bluuebunny/crossref_metadata_2025_split huggingface dataset:
Copper‐infused zinc porphyrin supramolecular polymersomes for triple synergistic combat against wound bacterial biofilm infections
Authors: Yang Lingkai , Du Ying , Yin Fuli , Shan Haojie , Liu Yannan , Zhou Yongfeng , Yu Xiaowei 
Published: October 2024

AbstractBacterial biofilm infections (BBI) on wound surfaces and implants pose a significant clinical challenge due to the impermeable nature of biofilms and obstacles in tissue repair. Traditional photothermal therapy (PTT) or chemodynamic therapy (CDT), whether used alone or in combination, often causes damage to surrounding normal tissues from high operating temperatures or elevated levels of reactive oxygen species, leading to unsatisfactory anti‐biofilm effects. This study introduces a novel copper ions loaded zinc porphyrin polymer vesicle (Cu‐PPS) that employs a triple synergistic approach involving PTT, CDT, and bacterial cuproptosis‐like death (BCD). Cu‐PPS exhibits exceptional photothermal efficiency of 51.06%, promoting the release of copper ions under photothermal stimulation, enhancing CDT and BCD effectiveness, and facilitating mature biofilm clearance and tissue repair. This approach achieves a bactericidal rate exceeding 99% and an anti‐biofilm rate of 93.32% in vitro and also excellent efficacy in treating BBI in vivo. This study presents an innovative therapeutic strategy for combating biofilm infections, addressing the challenges encountered in the clinical management of BBI.
Efficacy and safety of omalizumab combined with allergen immunotherapy in children with moderate to severe allergic asthma
Authors: Shen Wenxin , Zhou Qianlan , Zhang Qinzhen , Han Lina , Chen Li , Li Xiaowen , Dai Bing , Liu Si , Shan Lishen 
Published: October 2024

Key points
Omalizumab enables children who are intolerant to AIT to initiate AIT successfully.
Combination therapy better improves asthma and rhinitis symptoms, FeNO, and lung function compared to single SCIT or omalizumab treatment.
Combination therapy reduces the incidence of adverse reactions during the initial phase of SCIT and enhances its safety.
The Acetylene Bridge in Intramolecular Singlet Fission: A Boon or A Nuisance?
Authors: Majumder Kanad , Mukherjee Soham , Park Jungjin , Kim Woojae , Musser Andrew J. , Patil Satish 
Published: October 2024

AbstractVarious analogues of the alkylsilylacetylene group are frequently used as auxiliary groups to enhance the solubility and stability of the acene dimer core, widely used as platforms to investigate intramolecular singlet fission (iSF) mechanisms. However, while in the 2,2’‐linked dimers they are primarily auxiliary groups, these are essential fragments of the bridging units in 6,6’/5,5’‐linked dimers, the two preferred choices for dimerization. The starkly different iSF dynamics observed in the two variants raise the question of what role the acetylene bridges play. Here, we systematically designed a set of (oligo−)para‐phenylene bridged 2,2’‐linked pentacene dimers with an additional acetylene fragment in the bridging unit to mimic the structure of 6,6’‐linked dimers. Contrasting the results with previously reported analogous 2,2’‐linked and 6,6’‐linked pentacene dimers reveals that the acetylene bridges contribute to significant conformational freedom. This effect provides a mechanism to promote spin evolution within the triplet pair to achieve free triplets but also offers new parasitic pathways for triplet‐pair recombination, revealing that this structural motif can be both a boon and a nuisance. Additionally, our analysis reveals that these bridges directly modify the electronic states, highlighting significant pitfalls of the standard chromophore‐bridge‐chromophore framework used to design and interpret photophysics of iSF materials.
Contrasting Historical and Physical Perspectives in Asymmetric Catalysis: ΔΔG≠ versus Enantiomeric Excess
Authors: Ruth Marcel , Gensch Tobias , Schreiner Peter R. 
Published: October 2024

AbstractWith the rise of machine learning (ML), the modeling of chemical systems has reached a new era and has the potential to revolutionize how we understand and predict chemical reactions. Here, we probe the historic dependence on utilizing enantiomeric excess (ee) as a target variable and discuss the benefits of using relative Gibbs free activation energies (ΔΔG≠), grounded firmly in transition‐state theory, emphasizing practical benefits for chemists. This perspective is intended to discuss best practices that enhance modeling efforts especially for chemists with an experimental background in asymmetric catalysis that wish to explore modelling of their data. We outline the enhanced modeling performance using ΔΔG≠, escaping physical limitations, addressing temperature effects, managing non‐linear error propagation, adjusting for data distributions and how to deal with unphysical predictions,in order to streamline modeling for the practical chemist and provide simple guidelines to strong statistical tools. For this endeavor, we gathered ten datasets from the literature covering very different reaction types. We evaluated the datasets using fingerprint‐, descriptor‐, and graph neural network‐based models. Our results highlight the distinction in performance among varying model complexities with respect to the target representation, emphasizing practical benefits for chemists.
Spatially Controlled DNA Frameworks for Sensitive Detection and Specific Isolation of Tumor Cells
Authors: Luo Lei , Li Jiaojiao , Zhou Yuan , Xiang Dongliu , Luan Yanan , Wang Qing , Huang Jin , Liu Jianbo , Yang Xiaohai , Wang Kemin 
Published: October 2024

AbstractHigh‐affinity, specific, and sensitive probes are crucial for the specific recognition and identification of tumor cells from complex matrices. Multivalent binding is a powerful strategy, but the irrational spatial distribution of the functional moieties may reduce the probe performance. Here, we constructed a Janus DNA triangular prism nanostructure (3Zy1‐JTP‐3) for sensitive detection and specific isolation of tumor cells. Benefiting from spatial features of the triangular prism, the fluorescence intensity induced by 3Zy1‐JTP‐3 was almost 4 times that of the monovalent structure. Moreover, the DNA triangular prisms were connected to form hand‐in‐hand multivalent DNA triangular prism structures (Zy1‐MTP), in which the fluorescence intensity and affinity were increased to 9‐fold and 10‐fold of 3Zy1‐JTP‐3, respectively. Furthermore, 3Zy1‐JTP‐3 and Zy1‐MTP were combined with magnetic beads, and the latter showed higher capture efficiency (>90 %) in whole blood. This work provides a new strategy for the efficient capture of rare cells in complex biological samples.
Dual Redox Reactions of Silver Hexacyanoferrate Prussian Blue Analogue Enable Superior Electrochemical Performance for Zinc‐ion Storage**
Authors: Wang Liubin , Liu Ningbo , Li Qiaqia , Wang Xiaohan , Liu Jing , Xu Yinuo , Luo Zhiqiang , Zhang Ning , Li Fujun 
Published: October 2024

AbstractPrussian blue analogues (PBAs) have been employed as host materials of aqueous zinc‐ion batteries (ZIBs), however, they suffer from low capacity and poor cycling stability due to limited electron transfer and the presence of interstitial water in PBAs. Herein, a vacancy and water‐free silver hexacyanoferrate K0.95Ag3.05Fe(CN)6 (AgHCF‐3) was synthesized by adjusting the ratio of K and Ag in the framework. It offers nearly four electrons involving two sequential redox reactions, namely, Fe3+/Fe2+ and Ag+/Ag0, to deliver a large capacity of 179.6 mAh g−1 at 20 mA g−1 with Coulomb efficiency of ~100 %. The Zn//AgHCF‐3 cell delivers an estimated energy density of 200 Wh kg−1, surpassing reported PBAs‐based ZIBs. The formation of Ag0 in the cycling process merits favorable rate performance of AgHCF‐3 (156.4 mAh g−1 at 200 mA g−1 with 80.3 % capacity retention after 100 cycles). This investigation paves new pathways for high‐capacity PBA cathodes.
Energy Dissipation and Toughening of Covalent Networks via a Sacrificial Conformation Approach
Authors: Wang Hao , Wei Zhiyou , Liu Zhiwei , Zheng Bin , Zhang Zhaoming , Yan Xuzhou , He Linli , Li Tao , Zhao Dong 
Published: October 2024

AbstractCovalent polymer networks find wide utility in diverse engineering applications owing to their desirable stiffness and resilience. However, the rigid covalent chemical structure between crosslinking points imposes limitations on enhancing their toughness. Although the incorporation of sacrificial chemical bonds has shown promise in improving toughness through energy dissipation, composite networks struggle to maintain both rapid recovery and stiffness. Consequently, a significant challenge persists in achieving a covalent network that combines high strength, stiffness, toughness, and fast recovery performance. To address this challenge, we propose a novel sacrificial structure termed “sacrificial conformation.” In this approach, β‐cyclodextrin is covalently embedded into the network skeleton as the sacrificial conformation element. Compared to traditional covalent networks (LCN), well‐designed cyclodextrin‐embedded covalent network (CCN) exhibit a 100‐fold increase in Young's modulus and a 60‐fold increase in toughness. Importantly, CCN maintains excellent elasticity, ensuring swift recovery after deformation. This sacrificial conformational strategy enables efficient energy dissipation without necessitating the rupture of chemical bonds, thereby overcoming the limitations of traditional approaches. This advancement holds great promise for the design and fabrication of advanced elastomers and hydrogels with superior mechanical properties and dynamic behavior.
2,2′‐Bipyridyl‐4,4′‐Dicarboxylic Acid Modified Buried Interface of High‐Performance Perovskite Solar Cells
Authors: Zhao Mingming , Gu Wei‐Min , Jiang Ke‐Jian , Jiao Xinning , Gong Kun , Li Fengzhu , Zhou Xueqin , Song Yanlin 
Published: October 2024

AbstractThe regulation of interfaces remains a critical and challenging aspect in the pursuit of highly efficient and stable perovskite solar cells (PSCs). Here, 2,2′‐bipyridyl‐4,4′‐dicarboxylic acid (HBPDC) is incorporated as an interfacial layer between SnO2 and perovskite layers in PSCs. The two carboxylic acid moieties on HBPDC bind to SnO2 through esterification, while its nitrogen atoms, possessing lone electron pairs, interact with uncoordinated lead (Pb2+) atoms through Lewis acid‐base interactions. This dual functionality enables simultaneous passivation of surface defects on both the SnO2 and buried perovskite layers. In addition, the electron‐deficient nature of HBPDC enhances interfacial energy band alignment and facilitates electron transfer from the perovskite to SnO2. Furthermore, the incorporation of HBPDC strengthens the interfacial adhesion, improving mechanical reliability. As a result, the PSCs exhibited an impressive power conversion efficiency (PCE) of 25.41 % under standard AM 1.5G conditions, along with remarkable environmental stability.
Programmable Circular Multivalent Nanobody‐Targeting Chimeras (mNbTACs) for Multireceptor‐Mediated Protein Degradation and Targeted Drug Delivery
Authors: Jiang Shiqi , Lv Xinru , Ouyang Zhenlin , Chi Hongli , Zeng Yuchen , Wang Yani , He Jiaxuan , Chen Jinling , Chen Jingyi , An Keli , Cheng Ming , Wen Yurong , Li Juan , Zhang Penghui 
Published: October 2024

AbstractMultispecific therapeutics hold significant promise in drug delivery, protein degradation, and cell recruitment to address clinical issues of tumor heterogeneity, resistance, and immune evasion. However, their modular engineering remains challenging. We developed a targeted degradation platform, termed multivalent nanobody‐targeting chimeras (mNbTACs), by encoding diverse nanobody codons on a circular template using DNA printing technology. The homo‐ or hetero‐ mNbTACs specifically recognized membrane targets in a multivalent manner and simultaneously recruited scavenger receptors to favor clathrin‐/caveolae‐dependent endocytosis and lysosomal degradation of multiple proteins with high efficiency and selectivity. We demonstrated that a bispecific doxorubicin‐loaded mNbTAC, named Doxo‐mvNbsPPH, passively accumulated at tumor sites, specifically interacted with PD−L1 and HER2 targets, and was rapidly transported into lysosome, inducing potent immunogenic cell death and alleviating immune checkpoint evasion. The synergistic boosting of innate and adaptive immunity promoted the infiltration and proliferation of CD8+ T cells in tumor microenvironment (an 11‐fold increase) with high toxicity and low exhaustion, eventually enhancing antitumor efficacy. Our mNbTAC platform provides multispecific therapeutics with variable valences and programmed species, whereas it induces targeted protein degradation through multireceptor‐mediated endocytosis and lysosomal degradation without the need for lysosome‐targeting receptors, representing a general and modular tool to harness extracellular proteome for disease treatment.
A Covalent Triazine Framework for Photocatalytic Anti‐Markovnikov Hydrofunctionalizations
Authors: Maiti Rakesh , Chakraborty Jeet , Kumar Sahoo Prakash , Nath Ipsita , Dai Xingchao , Rabeah Jabor , De Geyter Nathalie , Morent Rino , Van Der Voort Pascal , Das Shoubhik 
Published: October 2024

AbstractPorous materials‐based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)‐based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C−N and C−O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron‐donating and ‐withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late‐stage functionalization of bio‐active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provide mechanistic insights into these reactions.
Novel Silicate Platform as Weakly‐Coordinating Anions for Diverse Organometallic and Electrochemical Applications
Authors: He Tianyi , Bruening Meaghan A. , Espinosa Matthew , Agapie Theodor 
Published: October 2024

AbstractWeakly‐coordinating anions (WCAs) are employed in a wide range of applications, but limitations remain, including high reactivity, limited redox window, complicated synthesis, high cost, low solublity, and low structural tunabililty. Herein, we report a new class of WCA based on alkyl or aryl (R) substituted silicates bearing fluorinated pinacolate ligands, “[RSiF24]−”. Anions bearing a variety of R groups were prepared, enabling facile tuning of sterics and solubility. A range of cations employed in chemical reactivity has been supported by these anions, including ether‐free alkali cations, Ag+, Ph3C+, Fc+, [NiI(COD)2]+. [Pd(dppe)(NCMe)Me]+ has been generated by salt metathesis or protonation of a metal‐alkyl bond, showcasing the ability of the [RSiF24]− anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu4N]+ variant show an exceptionally wide stability window for the [MeSiF24]− anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.
Triplet Energy Gap‐Regulated Room Temperature Phosphorescence in Host–Guest Doped Systems
Authors: Li Jiayu , Hao Subin , Li Mengke , Chen Yanqi , Li Hailin , Wu Shiqi , Yang Sirui , Dang Li , Su Shi‐Jian , Li Ming‐De 
Published: October 2024

AbstractThe organic room temperature phosphorescence (RTP) materials via host–guest doped method receive considerable attention in the fields of optoelectronics, bioimaging, and information encryption. Despite many host–guest doped materials with excellent RTP properties have been developed, their luminous mechanism is still limited. Here, a series of host–guest doped materials, using benzophenone as the host and quinone compounds as the guests, were constructed to investigate the effect of the triplet energy gap (ΔET) between the host and guest on triplet states population. The guest's triplet state is proposed to be a “triplet energy reservoir”, gathering the triplet excitons to emit RTP when ΔET is large and returning triplet excitons to the host when ΔET is small. By combining the results of steady‐state and delayed emission spectra, time‐resolved transient absorption spectra, and theoretical calculations, a bidirectional energy transfer process is proved, which are triplet‐triplet energy transfer and reverse triplet‐triplet energy transfer processes. The thermal equilibrium of these two energy transfer processes can be regulated by the ΔET and temperature. The potential applications of these RTP properties are also realized in data encryption and anti‐counterfeiting. This work provides valuable insight into the design of host–guest doped materials based on energy transfer mechanisms.
Multi‐branched octopus‐like plasticizers with excellent plasticizing performance in poly(vinyl chloride)
Authors: Tang Hao , Du Yicheng , Ying Jiaying , Shen Yirui , Zhu Xiaoyuan , Liu Dekai , Lang Bo , Jiang Pingping 
Published: October 2024

AbstractThe development of alternatives is a priority issue for the plasticizer industry due to the reproductive toxicity and potential carcinogenicity of phthalate plasticizers. Herein we demonstrate the synthesis and characterization of multi‐branched octopus‐like plasticizers applied in poly(vinyl chloride) (PVC). The plasticizers were achieved through a straightforward one‐step esterification reaction, resulting in four polyol ester plasticizers (glyceryl tri‐n‐octanoate [GTOE], pentaerythritol tetra‐n‐octanoate [PQOE], xylitol penta‐n‐octanoate [XPOE], and mannitol hexa‐n‐octanoate [MHOE]). The multi‐branched structure enhances the interactions between plasticizers and PVC molecules leading to superior plasticizing properties, particularly mechanical properties, thermal stability, and migration resistance compared with commercial plasticizers di(2‐ethylhexyl) phthalate (DEHP), dioctyl terephthalate (DOTP), and acetyl tributyl citrate (ATBC). Concretely, the elongation at break of MHOE/PVC (825%) and PQOE/PVC (814.63%) was better than that of DEHP/PVC (670.02%), DOTP/PVC (490.62%) and ATBC/PVC (566.78%). The T5% of GTOE/PVC, PQOE/PVC, XPOE/PVC, and MHOE/PVC were 46.97, 67.24, 60.09 and 48.14°C higher than ATBC/PVC respectively. In the volatility resistance testing after 48 h, the weight loss of GTOE/PVC, PQOE/PVC, XPOE/PVC, and MHOE/PVC was 5.63%, 3.64%, 2.95%, and 8.88% respectively, which was far less than DEHP/PVC (15.58%), DOTP/PVC (11.83%) and ATBC/PVC (18.15%). Consequently, the obtained plasticizers demonstrate enhanced plasticizing efficiency, presenting promising alternatives to phthalate plasticizers and expanding the repertoire of choices within the plasticizer industry.
Organocatalyzed Asymmetric Conjugate Addition of Cyclic β‐Keto Esters to (E)‐β‐Nitroacrylate Derivatives
Authors: Matsushima Yasuyuki , Iijima Yoshiyuki , Tanabe Chinatsu , Nakashima Kosuke , Hirashima Shin‐ichi , Miura Tsuyoshi 
Published: October 2024

AbstractA diaminomethylenemalononitrile organocatalyst efficiently promoted the asymmetric conjugate addition of cyclic β‐keto esters to (E)‐β‐nitroacrylate derivatives, yielding the corresponding β‐nitro esters derivatives with excellent enantioselectivities (up to >99 % ee). This is the first successful example of highly stereoselective conjugate addition of cyclic β‐keto esters to (E)‐β‐nitroacrylate derivatives to obtain anti‐isomers.
Computational insights in design of Crimean–Congo hemorrhagic fever virus conserved immunogenic nucleoprotein peptides containing multiple epitopes
Authors: Kaushal Neha , Baranwal Manoj 
Published: October 2024

AbstractCrimean–Congo hemorrhagic fever virus (CCHFV) belongs to Nairoviridae family and has tripartite RNA genome. It is endemic in various countries of Asia, Africa, and Europe and is primarily transmitted by Hyalomma ticks but nosocomial transmission also been reported. Vaccines for CCHF are in early phase of clinical trial; therefore, this work is centered on identification of potential immunogenic peptide as vaccine candidates with application of different immunoinformatics approaches. Eleven conserved (>90%) peptides of CCHFV nucleoprotein were selected for CD8+ T‐cell (NetMHCpan 4.1b and NetCTLpan 1.1 server) and CD4+ T‐cell (NetMHCIIpan‐4.0 server and Tepitool) epitope prediction. Three peptides containing multiple CD8+ and CD4+ T‐cell and B‐cell epitopes were identified on basis of consensus prediction approach. Peptides displayed good antigenicity score of 0.45–0.68 and predicted to bind with diverse human leukocyte antigen (HLA) alleles. Molecular docking was performed with epitopes to HLA and HLA‐epitopes complex to T‐cell receptor (TCR). In most of the cases, docked complex of HLA‐epitope and HLA‐epitopes‐TCR have the binding energy close to respective natural bound peptide complex with HLA and TCR. Molecular dynamic simulation also revealed that HLA‐peptide complexes have minimum fluctuation and deviation than HLA‐peptide‐TCR docked over 50 ns simulation run. Considering these findings, identified peptides can serve as potential vaccine candidates for CCHFV disease.
Photovoltaic Molecule‐Based Phototheranostics With A‐D‐A Structure for Near‐Infrared Fluorescence Imaging‐Guided Synergetic Photodynamic and Photothermal Therapy of Tumors
Authors: Chen Liang , Huang Jierou , Tong Ming , He Xinchun , Liu Li , Chen Haiou , Yi Jianing 
Published: October 2024

ABSTRACTPhototheranostics with near‐infrared fluorescence and reactive oxygen species generation ability and high photothermal conversion efficiency (PCE) plays a significant role in fluorescence imaging‐guided synergetic photodynamic and photothermal therapy of tumors. Here, a star molecule in organic photovoltaic materials, NCBDT‐4C with an A‐D‐A conjugated structure, was assembled with DSPE‐PEG‐NH2 to prepare water dispersive nanoparticles (NPs). The prepared NCBDT‐4Cl NPs exhibited a maximum NIR absorption peak at 764 nm and a maximum fluorescence peak at 798 nm. These NPs could generate superoxide anion, singlet oxygen (1O2), and heat under 808 nm laser irradiation. The 1O2 generation quantum yield and PCE of the NPs were 37.5% and 53.6%, respectively. The combination of photodynamic and photothermal therapy of cancer was demonstrated in vitro and in vivo. This work presents the advanced application of organic photovoltaic materials in cancer phototherapy.