bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enhancing Photocatalytic CO2 Conversion through Oxygen‐Vacancy‐Mediated Topological Phase Transition
Authors: Yang Sudong , Guo Xu , Li Xiaoning , Wu Tianze , Zou Longhua , He Zhiying , Xu Qing , Zheng Junjie , Chen Lin , Wang Qingyuan , Xu Zhichuan J. 
Published: January 2024

AbstractWeak adsorption of gas reactants and strong binding of intermediates present a significant challenge for most transition metal oxides, particularly in the realm of CO2 photoreduction. Herein, we demonstrate that the adsorption can be fine‐tuned by phase engineering of oxide catalysts. An oxygen vacancy mediated topological phase transition in Ni‐Co oxide nanowires, supported on a hierarchical graphene aerogel (GA), is observed from a spinel phase to a rock‐salt phase. Such in situ phase transition empowers the Ni‐Co oxide catalyst with a strong internal electric field and the attainment of abundant oxygen vacancies. Among a series of catalysts, the in situ transformed spinel/rock‐salt heterojunction supported on GA stands out for an exceptional photocatalytic CO2 reduction activity and selectivity, yielding an impressive CO production rate of 12.5 mmol g−1 h−1 and high selectivity of 96.5 %. This remarkable performance is a result of the robust interfacial coupling between two topological phases that optimizes the electronic structures through directional charge transfer across interfaces. The phase transition process induces more Co2+ in octahedral site, which can effectively enhance the Co‐O covalency. This synergistic effect balances the surface activation of CO2 molecules and desorption of reaction intermediates, thereby lowering the energetic barrier of the rate‐limiting step.
Controlling Monoterpene Isomerization by Guiding Challenging Carbocation Rearrangement Reactions in Engineered Squalene‐Hopene Cyclases
Authors: Ludwig Julian , Curado‐Carballada Christian , Hammer Stephan C. , Schneider Andreas , Diether Svenja , Kress Nico , Ruiz‐Barragán Sergi , Osuna Sílvia , Hauer Bernhard 
Published: January 2024

AbstractThe interconversion of monoterpenes is facilitated by a complex network of carbocation rearrangement pathways. Controlling these isomerization pathways is challenging when using common Brønsted and Lewis acid catalysts, which often produce product mixtures that are difficult to separate. In contrast, natural monoterpene cyclases exhibit high control over the carbocation rearrangement reactions but are reliant on phosphorylated substrates. In this study, we present engineered squalene‐hopene cyclases from Alicyclobacillus acidocaldarius (AacSHC) that catalyze the challenging isomerization of monoterpenes with unprecedented precision. Starting from a promiscuous isomerization of (+)‐β‐pinene, we first demonstrate noticeable shifts in the product distribution solely by introducing single point mutations. Furthermore, we showcase the tuneable cation steering by enhancing (+)‐borneol selectivity from 1 % to >90 % (>99 % de) aided by iterative saturation mutagenesis. Our combined experimental and computational data suggest that the reorganization of key aromatic residues leads to the restructuring of the water network that facilitates the selective termination of the secondary isobornyl cation. This work expands our mechanistic understanding of carbocation rearrangements and sets the stage for target‐oriented skeletal reorganization of broadly abundant terpenes.
Spin‐state Conversion by Asymmetrical Orbital Hybridization in Ni‐doped Co3O4 to Boost Singlet Oxygen Generation for Microbial Disinfection
Authors: Duan Meilin , Huang Chao , Zhang Gong , Shi Hao , Zhang Pengfei , Li Limin , Xu Tong , Zhao Zhen , Fu Zhujun , Han Jingrui , Xu Yuanhong , Ding Xiaoteng 
Published: January 2024

AbstractSinglet oxygen (1O2) plays a significant role in environmental and biomedical disinfection fields. Electrocatalytic processes hold great potential for 1O2 generation, but remain challenging. Herein, a facile Ni doping converted spin‐state transition approach is reported for boosting 1O2 production. Magnetic analysis and theoretical calculations reveal that Ni occupied at the octahedral site of Co3O4 can effectively induce a low‐to‐high spin‐state transition. The high‐spin Ni−Co3O4 generate appropriate binding strength and enhance electron transfer between the Co centers with oxygen intermediates, thereby improving the catalytic activity of Ni−Co3O4 for effective generating 1O2. In neutral conditions, 1×106 CFU mL−1 Gram‐negative ESBL‐producing Escherichia coli (E. coli) could be inactivated by Ni−Co3O4 system within 5 min. Further antibacterial mechanisms indicate that 1O2 can lead to cell membrane damage and DNA degradation so as to irreversible cell death. Additionally, the developed Ni−Co3O4 system can effectively inactivate bacteria from wastewater and bioaerosols. This work provides an effective strategy for designing high‐spin electrocatalysis to boost 1O2 generation for disinfection process.
Switching from Thermally Activated Delayed Fluorescence in Single Crystals for Low‐Threshold Laser to Room‐temperature Phosphorescence in Amorphous‐Film for Highly Efficient OLEDs
Authors: Gong Hao , Song Yixing , He Jingping , Wang Ping , Xiang Yuhao , Li Shuai , Yao Jiannian , Liao Bo , Liao Qing , Fu Hongbing 
Published: January 2024

AbstractMetal‐organic phosphorescent complexes containing Ir or Pt are work horse in organic light‐emitting diode (OLED) technology, which can harvest both singlet and triplet excitons in electroluminescence (EL) owing to strong heavy‐atom effect. Recently, organic room‐temperature phosphorescence (ORTP) have achieved high photoluminescence quantum yield (PLQY) in rigid crystalline state, which, however, is unsuitable for OLED fabrication, therefore leading to an EL efficiency far low behind those of metal‐organic phosphorescent complexes. Here, we reported a luminescence mechanism switch from thermally activated delayed fluorescence (TADF) in single crystal microwires to ORTP in amorphous thin‐films, based on a tert‐butylcarbazole difluoroboron β‐diketonate derivative of DtCzBF2. Tightly packed and well‐faceted single‐crystal microwires exhibit aggregation induced emission (AIE), enabling TADF microlasers at 473 nm with an optical gain coefficient as high as 852 cm−1. In contrast, loosely packed dimers of DtCzBF2 formed in guest‐host amorphous thin‐films decrease the oscillator strength of fluorescence transition but stabilize triplets for ORTP with a PLQY up to 61 %, leading to solution‐processed OLEDs with EQE approaching 20 %. This study opens possibilities of low‐cost ORTP emitters for high performance OLEDs and future low‐threshold electrically injected organic semiconductor lasers (OSLs).
Molecular Crystals Constructed by Polar Molecular Cages: A Promising System for Exploring High‐performance Infrared Nonlinear Optical Crystals
Authors: Zhao Xin , Lin Chensheng , Wang Chao , Tian Haotian , Yan Tao , Li Bingxuan , Ye Ning , Luo Min 
Published: January 2024

AbstractPolar molecular crystals, with their densely stacked polar nonlinear optical (NLO) active units, are favored for their large second harmonic generation (SHG) responses and birefringence. However, their potential for practical applications as Infrared (IR) NLO materials has historically been underappreciated due to the weak inter‐molecular interaction forces that may compromise their physicochemical properties. In this study, we propose molecular crystals with polar molecular cages as a treasure‐house for the development of superior IR NLO materials and a representative system, binary chalcogenide molecular crystals, composed of [P4Sn] (n=3–9) polar molecular cages, is introduced. These crystals may not only achieve wide band gap, large SHG response, and birefringence in a single structure, but also exhibit favorable physicochemical properties. We subsequently obtained a polar molecular crystal, α‐P4S5, which demonstrated exceptional IR optical properties, including a strong SHG response (1.1×AGS), wide band gap (3.02 eV), large birefringence (0.134@2050 nm), and a broad transmission range (0.41–14.7 μm). Moreover, it showed excellent water resistance and hardness. These findings highlight the potential of polar molecular crystals as a promising platform for the development of high‐performance IR NLO materials.
Identification of long noncoding RNAs of silkworm at the early stage of Bombyx mori bidensovirus infection
Authors: Chen Yeping , Wang Zihe , Wu Chengyue , Li Hao , Qian Heying , Wang Mengdong , Wu Ping , Guo Xijie , Zhang Zhendong 
Published: January 2024

AbstractBombyx mori bidensovirus (BmBDV) is one of the most important pathogens of silkworm. It mainly infects midgut cells of silkworm and causes losses to the sericulture industry. Long noncoding RNAs (lncRNAs) have been reported to play an important role in the regulation of antiviral immune response in silkworm. To explore whether lncRNAs are involved in BmBDV infection and immune response of silkworm, we performed a comparative transcriptome analysis to identify the lncRNAs and mRNAs between the BmBDV infected and noninfected silkworm larvae at the early stage. A total of 16,069 genes and 974 candidate lncRNAs were identified, among which 142 messenger RNA (mRNAs) and four lncRNAs were differentially expressed (DE). Target gene prediction revealed that 142 DEmRNAs were coexpressed with four DElncRNAs, suggesting that the expression of mRNA is mainly affected through trans‐regulation activities. A regulatory network of DElncRNAs and DEmRNAs was constructed, showing that many genes targeted by different DElncRNAs are involved in metabolism and immunity, which implies that these genes and lncRNAs play an important role in the replication of BmBDV. Our results will help us to improve our understanding of lncRNA‐mediated regulatory roles in BmBDV infection, providing a new perspective for further exploring the interaction between host and BmBDV.
The Role of Aromatic Alcohol Additives on Asymmetric Organocatalysis Reactions: Insights from Theory
Authors: Banerjee Subhrashis , Vanka Kumar 
Published: January 2024

AbstractThe presence of an aromatic additive has been seen to enhance, often significantly, the enantioselectivity and yield in asymmetric organocatalysis. Considering their success across a dizzying range of organocatalysts and organic transformations, it would seem unlikely that a common principle exists for their functioning. However, the current investigations with DFT suggest a general principle: the phenolic additive sandwiches itself, through hydrogen bonding and π⋅⋅⋅π stacking, between the organocatalyst coordinated electrophile and nucleophile. This is seen for a wide range of experimentally reported systems. That such complex formation leads to enhanced stereoselectivity is then demonstrated for two cases: the cinchona alkaloid complex (BzCPD), catalysing thiocyanation (2‐naphthol additive employed), as well as for L‐pipecolicacid catalysing the asymmetric nitroaldol reaction with a range of nitro‐substituted phenol additives. These findings, indicating that dual catalysis takes place when phenolic additives are employed, are likely to have a significant impact on the field of asymmetric organocatalysis.
Non‐symmetrical sparking may hint “zits” on a pulsar surface
Authors: Wang Zhengli , Lu Jiguang , Jiang Jingchen , Cao Shunshun , Wang Weiyang , Liang Enwei , Xu Renxin 
Published: January 2024

AbstractPulsar electrodynamics could be relevant to the physics of stellar surface, which remains poorly understood for more than half a centenary and is difficult to probe due to the absence of direct and clear observational evidence. Nevertheless, highly sensitive telescopes (e.g., China's Five‐hundred‐meter Aperture Spherical radio Telescope, FAST) may play an essential role to solve the problem since the predicted surface condition would have quite different characteristics in some models of pulsar structure, especially after the establishment of the standard model of particle physics. For instance, small hills (or “zits”) may exist on solid strangeon star surface with rigidity, preferential discharge, that is, gap sparking, may occur around the hills in the polar cap region. In this work, with the 110‐min polarization observation of PSR B095008 targeted by FAST, we report that the gap sparking is significantly non‐symmetrical to the meridian plane on which the rotational and magnetic axes lie. It is then speculated that this asymmetry could be the result of preferential sparking around zits which might rise randomly on pulsar surface. Some polarization features of both single pulses and the mean pulse, as well as the cross‐correlation function of different emission regions, have also been presented.
The anatomical pattern of ductal arborization in parotid glands using cone‐beam computerized sialography
Authors: Amiel Tevel , Shauly Oren , Istoyler Ella Gilenson , Alterman Michael , Keshet Naama , Mazor Sigal , Pikovsky Anna , Aframian Doron J. , Joskowicz Leo , Nadler Chen 
Published: January 2024

AbstractCone‐Beam Computed Tomography‐Sialography (Sialo‐CBCT) is used to demonstrate salivary ductal structure. This study aimed to conduct a volumetric analysis of the anatomical morphology of Normal‐Appearing Glands (NAGs) in parotid sialo‐CBCT. Our retrospective study included 14 parotid sialo‐CBCT scans interpreted as NAGs in 11 patients with salivary gland impairment. The main duct length and width, as well as number and width of secondary and tertiary ducts were manually evaluated. We found that the main parotid duct showed an average width of 1.39 mm, 1.15 mm, and 0.98 mm, for the proximal, middle and distal thirds, respectively. The arborization pattern showed approximately 20% more tertiary (average number 11.1 ± 2.7) than secondary ducts (average number 9.0 ± 2.4) and approximately 8% narrower tertiary ducts (average width 0.65 ± 0.11 mm) compared to the secondary ducts (average width 0.77 ± 0.14 mm). Our anatomical analysis of NAGs in parotid sialo‐CBCT demonstrated progressive narrowing of the main duct and increasing arborization and decreasing lumen size starting from the primary to the tertiary ducts. This is the most updated study regarding the anatomy of the parotid glands as demonstrated in sialo‐CBCT. Our results may provide clinicians with the basic information for understanding aberration from normal morphology, as seen in salivary gland pathologies as well facilitate planning of treatment strategies, such as minimally invasive sialo‐endoscopies, commonly practiced today.
The incremental healthcare cost associated with cancer in Belgium: A registry‐based data analysis
Authors: Gorasso Vanessa , Vandevijvere Stefanie , Van der Heyden Johan , Pelgrims Ingrid , Hilderink Henk , Nusselder Wilma , Demoury Claire , Schmidt Masja , Vansteelandt Stijn , De Smedt Delphine , Devleesschauwer Brecht 
Published: January 2024

AbstractBackgroundSimilar to many countries, Belgium experienced a rapid increase in cancer diagnoses in the last years. Considering that a large part of cancer types could be prevented, our study aimed to estimate the annual healthcare burden of cancer per site, and to compare cost with burden of disease estimates to have a better understanding of the impact of different cancer sites in Belgium.MethodsWe used nationally available data sources to estimate the healthcare expenditure. We opted for a prevalence‐based approach which measures the disease attributable costs that occur concurrently for 10‐year prevalent cancer cases in 2018. Average attributable costs of cancer were computed via matching of cases (patients with cancer by site) and controls (patients without cancer). Years of life lost due to disability (YLD) were used to summarize the health impact of the selected cancers.ResultsThe highest attributable cost in 2018 among the selected cancers was on average €15,867 per patient for bronchus and lung cancer, followed by liver cancer, pancreatic cancer, and mesothelioma. For the total cost, lung cancer was the most costly cancer site with almost €700 million spent in 2018. Lung cancer was followed by breast and colorectal cancer that costed more than €300 million each in 2018.ConclusionsIn our study, the direct attributable cost of the most prevalent cancer sites in Belgium was estimated to provide useful guidance for cost containment policies. Many of these cancers could be prevented by tackling risk factors such as smoking, obesity, and environmental stressors.
Enantioselective Total Synthesis of the Morphogen (−)‐Thallusin and Mediated Uptake of Fe(III) into the Green Seaweed Ulva
Authors: Wienecke Paul , Ulrich Johann F. , Morales‐Reyes Cristina F. , Dhiman Seema , Wichard Thomas , Arndt Hans‐Dieter 
Published: January 2024

AbstractA fully enantioselective, catalytic synthesis of the algal morphogen (−)‐thallusin using polyene cyclization chemistry is reported. The synthesis features dedicated precursor design, introduction of a TMS‐substituted arene as a regioselective terminator, very high enantiomer excess (ee) on gram scale, and productive scaffold functionalization. Furthermore, an ee determination methodology of thallusin samples was developed, and the ee of biosynthesized thallusin was determined. Fe(III)‐uptake studies demonstrated that the cellular uptake of iron facilitated by thallusin derivatives was independent of their morphogenic activity, suggesting their active import via siderophore transporters as a shuttle system.
Neural connections of the torus semicircularis in the adult Zebrafish
Authors: Yáñez Julián , Eguiguren Maider Hernández , Anadón Ramón 
Published: January 2024

AbstractThe torus semicircularis (TS) of teleosts is a key midbrain center of the lateral line and acoustic sensory systems. To characterize the TS in adult zebrafish, we studied their connections using the carbocyanine tracers applied to the TS and to other related nuclei and tracts. Two main TS nuclei, central and ventrolateral, were differentiable by their afferent connections. From central TS, (TSc) numerous toropetal cells were labeled bilaterally in several primary octaval nuclei (anterior, magnocellular, descending, and posterior octaval nuclei), in the secondary octaval nucleus, in the caudal octavolateralis nucleus, and in the perilemniscular region. In the midbrain, numerous toropetal cells were labeled in the contralateral TSc. In the diencephalon, toropetal cells labeled from the TSc were observed ipsilaterally in the medial prethalamic nucleus and the periventricular posterior tubercle nucleus. TSc toropetal neurons were also labeled bilaterally in the hypothalamic anterior tuberal nucleus (ATN) and ipsilaterally in the parvicellular preoptic nucleus but not in the telencephalon. Tracer application to the medial octavolateralis nucleus revealed contralateral projections to the ventrolateral TS (TSvl), whereas tracer application to the secondary octaval nucleus labeled fibers bilaterally in TSc and neurons in rostral TSc. The TSc sends ascending fibers to the ipsilateral lateral preglomerular region that, in turn, projects to the pallium. Application of DiI to the optic tectum labeled cells and fibers in the TSvl, whereas application of DiI to the ATN labeled cells and fibers in the TSc. These results reveal that the TSvl and TSc are mainly related with the mechanosensory lateral line and acoustic centers, respectively, and that they show different higher order connections.
Protein Deceleration and Sequencing Using Si3N4‐CNT Hybrid Nanopores
Authors: Si Wei , Zhang Zhen , Chen Jiayi , Wu Gensheng , Zhang Yin , Sha Jingjie 
Published: January 2024

AbstractProtein sequencing is crucial for understanding the complex mechanisms driving biological functions and is of utmost importance in molecular diagnostics and medication development. Nanopores have become an effective tool for single molecule sensing, however, the weak charge and non‐uniform charge distribution of protein make capturing and sensing very challenging, which poses a significant obstacle to the development of nanopore‐based protein sequencing. In this study, to facilitate capturing of the unfolded protein, highly charged peptide was employed in our simulations, we found that the velocity of unfolded peptide translocating through a hybrid nanopore composed of silicon nitride membrane and carbon nanotube is much slower compared to bare silicon nitride nanopore, it is due to the significant interaction between amino acids and the surface of carbon nanotube. Moreover, by introducing variations in the charge states at the boundaries of carbon nanotube nanopores, the competition and combination of the electrophoretic and electroosmotic flows through the nanopores could be controlled, we then successfully regulated the translocation velocity of unfolded proteins through the hybrid nanopores. The proposed hybrid nanopore effectively retards the translocation velocity of protein through it, facilitates the acquisition of ample information for accurate amino acid identification.
An ab Initio Study of High‐Energetic Trioxatriazinane Derivatives: Conformational Analysis, Nitrogen Inversion, Heats of Formation, Dissociation Reaction, and Dimerization
Authors: Alkorta Ibon , Elguero José 
Published: January 2024

AbstractHigh‐energetic materials belong to two main classes: propellants and explosives. The still rather unexplored family of 1,3,5,2,4,6‐trioxatriazinanes, N3O3R3, has a representative of each class. We have selected three compounds, R = H, R = CH3 and R = NO2, this last compound being known as TNTOTA, “trinitro‐trioxa‐triazinane”. Of these compounds we have studied the conformational analysis, the nitrogen inversion, the heats of formation, and the dissociation reaction into the three monomers. In addition, the corresponding 1,3,2,4‐dioxadiazetidines (N2O2R2) have also been studied.
Identification of Core‐Fucosylated Glycoproteins by Single‐Step Truncation of N‐Glycans
Authors: Min Yao , Zhao Xinyuan , Ying Wantao 
Published: January 2024

AbstractAlpha‐1,6 core fucosylation (CF) is a unique glycoform of N‐glycans, and studies showed that CF modifications are involved in the occurrence and progression of various diseases and may provide potential disease biomarkers. Current strategies for the CF glycoproteome are often based on multistep enrichment of glycoproteins or glycopeptides and sequential cleavage with different glycosidases to truncate the N‐glycans. Although the detection ability of low‐abundance glycoproteins is improved, sample loss, high cost, and the time‐consuming multistep operation also affect the reproducibility of results and the practicality of the method. Here we developed a single‐step truncation (SST) strategy and evaluated its potential for the CF glycoproteome of human serum. The SST strategy has the advantages of fewer operational steps, lower cost, higher number of identifications, and better quantitative stability compared with previous approaches and provides an efficient solution for large‐scale quantitative analysis of the CF glycoproteome. © 2024 Wiley Periodicals LLC.Basic Protocol 1: Single‐step truncation strategy for core fucosylation glycoproteome analysis in human serumBasic Protocol 2: Liquid chromatography–tandem mass spectrometry quantification of site‐specific core fucosylation glycopeptidesAlternate Protocol: Pretreatment of cellular samples of core fucosylation glycoproteome with single‐step truncation strategy