bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mechanical single-molecule potentiometers with large switching factors from ortho-pentaphenylene foldamers
Authors: Li Jinshi , Shen Pingchuan , Zhen Shijie , Tang Chun , Ye Yiling , Zhou Dahai , Hong Wenjing , Zhao Zujin , Tang Ben Zhong 
Published: January 2021

AbstractMolecular potentiometers that can indicate displacement-conductance relationship, and predict and control molecular conductance are of significant importance but rarely developed. Herein, single-molecule potentiometers are designed based on ortho-pentaphenylene. The ortho-pentaphenylene derivatives with anchoring groups adopt multiple folded conformers and undergo conformational interconversion in solutions. Solvent-sensitive multiple conductance originating from different conformers is recorded by scanning tunneling microscopy break junction technique. These pseudo-elastic folded molecules can be stretched and compressed by mechanical force along with a variable conductance by up to two orders of magnitude, providing an impressively higher switching factor (114) than the reported values (ca. 1~25). The multichannel conductance governed by through-space and through-bond conducting pathways is rationalized as the charge transport mechanism for the folded ortho-pentaphenylene derivatives. These findings shed light on exploring robust single-molecule potentiometers based on helical structures, and are conducive to fundamental understanding of charge transport in higher-order helical molecules.
Biomimetic selenocystine based dynamic combinatorial chemistry for thiol-disulfide exchange
Authors: Canal-Martín Andrea , Pérez-Fernández Ruth 
Published: January 2021

AbstractDynamic combinatorial chemistry applied to biological environments requires the exchange chemistry of choice to take place under physiological conditions. Thiol-disulfide exchange, one of the most popular dynamic combinatorial chemistries, usually needs long equilibration times to reach the required equilibrium composition. Here we report selenocystine as a catalyst mimicking Nature’s strategy to accelerate thiol-disulfide exchange at physiological pH and low temperatures. Selenocystine is able to accelerate slow thiol-disulfide systems and to promote the correct folding of an scrambled RNase A enzyme, thus broadening the practical range of pH conditions for oxidative folding. Additionally, dynamic combinatorial chemistry target-driven self-assembly processes are tested using spermine, spermidine and NADPH (casting) and glucose oxidase (molding). A non-competitive inhibitor is identified in the glucose oxidase directed dynamic combinatorial library.
Thermal resistivity and hydrodynamics of the degenerate electron fluid in antimony
Authors: Jaoui Alexandre , Fauqué Benoît , Behnia Kamran 
Published: January 2021

AbstractDetecting hydrodynamic fingerprints in the flow of electrons in solids constitutes a dynamic field of investigation in contemporary condensed matter physics. Most attention has been focused on the regime near the degeneracy temperature when the thermal velocity can present a spatially modulated profile. Here, we report on the observation of a hydrodynamic feature in the flow of quasi-ballistic degenerate electrons in bulk antimony. By scrutinizing the temperature dependence of thermal and electric resistivities, we detect a size-dependent departure from the Wiedemann-Franz law, unexpected in the momentum-relaxing picture of transport. This observation finds a natural explanation in the hydrodynamic picture, where upon warming, momentum-conserving collisions reduce quadratically in temperature both viscosity and thermal diffusivity. This effect has been established theoretically and experimentally in normal-state liquid 3He. The comparison of electrons in antimony and fermions in 3He paves the way to a quantification of momentum-conserving fermion-fermion collision rate in different Fermi liquids.
Exposure to natural hazard events unassociated with policy change for improved disaster risk reduction
Authors: Nohrstedt Daniel , Mazzoleni Maurizio , Parker Charles F. , Di Baldassarre Giuliano 
Published: January 2021

AbstractNatural hazard events provide opportunities for policy change to enhance disaster risk reduction (DRR), yet it remains unclear whether these events actually fulfill this transformative role around the world. Here, we investigate relationships between the frequency (number of events) and severity (fatalities, economic losses, and affected people) of natural hazards and DRR policy change in 85 countries over eight years. Our results show that frequency and severity factors are generally unassociated with improved DRR policy when controlling for income-levels, differences in starting policy values, and hazard event types. This is a robust result that accounts for event frequency and different hazard severity indicators, four baseline periods estimating hazard impacts, and multiple policy indicators. Although we show that natural hazards are unassociated with improved DRR policy globally, the study unveils variability in policy progress between countries experiencing similar levels of hazard frequency and severity.
Sulfur monoxide dimer chemistry as a possible source of polysulfur in the upper atmosphere of Venus
Authors: Pinto Joseph P. , Li Jiazheng , Mills Franklin P. , Marcq Emmanuel , Evdokimova Daria , Belyaev Denis , Yung Yuk L. 
Published: January 2021

AbstractThe abundance of SO dimers (SO)2 in the upper atmosphere of Venus and their implications for the enigmatic ultraviolet absorption has been investigated in several studies over the past few years. However, the photochemistry of sulfur species in the upper atmosphere of Venus is still not well understood and the identity of the missing ultraviolet absorber(s) remains unknown. Here we update an existing photochemical model of Venus’ upper atmosphere by including the photochemistry of SO dimers. Although the spectral absorption profile of SO dimers fits the unknown absorber, their abundance is found to be too low for them to contribute significantly to the absorption. It is more likely that their photolysis and/or reaction products could contribute more substantively. Reactions of SO dimers are found to be important sources of S2O, and possibly higher order SnO species and polysulfur, Sn. All of these species absorb in the critical ultraviolet region and are expected to be found in both the aerosol and gas phase. indicating that in-situ high resolution aerosol mass spectrometry might be a useful technique for identifying the ultraviolet absorber on Venus.
Structure and dynamics of the drug-bound bacterial transporter EmrE in lipid bilayers
Authors: Shcherbakov Alexander A. , Hisao Grant , Mandala Venkata S. , Thomas Nathan E. , Soltani Mohammad , Salter E. A. , Davis James H. , Henzler-Wildman Katherine A. , Hong Mei 
Published: January 2021

AbstractThe dimeric transporter, EmrE, effluxes polyaromatic cationic drugs in a proton-coupled manner to confer multidrug resistance in bacteria. Although the protein is known to adopt an antiparallel asymmetric topology, its high-resolution drug-bound structure is so far unknown, limiting our understanding of the molecular basis of promiscuous transport. Here we report an experimental structure of drug-bound EmrE in phospholipid bilayers, determined using 19F and 1H solid-state NMR and a fluorinated substrate, tetra(4-fluorophenyl) phosphonium (F4-TPP+). The drug-binding site, constrained by 214 protein-substrate distances, is dominated by aromatic residues such as W63 and Y60, but is sufficiently spacious for the tetrahedral drug to reorient at physiological temperature. F4-TPP+ lies closer to the proton-binding residue E14 in subunit A than in subunit B, explaining the asymmetric protonation of the protein. The structure gives insight into the molecular mechanism of multidrug recognition by EmrE and establishes the basis for future design of substrate inhibitors to combat antibiotic resistance.
Coulomb interactions between dipolar quantum fluctuations in van der Waals bound molecules and materials
Authors: Stöhr Martin , Sadhukhan Mainak , Al-Hamdani Yasmine S. , Hermann Jan , Tkatchenko Alexandre 
Published: January 2021

AbstractMutual Coulomb interactions between electrons lead to a plethora of interesting physical and chemical effects, especially if those interactions involve many fluctuating electrons over large spatial scales. Here, we identify and study in detail the Coulomb interaction between dipolar quantum fluctuations in the context of van der Waals complexes and materials. Up to now, the interaction arising from the modification of the electron density due to quantum van der Waals interactions was considered to be vanishingly small. We demonstrate that in supramolecular systems and for molecules embedded in nanostructures, such contributions can amount to up to 6 kJ/mol and can even lead to qualitative changes in the long-range van der Waals interaction. Taking into account these broad implications, we advocate for the systematic assessment of so-called Dipole-Correlated Coulomb Singles in large molecular systems and discuss their relevance for explaining several recent puzzling experimental observations of collective behavior in nanostructured materials.
Catalytic activity of graphene-covered non-noble metals governed by proton penetration in electrochemical hydrogen evolution reaction
Authors: Hu Kailong , Ohto Tatsuhiko , Nagata Yuki , Wakisaka Mitsuru , Aoki Yoshitaka , Fujita Jun-ichi , Ito Yoshikazu 
Published: January 2021

AbstractGraphene-covering is a promising approach for achieving an acid-stable, non-noble-metal-catalysed hydrogen evolution reaction (HER). Optimization of the number of graphene-covering layers and the density of defects generated by chemical doping is crucial for achieving a balance between corrosion resistance and catalytic activity. Here, we investigate the influence of charge transfer and proton penetration through the graphene layers on the HER mechanisms of the non-noble metals Ni and Cu in an acidic electrolyte. We find that increasing the number of graphene-covering layers significantly alters the HER performances of Ni and Cu. The proton penetration explored through electrochemical experiments and simulations reveals that the HER activity of the graphene-covered catalysts is governed by the degree of proton penetration, as determined by the number of graphene-covering layers.
Extracellular vesicle-associated repetitive element DNAs as candidate osteosarcoma biomarkers
Authors: Cambier Linda , Stachelek Kevin , Triska Martin , Jubran Rima , Huang Manyu , Li Wuyin , Zhang Jianying , Li Jitian , Cobrinik David 
Published: January 2021

AbstractOsteosarcoma (OS) is the most common malignant bone tumor in children and young adults. Despite that high-risk factors have been identified, no test for early detection is available. This study aimed to identify circulating nucleic acid sequences associated with serum extracellular vesicle (EV) preparations at the time of OS diagnosis, as a step towards an OS early detection assay. Sequencing of small nucleic acids extracted from serum EV preparations revealed increased representation of diverse repetitive element sequences in OS patient versus control sera. Analysis of a validation cohort using qPCR of PEG-precipitated EV preparations revealed the over-representation of HSATI, HSATII, LINE1-P1, and Charlie 3 at the DNA but not RNA level, with receiver operating characteristic (ROC) area under the curve (AUC) ≥ 0.90. HSATI and HSATII DNAs co-purified with EVs prepared by precipitation and size exclusion chromatography but not by exosome immunocapture, indicative of packaging in a non-exosomal complex. The consistent over-representation of EV-associated repetitive element DNA sequences suggests their potential utility as biomarkers for OS and perhaps other cancers.
Efficacy of loading dose colistin versus carbapenems for treatment of extended spectrum beta lactamase producing Enterobacteriaceae
Authors: Katip Wasan , Yoodee Jukapun , Uitrakul Suriyon , Oberdorfer Peninnah 
Published: January 2021

AbstractColistin provides in vitro activity against numerous ESBL-producing and carbapenem-resistant bacteria. However, clinical information with respect to its utilization in infection caused by ESBL producers is limited. The aim of this study was a comparison of mortality rates of loading dose (LD) colistin and carbapenems as definitive therapies in a cohort of patients with infections caused by ESBL-producing Escherichia coli and Klebsiella pneumoniae. A retrospective cohort study in 396 patients with ESBL-producing E.coli and K.pneumoniae infection at a university-affiliated hospital was conducted between 1 January 2005 and 30 June 2015 to compare outcomes of infected patients who received LD colistin (95 patients) with carbapenems (301 patients). The three primary outcomes were 30-day mortality, clinical response and microbiological response. The most common infection types were urinary tract infection (49.49%), followed by pneumonia (40.66%), bacteremia (13.64%), skin and soft tissue infections (4.80%) and intra-abdominal infection (3.03%). LD colistin group provided higher 30-day mortality when compared with carbapenems group (HR 7.97; 95% CI 3.68 to 17.25; P = 0.001). LD colistin was also independently associated with clinical failure (HR 4.30; 95% CI 1.93 to 9.57; P = 0.001) and bacteriological failure (HR 9.49; 95% CI 3.76 to 23.96; P = 0.001) when compared with those who received carbapenems. LD colistin treatment was associated with poorer outcomes, i.e. mortality rate, clinical response and microbiological response. Moreover, when adjusted confounding factors, LD colistin was still less effective than carbapenems. It should be noted that, however, the use of Vitek-2 to assess colistin susceptibility could provide inaccurate results. Also, the difference in baseline characteristics could still remain in retrospective study although compensation by hazard ratio adjustment was performed. Therefore, clinical utilization of LD colistin should be recommended as an alternative for treatment ESBL-producing Enterobacteriaceae only in the circumstances where carbapenems cannot be utilized, but this recommendation must be considered carefully.
Reconstruction of forest dynamics in the Western Palaearctic based on phylogeographic analysis of the ringlet butterfly Erebia aethiops
Authors: Wendt Martin , Husemann Martin , Kramp Katja , Schmitt Thomas 
Published: January 2021

AbstractGlacial refugia are centers of high biodiversity. Therefore, knowledge on their locations and reactions of associated populations and landscapes to climatic changes is crucial for conservation management. We here investigated the biogeography of a butterfly species linked to open forest habitats. Using mitochondrial and nuclear markers in combination with Bayesian simulations, we analyzed the location and age of potential glacial refugia of the species. We identified five putative refugia in Europe. Considering the ecological needs of our study species, tree density within these refugial areas, in contrast to earlier assumptions, must have exceeded the level of individually scattered trees. Our results also provide evidence that especially the refuge areas in the Carpathians were previously underestimated regarding their age: the refugia in the Southern Carpathians presented suitable conditions throughout several glacial cycles, probably since the Mindel or Riss cycles. Additionally, our analyses provided support for a forest refugium near the Tatra Mountains persisting the last glacial maximum. Our results underline the usefulness of this and probably other butterfly species as indicators of forest refugia.
Octenidine-based hydrogel shows anti-inflammatory and protease-inhibitory capacities in wounded human skin
Authors: Seiser Saskia , Janker Lukas , Zila Nina , Mildner Michael , Rakita Ana , Matiasek Johannes , Bileck Andrea , Gerner Christopher , Paulitschke Verena , Elbe-Bürger Adelheid 
Published: January 2021

AbstractOctenidine dihydrochloride (OCT) is a widely used antiseptic molecule, promoting skin wound healing accompanied with improved scar quality after surgical procedures. However, the mechanisms by which OCT is contributing to tissue regeneration are not yet completely clear. In this study, we have used a superficial wound model by tape stripping of ex vivo human skin. Protein profiles of wounded skin biopsies treated with OCT-containing hydrogel and the released secretome were analyzed using liquid chromatography-mass spectrometry (LC–MS) and enzyme-linked immunosorbent assay (ELISA), respectively. Proteomics analysis of OCT-treated skin wounds revealed significant lower levels of key players in tissue remodeling as well as reepithelization after wounding such as pro-inflammatory cytokines (IL-8, IL-6) and matrix-metalloproteinases (MMP1, MMP2, MMP3, MMP9) when compared to controls. In addition, enzymatic activity of several released MMPs into culture supernatants was significantly lower in OCT-treated samples. Our data give insights on the mode of action based on which OCT positively influences wound healing and identified anti-inflammatory and protease-inhibitory activities of OCT.
p-adic numbers encode complex networks
Authors: Hua Hao , Hovestadt Ludger 
Published: January 2021

AbstractThe Erdős-Rényi (ER) random graph G(n, p) analytically characterizes the behaviors in complex networks. However, attempts to fit real-world observations need more sophisticated structures (e.g., multilayer networks), rules (e.g., Achlioptas processes), and projections onto geometric, social, or geographic spaces. The p-adic number system offers a natural representation of hierarchical organization of complex networks. The p-adic random graph interprets n as the cardinality of a set of p-adic numbers. Constructing a vast space of hierarchical structures is equivalent for combining number sequences. Although the giant component is vital in dynamic evolution of networks, the structure of multiple big components is also essential. Fitting the sizes of the few largest components to empirical data was rarely demonstrated. The p-adic ultrametric enables the ER model to simulate multiple big components from the observations of genetic interaction networks, social networks, and epidemics. Community structures lead to multimodal distributions of the big component sizes in networks, which have important implications in intervention of spreading processes.
Hydrogen–methane breath testing results influenced by oral hygiene
Authors: Erdrich Sharon , Tan Edwin C. K. , Hawrelak Jason A. , Myers Stephen P. , Harnett Joanna E. 
Published: January 2021

AbstractThe measurement of hydrogen–methane breath gases is widely used in gastroenterology to evaluate malabsorption syndromes and bacterial overgrowth. Laboratories offering breath testing provide variable guidance regarding oral hygiene practices prior to testing. Given that oral dysbiosis has the potential to cause changes in breath gases, it raises concerns that oral hygiene is not a standard inclusion in current breath testing guidelines. The aim of this study was to determine how a pre-test mouthwash may impact hydrogen–methane breath test results. Participants presenting for breath testing who had elevated baseline gases were given a chlorhexidine mouthwash. If a substantial reduction in expired hydrogen or methane occurred after the mouthwash, breath samples were collected before and after a mouthwash at all breath sample collection points for the duration of testing. Data were evaluated to determine how the mouthwash might influence test results and diagnostic status. In 388 consecutive hydrogen–methane breath tests, modifiable elevations occurred in 24.7%. Administration of a chlorhexidine mouthwash resulted in significantly (p ≤ 0.05) reduced breath hydrogen in 67% and/or methane gas in 93% of those consenting to inclusion. In some cases, this modified the diagnosis. Mean total gas concentrations pre- and post-mouthwash were 221.0 ppm and 152.1 ppm (p < 0.0001) for hydrogen, and 368.9 ppm and 249.8 ppm (p < 0.0001) for methane. Data suggest that a single mouthwash at baseline has a high probability of returning a false positive diagnosis. Variations in gas production due to oral hygiene practices has significant impacts on test interpretation and the subsequent diagnosis. The role of oral dysbiosis in causing gastrointestinal symptoms also demands exploration as it may be an underlying factor in the presenting condition that was the basis for the referral.
Investigation of a connection between abdominal wall defects and severity of the herniation in fetuses with gastroschisis and omphalocele
Authors: Logsdon Natasha T. , Gallo Carla M. , Favorito Luciano Alves , Sampaio Francisco J. 
Published: January 2021

AbstractAnalyze the biometric parameters and the size (area) of abdominal wall defect (AWD) in fetuses with gastroschisis and omphaloceles and correlate them with the herniated internal organs. We studied 22 fetuses (11 with AWDs and 11 without anomalies). In all fetuses we evaluated the xiphopubic distance (XPD) and iliac crest distance (ICD). In fetuses with AWDs we dissected the abdominal wall and measured the width and length of the defect for calculating its area and studying the correlation between the size of the defect with the organs that were herniated. For statistical analysis, the Anova and Tukey post-test were used (p < 0.05). The XPD in the control group had mean of 4.2 mm (2.3–5.9; SD ± 1.11), while in the AWDs it was 4.2 mm (2.9–5.5; SD ± 0.98) (p = 0.4366). The ICD had mean values of 2.5 mm (1.6–3.4; SD ± 0.58) in the control group, and 2.3 mm (1.2–3.0; SD ± 0.56) in AWDs fetuses (p = 0.6963). The number of herniate organs do not have significant correlation with the area of the defect (r2 = 0.2504, p = 0.5068). There is no correlation between the size (area) of abdominal wall defects and the number of the internal organs that herniated. Therefore, the hole size is not a predictor of the severity of the gastroschisis or omphalocele.
Adaptation to mis-pronounced speech: evidence for a prefrontal-cortex repair mechanism
Authors: Blanco-Elorrieta Esti , Gwilliams Laura , Marantz Alec , Pylkkänen Liina 
Published: January 2021

AbstractSpeech is a complex and ambiguous acoustic signal that varies significantly within and across speakers. Despite the processing challenge that such variability poses, humans adapt to systematic variations in pronunciation rapidly. The goal of this study is to uncover the neurobiological bases of the attunement process that enables such fluent comprehension. Twenty-four native English participants listened to words spoken by a “canonical” American speaker and two non-canonical speakers, and performed a word-picture matching task, while magnetoencephalography was recorded. Non-canonical speech was created by including systematic phonological substitutions within the word (e.g. [s] → [sh]). Activity in the auditory cortex (superior temporal gyrus) was greater in response to substituted phonemes, and, critically, this was not attenuated by exposure. By contrast, prefrontal regions showed an interaction between the presence of a substitution and the amount of exposure: activity decreased for canonical speech over time, whereas responses to non-canonical speech remained consistently elevated. Grainger causality analyses further revealed that prefrontal responses serve to modulate activity in auditory regions, suggesting the recruitment of top-down processing to decode non-canonical pronunciations. In sum, our results suggest that the behavioural deficit in processing mispronounced phonemes may be due to a disruption to the typical exchange of information between the prefrontal and auditory cortices as observed for canonical speech.