bluuebunny/crossref_metadata_2025_split huggingface dataset:
18.9% Efficiency Ternary Organic Solar Cells Enabled by Isomerization Engineering of Chlorine‐Substitution on Small Molecule Donors
Authors: Zhang Chenyang , Li Jing , Deng Wanyuan , Dai Junpeng , Yu Jifa , Lu Guanghao , Hu Hanlin , Wang Kai 
Published: April 2023

AbstractTernary organic solar cells (OSCs) represent an efficient and facile strategy to further boost the device performance. However, the selection criteria and rational design of the third guest small molecule (SM) material still remain less understood. In this study, two new SM donor isomers, with α‐chlorinated thiophene (αBTCl) and β‐chlorinated thiophene (βBTCl) as side chains, are systematically designed, synthesized and incorporated as a third component in PM6:L8‐BO binary blends. It is noticed that introducing the SM donors guest has extended the absorption of photo‐active layer, induced desired component distribution vertically with enhanced crystallinity and reduced recombination process, leading to increased short‐circuit current (JSC) and improved fill factor. Moreover, due to the synergetic suppressed nonradiative loss and preferable morphology, the ternary OSCs feature improves open‐circuit voltage (VOC). Consequently, an impressive champion power conversion efficiency of 18.96% and 18.55% is achieved by αBTCl‐based and βBTCl‐based ternary OSCs, respectively. Furthermore, a record efficiency of 17.46% is obtained with a 330 nm thickness of αBTCl‐based ternary OSCs. This study demonstrates that molecular isomerization can be a promising design approach for SM donors to construct high‐performance ternary OSCs with simultaneous enhancement of all photovoltaic parameters.
Precipitation‐Based Silk Fibroin Fast Gelling, Highly Adhesive, and Magnetic Nanocomposite Hydrogel for Repair of Irregular Bone Defects
Authors: Zou Yan‐Pei , Liang Hai‐Feng , Wang Ben , Zhang Qi‐Chen , Su Di‐Han , Lu Shun‐Yi , Zhang Qian‐Yi , Wu Tao , Xiao Lan , Xiao Yin , Dong Jian , Jiang Li‐Bo , Li Xi‐Lei 
Published: April 2023

AbstractCritical‐sized bone defects, especially for irregular shapes, remain a significant challenge in orthopedics. Although various biomaterials are developed for bone regeneration, their application for repair of irregular bone defects is limited by the complicated preparation procedures involved, and their lack of shape‐adaptive capacity, physiological adhesion, and potent osteogenic bioactivity. In the present study, a simple strategy of precipitation by introducing tannic acid (TA) with abundant phenolic hydroxyl groups and Fe3O4 nanoparticles, as metal‐phenolic networks (MPN), is developed to easily prepare a fast gelling, shape‐adaptive, and highly adhesive regenerated silk fibroin (RSF)/TA/Fe3O4 hydrogel system that can respond to a static magnetic field (SMF). The RSF/TA/Fe3O4 hydrogel exhibits sufficient adhesion in biological microenvironments and good osteogenic effect in vitro and in vivo, under an external SMF, and thus, can be applied to repair critical‐sized bone defects. Moreover, bioinformatics analysis reveals that the synergistic mechanism of Fe3O4 NPs and SMF on osteogenic effects can be promotion of osteoblast differentiation via activation of the cyclic guanosine monophosphate (cGMP)/protein kinase G (PKG)/extracellular signal‐regulated kinase (ERK) signaling pathway. This study provides a promising biomaterial with potential clinical application for the future treatment of (irregular) critical‐sized bone defects.
Verification of Therapeutic Effect through Accelerator Mass Spectrometry‐Based Single Cell Level Quantification of hESC‐Endothelial Cells Distributed into an Ischemic Model
Authors: Oh Min‐Seok , Lee Seul‐Gi , Lee Gwan‐Ho , Kim C‐Yoon , Song Jong Han , Yu Byung‐Yong , Chung Hyung Min 
Published: April 2023

AbstractAs the potential of pluripotent stem cell‐derived differentiated cells has been demonstrated in regenerative medicine, differentiated vascular endothelial cells (ECs) are emerging as a therapeutic agent for the cardiovascular system. To verify the therapeutic efficacy of differentiated ECs in an ischemic model, human embryonic stem cells (hESCs) are induced as EC lineage and produce high‐purity ECs through fluorescence‐activated cell sorting (FACS). When hESC‐ECs are transplanted into a hindlimb ischemic model, it is confirmed that blood flow and muscle regeneration are further improved by creating new blood vessels together with autologous ECs than the primary cell as cord blood endothelial progenitor cells (CB‐EPCs). In addition, previously reported studies show the detection of transplanted cells engrafted in blood vessels through various tracking methods, but fail to provide accurate quantitative values over time. In this study, it is demonstrated that hESC‐ECs are engrafted approximately sevenfold more than CB‐EPCs by using an accelerator mass spectrometry (AMS)‐based cell tracking technology that can perform quantification at the single cell level. An accurate quantification index is suggested. It has never been reported in in vivo kinetics of hESC‐ECs that can act as therapeutic agents.
Effects of Individual Amino Acids on the Blood Circulation of Biosynthetic Protein Nanocages: Toward Guidance on Surface Engineering
Authors: Liang Ao , Zhou Wei , Zhang Hui , Zhang Juan , Zhang Xian‐En , Fang Ti , Li Feng 
Published: April 2023

AbstractProtein nanocages (PNCs) hold great promise for developing multifunctional nanomedicines. Long blood circulation is a key requirement of PNCs for most in vivo application scenarios. In addition to the classical PEGylation strategy, short peptides with a specific sequence screened via phage display are also very effective in prolonging the blood half‐life (t1/2) of PNCs. However, there is a lack of knowledge on how individual amino acids affect the circulation of PNCs. Here the effects of the 20 proteinogenic amino acids in the form of an X3 or X5 tag (X represents an amino acid) are explored on the pharmacokinetics of PNCs, which lead to the formation of a heatmap illustrating the extent of t1/2 prolongation by each proteinogenic amino acid. Significantly, oligo‐lysine and oligo‐arginine can effectively prolong the t1/2 of strongly negatively charged PNCs through charge neutralization, while oligo‐cysteine can also do so, but via a different mechanism, mediating the covalent binding of PNCs with plasma albumin as a stealth material. These findings are extendible and offer guidance for surface‐engineering biosynthetic PNCs and other nanoparticles.
Visible Light‐Driven Conversion of Carbon‐Sequestrated Seawater into Stoichiometric CO and HClO with Nitrogen‐Doped BiOCl Atomic Layers
Authors: Shi Yanbiao , Shou Hongwei , Li Hao , Zhan Guangming , Liu Xupeng , Yang Zhiping , Mao Chengliang , Cheng Jundi , Zhang Xu , Jiang Yaqian , Zhao Shengxi , Wang Jiaxian , Liu Xiao , Song Li , Sun Hongwei , Zhang Lizhi 
Published: April 2023

AbstractSeawater is one of the most important CO2 sequestration media for delivering value‐added chemicals/fuels and active chlorine; however, this scenario is plagued by sluggish reaction rates and poor product selectivity. Herein, we first report the synthesis of nitrogen‐doped BiOCl atomic layers to directly split carbon‐sequestrated natural seawater (Yellow Sea, China) into stoichiometric CO (92.8 μmol h−1) and HClO (83.2 μmol h−1) under visible light with selectivities greater than 90 %. Photoelectrons enriched on the exposed BiOCl{001} facet kinetically facilitate CO2‐to‐CO reduction via surface‐doped nitrogen bearing Lewis basicity. Photoholes, mainly located on the lateral facets of van der Waals gaps, promote the selective oxidation of Cl− into HClO. Sequestrated CO2 also maintains the pH of seawater at around 4.2 to prevent the alkaline earth cations from precipitating. The produced HClO can effectively kill typical bacteria in the ballast water of ocean‐going cargo ships, offering a green and safe way for onsite sterilization.
Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO2 Capture from Air: Roles of Atmospheric Water
Authors: Carneiro Juliana S. A. , Innocenti Giada , Moon Hyun June , Guta Yoseph , Proaño Laura , Sievers Carsten , Sakwa‐Novak Miles A. , Ping Eric W. , Jones Christopher W. 
Published: April 2023

AbstractDirect air capture (DAC) processes for extraction of CO2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al2O3, is explored in detail. By combining CO2 adsorption measurements, oxidative degradation rates, elemental analyses, solid‐state NMR and in situ IR spectroscopic analysis in conjunction with 18O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.
Fucose Binding Motifs on Mucin Core Glycopeptides Impact Bacterial Lectin Recognition**
Authors: Behren Sandra , Yu Jin , Pett Christian , Schorlemer Manuel , Heine Viktoria , Fischöder Thomas , Elling Lothar , Westerlind Ulrika 
Published: April 2023

AbstractMucin glycoproteins are essential components of the mucosal barrier, which protects the host from pathogens. Throughout evolution, bacteria have developed strategies to modulate and penetrate this barrier, and cause virulence by interacting with mucin O‐glycans at the epithelial cell‐surface. O‐fucosylated glycan epitopes on mucins are key ligands of many bacterial lectins. Here, a chemoenzymatic synthesis strategy is described to prepare a library of fucosylated mucin core glycopeptides to enable studies of mucin‐interacting and fucose‐binding bacterial lectins. Glycan cores with biologically important Lewis and H‐antigens were prepared decorating the peptide backbone at different sites and densities. The fucosylated mucin glycopeptides were applied in microarray binding studies to explore the importance of glycan core and peptide backbone presentation of these antigens in binding interactions with the P. aeruginosa lectin LecB and the C. difficile toxin A.
Regulating Spin Polarization through Cationic Vacancy Defects in Bi4Ti3O12 for Enhanced Molecular Oxygen Activation
Authors: Zhang Dongpeng , Li Yanxiao , Wang Pengfei , Qu Jinyong , Zhan Sihui , Li Yi 
Published: April 2023

AbstractMolecular oxygen (O2) activation technology is of great significance in environmental purification due to its eco‐friendly operation and cost‐effective nature. However, the activation of O2 is limited by spin‐forbidden transitions, and efficient molecular oxygen activation depends on electronic behavior and surface adsorption. Herein, we prepared cationic defect‐rich Bi4Ti3O12 (BTO‐MV2) catalysts containing Ti vacancies (VTi) for O2 activation in water purification. The VTi on BTO nanosheets can induce electron spin polarization, increasing the number of spin‐down photogenerated electrons and reducing the recombination of electron‐hole pairs. An active surface VTi is also formed, serving as a center for adsorbing O2 and extracting electrons, effectively generating ⋅OH, O2⋅− and 1O2. The degradation rate constant of tetracycline achieved by BTO‐MV2 is 3.3 times faster than BTO, indicating a satisfactory prospect for practical application. This work provides an efficient pathway to activate molecular oxygen by constructing new active sites through cationic vacancy modification technology.
Styryl‐NIR Mitochondrial Probes with Rapid HOCl Detection in Live‐Cells
Authors: Rajput Deeksha , Mahalingavelar Paramasivam , Soppina Virupakshi , Kanvah Sriram 
Published: April 2023

AbstractHypochlorous acid (HOCl) is critical for maintaining immune system balance, but it can harm mitochondria by hindering enzyme activity, leading to decreased ATP and increased cell death. In this study, we have designed a fluorophore with a pyridinium scaffold for selective staining of the mitochondria and to detect hypochlorite. The fluorophore exhibits strong solvatochromic emission due to intramolecular charge transfer and excellent sub‐cellular localization in the mitochondria. Additionally, it shows a rapid response to HOCl with high selectivity among different reactive oxygen/nitrogen compounds with a detection limit of 2.31 μM. Moreover, it is also utilized for the exogenous and endogenous detection of HOCl in live cells, which may help study the role of hypochlorite in organelles at the cellular level. DFT and TDDFT calculations have been carried out to understand the relationship between the structure and properties of the cationic probes with respect to the α‐cyano substitution and extension of π‐conjugation. The selective detection of HOCl by C4 over other cationic probes has also been well‐demonstrated, showing how the binding of HOCl affects the electronic properties of C4 through the analysis of non‐bonding orbitals (NBO) population, electrostatic potential surface (ESP), and density of states (DOS) projected DOS investigations.
PLAU contributes to the development of cholangiocarcinoma via activating NF‐κB signaling pathway
Authors: Hu Mei‐Di , Jia Ling‐Hua , Wang Ming‐long 
Published: April 2023

AbstractCholangiocarcinoma (CCA) is a type of epithelial cancer with poor outcomes and late diagnosis. Accumulating evidence has demonstrated the promoting role of plasminogen activator, urokinase (PLAU) in several tumor types, while its function in CCA is largely unknown. The expression of PLAU in CCA was determined by data from Gene Expression Omnibus (GEO) and The Cancer Genome Atlas (TCGA) database and further confirmed in human tissues using immunohistochemical (IHC) staining. Moreover, PLAU‐silencing CCA cell models were constructed for subsequent functional assays in vitro and in vivo. PLAU expression in CCA was significantly higher than that in normal tissues. High PLAU expression was positively correlated with poor patients' survival. PLAU knockdown remarkably suppressed proliferation and migration of CCA cells, whereas enhanced apoptosis. Consistently, tumor growth in mice injected with PLAU‐silencing CCA cells was also impaired. Furthermore, we revealed that the activation of NF‐κB signaling was required for PLAU‐induced malignant phenotypes of CCA cells. Inhibiting the high expression of PLAU in CCA may be a potential entry point for targeted therapy in CCA patient.
Efficient Red Organic Light Emitting Diodes of Nona Coordinate Europium Tris(β‐Diketonato) Complexes Bearing 4′‐Phenyl‐2,2′:6′,2′′‐Terpyridine
Authors: Ilmi Rashid , Wang Jingyu , Dutra José D. L. , Zhou Liang , Wong Wai‐Yeung , Raithby Paul R. , Khan Muhammad S. 
Published: April 2023

AbstractTwo novel nona‐coordinated Eu(III) complexes [Eu(btfa)3(Ph‐TerPyr)] (Eu‐1) and [Eu(NTA)3(Ph‐TerPyr)] (Eu‐2) have been synthesized and characterized. The structure of the complexes was elucidated by density functional theory (DFT) methods. The experimental photophysical properties of the complexes were investigated and complemented with theoretical calculations. Effective energy transfer (ET) pathways for the sensitized red luminescence is discussed. The complexes were tested as emitting layers (EML) in organic light emitting diodes (OLEDs). At the optimum doping concentration of 4 wt.%, the double‐EML OLEDs of Eu‐1 exhibited red electroluminescence (EL) with an EQE of 4.0 % and maximum brightness (B)=1179 cd/m2, maximum current efficiency (ηc)=5.64 cd/A, and maximum power efficiency (ηp)=4.78 lm/W at the current density (J) of 10 mA/cm2. Interestingly, the double‐EML OLEDs of Eu‐2 at the optimum concentration of 3 wt.%, displayed an outstanding EL performance with EQE of 7.32 % and B=838 cd/m2, ηc=10.19 cd/A and ηp=10.33 lm/W at J=10 mA/cm2. The EL performance of this device is among the best reported for devices incorporating a europium complex as a red emitter.
Near‐Room‐Temperature Synergetic Response of Magnetism, Dielectricity and Luminescence Based on (C5NH13Cl)2MnBr4
Authors: Yao Hai‐Quan , Li Long‐He , Zhang Shi‐Yong , Peng Yan , Liu Sui‐Jun , Wen He‐Rui , Zhang Jinlei , Ye Heng‐Yun , Song You , Hu Zhao‐Bo 
Published: April 2023

AbstractMultifunctional materials with working temperatures near room temperature are crucial for practical applications. Until now, it is still a great challenge to obtain such materials. In this paper, a complex of (C5NH13Cl)2MnBr4 (1) with a structural phase transition near room temperature is reported. The phase transition induces switchable magnetic properties, dielectric anomalies and luminescent response over the same range of temperatures. It is the first time the synergetic effect of magnetism, dielectricity and luminescence near room temperature have been observed in the same molecular complex.
Cooperative Supramolecular Polymerization of Triphenylamine bis‐Urea Macrocycles
Authors: Prakash Rahul , Islam Md Faizul , Kothalawala Rajeen Madawa , Hossain Muhammad Saddam , Smith Mark D. , Shimizu Linda S. 
Published: April 2023

AbstractHerein, we probe the hydrogen bond‐driven self‐assembly of a triphenylamine (TPA) bis‐urea macrocycle in the presence and absence of guests. Comprised of methylene urea‐bridged TPAs with exterior tridodecyloxy benzene solubilizing groups, the macrocycle exhibits concentration‐dependent aggregate formation in THF and H2O/THF mixtures as characterized by 1H NMR and DOSY experiments. Its assembly processes were further probed by temperature‐dependent UV/Vis and fluorescence spectroscopy. Upon heating, UV/Vis spectra exhibit a hypsochromic shift in the λmax, while fluorescence spectra show an increase in emission intensity. Conversely, the protected macrocycle that lacks hydrogen bond donors demonstrates no significant change. Thermodynamic analysis indicates a cooperative self‐assembly pathway with distinct nucleation and elongation regimes. The morphology and structure of the aggregate were elucidated by dynamic light scattering, atomic force microscopy, scanning and transmission electron microscopy. Variable temperature emission spectra were utilized to monitor the impact of guests, such as diphenylacetylene, that can be bound in the columnar channels. The findings suggest that the elongation of assemblies is influenced by the presence of these guests. In comparison, diphenyl sulfoxide, likely functioning as a chain stopper, limited the assembly size. These studies suggest that judicious selection of (co)monomers may modulate the function and utility of these supramolecular systems.
Polarization‐Sensitive Detector of Two‐Dimensional Multilayer Hybrid Perovskite Crystals Showing High Polarization Ratio to Weak Light
Authors: Li Wenjing , Ma Yu , Liu Yi , Xu Haojie , Tang Liwei , Chen Yaoyao , Yang Tian , Gao Changhao , Luo Junhua , Sun Zhihua 
Published: April 2023

AbstractTwo‐dimensional (2D) hybrid perovskite materials have been widely used for polarization‐sensitive photodetection due to their fascinating optical and physical attributes. However, studies on those materials that enable strong polarized‐light activities under a weak‐light condition remain quite scarce. Here, by tailoring aromatic cation into 3D prototype, we have successfully obtained a new 2D hybrid perovskite, (FPEA)2(MA)Pb2Br7 (1, where FPEA is 4‐fluorophenethylammonium and MA is methylammonium). The alternative alignment of inorganic and organic structural components results in significant anisotropy, including optical absorption and electric conductivity. The coupling effect of these anisotropic properties in 1 gives rise to strong dichroic activities toward detecting polarized light. Especially, under weak light intensity (∼330 nW/cm2), it can still generate a large polarization ratio up to 1.35, which is even higher than those of some typical 2D materials (i. e., GeSe ∼1.09). Besides, single crystal‐based photodetector of 1 displays fascinating detecting performances, including large photocurrent on/off ratio (∼104), fast response time (∼154/182 μs) and excellent antifatigued stability. These findings disclose the potentials of 1 as a robust candidate for detecting weak polarized light, which has practical applications in the field of polarized optoelectronics.
New highly efficient high‐breakdown estimator of multivariate scatter and location for elliptical distributions
Authors: Fishbone Justin , Mili Lamine 
Published: April 2023

AbstractHigh‐breakdown‐point estimators of multivariate location and shape matrices, such as the ‐estimator with smoothed hard rejection and the Rocke ‐estimator, are generally designed to have high efficiency for Gaussian data. However, many phenomena are non‐Gaussian, and these estimators can therefore have poor efficiency. This article proposes a new tunable ‐estimator, termed the ‐estimator, for the general class of symmetric elliptical distributions, a class containing many common families such as the multivariate Gaussian, ‐, Cauchy, Laplace, hyperbolic, and normal inverse Gaussian distributions. Across this class, the ‐estimator is shown to generally provide higher maximum efficiency than other leading high‐breakdown estimators while maintaining the maximum breakdown point. Furthermore, the ‐estimator is demonstrated to be distributionally robust, and its robustness to outliers is demonstrated to be on par with these leading estimators while also being more stable with respect to initial conditions. From a practical viewpoint, these properties make the ‐estimator broadly applicable for practitioners. These advantages are demonstrated with an example application—the minimum‐variance optimal allocation of financial portfolio investments.
Micro‐ and Nanoscale Heterogeneities in Zeolite Beta as Measured by Atom Probe Tomography and Confocal Fluorescence Microscopy
Authors: van Vreeswijk Sophie H. , Parker Luke A. , Maris J. J. Erik , Poplawsky Jonathan D. , Weckhuysen Bert M. 
Published: April 2023

AbstractMicro‐ and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol‐to‐hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub‐nanometre resolution. APT revealed 10–20 nanometre‐sized Al‐rich regions and short‐range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon‐rich areas of tens of nanometres within the zeolite crystals. Lastly, a short length‐scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon‐containing molecules next to the acidic sites in the zeolite.