bluuebunny/crossref_metadata_2025_split huggingface dataset:
Broadband Ultrafast Nonlinear Optical Limiting at a Porphyrin‐Based 2D Polymer
Authors: Liu Fang , Guan Zihao , Wei Zhiyuan , Fu Lulu , Zhao Yang , Chen Lu , Shan Naying , Huang Zhipeng , Humphrey Mark G. , Zhang Chi 
Published: May 2024

AbstractUltrafast lasers have significantly contributed to the advancement of research and technology; however, high‐intensity lasers bring potential risks to precision instruments and the human eye. Developing optical limiting (OL) devices capable of reasonably controlling laser energy to an acceptable energy level is imperative. Nevertheless, achieving both exceptional OL performance and broad‐spectrum laser intensity tunability proves highly challenging. In this work, the synthesis of a porphyrin‐based 2D polymer (Por‐2DP) using a template‐assisted self‐coupling polymerization, constructing a 2D framework through the carbon‐carbon single bond coupling of porphyrin monomer is presented. The resultant Por‐2DP demonstrates remarkable broadband nonlinear absorption performance, spanning the visible and near‐infrared spectral regions under an ultrafast pulse laser (35 fs) for the first time. OL thresholds at excitation wavelengths of 515, 800, and 1550 nm are determined to be 1.44, 0.48, and 0.54 mJ cm−2, respectively, surpassing reported 2D materials to date. Additionally, the Por‐2DP exhibits prominent photostability, enabling sustained operation under intense light conditions for a long time, thereby enhancing OL practical applicability. This study not only introduces a novel OL material and device but also promotes the application of innovative 2D organic polymers in NLO field.
Ultrasensitive Piezochromic Molecular Crystals: Mechanical Pressure‐Induced Controlled Regulation of TADF and RTP
Authors: Pattanayak Pradip , Modak Niladri , Guchhait Shyamal , Ghosh Nirmalya , Purkayastha Pradipta 
Published: May 2024

AbstractConsidering that regulation of thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) is necessary for a fluorophore to survive and properly show its characteristic features, it is successfully shown herein that a carefully designed novel pyrene derivative can exhibit remarkable aggregation‐induced emission (AIE) overcoming the characteristic fast excitonic decay of pyrene compounds. Moreover, it is established that J‐aggregation in the red‐emitting molecular crystals of the compound reduces the singlet‐triplet energy gap (∆EST), allowing TADF with a very high photoluminescence quantum yield (PLQY) of 72%. Whereas, anisotropic grinding of the same crystals generates well‐defined microcrystals that show RTP as the nature of aggregation changes. Impressively, under isotropic hydrostatic pressure, the crystals show near‐infra‐red (NIR) emission with a very high piezochromic luminescence sensitivity of 46.2 nm GPa−1. The results have established that formation of stable H‐aggregates in the microcrystals is responsible for the ultra‐long RTP. A highly sophisticated full‐spectrum Mueller‐matrix analysis is used for the first time in such systems to demonstrate the details of the effect of perturbation (pressure) on molecular conformation.
Enhancing Fast RISC in Hot‐Exciton Thermally Activated Delayed Fluorescence Emitter Through Fused Ring Modification: A Theoretical Insights
Authors: Nathiya Singaravel 
Published: May 2024

AbstractRecent progress has shown promising advancements in enhancing the Reverse intersystem crossing (RISC) process between high‐energy triplet states (Tn, n ≥ 1) and radiative singlet states (Sm) through the utilization of the classic D‐A‐D' strategy. In this study, 12 molecules employing phenyl carbazole and a peripheral phenanthroimidazole as the donors and fused cores as acceptors are theoretically designed. Additionally, electron‐withdrawing groups such as fluorine and cyano, as well as electron‐donating group like methoxy, are incorporated into anthracene, napthaoxadiazole, and napthothiadiazole derivatives, acting as fused core components. Theoretical analyses reveal that among the molecules examined, eight adhere to the three golden principle rules, demonstrating a large energy gap between S1‐T1, the minimal ΔES1‐T2, and large T2‐T1. Additionally, these molecules exhibit significant Spin‐orbit coupling (SOC) and maintain a strong Hybridized local and charge transfer (HLCT) character, facilitating the fast hRISC from T2 to S1. The auxiliary inclusion of heteroatoms, such as oxygen and sulfur, on the anthracene core, aligns with the prerequisite strategy, ultimately reinforcing the SOC. Furthermore, replacing the methoxy group on the Nz bridge significantly enhances the SOC, resulting in a substantial increase in the hRISC rate (10 +08 s−1). Overall, the findings substantially elevate the photophysical attributes of the designed molecules through the utilization of the hRISC channel.
Generating Multi‐Depth 3D Holograms Using a Fully Convolutional Neural Network
Authors: Yan Xingpeng , Liu Xinlei , Li Jiaqi , Zhang Yanan , Chang Hebin , Jing Tao , Hu Hairong , Qu Qiang , Wang Xi , Jiang Xiaoyu 
Published: May 2024

AbstractEfficiently generating 3D holograms is one of the most challenging research topics in the field of holography. This work introduces a method for generating multi‐depth phase‐only holograms using a fully convolutional neural network (FCN). The method primarily involves a forward–backward‐diffraction framework to compute multi‐depth diffraction fields, along with a layer‐by‐layer replacement method (L2RM) to handle occlusion relationships. The diffraction fields computed by the former are fed into the carefully designed FCN, which leverages its powerful non‐linear fitting capability to generate multi‐depth holograms of 3D scenes. The latter can smooth the boundaries of different layers in scene reconstruction by complementing information of occluded objects, thus enhancing the reconstruction quality of holograms. The proposed method can generate a multi‐depth 3D hologram with a PSNR of 31.8 dB in just 90 ms for a resolution of 2160 × 3840 on the NVIDIA Tesla A100 40G tensor core GPU. Additionally, numerical and experimental results indicate that the generated holograms accurately reconstruct clear 3D scenes with correct occlusion relationships and provide excellent depth focusing.
Supramolecular Nanofibers Ameliorate Bleomycin‐Induced Pulmonary Fibrosis by Restoring Autophagy
Authors: Zheng Debin , Guo Jiasen , Liang Ziyi , Jin Yueyue , Ding Yinghao , Liu Jingfei , Qi Chao , Shi Kaiwen , Xie Limin , Zhu Meiqi , Wang Ling , Hu Zhiwen , Yang Zhimou , Liu Qian , Li Xiaoxue , Ning Wen , Gao Jie 
Published: May 2024

AbstractIdiopathic pulmonary fibrosis (IPF) is a progressive and ultimately fatal interstitial lung disease, with limited therapeutic options available. Impaired autophagy resulting from aberrant TRB3/p62 protein‐protein interactions (PPIs) contributes to the progression of IPF. Restoration of autophagy by modulating the TRB3/p62 PPIs has rarely been reported for the treatment of IPF. Herein, peptide nanofibers are developed that specifically bind to TRB3 protein and explored their potential as a therapeutic approach for IPF. By conjugating with the self‐assembling fragment (Ac‐GFFY), a TRB3‐binding peptide motif A2 allows for the formation of nanofibers with a stable α‐helix secondary structure. The resulting peptide (Ac‐GFFY‐A2) nanofibers exhibit specific high‐affinity binding to TRB3 protein in saline buffer and better capacity of cellular uptake to A2 peptide. Furthermore, the TRB3‐targeting peptide nanofibers efficiently interfere with the aberrant TRB3/p62 PPIs in activated fibroblasts and fibrotic lung tissue of mice, thereby restoring autophagy dysfunction. The TRB3‐targeting peptide nanofibers inhibit myofibroblast differentiation, collagen production, and fibroblast migration in vitro is demonstrated, as well as bleomycin‐induced pulmonary fibrosis in vivo. This study provides a supramolecular method to modulate PPIs and highlights a promising strategy for treating IPF diseases by restoring autophagy.
A Tumor Environment‐Activated Photosensitized Biomimetic Nanoplatform for Precise Photodynamic Immunotherapy of Colon Cancer
Authors: Xiong Mengmeng , Zhang Ying , Zhang Huan , Shao Qiaoqiao , Hu Qifan , Ma Junjie , Wan Yiqun , Guo Lan , Wan Xin , Sun Haitao , Yuan Zhongyi , Wan Hao 
Published: May 2024

AbstractAggressive nature of colon cancer and current imprecise therapeutic scenarios simulate the development of precise and effective treatment strategies. To achieve this, a tumor environment‐activated photosensitized biomimetic nanoplatform (PEG2000‐SiNcTI‐Ph/CpG‐ZIF‐8@CM) is fabricated by encapsulating metal‐organic framework loaded with developed photosensitizer PEG2000‐SiNcTI‐Ph and immunoadjuvant CpG oligodeoxynucleotide within fusion cell membrane expressing programmed death protein 1 (PD‐1) and cluster of differentiation 47 (CD47). By stumbling across, systematic evaluation, and deciphering with quantum chemical calculations, a unique attribute of tumor environment (low pH plus high concentrations of adenosine 5′‐triphosphate (ATP))‐activated photodynamic effect sensitized by long‐wavelength photons is validated for PEG2000‐SiNcTI‐Ph/CpG‐ZIF‐8@CM, advancing the precision of cancer therapy. Moreover, PEG2000‐SiNcTI‐Ph/CpG‐ZIF‐8@CM evades immune surveillance to target CT26 colon tumors in mice mediated by CD47/signal regulatory proteins α (SIRPα) interaction and PD‐1/programmed death ligand 1 (PD‐L1) interaction, respectively. Tumor environment‐activated photodynamic therapy realized by PEG2000‐SiNcTI‐Ph/CpG‐ZIF‐8@CM induces immunogenic cell death (ICD) to elicit anti‐tumor immune response, which is empowered by enhanced dendritic cells (DC) uptake of CpG and PD‐L1 blockade contributed by the nanoplatform. The photodynamic immunotherapy efficiently combats primary and distant CT26 tumors, and additionally generates immune memory to inhibit tumor recurrence and metastasis. The nanoplatform developed here provides insights for the development of precise cancer therapeutic strategies.
Atom‐Modified gDNA Enhances Cleavage Activity of TtAgo Enabling Ultra‐Sensitive Nucleic Acid Testing
Authors: Zhang Jun , Chen Miaomiao , Jiang Huan , Sun Huifang , Ren Jianing , Yang Xin , Liu Shanshan , Wang Dongsheng , Huang Zhen , Liu Jianping , Ma Daiyuan , Guo Xiaolan , Luo Guangcheng 
Published: May 2024

AbstractThe DNA‐guided (gDNA) Argonaute from Thermus thermophilus (TtAgo) has little potential for nucleic acid detection and gene editing due to its poor dsDNA cleavage activity at relatively low temperature. Herein, the dsDNA cleavage activity of TtAgo is enhanced by using 2′‐fluorine (2′F)‐modified gDNA and developes a novel nucleic acid testing strategy. This study finds that the gDNA with 2′F‐nucleotides at the 3′‐end (2′F‐gDNA) can promote the assembly of the TtAgo‐guide‐target ternary complex significantly by increasing its intermolecular force to target DNA and TtAgo, thereby providing ≈40‐fold activity enhancement and decreasing minimum reaction temperature from 65 to 60 °C. Based on this outstanding advance, a novel nucleic acid testing strategy is proposed, termed FAST, which is performed by using the 2′F‐gDNA/TtAgo for target recognition and combining it with Bst DNA polymerase for nucleic acid amplification. By integrating G‐quadruplex and Thioflavin T, the FAST assay achieves one‐pot real‐time fluorescence analysis with ultra‐sensitivity, providing a limit of detection up to 5 copies (20 µL reaction mixture) for miR‐21 detection. In summary, an atom‐modification‐based strategy has been developed for enhancing the cleavage activity of TtAgo efficiently, thereby improving its practicability and establishing a TtAgo‐based nucleic acid testing technology with ultra‐sensitivity and high‐specificity.
Intraspecific divergence in a coastal plant, Euphorbia jolkinii, at a major biogeographic boundary in East Asia
Authors: Iwata Hiroyuki , Ito Takuro , Park Jong‐Soo , Kokubugata Goro , Kakezawa Akihiro , Kurosawa Takahide , Nishimura Akihiro , Noda Hiroshi , Takayama Koji 
Published: May 2024

AbstractPremiseQuaternary climatic fluctuations and long‐distance seed dispersal across the sea are critical factors affecting the distribution of coastal plants, but the spatiotemporal nature of population expansion and distribution change of East Asian coastal plants during this period are rarely examined. To explore this process, we investigated the genome‐wide phylogenetic patterns of Euphorbia jolkinii Boiss. (Euphorbiaceae), which grows widely on littoral areas of Japan, Korea, and Taiwan.MethodsWe used plastome sequences and genome‐wide single nucleotide polymorphisms in samples across the species range to reveal phylogeographic patterns and spatiotemporal distributional changes. We conducted ecological niche modeling for the present and the last glacial maximum (LGM).ResultsGenetic differentiation was observed between the northern and southern populations of E. jolkinii, separated by the major biogeographic boundary, the Tokara Gap. These two groups of populations differentiated during the glacial period and subsequently intermingled in the intermorainic areas of the central Ryukyu Islands after the LGM. Ecological niche models suggested that the potential range of E. jolkinii was restricted to southern Kyushu; however, it was widespread in the southern Ryukyu Islands and Taiwan during the LGM.ConclusionsThis study provides evidence of genetic differentiation among coastal plant populations separated by the prominent biogeographical boundary. Although coastal plants are typically expected to maintain population connectivity through sea‐drifted seed dispersal, our findings suggest that genetic differences may arise because of a combination of limited gene flow and changes in climate during the glacial period.
Design, Preparation, and Implementation of Axially Chiral Benzotetramisoles as Lewis Base Catalysts for Asymmetric Cycloadditions
Authors: Lin Zitong , Yu Ying , Liu Rixin , Zi Weiwei 
Published: May 2024

AbstractDeveloping novel catalysts with potent activity is of great importance in organocatalysis. In this study, we designed and prepared a new class of benzotetramisole Lewis base catalysts (AxBTM) that have both central and axial chirality. This unique feature of these catalysts results in a three‐dimensional microenvironment with multi‐layers of chirality. The performance of the developed catalysts was tested in a series of cycloaddition reactions. These included the AxBTM‐catalyzed (2+2) cycloaddition between α‐fluoro‐α‐aryl anhydride with imines or oxindoles, and the sequential gold/AxBTM‐catalyzed (4+2) cycloaddition of enynamides with pentafluorophenyl esters. The interplay between axial and central chirality had a collaborative effect in regulating the stereochemistry in these cycloadditions, leading to high levels of stereoselectivity that would otherwise be challenging to achieve using conventional BTM catalysts. However, the (2+2) and (4+2) cycloadditions have different predilections for axial and central chirality combinations.
Omegasomes control formation, expansion, and closure of autophagosomes
Authors: Nähse Viola , Stenmark Harald , Schink Kay O. 
Published: May 2024

AbstractAutophagy, an essential cellular process for maintaining cellular homeostasis and eliminating harmful cytoplasmic objects, involves the de novo formation of double‐membraned autophagosomes that engulf and degrade cellular debris, protein aggregates, damaged organelles, and pathogens. Central to this process is the phagophore, which forms from donor membranes rich in lipids synthesized at various cellular sites, including the endoplasmic reticulum (ER), which has emerged as a primary source. The ER‐associated omegasomes, characterized by their distinctive omega‐shaped structure and accumulation of phosphatidylinositol 3‐phosphate (PI3P), play a pivotal role in autophagosome formation. Omegasomes are thought to serve as platforms for phagophore assembly by recruiting essential proteins such as DFCP1/ZFYVE1 and facilitating lipid transfer to expand the phagophore. Despite the critical importance of phagophore biogenesis, many aspects remain poorly understood, particularly the complete range of proteins involved in omegasome dynamics, and the detailed mechanisms of lipid transfer and membrane contact site formation.
Combinatorial entropy determines the early stages of nucleation
Authors: Koo Da‐Hyun , Park Ho Jun , Choi Jeong‐Mo 
Published: May 2024

AbstractBiomolecular phase separation, a complex phenomenon within living systems, has garnered significant interest due to its diverse roles in cellular organization and function. Despite its importance, studying phase separation dynamics experimentally, particularly in the early stages, poses challenges. Our study investigates the dynamics of biomolecular phase separation using a graph‐based simulation module, particularly emphasizing its early stages. Through a simplified model, we dissect the influences of various factors on collective behavior, highlighting the crucial role of combinatorial entropy in percolation dynamics. This study offers valuable insights into the fundamental principles governing biomolecular phase separation, with implications for understanding cellular processes and disease mechanisms.
NOE analysis using dual injection DNP‐NMR for studies of solvent–solute interactions at low concentrations
Authors: Kim Jihyun 
Published: May 2024

AbstractDynamic nuclear polarization (DNP) offers significant signal enhancement compared to conventional nuclear magnetic resonance (NMR) in measuring the nuclear Overhauser effect. Owing to this enhancement, DNP enables the quantitative analysis of solvent–solute interactions, which are typically challenging to assess using standard NMR techniques. However, current experimental setups generally require the use of samples with relatively high solute concentrations because of large dilution factors. This limits the studies on solvent–solute interactions for bio‐related molecules, particularly those with low solubility. In such cases, the concentration of solute post‐dilution often falls below the detection limits. Herein, we introduce a novel dual injection system designed to considerably increase the dilution factor, thereby enabling the use of samples with lower solute concentrations while maintaining detectable signal levels. The effectiveness of this system was demonstrated in experiments using trifluoroacetic acid at concentrations 50 times lower than those used in the conventional method.
Development and validation of HPLC‐ultraviolet method for quantitative determination of pritelivir in human placental perfusion medium
Authors: Wang Xiaoming , Patrikeeva Svetlana , Nanovskaya Tatiana , Bryant Valentina 
Published: May 2024

AbstractA simple and reliable HPLC‐ultraviolet (HPLC‐UV) method was developed and validated for the quantification of pritelivir in the samples of medium from the experiments utilizing the ex vivo technique of dual perfusion of the human placental lobule. Phenacetin was used as an internal standard (IS) in our HPLC‐UV method. Chromatographic separation of pritelivir and phenacetin was achieved on a Waters Symmetry C18 HPLC column (100 × 2.1 mm, 3.5 μm) at ambient temperature (22–25°C). The mobile phase was composed of 50% methanol in deionized water (v/v), the flow rate for isocratic elution was established at 0.25 mL/min, and the detection wavelength for pritelivir and IS was set at 254 nm. Pritelivir and IS were extracted with the protein precipitation method using methanol as a solvent. The calibration curve for pritelivir exhibited linearity (r2 > 0.99) within the concentration range from 0.155 to 6.62 μg/mL. Within‐ and between‐day accuracy ranged from 97% to 110% with relative standard deviation (RSD) values not exceeding 10%. The extraction recovery of pritelivir and IS ranged from 89% to 91% with RSD not exceeding 7%. Pritelivir was stable under the storage and sample handling conditions. This validated HPLC‐UV method was utilized to quantify pritelivir in the placental perfusion medium samples, and the resulting concentrations were authenticated with incurred sample reanalysis to confirm the reliability of the method.
Spray‐dried Ni‐Co Bimetallic Catalysts for Dry Reforming of Methane
Authors: Küchen Gerrit , Olszok Vinzent , Kreitz Bjarne , Mahr Christoph , Rosenauer Andreas , Turek Thomas , Weber Alfred P. , Wehinger Gregor D. 
Published: May 2024

AbstractDry reforming of methane (DRM) is an attractive reaction for synthesis gas production, since it converts two greenhouse gases into valuable chemical feedstock. Silica supported bimetallic catalysts with constant metal loading but varying Ni/Co ratios (xNi=1, 0.8, 0.6, 0.5, 0.4, 0.2, 0) were produced via spray‐drying for the application in DRM, aiming at the identification of compositions with superior activity. In this study, building block particles refer to an inert framework, supporting the catalyst. The elemental distribution of Si, Ni, and Co within such building block particles was evaluated using scanning transmission electron microscopy. Additionally, X‐ray diffraction and temperature‐programmed reduction experiments confirmed that Ni and Co initially exist in an oxidic state within the SiO2 framework after production and later transform into an alloyed metallic state upon reduction with hydrogen, as confirmed by X‐ray photoelectron spectroscopy. A systematic comparison of the activity over a temperature range (323–1150 K) was performed using temperature scanning measurements. The highest intrinsic activity was found with the bimetallic Ni40Co60 particles.
The [(NH3)4Cu2O2]2+‐Peroxo Complex as the Key Intermediate for NH3‐SCR Activity and Deactivation of Cu‐CHA Catalysts.
Authors: Janssens Ton V.W. , Borfecchia Elisa , Lomachenko Kirill A. , Grönbeck Henrik , Berlier Gloria 
Published: May 2024

AbstractIn NH3‐SCR over Cu‐CHA catalysts in the low‐temperature range 150–300 °C, the activation of oxygen occurs via oxidation of a pair of mobile (NH3)2CuI‐complexes located in the cages of the zeolite. In this step, a reactive [(NH3)4Cu2O2]2+‐peroxo complex (μ‐η2,η2‐peroxo diamino dicopper(II)‐complex) is formed. The chemistry of this complex determines several catalytic properties of the Cu‐CHA catalyst. The reaction of NO with the [(NH3)4Cu2O2]2+‐peroxo complex governs the NH3‐SCR activity. A reaction of the [(NH3)4Cu2O2]2+‐peroxo complex with ammonia hinders the reaction of NO with the complex, thus leading to an inhibition of the NH3‐SCR reaction. Finally, the deactivation in presence of SO2 is due to a reaction of SO2 with the [(NH3)4Cu2O2]2+‐peroxo complex, leading to the formation of Cu−S compounds in the catalyst. In this review, the characterization and the reactions of the [(NH3)4Cu2O2]2+‐peroxo complex with NO, NH3, and SO2, and mean‐field kinetic models based on first principles calculations for NH3‐SCR activity and SO2 poisoning are discussed.
A Monometallic Bis(cyaphido) Complex
Authors: Levis Madeleine C. , Helm Monte L. , Turner John F. C. , Crossley Ian R. 
Published: May 2024

AbstractThe first example of a bis(cyaphido) complex, trans‐[Ru(dppe)2(C≡P)2], is described, unequivocally demonstrating the synthetic accessibility and stability of complexes that feature more than one cyaphido ligand. Synthesis is achieved from the precedent cation [Ru(dppe)2(C≡P)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiC≡P. The heteroleptic analogue trans‐[Ru(dppe)2(C≡N)(C≡P)] is also prepared from the same cation and NaCN; both cyaphido complexes are structurally characterized, enabling the first direct comparison of cyaphide with cyanide, its isoelectronic and isolobal counterpart. This demonstrates an enhanced π‐acidity for −C≡P over −C≡N, while computational studies reveal also a higher π‐donor character for the cyaphido ligand.