bluuebunny/crossref_metadata_2025_split huggingface dataset:
In Vivo Fluorescence Imaging‐Guided Development of Near‐Infrared AIEgens
Authors: Yu Jia , Jiang Guoyu , Wang Jianguo 
Published: January 2023

AbstractIn vivo fluorescence imaging has received extensive attention due to its distinguished advantages of excellent biosafety, high sensitivity, dual temporal‐spatial resolution, real‐time monitoring ability, and non‐invasiveness. Aggregation‐induced emission luminogens (AIEgens) with near‐infrared (NIR) absorption and emission wavelengths are ideal candidate for in vivo fluorescence imaging for their large Stokes shift, high brightness and superior photostability. NIR emissive AIEgens provide deep tissue penetration depth as well as low interference from tissue autofluorescence. Here in this review, we summarize the molecular engineering strategies for constructing NIR AIEgens with high performances, including extending π‐conjugation system and strengthen donor (D)‐acceptor (A) interactions. Then the encapsulation strategies for increasing water solubility and biocompatibility of these NIR AIEgens are highlighted. Finally, the challenges and prospect of fabricating NIR AIEgens for in vivo fluorescence imaging are also discussed. We hope this review would provide some guidelines for further exploration of new NIR AIEgens.
Hepatic effect of subacute Fe2O3 nanoparticles exposure in Sprague–Dawley rats by LC–MS/MS based lipidomics
Authors: Ren Dongxia , Shao Huangfang , Liu Yang , Wang Xue , Li Yulin , Li Yun 
Published: January 2023

AbstractFe2O3 nanoparticles (Fe2O3 NPs) are one of the components of food additives numbered E172 and have been widely used as food pigments to color sweets. Although a large number of studies have reported that Fe2O3 NPs could induce hepatotoxicity, the pathogenesis is still unclear, especially the subacute effects on the metabolic network after oral exposure. Therefore, it is necessary to define a highly sensitive strategy to investigate the potential effects of Fe2O3 NPs and the mechanism. In this study, an animal experiment showed that Fe2O3 NPs had no obvious toxic effects on body weight, histopathology and oxide stress. In order to further investigate the potential effects of Fe2O3 NPs in vivo, a more sensitive LC–MS/MS‐based lipidomic study was performed. The results of multivariate statistical analysis and western blot analysis showed that Fe2O3 NP exposure significantly affects the hepatic glycerophospholipid metabolism, decreasing triacylglycerol, diglyceride, lysophosphatidylethanolamine and free fatty acids, and increasing phosphatidylcholine, lysophosphatidylinositol and coenzyme Q9. These data provide further insight into the hepatic subacute effects of Fe2O3 NPs obtained by conventional toxicology methods.
Higher prevalence of idiopathic normal pressure hydrocephalus‐like MRI features in progressive supranuclear palsy: An imaging reminder of atypical parkinsonism
Authors: Fu Mu‐Hui , Huang Chih‐Cheng , Wu Kay L. H. , Chen Ying‐Fa , Kung Yu‐Chih , Lee Cheng‐Chang , Liu Jia‐Shou , Lan Min‐Yu , Chang Yung‐Yee 
Published: January 2023

AbstractObjectivesThe classic triad of idiopathic normal pressure hydrocephalus (NPH) encompass gait disturbance, cognitive impairment, and urinary incontinence. These symptoms overlap with parkinsonism but with distinct treatment. Lacking applicable differentiation also hampers the prediction to therapeutic response. Here, we try to clarify this issue among different Parkinsonian syndromes and propose some innovative thinking while approaching a patient with parkinsonism and hydrocephalus concomitantly.MethodsTwenty‐four patients with clinical probable multiple system atrophy (MSA), 34 with probable progressive supranuclear palsy (PSP), and 58 with sex‐ and age‐matched Parkinson's disease (PD) were enrolled. Evans’ index (EI), callosal angle (CA), antero‐posterior (AP) diameter of the midbrain, length of the midbrain tegmentum diameter (MBTegm), and disproportionately enlarged subarachnoid space hydrocephalus (DESH) were evaluated using the conventional MRI. Logistic regression was applied to identify the independent variables in hydrocephalus.ResultsPatients with PSP had higher mean EI than those with MSA and PD. Around 38.2% of patients with PSP had accompanied hydrocephalus (EI > 0.3). Parkinsonism subtypes (PD, MSA, or PSP), AP diameter of the midbrain, and MBTegm were significantly different among patients with and without hydrocephalus. After regression analysis, parkinsonism subtype stood out to be the most key risk factor of hydrocephalus. The comparison between patients with PSP with and without hydrocephalus did not disclose specific clinical characteristics or risk factors.ConclusionsThis study demonstrates that the presence of NPH‐like MRI features is much higher in PSP patients, and this tendency is decided upon the determination of parkinsonism subtype. Sharing pathophysiological characteristics in these two diseases is implied. More diagnostic tools are needed to better differentiate the two diseases and decide the treatment. To closely observe hydrocephalic parkinsonism patients and well inform the possible limited shunting benefits if PSP core features appear, will be more pivotal and practical at present clinical practice.
Photocatalytic C−H Amination of Electron‐rich Aromatic Hydrocarbons by Carbon Nitride Photocatalysis
Authors: Mazzanti Stefano , Markushyna Yevheniia , Savateev Oleksandr 
Published: January 2023

AbstractConstruction of C−N bond is a central process in organic synthesis. Typically, it relies on noble‐metal catalysts and prefunctionalized substrates, such as aryl halides. Alternative and more appealing method is a direct C−H amination of hydrocarbons that is based on intrinsic reactivity of the in situ generated radical cations, which are more electrophilic compared to their closed‐shell precursors. In this work, we employ potassium poly(heptazine imide) (K‐PHI), a graphitic carbon nitride semiconductor, to enable C−H amination of electron rich aromatic hydrocarbons with NH3 and pyrazole under oxidative conditions. Screening of oxidants, indicate those molecules that are able to accept not only electrons, but also protons, such as O2, PhNO2 and Ph2S2, mediate the reaction. As such, multisite proton‐coupled electron transfer (MS‐PCET) from the photocharged state of K‐PHI to the acceptor of electrons and protons is the key element in the studied photocatalytic process.
Coordinating Additives as Activity Modulators in Diiodo Latent Olefin Metathesis Catalysts
Authors: Nechmad Noy B. , Iudanov Keren , Tarannam Naziha , Kobernik Victoria , Kozuch Sebastian , Lemcoff N. Gabriel 
Published: January 2023

AbstractThe ruthenium alkylidene catalyzed ring‐closing metathesis (RCM) of 5‐membered rings is an intramolecular reaction that is highly favored due to entropic and enthalpic contributions. Counterintuitively, by using trifluoromethyl sulfur‐chelated ruthenium benzylidene (Ru−SCF3−I), RCM of a diene with a hindered dimethyl terminus, diethyl 2‐allyl‐2‐(3‐methylbut‐2‐en‐1‐yl) malonate (S1), could be achieved at high concentrations but not at low concentrations. This finding led to the discovery that several additives, including ethyl acetate, significantly enhance the latent catalyst's activity. DFT computations and NMR control experiments suggest that additive coordination influences the catalytic cycle. Moreover, the “ethyl acetate effect” was studied in ring‐opening metathesis polymerizations (ROMP), providing a more efficient initiation when the reactions are run in environmentally friendly ethyl acetate as the solvent. The strong influence of simple coordinating additives (sometimes present in the substrate itself) on the activation of latent catalysts provides important insights into the reaction mechanism and opens a doorway towards improving the efficiency of these types of catalysts.
Enhancement of NIR‐Absorbing Ability of Bis(diarylmethylium)‐Type Dicationic Dyes Based on an Ortho‐Substitution Strategy.
Authors: Harimoto Takashi , Suzuki Takanori , Ishigaki Yusuke 
Published: January 2023

AbstractElectrochromic systems capable of switching near‐infrared (NIR) absorption are fascinating from the viewpoint of applications in the materials and life sciences. Although 11,11,12,12‐tetraaryl‐9,10‐anthraquinodimethanes (AQDs) with a folded form undergo one‐stage two‐electron oxidation to produce twisted dicationic dyes exhibiting NIR absorption, there is a need to establish a design strategy that can enhance the NIR‐absorbing abilities of the corresponding dicationic dyes. In this study, we designed and synthesized a series of AQD derivatives with various substituents introduced at the ortho‐position(s) of the 4‐methoxyphenyl group. X‐ray and spectroscopic analyses revealed that NIR‐absorbing properties can be changed by introduction of the ortho‐substituents. Thus, control of the steric and electronic effects of the ortho‐substituents on the 4‐methoxyphenyl groups was demonstrated to be an effective strategy for fine‐tuning of the HOMO and LUMO levels for neutral AQDs and twisted dications, respectively, resulting in the modification of electrochemical and spectroscopic properties under an “ortho‐substitution strategy”.
Synthesis of 9,10‐Phenanthrenes via Rh(III)‐Catalyzed [4+2] Annulation of 2‐Biphenylboronic Acids with Diazo Compounds
Authors: Tian Miaomiao , Yang Lingyun , Liu Bingxian , Chang Junbiao 
Published: January 2023

Comprehensive SummaryA Rh(III)‐catalyzed, transmetalation triggered C—H activation/annulation of 2‐biphenylboronic acids with diazo compounds from β‐keto esters or 1,3‐dicarboxylates has been developed, leading to the synthesis of two kinds of 9,10‐phenanthrenes. Notably, a rhodacyle was synthesized by treating the rhodium catalyst with stoichiometric amounts of 2‐biphenylboronic acids and pyridine, which was further verified to be active for the catalytic system. The reactions proceeded under redox‐neutral and air‐tolerant conditions to produce a series of all‐carbon six‐membered rings with high efficiency.
Switching of Organic Fluorophores by Glycerol‐sulfite Interactions for Single‐Molecule Super‐Resolution Microscopy**
Authors: Engdahl Anders Kokkvoll , Grauberger Oleg , Brockhinke Andreas , Schüttpelz Mark , Huser Thomas 
Published: January 2023

AbstractPhotoinduced off‐switching of organic fluorophores is used in super‐resolution microscopy to separate and localize single fluorescent molecules. However, this method typically relies on the use of complex imaging buffers that make use of enzymatic oxygen scavengers to remove oxygen and primary thiols to reversibly reduce excited fluorophores to a non‐fluorescent state. Here, we show that the interactions between sodium sulfite and glycerol can also be used for efficient switching of common organic fluorophores. The addition of glycerol to the imaging buffer allows us to tune the dye switching from intermittent fluorescence to the off‐state. We additionally show that sodium sulfite‐glycerol‐based buffers are especially useful for imaging at low laser illumination intensities in high‐refractive index solutions and samples embedded in agarose gel. This significantly simplifies the implementation of different super‐resolution microscopy modalities such as direct STochastic Optical Reconstruction Microscopy (dSTORM) and Super‐resolution Optical Fluctuation Imaging (SOFI).
Genomic prediction of threshability in naked barley
Authors: Massman Chris , Meints Brigid , Hernandez Javier , Kunze Karl , Smith Kevin P. , Sorrells Mark E. , Hayes Patrick M. , Gutierrez Lucia 
Published: January 2023

AbstractThreshability, defined here as the propensity of grains to lose their hull after harvest, is a key trait in naked barley (Hordeum vulgare L.). While threshability is a defining characteristic of naked grains and has been found to be associated with grain size and shape, its genetic architecture is poorly described. The goals of this study were to identify quantitative trait loci associated with threshability and evaluate their utility as covariates in genomic prediction models. A genome‐wide association study identified two loci on chromosomes 2H and 3H associated with threshability. The locus on chromosome 2H accounted for 9.9% of the phenotypic variance explained (PVE). The locus on chromosomes 3H accounted for 7.8% of the PVE. With effects on threshability of 0.18 and 0.29 for each marker, respectively, these markers could have a limited impact when implemented in marker‐assisted selection. Predictive ability for threshability was 0.842 using a structured genomic best linear unbiased prediction model. Incorporation of the markers with significant associations as covariates in the model did not improve predictive ability. Predictive ability was improved by the use of a multi‐trait model including grain test weight. The high predictive ability for threshability overall indicate that genomic selection would be useful in selection for threshability in naked barley.
Impacts of delta and omicron variants on inactivated SARS‐CoV‐2 vaccine‐induced T cell responses in patients with autoimmune diseases and healthy controls
Authors: Wang Shuyi , Li Jin , Wang Shuang , Ye Yujin , Li Mengyuan , Liu Yihao , Chen Binfeng , Lai Yimei , Li Liubing , Zhuang Lili , Peng Sui , Yang Niansheng , Zhang Hui , Xiao Haipeng 
Published: January 2023

AbstractBackgroundSevere acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) infection causes coronavirus disease 2019 (COVID‐19), which is still devastating economies and communities globally. The increasing infections of variants of concern (VOCs) in vaccinated population have raised concerns about the effectiveness of current vaccines. Patients with autoimmune diseases (PAD) under immunosuppressant treatments are facing higher risk of infection and potentially lower immune responses to SARS‐CoV‐2 vaccination.MethodsBlood samples were collected from PAD or healthy controls (HC) who finished two or three doses of inactivated vaccines. Spike peptides derived from wild‐type strain, delta, omicron BA.1 were utilised to evaluate T cell responses and their cross‐recognition of delta and omicron in HC and PAD by flow cytometry and ex vivo IFNγ‐ELISpot.ResultsWe found that inactivated vaccine‐induced spike‐specific memory T cells were long‐lasting in both PAD and HC. These spike‐specific T cells were highly conserved and cross‐recognized delta and omicron. Moreover, a third inactivated vaccine expanded spike‐specific T cells that responded to delta and omicron spike peptides substantially in both PAD and HC. Importantly, the polyfunctionality of spike‐specific memory T cells was preserved in terms of cytokine and cytotoxic responses. Although the extent of T cell responses was lower in PAD after two‐dose, T cell responses were boosted to a greater magnitude in PAD by the third dose, bringing comparable spike‐specific T cell immunity after the third dose.ConclusionInactivated vaccine‐induced spike‐specific T cells remain largely intact against delta and omicron variants. This study expands our understanding of inactivated vaccine‐induced T cell responses in PAD and HC, which could have important indications for vaccination strategy.
New Intermetalloid Ge9‐clusters with Copper and Gold: Filling Vacancies in the Cluster Chemistry of [Ge9(Hyp)3]− (Hyp=Si(SiMe3)3)
Authors: Gienger Christian , Schynowski Leah , Schaefer Janis , Schrenk Claudio , Schnepf Andreas 
Published: January 2023

AbstractWe present a series of new intermetalloid clusters (R3P)CuGe9((Hyp)3, (R=Me, Et, iPr, nBu, tBu) (Hyp=Si(SiMe3)3) (R3P)AuGe9(Hyp)3MGe9(Hyp)3 (R=Ph, Me; M=Au, Cu). In conjunction with already known clusters, these give new insights into the bonding situation of metal bridged Ge9 clusters as well as a better understanding of the formation of these clusters. Additionally, the intermetalloid clusters with the smallest phosphine PMe3 show new bonding motives.
Strapped Porphyrins as Model Systems for Atropisomeric Photosensitizer Drugs
Authors: Donohoe Claire , Charisiadis Asterios , Maguire Sophie , Twamley Brendan , Schaberle Fábio A. , Gomes‐da‐Silva Lígia C. , Senge Mathias O. 
Published: January 2023

AbstractThe time dependence of atropisomer interconversion has limited the pursuit of single atropisomer drug candidates, even in circumstances where one atropisomer presents favorable biological activity over another. Moderate interconversion energy barriers risk compromising drug stability. As a result, examples of atropisomerically pure drugs in current clinical use are rare. However, in recent years, there has been a shift towards the development of single, stable atropisomer drug candidates with enhanced activity. Consequently, development of methods which effectively restrict rotation in a configuration which favors activity is highly beneficial. The picket fence porphyrin α4 atropisomer configuration has been previously demonstrated to improve the cell internalization of the pre‐clinical drug, redaporfin, applied in photodynamic therapy. In this work, the α4 configuration was modelled with novel porphyrin photosensitizers through strapped moieties which effectively fixed the atropisomeric configuration. The stable cis‐αα configuration demonstrated enhanced cell membrane permeation, effectively predicting the behavior of the α4 configuration and indicates that strapped porphyrins can serve as stable model systems for the investigation of photoactive drugs.
Analysis and comparison of boundary condition variants in the free‐surface lattice Boltzmann method
Authors: Schwarzmeier Christoph , Rüde Ulrich 
Published: January 2023

AbstractThe accuracy of the free‐surface lattice Boltzmann method (FSLBM) depends significantly on the boundary condition employed at the free interface. Ideally, the chosen boundary condition balances the forces exerted by the liquid and gas pressure. Different variants of the same boundary condition are possible, depending on the number and choice of the particle distribution functions (PDFs) to which it is applied. This study analyzes and compares four variants, in which (i) the boundary condition is applied to all PDFs oriented in the opposite direction of the free interface's normal vector, including or (ii) excluding the central PDF. While these variants overwrite existing information, the boundary condition can also be applied (iii) to only missing PDFs without dropping available data or (iv) to only missing PDFs but at least three PDFs as suggested in the literature. It is shown that neither variant generally balances the forces exerted by the liquid and gas pressure at the free surface. The four variants' accuracy was compared in five different numerical experiments covering various applications. These include a standing gravity wave, a rectangular and cylindrical dam break, a rising Taylor bubble, and a droplet impacting a thin pool of liquid. Overall, variant (iii) was substantially more accurate than the other variants in the numerical experiments performed in this study.
Mechanisms of speed encoding in the human middle temporal cortex measured by 7T fMRI
Authors: Gaglianese Anna , Fracasso Alessio , Fernandes Francisco G. , Harvey Ben , Dumoulin Serge O. , Petridou Natalia 
Published: January 2023

AbstractPerception of dynamic scenes in our environment results from the evaluation of visual features such as the fundamental spatial and temporal frequency components of a moving object. The ratio between these two components represents the object's speed of motion. The human middle temporal cortex hMT+ has a crucial biological role in the direct encoding of object speed. However, the link between hMT+ speed encoding and the spatiotemporal frequency components of a moving object is still under explored. Here, we recorded high resolution 7T blood oxygen level‐dependent BOLD responses to different visual motion stimuli as a function of their fundamental spatial and temporal frequency components. We fitted each hMT+ BOLD response with a 2D Gaussian model allowing for two different speed encoding mechanisms: (1) distinct and independent selectivity for the spatial and temporal frequencies of the visual motion stimuli; (2) pure tuning for the speed of motion. We show that both mechanisms occur but in different neuronal groups within hMT+, with the largest subregion of the complex showing separable tuning for the spatial and temporal frequency of the visual stimuli. Both mechanisms were highly reproducible within participants, reconciling single cell recordings from MT in animals that have showed both encoding mechanisms. Our findings confirm that a more complex process is involved in the perception of speed than initially thought and suggest that hMT+ plays a primary role in the evaluation of the spatial features of the moving visual input.
Role of signal transduction pathways in IL‐1β‐induced apoptosis: Pathological and therapeutic aspects
Authors: Wang Peixuan , Qian Hong , Xiao Manxue , Lv Jingwen 
Published: January 2023

AbstractBackgroundInterleukin‐1β (IL‐1β) is a pro‐inflammatory cytokine mainly produced by monocytes and macrophages with a wide range of biological effects. Evidence has shown that IL‐1β plays a vital role in the process of apoptosis; however, the specific mechanisms, by which IL‐1β induces apoptosis, vary due to different cellular and experimental conditions. Therefore, this present reviewstudy aimed to systematically review the association between the molecular mechanisms of IL‐1β‐induced apoptosis in pathological processes and the role of signaling pathways. This article also sought to briefly investigate the potential of signaling pathway‐targeted therapy in the prevention and treatment of disease.MethodsThis is a literature review article. The present discourse aim is first to scrutinize and assess the available literature on IL‐1β and apoptosis. The relevant studies using the keywords of “IL‐1β‐induced apoptosis” and “signaling pathways” were searched in the databases of PubMed, Scopus, Google Scholar, and Web of Science. Gathered relevant material, and extracted information was then assessed.ResultsIL‐1β can induce apoptosis in various types of cells under different external stimuli via the mitochondrial pathway, death receptor pathway and endoplasmic reticulum pathway, and that the different pathways are often interconnected. The NF‐kB signaling pathway, p38MAPK, and JNK signaling pathways mainly play a proapoptotic part, and the ERK1/2 pathway has a bidirectional role in regulating apoptosis, while activation of the PI3K‐Akt signaling pathway can inhibit apoptosis.ConclusionThis review indicates that IL‐1β‐induced apoptosis plays an important role in pathogenesis and development of pathology of many inflammatory diseases. Elucidating the role of the signaling pathways will aid the development of targeted therapeutic treatments.