bluuebunny/crossref_metadata_2025_split huggingface dataset:
Upconversion Luminescence with Bis‐pyclen Yb(III) Chelates: Crown vs. Linear Polyether Linkers in Discrete Heteropolynuclear Architectures
Authors: Hamon Nadège , Godec Léna , Sanchez Samuel , Beyler Maryline , Charbonnière Loïc J. , Tripier Raphaël 
Published: November 2024

AbstractLigands combining two lateral bis‐pyridyl‐phosphonated‐pyclens were synthesized, using a flexible linear pegylated linker (L2) or a bulkier K22 crown‐ether (L3). A functionalized pyridyl‐phosphonated‐pyclen (L1) was also prepared as a mononuclear analogue. Coordination behavior of lanthanide cations was studied via NMR titration with Lu for L1, and UV/Vis and luminescence spectroscopy with Yb for L2/L3. Strong coordination of two Yb atoms enabled isolation and spectroscopic characterization of dinuclear complexes in H2O and D2O. Excited state lifetime analysis at 980 nm revealed strong protection of Yb cations, with no coordinated water molecule. Upon titration of the isolated dinuclear Yb complexes with Tb cations, cooperative upconversion (UC) sensitization of Tb in the visible was observed upon excitation of Yb at 980 nm in D2O. In the absence of Tb, the Yb complexes also exhibited cooperative luminescence with a weak emission band around 500 nm upon NIR Yb excitation. Efficient UC with Tb was only observed after thermal treatment, suggesting a slow kinetic of formation of the UC species. [Yb2TbL3] showed weak Tb centered UC emission, while the dinuclear complex of L2 displayed more intense UC emission up to two equivalents of Tb, forming [(Yb2L2)Tbx] (x=1–2), with the tetranuclear heterometallic complex being the most intense emitter. Log‐Log plot analysis confirmed the two‐photon nature of the UC process.
Controlling the Mechanism of Nucleation and Growth Enables Synthesis of UiO‐66 Metal–Organic Framework with Desired Macroscopic Properties
Authors: Artsiusheuski Mikalai A. , Casati Nicola P. M. , Clark Adam H. , Nachtegaal Maarten , Verel René , van Bokhoven Jeroen A. , Sushkevich Vitaly L. 
Published: November 2024

AbstractBy combining in situ X‐ray diffraction, Zr K‐edge X‐ray absorption spectroscopy and 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, we show that the properties of the final MOF are influenced by H2O and HCl via affecting the nucleation and crystal growth at the molecular level. The nucleation implies hydrolysis of monomeric zirconium chloride complexes into zirconium‐oxo species, and this process is promoted by H2O and inhibited by HCl, allowing to control crystal size by adjusting H2O/Zr and HCl/Zr ratios. The rate‐determining step of crystal growth is represented by the condensation of monomeric and oligomeric zirconium‐oxo species into clusters, or nodes, with the structure identical to that in secondary building units (SBU) of UiO‐66 framework. The rapid crystallization in the absence of HCl leads to formation of defective secondary building units with missing zirconium atoms, providing a pathway to control the number of defects in UiO‐66 crystals. Remarkably, we have shown that assembling of the metal nodes and linkers into the UiO‐66 structure is not the rate‐limiting step, and the degree of deprotonation of the linker has no direct effect on the crystallization kinetics or crystal size of product.
Bead‐Based DNA Synthesis and Sequencing for Integrated Data Storage Using Digital Microfluidics
Authors: Piao Yuhao , Fang Yitong , Li Bin , Man Tiantian , Chen Jie , Zhu Fulin , Wang Weiqiang , Wan Ying , Deng Shengyuan 
Published: November 2024

AbstractDNA is considered as a prospective candidate for the next‐generation data storage medium, due to its high coding density, long cold‐storage lifespan, and low energy consumption. Despite these advantages, challenges remain in achieving high‐fidelity, fully integrated, and cost‐efficient DNA storage system. In this study, a homemade digital microfluidic (DMF)‐based compact DNA data storing pipeline is orchestrated to complete the entire process from the synthesis to the sequencing. The synthetic half employs phosphoramidite chemistry on 200 nm magnetic beads (MBs), where the dimethyltrityl protecting group is removed by droplet manipulation of trichloroacetic acid. The sequencing counterpart relies on pyrophosphate releasing originated from polymerase‐catalyzed primer extension, which leads to photon‐countable chemiluminescence (CL) signal in 2.5‐μL drops of trienzyme cascading reactions. Further by DNA denaturation, repeated pyrosequencing plus plurality voting can improve the nucleobase accuracy beyond 95 %. As a proof‐of‐concept trial, semantic information is saved in DNA via the Huffman coding algorithm plus the Reed‐Solomon error‐correction, and then robustly retrieved from this streamlined platform. As a result, it took a net total of approximately 6.5 h to writing and reading 8 bytes of data, that equal to a storaging speed of 49 min/byte, much quicker than the previously reported 2.8–4.2 h/byte. This bead‐based miniaturized device promises an unattended protocol for achieving high‐throughput, full‐packaged, and above all, neatly precision DNA storage.
Unveiling Surface Reconstruction as the Primary Trigger for Capacity Loss in Ultra‐High Nickel Cathodes
Authors: Qiu Lang , Zhang Mengke , Hua Weibo , Wang Yi , Deng Yuting , Li Zhuangzhi , Song Yang , Wu Zhenguo , Xiao Yao , Guo Xiaodong 
Published: November 2024

AbstractMechanical failures, such as cracks and nanopores, along with the associated surface reconstruction, have long been regarded as the primary causes of capacity decay in ultra‐high Ni layered oxides. However, the impact of these failures on performance degradation has not yet been effectively elucidate and distinguished. Herein, we develop ultra‐high Ni cathodes with tailored morphological structures by incorporating B and Mo to optimize lithiation kinetics, which can suppress lattice strain, particle cracking, and surface reconstruction during charging/discharging. And the role of chemo‐mechanical failures in capacity loss is systematically investigated. Surprisingly, contrary to the traditional view, structural and electrochemical characterizations of the cycled cathodes demonstrate that intragranular cracks, intergranular cracks, and nanopores are not the primary contributing factors of capacity loss. Instead, surface reconstruction triggers rapid capacity decay. Notably, compared to nanopores, intragranular cracks expose a significantly larger quantity of active substances, thereby promoting interfacial side reactions and accelerating surface structural reconstruction during cycling.
Polymeric Carbon Nitride Edged with Spatially Isolated Donor and Acceptor for Sunlight‐Driven H2O2 Synthesis and In‐Situ Utilization
Authors: Zhang Qiang , Gu Kaiye , Dong Chaoran , Xue Chao , Che Huinan , Zhang Kan , Ao Yanhui 
Published: November 2024

AbstractOn‐site H2O2 activation attracts much attention in energy conversion and environment remediation et al., yet remains challenging in its highly efficient and sustainable synthesis. Herein, we grafted a pair of spatially isolated donor (methoxyphenyl unit) and acceptor (anthraquinone unit) in polymeric carbon nitride edges, which induce directional electron‐hole transfer to the two spatially separated dual active centers. Specifically, photogenerated electrons in the anthraquinone unit facilitate the 2e− ORR, while the methoxyphenyl unit, which gathers photogenerated holes, enables rapid 4e− WOR. More impressively, the anthraquinone unit also exhibits strong proton extraction capabilities to boost the generation of *OOH intermediates and H2O2. Consequently, the synthesized donor‐polymeric carbon nitride‐acceptor (DPA) catalyst shows a remarkable H2O2 yield of 6497.1 μM h−1 g−1 in pure water, surpassing traditional DP and PA catalysts. Because of its high efficiency, the H2O2 product can efficiently degrade and mineralize various organic contaminants in a continuous‐flow self‐Fenton reactor under sunlight irradiation. Our work presents an unprecedented approach to designing photocatalysts with efficient H2O2 synthesis and practical application from a molecular engineering perspective.
Anomere Amide Ermöglichen Aminative Alken‐Aryl‐ und Alken‐Alken‐Kupplungen
Authors: Stein Colin , Tyler Jasper L. , Wiener Julius , Boser Florian , Daniliuc Constantin G. , Glorius Frank 
Published: November 2024

AbstractTrotz der Bedeutung von Kreuzkupplungsreaktionen, bei denen C−N‐Bindungen gebildet werden, stellen aminative Kupplungsansätze, bei denen zwei Fragmente direkt am Heteroatom verknüpft werden, eine selten genutzte retrosynthetische Strategie für den molekularen Aufbau dar. In diesem Artikel berichten wir über das Design, die Synthese und die Implementierung eines anomeren Amid‐Reagenzes, welches in der Lage ist, aminative Alken‐Aryl‐ und Alken‐Alken‐Kupplungsreaktionen in hoher Regioselektivität zu ermöglichen. Diese Transformation entspricht einer Abfolge von katalysatorfreier 1,2‐Chloraminierung, N‐Entschützung und formalem Nitrentransfer in einem einzigen Reaktionsgefäß. Die Einfachheit sowohl des Protokolls als auch der benötigten Bausteine machte die Nutzung von Hochdurchsatzscreening (engl. HTE) attraktiv, um schnell und effizient einen großen Bereich des chemischen Raums zu erkunden und die Grenzen der Reaktivität aufzuzeigen. Zusätzlich wurde die Substratbreite auf größerem Maßstab erkundet. Darüber hinaus zeigen alternative Reaktivitätsmodi der funktionalisierten Zwischenprodukte, welche durch dieses Protokoll geliefert werden, die divergente Natur dieser aminativen Kupplungsstrategie auf.
Divergent Activity Shifts of Tin‐Based Catalysts for Electrochemical CO2 Reduction: pH‐Dependent Behavior of Single‐Atom Versus Polyatomic Structures
Authors: Wang Yuhang , Zhang Di , Sun Bin , Jia Xue , Zhang Linda , Cheng Hefeng , Fan Jun , Li Hao 
Published: November 2024

AbstractTin (Sn)‐based catalysts have been widely studied for electrochemical CO2 reduction reaction (CO2RR) to produce formic acid, but the intricate influence of the structural sensitivity in single‐atom Sn (e.g., Sn−N−C) and polyatomic Sn (e.g., SnOx and SnSx; x=1,2) on their pH‐dependent performance remains enigmatic. Herein, we integrate large‐scale data mining (with >2,300 CO2RR catalysts from available experimental literature during the past decade), ab initio computations, machine learning force field accelerated molecular dynamic simulations, and pH‐field coupled modelling to unravel their pH dependence. We reveal a fascinating contrast: the electric field response of the binding strength of *OCHO on Sn−N4−C and polyatomic Sn exhibits opposite behaviors due to their differing dipole moment changes upon *OCHO formation. Such response leads to an intriguing opposite pH‐dependent volcano evolution for Sn−N4−C and polyatomic Sn. Subsequent experimental validations of turnover frequency and current density under both neutral and alkaline conditions well aligned with our theoretical predictions. Most importantly, our analysis suggests the necessity of distinct optimization strategies for *OCHO binding energy on different types of Sn‐based catalysts.
Targeted Synthesis of Interpenetration‐Free Mesoporous Aromatic Frameworks by Manipulating Catalysts as Templates
Authors: Wang Zihao , Jiang Li , Jia Jiangtao , Zhu Guangshan 
Published: November 2024

AbstractReticular chemistry allows the design and synthesis of mesoporous networks by extending the size of the building blocks. However, interpenetration of the nets easily happens against the designed mesoporous networks, thereby falling short of achieving the intended specific surface area and pore size. Controlling the framework interpenetration has always been a challenge in the synthesis section of reticular chemistry. In this work, based on our previously reported type of highly porous aromatic frameworks (named PAF‐1), we extended the tetrahedral building blocks to target an iso‐reticular mesoporous PAF‐333. A series of Ni(0) ligands with different sizes were employed to confirm that suitable‐sized catalyst ligands could successfully inhibit skeleton interpenetration in the coupling reaction through the steric hindrance effect. The obtained mesoporous PAF‐333 possessed a pore size of approximately 3.2 nm matching well with the value from the predicted non‐interpenetrated structure. PAF‐333 showed great high‐pressure hydrogen and methane storage potential with a 13.4 wt % H2 uptake at 77 K, 100 bar and a 0.537 g g−1 CH4 uptake at 298 K, 98 bar, ranking at the top of the reported porous adsorbents in the gas storage applications.
Mineralizing Biofilm towards Sustainable Conversion of Plastic Wastes to Hydrogen
Authors: Li Baoyuan , Xu Zhijun , Wang Ruifang , Nie Rui , Tao Zhengyu , Huang Xin 
Published: November 2024

AbstractThe integration of inorganic materials with biological machinery to convert plastics into fuels offers a promising strategy to alleviate environmental pollution and energy crisis. Herein, we develop a type of hybrid living material via biomineralization of CdS onto Shewanella oneidensis‐based biofilm, which is capable of sustainable hydrogen production from poly(lactic acid) (PLA) wastes under daylight. We reveal that the formed biofilm microstructure provides an independent anaerobic microenvironment that simultaneously supports cellular viability, maintains hydrogenase activity, and preserves the functional stability of CdS, giving rise to the efficient plastic‐to‐hydrogen conversion efficiency as high as 3751 μmol H2 g‐1 PLA. Besides, by genetically engineering transmembrane pili conduit and incorporating conductive nanomaterials to strengthen the electron transfer across cellular interface and biofilm matrices, we show that the conversion efficiency is further enhanced to 5862 μmol H2 g‐1 PLA. Significantly, we exhibit that a long‐term sustainable plastic‐to‐hydrogen conversion of 63 d could be achieved by periodically replenishing PLA wastes. Overall, by the synergistic integration of biotic‐abiotic characteristics the developed biofilm‐based biomineralized hybrid living material is anticipated to provide a new platform toward the efficient conversion of plastic wastes into valuable fuels, and bridge the gap between environmental contamination and green energy production.
Narrative exposure therapy in a child protection context: Breaking intergenerational cycles by providing a pathway through past trauma
Authors: Carpenter Samuel , Sarkar Agnik 
Published: November 2024

AbstractTrauma is a central theme in child protection. Responding to and preventing traumatic harm to children is a key function of statutory child protection agencies and systems in Australia. Parents who encounter these systems are also known to be a highly traumatised cohort, often experiencing trauma throughout their own early development and into their adult lives. Despite these being broadly accepted principles amongst practitioners, there are limited pathways for parents to undertake trauma‐processing therapy as an integrated part of current child protection practice. Narrative exposure therapy (NET) is a manualised therapy model that has been used successfully to support individuals with life‐threatening trauma to process these experiences and take agency over their lives. The successful use of this model by non‐traditional therapists such as community health workers, in brief timeframes, has made it a valuable approach in settings with a high need for therapeutic support and low resources, such as refugee accommodation. Although these themes also have synergy with the child protection setting, there is relatively little research on the use of NET in this setting. This paper is written by practitioners and for practitioners and examines the real‐world application of NET with parents involved with a non‐statutory reunification service in the South Australian child protection system, grounded in a trauma‐informed model of practice. As such, the paper considers extending the possible value of NET into an area of limited previous use. The paper highlights observational findings suggesting that NET has the potential to be an effective tool for bringing focus to the trauma experiences of the parent, so that they may process these and develop greater capacity to parent safely as well as engage more productively with the demands of the child protection system.
Exploration of the Differences in Coordination Behaviors and Spectrographic Properties of Two Novel Seven‐Nucleated Ni (II) Complexes of a Salamo‐Type Flexible‐Bisoxime Ligand
Authors: Zhang Yang , Chen Rui , Shi Hao‐Nan , Yan Yi‐Bin , Dong Wen‐Kui 
Published: November 2024

ABSTRACTA salamo‐type bis‐oxime ligand H2L was synthesized, which reacted with Ni (NO3)2·6H2O in different reaction solvents to synthesize two novel heptanuclear Ni (II) complexes: [Ni7(L)3(μ3‐OH)8(EtOH)6]·2CH2Cl2 (1) and [Ni7(L)3(μ3‐OMe)2(μ3‐OH)6(MeOH)6]·CH2Cl2 (2). X‐ray crystal diffraction results showed that each Ni (II) ion exhibits a distorted octahedral geometry. Its uniqueness lies in the fact that the Ni (II) ion in Complex 1 not only coordinates with ligand units but also coordinates with ethanol solvent molecules and water molecules participating in bridging. Complex 2 is composed of water molecules and methanol molecules connected together. Interestingly, the coordination mode is different due to the different reaction solvents. The energy gap changes of the ligand, and its complexes were then explored by DFT calculations. In addition, the influence of the weak interaction force was confirmed through the in‐depth study of electrostatic potential, IRI, freedom analysis, and Hirshfeld surfaces analyses, which is important for explaining the formation of reaction sites and supramolecular structures. UV‐visible spectrometric titration tests showed that the binding ratios of the ligand to Ni (II) ions are all 3:7, which is consistent with the crystal structure. Finally, fluorescence characterization studies showed that both complexes exhibited reduced fluorescence compared to H2L.
Quantitative Determination of Metal Center Coordination Numbers in Resin‐Based Supported Catalysts via CO2 Adsorption
Authors: Meng Qi , Fan Yun , Wang Bozhi , Ni Shuaibo , Chen Shengbin , Jin Hao , Teng Qiaoqiao 
Published: November 2024

ABSTRACTA novel method was described for quantitatively determining the metal centers' average coordination numbers in as‐prepared supported metal catalysts using polyamine‐modified resin carriers via CO2 adsorption. Using porous resin (PS) and pentaethylenehexamine (PEHA) as starting materials, a new polyamine‐modified resin carrier PS‐PEHA was obtained to anchor various metals (Cu, Pd, Co, Ni, and Zn), thereby preparing a range of supported catalysts. The structures of the metal catalysts were characterized through FT‐IR, XPS, SEM, EDS, BET, and ICP‐OES. DVS was employed to study the carrier and catalyst performance of CO2 adsorption. The average coordination numbers of the metal centers were quantitatively determined based on their differences in CO2 adsorption capacities. The coordination numbers determined were Co (3.5), Ni (3.5), Pd (4.8), Zn (3.6), and Cu (5.9).
Synthesis, Characterization, and Investigation of Advanced Biological Properties of Non‐Ionic Group Substituted Water‐Soluble BODIPYs
Authors: Sekban Lamia Sevire , Kaplan Ekrem , Özdemir Sadin , Tollu Gülşah , Hamuryudan Esin , Özçeşmeci Mukaddes 
Published: November 2024

ABSTRACTIn this study, glycerol, glycosyl, and tetraethyleneglycol monomethyl ether group substituted BODIPY compounds were successfully synthesized and characterized. The antioxidant, antidiabetic, antibiofilm, microbial cell viability, antimicrobial, antimicrobial photodynamic therapy, and DNA cleavage abilities of the BODIPY derivates were also tested. The highest antioxidant activity at 100 mg/L was 87.12% for BODIPY‐1, 85.61% for BODIPY‐2, and 92.78% for BODIPY‐3. The most effective inhibition of microbial cell viability was obtained for these BODIPY molecules at 100% at 50 and 100 mg/L. It was also observed that these BODIPY molecules exhibited excellent biofilm inhibition activities. The derivates were found to exhibit higher antibiofilm abilities against Staphylococcus aureus compared to Pseudomonas aeruginosa. When the antidiabetic effects of water‐soluble BODIPY compounds were examined, the highest effect was found to be 64.40% for BODIPY‐1 at 200 mg/L.
AIE Active Polymeric Fluorescent Nanoaggregates from Glycogen for Sensitive Detection of Tetracycline
Authors: Panigrahi Abhiram , Vishwakarma Ravindra , Sarma Tridib K. 
Published: November 2024

AbstractDetection and monitoring of environmental contaminants such as antibiotic residues in aquatic environments is challenging. To address this, a variety of detection methods has been developed; out of which optical sensing using fluorescence is found as one of the most robust methods. However, most of the reported sensors are made from metal ions using tedious synthetic processes, on the other hand, optical sensors using biosourced polymers are rarely reported. Herein, an anionic glycogen functionalized aggregation induced emission (AIE) active system; NCMCTPN was prepared using a simple Schiff base condensation reaction of tetraphenylethene amine (TPENH2) and carboxymethyl cellulose dialdehyde (NCMCA) and its self‐assembled polymeric nanoaggregates were explored for sensitive and selective turn‐off fluorescence detection of a broad‐spectrum tetracycline antibiotic, in an aqueous medium with a limit of detection of 127.5 ppb. The combination of factors such as inner filter effect and photoinduced electron transfer from the polymeric nanoaggregates to tetracycline through activation of a non‐radiative decay process is possibly responsible for the high sensitivity of the fluorescent nanoprobe towards the antibiotic.
Syntheses of Variants of π(σ) Aromatic Modified N‐Methyl N‐Confused Porphyrinoids with Adaptive Properties
Authors: Panua Anirban , Velmurugan Gunasekaran , Comba Peter , Rath Harapriya 
Published: November 2024

AbstractRetrosynthetically designed and syntheses of three unprecedented core modified N‐confused porphyrinoids exhibiting vis‐NIR absorption with tunable aromaticity is reported. Controlled modification of types of oxidants (chloranil vs. DDQ) has led to the isolation of 18π‐aromatic porphyrinoid 7 (upon chloranil oxidation) while DDQ oxidation has led to 18 e σ‐aromatic porphyrinoids 8 and 9. All the three SN3 hybrid N‐confused porphyrinoids 7–9 have been thoroughly characterized via solution state spectroscopic measurements and in‐depth DFT studies for concluding π‐aromaticity of 7 and σ‐aromaticity of 8 and 9. While 7 could recognize the fluoride anion with high selectivity via deprotonation rather than an anion recognition based mechanism, acetate anion binding studies clearly revealed NH⋅⋅⋅AcO− H‐bonding interaction in the host‐guest complex [7‐AcO−] supporting an anion recognition based mechanism. Porphyrinoids 8 and 9 remain unsusceptible to anion recognition. The conformational preorganization and anion induced deprotonation leading to conformational reorganization have been extensively studied by solution state spectroscopic techniques and in depth DFT level theoretical calculations.