bluuebunny/crossref_metadata_2025_split huggingface dataset:
The quantity and quality of cardiovascular fat at mid‐life and future cognitive performance among women: The SWAN cardiovascular fat ancillary study
Authors: Qi Meiyuzhen , Janssen Imke , Barinas‐Mitchell Emma , Budoff Matthew , Brooks Maria M. , Karlamangla Arun S. , Derby Carol A. , Chang Chung‐Chou H. , Shields Kelly J. , El Khoudary Samar R. 
Published: May 2023

AbstractINTRODUCTIONCardiovascular fat is a novel risk factor that may link to dementia. Fat volume and radiodensity are measurements of fat quantity and quality, respectively. Importantly, high fat radiodensity could indicate healthy or adverse metabolic processes.METHODSThe associations of cardiovascular fat (including epicardial, paracardial, and thoracic perivascular adipose tissue [PVAT]) quantity and quality assessed at mean age of 51 with subsequent cognitive performance measured repeatedly over 16 years of follow‐up were examined using mixed models among 531 women.RESULTSHigher thoracic PVAT volume was associated with a higher future episodic memory (β[standard error (SE)] = 0.08 [0.04], P = 0.033), while higher thoracic PVAT radiodensity with lower future episodic (β[SE] = −0.06 [0.03], P = 0.045) and working (β[SE] = −0.24 [0.08], P = 0.003) memories. The latter association is prominent at higher volume of thoracic PVAT.DISCUSSIONMid‐life thoracic PVAT may have a distinct contribution to future cognition possibly due to its distinct adipose tissue type (brown fat) and anatomical proximity to the brain circulation.HIGHLIGHTS
Higher mid‐life thoracic perivascular adipose tissue (thoracic PVAT) volume is related to a better future episodic memory in women.
Higher mid‐life thoracic PVAT radiodensity is related to worse future working and episodic memories.
Negative association of high thoracic PVAT radiodensity with working memory is prominent at higher thoracic PVAT volume.
Mid‐life thoracic PVAT is linked to future memory loss, an early sign of Alzheimer's disease.
Mid‐life women's epicardial and paracardial fat are not related to future cognition.
Longitudinal changes in Alzheimer's‐related plasma biomarkers and brain amyloid
Authors: Bilgel Murat , An Yang , Walker Keenan A. , Moghekar Abhay R. , Ashton Nicholas J. , Kac Przemysław R. , Karikari Thomas K. , Blennow Kaj , Zetterberg Henrik , Jedynak Bruno M. , Thambisetty Madhav , Ferrucci Luigi , Resnick Susan M. 
Published: May 2023

AbstractINTRODUCTIONUnderstanding longitudinal plasma biomarker trajectories relative to brain amyloid changes can help devise Alzheimer's progression assessment strategies.METHODSWe examined the temporal order of changes in plasma amyloid‐β ratio (), glial fibrillary acidic protein (GFAP), neurofilament light chain (NfL), and phosphorylated tau ratios (, ) relative to 11C‐Pittsburgh compound B (PiB) positron emission tomography (PET) cortical amyloid burden (PiB−/+). Participants (n = 199) were cognitively normal at index visit with a median 6.1‐year follow‐up.RESULTSPiB groups exhibited different rates of longitudinal change in . Change in brain amyloid correlated with change in GFAP (r = 0.5, 95% CI = [0.26, 0.68]). The greatest relative decline in (−1%/year) preceded brain amyloid positivity by 41 years (95% CI = [32, 53]).DISCUSSIONPlasma may begin declining decades prior to brain amyloid accumulation, whereas p‐tau ratios, GFAP, and NfL increase closer in time.HIGHLIGHTS
Plasma declines over time among PiB− but does not change among PiB+.
Phosphorylated‐tau to Aβ42 ratios increase over time among PiB+ but do not change among PiB−.
Rate of change in brain amyloid is correlated with change in GFAP and neurofilament light chain.
The greatest decline in may precede brain amyloid positivity by decades.
Chemical Modification of a Bacterial Siderophore by a Competitor in Dual‐Species Biofilms
Authors: Uzi‐Gavrilov Shaked , Tik Zohar , Sabti Omer , Meijler Michael M. 
Published: May 2023

AbstractChemical communication between competing bacteria in multi‐species environments often enables both species to adapt and survive, and perhaps even thrive. P. aeruginosa and S. aureus are two bacterial pathogens found in natural biofilms, especially in the lungs of cystic fibrosis (CF) patients, where recent studies showed that there is often cooperation between the two species, leading to increased disease severity and antibiotic resistance. However, the mechanisms behind this cooperation are poorly understood. In this study, we analyzed co‐cultured biofilms in various settings, and we applied untargeted mass spectrometry‐based metabolomics analyses, combined with synthetic validation of candidate compounds. We unexpectedly discovered that S. aureus can convert pyochelin into pyochelin methyl ester, an analogue of pyochelin with reduced affinity for iron (III). This conversion allows S. aureus to coexist more readily with P. aeruginosa and unveils a mechanism underlying the formation of robust dual‐species biofilms.
Highly Selective Catalytic Oxi‐upcycling of Polyethylene to Aliphatic Dicarboxylic Acid under a Mild Hydrogen‐Free Process
Authors: Wang Kaili , Jia Rongrong , Cheng Ping , Shi Liyi , Wang Xiang , Huang Lei 
Published: May 2023

AbstractA low‐temperature hydrogen‐free process for upcycling polyethylene (PE) plastics into aliphatic dicarboxylic acid is developed using a heterogeneous catalyst Ru/TiO2. The low‐density PE (LDPE) conversion can reach 95 % in 24 h under a pressure of 1.5 MPa air at 160 °C with 85 % of the liquid product yield, which mainly is low molecular weight aliphatic dicarboxylic acid. Excellent performances can be also achieved for different PE feedstocks. This catalytic oxi‐upcycling process paving a new way of upcycling polyethylene waste.
Dynamic Axial‐to‐Helical Communication Mechanism in Poly[(allenylethynylenephenylene)acetylene]s under External Stimuli
Authors: Lago‐Silva María , Cid María Magdalena , Quiñoá Emilio , Freire Félix 
Published: May 2023

AbstractHelix inversion in chiral dynamic helical polymers is usually achieved by conformational changes at the pendant groups induced through external stimuli. Herein, a different mechanism of helix inversion in poly(phenylacetylene)s (PPAs) is presented, based on the activation/deactivation of supramolecular interactions. We prepared poly[(allenylethynylenephenylene)acetylene]s (PAEPAs) in which the pendant groups are conformationally locked chiral allenes. Therefore, their substituents are placed in specific spatial orientations. As a result, the screw sense of a PAEPA is fixed by the allenyl substituent with the optimal size/distance relationship to the backbone. This helical sense command can be surpassed by supramolecular interactions between another substituent on the allene and appropriate external stimuli, such as amines. So, a helix inversion occurs through a novel axial‐to‐helical communication mechanism, opening a new scenario for taming the helices of chiral dynamic helical polymers.
Chemically Gradient Hydrogen‐Bonded Organic Framework Crystal Film
Authors: Mohammed Abdul Khayum , Raya Jésus , Pandikassala Ajmal , Addicoat Matthew A. , Gaber Safa , Aslam Mohamed , Ali Liaqat , Kurungot Sreekumar , Shetty Dinesh 
Published: May 2023

AbstractHydrogen‐bonded organic frameworks (HOFs) are ordered supramolecular solid structures, however, nothing much explored as centimetre‐scale self‐standing films. The fabrication of such crystals comprising self‐supported films is challenging due to the limited flexibility and interaction of the crystals, and therefore studies on two‐dimensional macrostructures of HOFs are limited to external supports. Herein, we introduce a novel chemical gradient strategy to fabricate a crystal‐deposited HOF film on an in situ‐formed covalent organic polymer film (Tam‐Bdca‐CGHOF). The fabricated film showed versatility in chemical bonding along its thickness from covalent to hydrogen‐bonded network. The kinetic‐controlled Tam‐Bdca‐CGHOF showed enhanced proton conductivity (8.3×10−5 S cm−1) compared to its rapid kinetic analogue, Tam‐Bdca‐COP (2.1×10−5 S cm−1), which signifies the advantage of bonding‐engineering in the same system.
Imaging the Footprint of Nanoscale Electrochemical Reactions for Assessing Synergistic Hydrogen Evolution
Authors: Godeffroy Louis , Ciocci Paolo , Ortiz Peña Nathaly , Alloyeau Damien , Noël Jean‐Marc , Lemineur Jean‐François , Kanoufi Frédéric 
Published: May 2023

AbstractThis work proposes a novel method for measuring the intrinsic activity of single metal‐based nanoparticles towards water reduction in neutral media at industrially relevant current densities. Instead of using gas nanobubbles as proxy, the method uses optical microscopy to track the local footprint of the reaction through the precipitation of metal hydroxide, which is associated to the local pH increase during electrocatalysis. The results show the electrocatalytic activities of different types of metal nanoparticles and bifunctionnal core‐shell nanostructures made of Ni and Pt, and demonstrate the importance of metal hydroxide nano‐shells in enhancing electrocatalysis. This method should be generalizable to any electrocatalytic reaction involving pH changes such as nitrate or CO2 reduction.
Profiling Phosphoproteome Landscape in Circulating Extracellular Vesicles from Microliters of Biofluids through Functionally Tunable Paramagnetic Separation
Authors: Sun Jie , Li Qing , Ding Yajie , Wei Dong , Hadisurya Marco , Luo Zhuojun , Gu Zhongze , Chen Bobin , Tao W. Andy 
Published: May 2023

AbstractMany biological processes are regulated through dynamic protein phosphorylation. Monitoring disease‐relevant phosphorylation events in circulating biofluids is highly appealing but also technically challenging. We introduce here a functionally tunable material and a strategy, extracellular vesicles to phosphoproteins (EVTOP), which achieves one‐pot extracellular vesicles (EVs) isolation, extraction, and digestion of EV proteins, and enrichment of phosphopeptides, with only a trace amount of starting biofluids. EVs are efficiently isolated by magnetic beads functionalized with TiIV ions and a membrane‐penetrating peptide, octa‐arginine R8+, which also provides the hydrophilic surface to retain EV proteins during lysis. Subsequent on‐bead digestion concurrently converts EVTOP to TiIV ion‐only surface for efficient enrichment of phosphopeptides for phosphoproteomic analyses. The streamlined, ultra‐sensitive platform enabled us to quantify 500 unique EV phosphopeptides with only a few μL of plasma and over 1200 phosphopeptides with 100 μL of cerebrospinal fluid (CSF). We explored its clinical application of monitoring the outcome of chemotherapy of primary central nervous system lymphoma (PCNSL) patients with a small volume of CSF, presenting a powerful tool for broad clinical applications.
Surface‐Area Determination of Anisotropic Polymersomes by Amphiphilic Molecular Probe Loading
Authors: Li Wei , Zhang Shaohua , Rijpkema Sjoerd J. , Wilson Daniela A. 
Published: May 2023

AbstractThe surface area of anisotropic polymeric assemblies is a critical parameter concerning their properties. However, it is still a grand challenge for traditional techniques to determine the surface area. Here, a molecular probe loading (MPL) method is developed to measure the surface area of anisotropic polymersomes in the shape of tube, disc, and stomatocyte. This method uses an amphiphilic molecular probe, comprising hydrophobic pyrene as the anchor and hydrophilic tetraethylene glycol (EG4) as the float. The surface area of spherical polymersomes determined by dynamic light scattering is quantitatively correlated with the loading amount of probes, allowing the calculation of the average separation distance between the loaded probes. With the separation distance, we successfully determine the surface area of anisotropic polymersomes by measuring the loading amount. We envision that the MPL method will assist in the real‐time surface area characterization, enabling the customization of functions.
Enantioselective Synthesis of Biscyclopropanes Using Alkynes as Dicarbene Equivalents
Authors: Wang Chuntao , Wu Rui , Chen Kai , Zhu Shifa 
Published: May 2023

AbstractChiral biscyclopropanes are an important skeleton in many bioactive molecules. However, there are few routes to synthesize these molecules with high stereoselectivity due to the nature of multiple stereocenters. Herein, we report the first example of Rh2(II)‐catalyzed enantioselective synthesis of bicyclopropanes with alkynes as dicarbene equivalents. The bicyclopropanes with 4–5 vicinal stereocenters and 2–3 all‐carbon quaternary centers were constructed in excellent stereoselectivity. This protocol features high efficiency and excellent functional group tolerance. Moreover, the protocol was also extended to the cascaded cyclopropanation/cyclopropenation with excellent stereoselectivities. In these processes, both sp‐carbons of alkyne were converted into stereogenic sp3‐carbons. Experimental and density functional theory (DFT) calculations revealed that the cooperative weak hydrogen bonds between the substrates and the dirhodium catalyst may play key roles in this reaction.
Assembling a Heterobimetallic Actinide Metal‐Organic Framework by a Reaction‐Induced Preorganization Strategy
Authors: Mei Sen , Chen Lixi , Zhang Hailong , Li Zhiwei , Cheng Liwei , Lu Junhao , Li Xiaoqi , Yang Qian , Wang Yanlong , Liu Zhiyong , Chai Zhifang , Wang Shuao 
Published: May 2023

AbstractPeriodically arranging coordination‐distinct actinides into one crystalline architecture is intriguing but of great synthetic challenge. We report a rare example of a heterobimetallic actinide metal–organic framework (An‐MOF) by a unique reaction‐induced preorganization strategy. A thorium MOF (SCU‐16) with the largest unit cell among all Th‐MOFs was prepared as the precursor, then the uranyl was precisely embedded into the MOF precursor under oxidation condition. Single crystal of the resulting thorium‐uranium MOF (SCU‐16‐U) shows that a uranyl‐specific site was in situ induced by the formate‐to‐carbonate oxidation reaction. The heterobimetallic SCU‐16‐U exhibits multifunction catalysis properties derived from two distinct actinides. The strategy proposed here offers a new avenue to create mixed‐actinide functional material with unique architecture and versatile functionality.
Cu‐Bound Formates are Main Reaction Intermediates during CO2 Hydrogenation to Methanol over Cu/ZrO2
Authors: Meunier Frederic C. , Dansette Isaac , Paredes‐Nunez Anaelle , Schuurman Yves 
Published: May 2023

AbstractCu/ZrO2 is a promising catalyst for the hydrogenation of CO2 to methanol. Reaction pathways involving formates or hydroxycarbonyls have been proposed. We show here that three different types of formates can be observed under reaction conditions at 220 °C and 3 bar, one being located on metallic Cu and two others being bound to ZrO2. The surface concentrations of formates were determined through calibration curves and their reactivity measured during chemical transient experiments. The Cu‐bound formate represented only about 7 % of surface formates, but exhibited a higher reactivity and was found to be the only formate that could account for all the production of methanol. Copper is thus not there only to activate H2, but also bears other crucial intermediates. This work reemphasizes that fully quantitative IR analyses and transient methods are required to unravel the role of surface species.
Elucidating the Structures of Intermediate Fragments during Stepwise Dissociation of Monolayer‐Protected Silver Clusters
Authors: Chakraborty Papri , Malola Sami , Neumaier Marco , Weis Patrick , Häkkinen Hannu , Kappes Manfred M. 
Published: May 2023

AbstractFragmentation dynamics of ligated coinage metal clusters reflects their structural and bonding properties. So far methodological challenges limited probing structures of the fragments. Herein, we resolve the geometric structures of the primary fragments of [Ag29L12]3−, i.e. [Ag24L9]2−, [Ag19L6]− and [Ag5L3]− (L is 1,3‐benzene dithiolate). For this, we used trapped ion mobility mass spectrometry to determine collision cross sections of the fragments and compared them to structures calculated by density functional theory. We also report that following two sequential [Ag5L3]− elimination steps, further dissociation of [Ag19L6]− also involves a new channel of Ag2 loss and Ag−S and C−S bond cleavages. This reflects a competition between retaining the electronic stability of 8 e− superatom cluster cores and increasing steric strain of ligands and staples. These results are also of potential interest for future soft‐landing deposition studies aimed at probing catalytic behavior of Ag clusters on supports.
Transport properties investigations of nanocomposite membranes incorporating titanate nanowires for water desalination
Authors: de Resende Neuman Solange , Ohland Anderson Luis , Salim Vera M. M. , Borges Cristiano Piacsek 
Published: May 2023

AbstractImprovement of membrane properties is an important issue to enhance the efficiency of water permeation processes. Nanocomposite membranes are gaining prominence in this field due to the particular properties of these materials. In the present study, incorporating titanate nanowires (TNW) into the cellulose acetate (CA) matrix allowed getting a nanocomposite membrane with modified characteristics. Morphologic and physical–chemical properties of the synthesized membranes were characterized by Fourier transform infrared spectrometry and scanning electron microscopy analysis, presenting a dense, uniform membrane formation with a highly dispersed inorganic phase when low amounts of particles were added. The membranes were tested by measuring water flux and salt rejection. The results showed that the incorporation of inorganic nanostructures into polymer membranes affects their transport properties. It was observed an increase of three times in water flux, reaching from 1.33 to 4.0 L/h m2, with NaCl rejection over 65%. Membranes with such characteristics could be specially designed for nanofiltration or forward osmosis processes as a promising application for water desalination or energy generation.
Biomarker‐based precision dose finding for immunotherapy combined with radiotherapy
Authors: Lin Li‐Hsiang , Han Yan , Zhang Rui , Guo Beibei 
Published: May 2023

AbstractRecent success of sequential administration of immunotherapy following radiotherapy (RT), often referred to as immunoRT, has sparked the urgent need for novel clinical trial designs to accommodate the unique features of immunoRT. For this purpose, we propose a Bayesian phase I/II design for immunotherapy administered after standard‐dose RT to identify the optimal dose that is personalized for each patient according to his/her measurements of PD‐L1 expression at baseline and post‐RT. We model the immune response, toxicity, and efficacy as functions of dose and patient's baseline and post‐RT PD‐L1 expression profile. We quantify the desirability of the dose using a utility function and propose a two‐stage dose‐finding algorithm to find the personalized optimal dose. Simulation studies show that our proposed design has good operating characteristics, with a high probability of identifying the personalized optimal dose.
Manufacture of electrospun porous PLA fiber‐type film coated with CMC and its anti‐adhesion efficiency in white mice
Authors: Choi Sangmun , Chung Kyu Jin , Kim Youngjung , Kim Daeik , Hwang Sun Jin , Bae Su Ho , Ryoo Keon Sang 
Published: May 2023

AbstractThe electrospun polylactide (PLA) anti‐adhesion fiber‐type film coated with carboxymethylcellulose (CMC) was manufactured and evaluated for its usability through animal experiments. The PLA anti‐adhesion film developed in this study is an adhesion preventive film of a double composite structure with both hydrophobicity and hydrophilicity. This film has the anti‐adhesion effect due to hydrophobic PLA that do not melt easily in the body and at the same time is easily attached to the surgical site by hydrophilic CMC that reacts easily to body fluids and changes quickly to mucus. In this study, the diameter and the pore diameter of the PLA fiber and thickness of PLA film made by electrospinning was 0.2–0.4, 1–10, and 30–50 μm, respectively. Through observation of surface structure (×5000 magnification), the most suitable concentration of CMC to maintain pores on the PLA film as much as possible is 0.5% wt/vol. The CMC content in the PLA film coated with 0.5% wt/vol of CMC was measured to be 5.41% wt/wt and its tensile strength was about 2.92 times higher than that of the noncoated PLA film with CMC. The porosity of CMC‐coated PLA film (5.41% wt/wt) was found to be 76.4%. In the animal experiment, 20 white mice (10 as a control group and 10 as an experimental group) were used to determine the degree of adhesion prevention. As a result of observing adhesion and anti‐adhesion between the cecum and the peritoneum by performing U‐shaped laparotomy on white mice at the third week after surgery, the incidence of adhesion in the control group was 90%, whereas the experimental group was 20%.
Quantitative EEG as a diagnostic and prognostic tool in hemispheric stroke patients undergoing type A aortic dissection surgery
Authors: Wang Ya‐peng , Liu Wen‐xue , Jiang Yi , Lu Shan , Cheng Yong‐qing , Chen Yang , Wang Dong‐jin 
Published: May 2023

AbstractObjectiveThe diagnostic and prognostic value of quantitative electroencephalogram (qEEG) parameters, specifically the symmetry of amplitude‐integrated electroencephalography (aEEG) and relative band power (RBP), in the postoperative stroke of the cerebral hemisphere following type A aortic dissection, remains an area of inquiry.MethodsWe analyzed and processed 56 patients with type A aortic dissection who underwent bedside qEEG monitoring and analyzed the qEEG indices, brain CT, and clinical data of these patients. qEEG (symmetry of aEEG and RBP, and affected/unaffected hemisphere) indices were analyzed at discharge and 60 days after discharge.ResultsA total of 56 patients were studied. The 60‐day mortality rate was 12.5%. The affected hemisphere's diagnosis and mortality after 1‐year follow‐up were evaluated, and RBP beta demonstrated the highest area under the curve values with 95% confidence intervals (CI) of .849 (95% CI: .771–.928) and .91 (95% CI: .834–.986), respectively. According to the results of the logistic regression analysis, we have identified the strongest predictors for cerebral hemisphere stroke and 1‐year mortality in stroke patients. Specifically, aEEGmin exhibited the highest predictive power with an odds ratio (OR) of .735 for cerebral hemisphere stroke, whereas DTABR was confirmed as one of the strongest predictors with an OR of 1.619 for 1‐year mortality in stroke patients, indicating a high level of reliability. Spearman correlation coefficients showed that aEEGmax and aEEGmin were positively correlated with Alberta Stroke Program Early CT Score (aEEGmax: rho = .50, p < .001; aEEGmin: rho = .44, p < .001).ConclusionsQEEG has been proven to be a sensitive indicator for monitoring brain function and can be monitored continuously. It can help clinicians detect and treat these patients early and improve long‐term prognosis.