bluuebunny/crossref_metadata_2025_split huggingface dataset:
How Different are the Diamagnetic and Paramagnetic Contributions to Off‐Nucleus Shielding in Aromatic and Antiaromatic Rings?
Authors: Karadakov Peter B. 
Published: February 2023

AbstractThe spatial variations in the diamagnetic and paramagnetic contributions to the off‐nucleus isotropic shielding,
, and to the zz component of the off‐nucleus shielding tensor,
, around benzene (C6H6) and cyclobutadiene (C4H4) are investigated using complete‐active‐space self‐consistent field wavefunctions. Despite the substantial differences between
and
around the aromatic C6H6 and the antiaromatic C4H4, the diamagnetic and paramagnetic contributions to these quantities,
and
, and
and
, are found to behave similarly in the two molecules, shielding and deshielding, respectively, each ring and its surroundings. The different signs of the most popular aromaticity criterion, the nucleus‐independent chemical shift (NICS), in C6H6 and C4H4 are shown to follow from a change in the balance between the respective diamagnetic and paramagnetic contributions. Thus, the different NICS values for antiaromatic and antiaromatic molecules cannot be attributed to differences in the ease of access to excited states only; differences in the electron density, which determines the overall bonding picture, also play an important role.
Residual Dipolar Coupling Based Conformational Analysis Allows the Configurational Assessment of Steroids with up to Eight Stereocenters
Authors: Venturi Luca , Bua Emanuela , Caputo Giulia , Mileo Valentina 
Published: February 2023

AbstractResidual dipolar couplings (RDCs) induced by anisotropic media have been proved as a powerful tool for the structure elucidation of organic molecules in solution in nuclear magnetic resonance (NMR) based analysis. The value of dipolar couplings to solve complex conformational and configurational problems represents indeed an appealing analytical tool for the pharmaceutical industry particularly focusing on the stereochemistry characterization of NCEs since the early phase of the drug development process. In our work, RDCs were used for the conformational and configurational study of synthetic steroids with multiple stereocenters – prednisone and beclomethasone dipropionate (BDP) –. For both molecules the correct relative configuration was identified among all the possible diastereoisomers (32 and 128 respectively) arising from the compounds stereogenic carbons. Only for prednisone the use of additional experimental data (i. e. rOes) was necessary to resolve the right stereochemical structure.
Validity and reliability of the Polish Maladaptive Daydreaming Scale (PMDS‐16) and its short form (PMDS‐5)
Authors: Pietkiewicz Igor Jacob , Hełka Anna M. , Barłóg Mateusz , Tomalski Radosław 
Published: February 2023

AbstractMaladaptive daydreaming (MD) defines excessive use of fantasy, which replaces human interaction and/or interferes with academic, interpersonal, or vocational functioning. This study tests psychometric properties of the Polish version of the Maladaptive Daydreaming Scale (PMDS‐16) and a short 5‐item version derived from it (PMDS‐5), and their capacity to screen for MD. The relationship between MD, resilience and the quality of life was also explored. Validity and reliability were examined in a sample of 491 participants in nonclinical (n = 315) and mixed‐clinical (n = 176) groups who completed the tests online. The exploratory factor analysis with principal component analysis method of parameter estimation without rotation confirmed a one‐factor solution of both instruments. Reliability of both versions was corroborated by Cronbach's alpha coefficient (PMDS‐16: >.941; PMDS‐5: >.931). The cutoff score maximizing sensitivity and specificity for MD was 42 in both instruments, but the short version had better discriminating properties. People who identified themselves as maladaptive daydreamers in comparison to those who did not had significantly higher scores in both instruments. Maladaptive daydreamers also had lower quality of life in the psychological and social relationships domains and poorer resilience. Both PMDS‐16 and PMDS‐5 proved to have satisfactory psychometric properties. They have similar psychometric properties, although PMDS‐5 has better discriminating power and can be used effectively for the screening of MD.
Concentration‐Dependent Inhibition of Mesophilic PETases on Poly(ethylene terephthalate) Can Be Eliminated by Enzyme Engineering
Authors: Avilan Luisana , Lichtenstein Bruce R. , König Gerhard , Zahn Michael , Allen Mark D. , Oliveira Liliana , Clark Matilda , Bemmer Victoria , Graham Rosie , Austin Harry P. , Dominick Graham , Johnson Christopher W. , Beckham Gregg T. , McGeehan John E. , Pickford Andrew R. 
Published: February 2023

AbstractEnzyme‐based depolymerization is a viable approach for recycling of poly(ethylene terephthalate) (PET). PETase from Ideonella sakaiensis (IsPETase) is capable of PET hydrolysis under mild conditions but suffers from concentration‐dependent inhibition. In this study, this inhibition is found to be dependent on incubation time, the solution conditions, and PET surface area. Furthermore, this inhibition is evident in other mesophilic PET‐degrading enzymes to varying degrees, independent of the level of PET depolymerization activity. The inhibition has no clear structural basis, but moderately thermostable IsPETase variants exhibit reduced inhibition, and the property is completely absent in the highly thermostable HotPETase, previously engineered by directed evolution, which simulations suggest results from reduced flexibility around the active site. This work highlights a limitation in applying natural mesophilic hydrolases for PET hydrolysis and reveals an unexpected positive outcome of engineering these enzymes for enhanced thermostability.
Urine‐based liquid biopsy in bladder cancer: Opportunities and challenges
Authors: Wang Gang , Jin Wan , Xu Zilin , Ju Lingao , Shan Danni , Li Shenjuan , Yu Mengxue , Cao Xinyue , Liu Nan , Qian Kaiyu , Zhang Yi , Xiao Yu , Wang Xinghuan 
Published: February 2023

AbstractBladder cancer (BLCA) is a most common urological tumours with high rate of recurrence, which needs long‐term of follow‐up. To date, diagnosis and surveillance of BLCA still rely on cystoscopy, an invasive and expensive method that increases the difficulty for routine follow‐up. Therefore, exploring new biomarkers or tests is an effective way to improve the current clinical management of BLCA. Recent years, liquid biopsy has received increasing attention, especially for its great potential for clinical application in the non‐invasive detection of tumours. In addition, liquid biopsy involves a wide range of biomarkers, including DNA, RNA, proteins, extracellular vesicles and metabolites in blood, urine or other body fluids. For BLCA, urine is a most ideal body fluid to achieve non‐invasive diagnosis and surveillance. Here, we address recent developments of urine‐based biomarkers or tests for clinical diagnostic challenges in BLCA, such as early detection, minimal residual, recurrence monitoring and therapeutic response. Meanwhile, the many challenges of urine biomarkers that need to be overcome are also discussed.
Investigation of the factors responsible for the low oral bioavailability of alizarin using a sensitive LC‐MS/MS method: In vitro, in situ, and in vivo evaluations
Authors: Seo Seong‐Wook , Han Dong‐Gyun , Baek Young Mee , Park Min Chul , Yoo Jin‐Wook , Jung Yunjin , Maeng Han‐Joo , Myung Heejoon , Yoon In‐Soo 
Published: February 2023

AbstractAlizarin (1,2‐dihydroxyanthraquinone) is an anthraquinone reddish dye widely used for painting and textile dyeing. As the biological activity of alizarin has recently attracted increasing attention from researchers, its therapeutic potential as complementary and alternative medicine is of interest. However, no systematic research has been conducted on the biopharmaceutical and pharmacokinetic aspects of alizarin. Therefore, this study aimed to comprehensively investigate the oral absorption and intestinal/hepatic metabolism of alizarin using a simple and sensitive tandem mass spectrometry method developed and validated in‐house. The present method for the bioanalysis of alizarin has merits, including a simple pretreatment procedure, small sample volume, and adequate sensitivity. Alizarin exhibited pH‐dependent moderate lipophilicity and low solubility with limited intestinal luminal stability. Based on the in vivo pharmacokinetic data, the hepatic extraction ratio of alizarin was estimated to be 0.165–0.264, classified as a low level of hepatic extraction. In an in situ loop study, considerable fractions (28.2%–56.4%) of the alizarin dose were significantly absorbed in gut segments from the duodenum to ileum, suggesting that alizarin may be classified as the Biopharmaceutical Classification System class II. An in vitro metabolism study using rat and human hepatic S9 fractions revealed that glucuronidation and sulfation, but not NADPH‐mediated phase I reactions and methylation, are significantly involved in the hepatic metabolism of alizarin. Taken together, it can be estimated that the fractions of oral alizarin dose unabsorbed from the gut lumen and eliminated by the gut and liver before reaching the systemic circulation are 43.6%–76.7%, 0.474%–36.3%, and 3.77%–5.31% of the dose, respectively, resulting in a low oral bioavailability of 16.8%. Therefore, the oral bioavailability of alizarin depends primarily on its chemical degradation in the gut lumen and secondarily on first‐pass metabolism.
Colonization of a temperate river by mobile fish following habitat reconnection
Authors: Kiffney P. M. , Lisi P. J. , Liermann M. , Naman S. M. , Anderson J. H. , Bond M. H. , Pess G. R. , Koehler M. E. , Buhle E. R. , Buehrens T. W. , Klett R. S. , Cram J. M. , Quinn T. P. 
Published: February 2023

AbstractMobile species are particularly affected by artificial barriers requiring large investments to restore connectivity. However, few large‐scale, long‐term studies have investigated the ecological outcomes of restoring connectivity for these species. Our study, spanning 15–20 years, quantified response trajectories, which represent temporal trends following disturbance, of three native salmonids colonizing 20 km of protected habitat following restoration of fish passage at Landsburg Dam, Cedar River, WA, in 2003. Built in 1901, the dam blocked the upriver movement of native anadromous coho and Chinook salmon and nonanadromous mountain whitefish for 102 years. Restoration effectiveness was also assessed by comparing temporal trends in freshwater productivity of juvenile coho and Chinook salmon in the Cedar River after restoration to a nearby undammed subbasin. We also compared summer densities of juvenile coho and Chinook salmon, and mountain whitefish above the dam measured a decade after restoration to undammed reference systems. Anadromous salmon and nonanadromous mountain whitefish populations increased linearly or nonlinearly following restoration. The positive, asymptotic response represented by adult Chinook salmon counts indicates a slowing in population recovery rate, plateauing a decade after restoration. In contrast, annual abundance of adult coho salmon increased at a constant rate, indicating additional capacity 15 years post‐restoration. Salmonid compositional diversity, driven largely by juvenile coho salmon, also increased nonlinearly, plateauing in a decade. We observed substantial spatial variation in the temporal response, as juvenile coho salmon and mountain whitefish population expansion slowed linearly with upstream distance from the restoration site. There was evidence that some of the annual variation in salmonid biomass in summer was a result of discharge variability in winter and spring, with biomass declining as flow variability increased. Species reintroduction and establishment had no discernible effect on stream‐rearing salmonids living above the dam before restoration, while increasing coho freshwater productivity at the subbasin scale. Results from our study showed recolonization by three mobile species, each with a unique life history, takes at least a decade or more and was dependent on species and life stage, size of the spawning population, distance from restoration site, and annual variability in streamflow.
Long‐term exposure to an invasive fungal pathogen decreases Eptesicus fuscus body mass with increasing latitude
Authors: Simonis Molly C. , Hartzler Lynn K. , Turner Gregory G. , Scafini Michael R. , Johnson Joseph S. , Rúa Megan A. 
Published: February 2023

AbstractInvasive pathogens threaten wildlife health and biodiversity. Physiological responses of species highly susceptible to pathogen infections following invasion are well described. However, the responses of less susceptible species (relative to highly susceptible species) are not well known. Latitudinal gradients, which can influence body condition via Bergmann's rule and/or reflect the time it takes for an introduced pathogen to spread geographically, add an additional layer for how mammalian species respond to pathogen exposure. Our goal was to understand how hosts less susceptible to pathogen infections respond to long‐term pathogen exposure across a broad latitudinal gradient. We examined changes in body mass throughout pathogen exposure time across the eastern United States (latitude ranging 30.5° N–44.8° N) in Eptesicus fuscus, a bat species classified as less susceptible to infection (relative to highly susceptible species) by the invasive fungal pathogen that causes white‐nose syndrome, Pseudogymnoascus destructans (Pd). Using 30 years of spring through fall adult capture records, we created linear mixed‐effects models for female and male bats to determine how mass or mass variation changed across the eastern United States from pre‐Pd invasion years through Pd invasion (0–1 years with Pd), epidemic (2–4 years with Pd), and established years (5+ years with Pd). By Pd establishment, all female and male bats decreased body mass with increasing latitude across a spatial threshold at 39.6° N. Differences in bat mass north and south of the spatial threshold progressively increased over Pd exposure time‐steps such that body mass was lower in northern latitudes compared to southern latitudes by Pd establishment. Results indicated that the progressive differences in E. fuscus body mass with latitude across the eastern United States are due to long‐term pathogen exposure; however, other environmental and ecological pressures may contribute to decreases in E. fuscus body mass with latitude and long‐term pathogen exposure. As pathogen introductions and emerging infectious diseases become more prevalent on the landscape, it is imperative that we understand how less susceptible species directly and indirectly respond to long‐term pathogen exposure in order to maintain population health in surviving species.
The salmonid and the subsurface: Hillslope storage capacity determines the quality and distribution of fish habitat
Authors: Dralle D. N. , Rossi G. , Georgakakos P. , Hahm W. J. , Rempe D. M. , Blanchard M. , Power M. E. , Dietrich W. E. , Carlson S. M. 
Published: February 2023

AbstractWater in rivers is delivered via the critical zone (CZ)—the living skin of the Earth, extending from the top of the vegetation canopy through the soil and down to fresh bedrock and the bottom of significantly active groundwater. Consequently, the success of stream‐rearing salmonids depends on the structure and resulting water storage and release processes of this zone. Physical processes below the land surface (the subsurface component of the CZ) ultimately determine how landscapes “filter” climate to manifest ecologically significant streamflow and temperature regimes. Subsurface water storage capacity of the CZ has emerged as a key hydrologic variable that integrates many of these subsurface processes, helping to explain flow regimes and terrestrial plant community composition. Here, we investigate how subsurface storage controls flow, temperature, and energetic regimes that matter for salmonids. We illustrate the explanatory power of broadly applicable, storage‐based frameworks across a lithological gradient that spans the Eel River watershed of California. Study sites are climatically similar but differ in their geologies and consequent subsurface CZ structure that dictates water storage dynamics, leading to dramatically different hydrographs, temperature, and riparian regimes—with consequences for every aspect of salmonid life history. Lithological controls on the development of key subsurface CZ properties like storage capacity suggest a heretofore unexplored link between salmonids and geology, adding to a rich literature that highlights various fluvial and geomorphic influences on salmonid diversity and distribution. Rapidly advancing methods for estimating and observing subsurface water storage dynamics at large scales present new opportunities for more clearly identifying landscape features that constrain the distributions and abundances of organisms, including salmonids, at watershed scales.
Estimating recruitment rate and population dynamics at a migratory stopover site using an integrated population model
Authors: Tucker Anna M. , McGowan Conor P. , Nuse Bryan L. , Lyons James E. , Moore Clinton T. , Smith David R. , Sweka John A. , Anstead Kristen A. , DeRose‐Wilson Audrey , Clark Nigel A. 
Published: February 2023

AbstractConsideration of the full annual cycle population dynamics can provide useful insight for conservation efforts, but collecting data needed to estimate demographic parameters is often logistically difficult. For species that breed in remote areas, monitoring is often conducted during migratory stopover or at nonbreeding sites, and the recruitment rate of new breeding adults can be difficult to estimate directly. Here, we present an integrated population model that uses mark‐resight and count data to estimate survival probability, population growth rate, and recruitment rate for an Arctic‐breeding shorebird of conservation concern, the red knot (Calidris canutus rufa), from data collected during spring stopover in Delaware Bay, USA, from 2005 to 2018. At this site, red knots feed primarily on the eggs of spawning horseshoe crabs (Limulus polyphemus), a legally harvested species. We used this model to estimate the relationship between horseshoe crab abundance and red knot demographics, which informed a recent revision to the framework used to establish horseshoe crab harvest regulations. Our analysis indicates that the red knot population was most likely stable from 2005 to 2018 (average λ = 1.03, 95% credible interval [CRI]: 0.961, 1.15) despite low recruitment rates (average ρ = 0.088, 95% CRI: 0.012, 0.18). Adult survival probability was positively associated with horseshoe crab abundance in the same year (β = 0.35, 95% CRI: 0.09, 0.63), but we found no effect of horseshoe crab abundance two years previously on recruitment of new adults (β = −0.08, 95% CRI: −0.41, 0.38). Our approach demonstrates the utility of integrated population models for understanding population dynamics, even when data are only available from migratory stopover monitoring.
F‐Tag Induced Acyl Shift in the Photochemical Cyclization of o‐Alkynylated N‐Alkyl‐N‐acylamides to Indoles**
Authors: Simek Tosino Helena , Jung André , Fuhr Olaf , Muhle‐Goll Claudia , Jung Nicole , Bräse Stefan 
Published: February 2023

AbstractA photochemical cyclization of F‐tagged, o‐alkynylated N‐alkylamides to indoles catalyzed by [Ir(dF(CF3)ppy)2(dtbpy)]PF6 is presented. This straightforward and efficient reaction involves an intramolecular rearrangement due to the presence of an electron withdrawing group in the acyl moiety and is the first example of photochemically induced 1,3‐acyl shift in the cyclization towards 3‐acylindoles. A four‐step reaction sequence including the photoreaction as a key step to the desired indoles has been developed and optimized. The compatibility of differently substituted F‐tagged precursors with the photocyclization step was investigated and the robustness of this step towards modifications could be shown. In total, 16 so far unknown derivatives with diverse modifications in positions N1 and C2, bearing a pentadecafluorooctanoyl moiety as F‐tag, were synthesized in very good yields and fully characterized.
Ictal vocalizations in the Scn1a+/− mouse model of Dravet syndrome
Authors: Anderson Lyndsey L. , Everett‐Morgan Declan , Petkova Stela P. , Silverman Jill L. , Arnold Jonathon C. 
Published: February 2023

AbstractObjectiveIctal vocalizations have shown diagnostic utility in epilepsy patients. Audio recordings of seizures have also been used for seizure detection. The present study aimed to determine whether generalized tonic–clonic seizures in the Scn1a+/− mouse model of Dravet syndrome are associated with either audible mouse squeaks or ultrasonic vocalizations.MethodsAcoustic recordings were captured from group‐housed Scn1a+/− mice undergoing video‐monitoring to quantify spontaneous seizure frequency. We generated audio clips (n = 129) during a generalized tonic–clonic seizure (GTCS) that included 30 seconds immediately prior to the GTCS (preictal) and 30 seconds following the conclusion of the seizure (postictal). Nonseizure clips (n = 129) were also exported from the acoustic recordings. A blinded reviewer manually reviewed the audio clips, and vocalizations were identified as either an audible (<20 kHz) mouse squeak or ultrasonic (>20 kHz).ResultsSpontaneous GTCS in Scn1a+/− mice were associated with a significantly higher number of total vocalizations. The number of audible mouse squeaks was significantly greater with GTCS activity. Nearly all (98%) the seizure clips contained ultrasonic vocalizations, whereas ultrasonic vocalizations were present in only 57% of nonseizure clips. The ultrasonic vocalizations emitted in the seizure clips were at a significantly higher frequency and were nearly twice as long in duration as those emitted in the nonseizure clips. Audible mouse squeaks were primarily emitted during the preictal phase. The greatest number of ultrasonic vocalizations was detected during the ictal phase.SignificanceOur study shows that ictal vocalizations are exhibited by Scn1a+/− mice. Quantitative audio analysis could be developed as a seizure detection tool for the Scn1a+/− mouse model of Dravet syndrome.
Anxiety attenuates learning advantages conferred by statistical stability and induces loss of volatility‐attuning in brain activity
Authors: Rowe Elise G. , Harris Clare D. , Dzafic Ilvana , Garrido Marta I. 
Published: February 2023

AbstractAnxiety can alter an individual's perception of their external sensory environment. Previous studies suggest that anxiety can increase the magnitude of neural responses to unexpected (or surprising) stimuli. Additionally, surprise responses are reported to be boosted during stable compared to volatile environments. Few studies, however, have examined how learning is impacted by both threat and volatility. To investigate these effects, we used threat‐of‐shock to transiently increase subjective anxiety in healthy adults while they performed an auditory oddball task under stable and volatile environments and while undergoing functional Magnetic Resonance Imaging (fMRI) scanning. We then used Bayesian Model Selection (BMS) mapping to identify the brain areas where different models of anxiety displayed the highest evidence. Behaviourally, we found that threat‐of‐shock eliminated the accuracy advantage conferred by environmental stability over volatility. Neurally, we found that threat‐of‐shock led to attenuation and loss of volatility‐attuning of brain activity evoked by surprising sounds across most subcortical and limbic regions including the thalamus, basal ganglia, claustrum, insula, anterior cingulate, hippocampal gyrus and the superior temporal gyrus. Taken together, our findings suggest that threat eliminates learning advantages conferred by statistical stability compared to volatility. Thus, we propose that anxiety disrupts behavioural adaptation to environmental statistics, and that multiple subcortical and limbic regions are implicated in this process.