theC,N‐chelates. Structural aspects of the boron chelates were studied by variable temperature NMR and X‐ray diffraction.
Balanced Energy Gaps as a Key Design Rule for Solution‐Phase Organic Room Temperature Phosphorescence
Authors: Paredis Simon , Cardeynaels Tom , Kuila Suman , Deckers Jasper , Van Landeghem Melissa , Vandewal Koen , Danos Andrew , Monkman Andrew P. , Champagne Benoît , Maes Wouter 
Published: May 2023

AbstractMetal‐free organic emitters that display solution‐phase room temperature phosphorescence (sRTP) remain exceedingly rare. Here, we investigate the structural and photophysical properties that support sRTP by comparing a recently reported sRTP compound (BTaz−Th−PXZ) to two novel analogous materials, replacing the donor group by either acridine or phenothiazine. The emissive triplet excited state remains fixed in all three cases, while the emissive charge‐transfer singlet states (and the calculated paired charge‐transfer T2 state) vary with the donor unit. While all three materials show dominant RTP in film, in solution different singlet‐triplet and triplet‐triplet energy gaps give rise to triplet‐triplet annihilation followed by weak sRTP for the new compounds, compared to dominant sRTP throughout for the original PXZ material. Engineering both the sRTP state and higher charge‐transfer states therefore emerges as a crucial element in designing emitters capable of sRTP.
Adsorbents for adsorption separation of CO2 and CH4: A literature review
Authors: Shen Jiaxuan , Wang Xiaodong , Chen Yani 
Published: May 2023

AbstractNatural gas consisting mainly of methane is becoming increasingly prominent as a clean energy source. However, the major impurity, carbon dioxide, can adversely affect the performance of natural gas. Therefore, separating CO2 from CH4 is necessary to decrease the erosion of pipelines and increase the calorific value. This paper aimed at reviewing the performances, mechanisms, and novel developments of common adsorbents to adsorb pure CH4, pure CO2, and their mixtures. Several studies suggest that zeolites exhibit better separating performance than metal organic frameworks (MOFs) except the modified amine‐MIL group. Activated carbons may not be suitable adsorbents due to low selectivity between CO2 and CH4. The modified amine‐MIL group are the best type of adsorbent to separate CO2 from CH4 and its best operating conditions are at low pressure (<2 bar), low feed composition of CO2, and near room temperature using pressure swing adsorption (PSA) method.
Tuning Charge Transport of Oligopeptide Junctions via Interfacial Amino Acids†
Authors: Guo Jiaxin , Qi Pan , Zhang Yongkang , Guo Cunlan 
Published: May 2023

Comprehensive SummaryThe charge transport through peptides can imitate the corresponding processes in more complicated proteins, enabling us to develop high‐performance bioelectronic devices and to understand the mechanisms of biomolecular recognition and information transfer. While charge transport modulation through individual peptides has been achieved via various covalent strategies, the intermolecular modulation is still very challenging, which may capture the charge transport between proteins. To tackle this challenge, we used well‐defined self‐assembled monolayers (SAMs) of oligopeptides as a model to imitate the interface of proteins and explored an interfacial amino acid strategy for charge transport modulation. We showed that non‐covalently interfaced charged amino acids (e.g., arginine) effectively attenuated the charge transport of glutamic acid terminated polyglycine peptide SAMs. By analyzing the relationship of the charge transport with the molecular frontier orbital relative to the Fermi energy level of the electrode, the molecule‐electrodes coupling (Γ), and the trends in skewness and kurtosis with voltage and the dielectric constant (εr), we showed that the attenuation was from the decreased Γ and the reduced polarizability. We present an efficient strategy to modulate the charge transport of oligopeptide‐SAM junctions by intermolecular interactions, which will advance our understanding of charge transport in biological systems and facilitate developing future electronics.
Deep‐Red to Near‐Infrared Carbon Dots in Biosensing and Bio‐medical Applications
Authors: Huang Shan , Yan Li , Chen Xiaojun , Zhu Jun‐Jie 
Published: May 2023

Comprehensive SummaryWith the rapid development in the field of biomedical diagnosis and treatment, carbon dots (CDs) with favorable photostability, biocompatibility and high quantum yields for deep‐red to near‐infrared emission have attracted the attention of a majority of researchers. By enlarging the sp2 domain in the core of CDs, doping them with heteroatoms like nitrogen and sulfur, applying hydrothermal, electrochemical, or microwave‐assisted techniques, CDs can be made with the aforementioned photoemission capabilities. In view of these excellent properties, CDs are flourishing in biosensing and biomedical applications, so that a thorough description and discussion of this topic is beneficial to capture the up‐to‐date progress of CDs in this field, providing suggestions and considerations for readers.