bluuebunny/crossref_metadata_2025_split huggingface dataset:
Determination of pKa Values of C−H Bonds in Polar Fluorinated Arenes Referred to a New CF3SO2‐Substituted Anchor Compound
Authors: Kong Xiangmei , Liang Yunfei , Guo Zhenbo , Lin Tianxing , Liu Shan , Liu Zhiyi , Liu Tianfei , Cheng Jin‐Pei 
Published: November 2024

AbstractpKa values of C−H bonds remain unreported and challenging in fluorous solvents because of these solvents’ unique physicochemical properties, although they have been measured, theorized and predicted successfully in water and common organic solvents. Herein, a new CF3SO2‐substituted anchor compound designed for matching the physicochemical properties of polar fluorinated arenes is synthesized. Its self‐dissociation constants in these solvents are used as bases for experimentally determining the pKa values of 36 C−H compounds in them. These experimentally determined pKa values exhibit excellent linear free‐energy relationships and correlate well with their corresponding DFT‐calculated values. These data indicate that the polar fluorinated arenes are thermodynamically more favorable for deprotonation of ketone derivatives than acetonitrile as reaction media, resulting in enhanced deprotonation‐promoted CO2 fixation. The pKa values determined in this work can be used as an important guidance tool for reactions involving the formation and cleavage of C−H bonds in polar fluorinated arenes.
Targeting METTL3 as a checkpoint to enhance T cells for tumour immunotherapy
Authors: Wu Kaixin , Li Sa , Hong Guangliang , Dong Hongzhi , Tang Tongke , Liu He , Jin Lingmei , Lin Siyuan , Ji Jingyun , Hu Mingli , Chen Shuntian , Wu Haoyuan , Luo Guanzheng , Wu Haoyuan , Kong Xiangqian , Chen Jiekai , He Jiangping , Wu Hongling 
Published: November 2024

ABSTRACTBackgroundImmunotherapy has emerged as a crucial treatment modality for solid tumours, yet tumours often evade immune surveillance. There is an imperative to uncover novel immune regulators that can boost tumour immunogenicity and increase the efficacy of immune checkpoint blockade (ICB) therapy. Epigenetic regulators play critical roles in tumour microenvironment remodelling, and N6‐methyladenosine (m6A) is known to be involved in tumourigenesis. However, the role of m6A in regulating T‐cell function and enhancing anti‐tumour immunity remains unexplored.MethodsSeveral cancer cell lines were treated with STM2457, an enzymatic inhibitor of RNA m6A methyltransferase METTL3, and explored the transcriptome changes with RNA sequencing (RNA‐seq). We then utilised mouse melanoma (B16) and mouse colorectal adenocarcinoma (MC38) models to investigate the effects of METTL3 inhibition on immunotherapy, and analysed the dynamics of the tumour microenvironment via single‐cell RNA‐seq (scRNA‐seq). Furthermore, in vitro and in vivo T‐cell cytotoxicity killing assay and CRISPR Cas9‐mediated m6A reader YTHDF1‐3 knockout in B16 were performed to assess the role and the molecular mechanism of RNA m6A in tumour killing. Finally, the efficacy of METTL3 inhibition was also tested on human melanoma model (A375) and human T cells.ResultsWe demonstrate that inhibiting METTL3 augments tumour immunogenicity and sustains T‐cell function, thereby enhancing responsiveness to ICB therapy. Mechanistically, METTL3 inhibition triggers an interferon response within tumour cells, amplifying the anti‐tumour immune response, along with deletion of the m6A reader protein YTHDF2 in tumours inhibiting major histocompatibility complex (MHC)‐I degradation. Remarkably, these anti‐tumour effects are reliant on the immune system. Specifically, METTL3 inhibition enhances interferon‐gamma (IFNγ) and granzyme B (GzmB) expression, thereby strengthening T‐cell killing ability, and concurrently dampening the expression of exhaustion‐related genes.ConclusionTargeting METTL3 enhances anti‐tumour immunity by boosting T‐cell cytotoxicity and reversing T‐cell exhaustion. Our study positions METTL3 as an epigenetic checkpoint, highlighting the potential of targeting METTL3 to invigorate intrinsic anti‐tumour defenses and overcome immune resistance.Key points
Targeting METTL3 augments tumour cell immunogenicity and sustains T‐cell function.
T cell with METTL3 inhibition can reverse T‐cell exhaustion, and promote expression of IFNγ and GzmB, thereby enhancing cytotoxicity in anti‐PD‐1 therapy.
YTHDF2 deletion in tumours prolong the lifespan of MHC‐I mRNAs.
Data Compression Using Optimized Compressive Sensing in Cognitive Radio Network
Authors: A Kumar , Nithyavathy N. 
Published: November 2024

ABSTRACTIn cognitive radio networks, cooperative spectrum sensing can greatly improve detection performance and reduce test time because cognitive users work cooperatively to detect spectrum signals. However, it is important to reduce the number of measurements taken from the original signal. To overcome these challenges, this study proposes optimized compressive sensing (CS) to reduce processing time and speed up spectrum sensing. To optimize the performance of CS, the penguin optimization algorithm (POA) is used in this approach. The optimal CS matrix is selected using this algorithm. In this algorithm, mean square error (MSE) is considered an objective function. It selects the CS matrix with the minimum error as the optimal matrix. Step size optimized sparsity adaptive matching pursuit algorithm (SSOSAMP) is used to reconstruct the compressed signal using the optimized sensitivity matrix. MATLAB is used to implement this proposed approach. Simulation results show that the proposed system achieves an SNR of 27.43%, a reconstruction probability of 94.28%, and an MSE of 4.27%.
A Miniaturized Embedded Frequency Selective Surface‐Based EMI Shield for Microwave Ovens
Authors: Jayanandan T. , Alex Zachariah C. 
Published: November 2024

ABSTRACTThis work presents a new miniaturized frequency selective surface (FSS) design to be employed as an electromagnetic (EM) shield in the 2.45 GHz (ISM band) range, with optically transparent glass substrate. A step‐by‐step procedure on the miniaturization technique and the corresponding frequency response is presented. The proposed FSS layout consists of an optimized square loop and a central reactive element consisting of meandered lines. The metal layout is embedded between borosilicate glass as substrate on top and bottom sides, achieving a final periodicity of 0.12λ. A miniaturization of 69.05% was achieved, and the equivalent circuit model was synthesized to understand the EM behavior of the proposed FSS design, and results were compared. The shielding effectiveness of 53.25 dB was achieved with polarization insensitivity for both TE and TM modes, and the angular stability was also studied. A prototype of the proposed work was fabricated, and the frequency characteristics were studied in the anechoic chamber setup. Ellipsometer setup was used to study the optical properties of prototype, and optical transparency of 81.8% was achieved. The measured and simulated results show close agreement and confirm the usability of the proposed FSS in glass‐based electromagnetic interference (EMI) shielding applications in ISM band.
Divergent Population Trends of Two Sympatric Auk Species in the Rapidly Warming Gulf of Maine
Authors: Durham Sarah E. , Saunders Sarah P. , Diamond Antony W. , Riecke Thomas V. , Major Heather L. 
Published: November 2024

ABSTRACTRapidly warming global temperatures are having a widespread influence on wildlife communities across taxa, with southern‐edge populations often experiencing the greatest negative impacts. However, sympatric species may exhibit divergent demographic responses due to differences in life history strategies and niche separation. We used integrated population models to estimate abundance, survival, and productivity for Atlantic Puffins and Razorbills nesting at the southern edge of their breeding range in the rapidly warming Gulf of Maine. We then conducted transient life table response experiments to understand the relative importance of demographic parameters in driving population dynamics. We found that the Atlantic Puffin population remained relatively stable over the 22‐year study period, whereas the Razorbill population increased substantially. Estimates of mean survival and productivity were similar between the study species but were at the lower range of values reported in the literature across their range. Despite similar estimates of mean productivity, interannual variation in this demographic rate was much higher in Puffins than Razorbills. Overall, adult survival was found to be the primary driver of population dynamics for both species yet shows evidence of long‐term decline in Puffins. For Razorbills, we found similar evidence of long‐term decline in first‐year survival. Overall, our findings suggest that these sympatric species may be responding differently to shared environmental conditions. Given the observed long‐term decrease in Puffin adult survival, future monitoring and conservation efforts for this species should be focused outside the breeding season in critical overwintering areas and migratory locations where adult mortality is typically concentrated. Similarly, given the observed long‐term decline in Razorbill first‐year survival, additional monitoring and tracking of chicks is warranted for this species to understand where immature individuals are going after they fledge from the colony.
Global Data Compilation Across Climate Gradients Supports the Use of Common Allometric Equations for Three Transatlantic Mangrove Species
Authors: Price Charles A. , Branoff Benjamin , Cummins Karen , Kakaï Romain Glèlè , Ogurcak Danielle , Papeș Monica , Ross Michael , Whelan Kevin R. T. , Schroeder Todd A. 
Published: November 2024

ABSTRACTPredicting the distribution, structure, and biomass of mangrove forests is an area of high research interest. Across the Atlantic East Pacific biogeographic region, three species are common and abundant members of local mangrove communities; Rhizophora mangle, Avicennia germinans, and Laguncularia racemosa. Biomass prediction for these species has relied on two approaches: site‐specific allometries based on the idea that environmental/climatic differences between sites drive growth differences, or the use of common allometric equations based on the idea that site driven differences are minimal. Meta‐analyses of global compilations of interspecific plot level data (e.g., mean canopy height, stand basal area) show trends in size and structure with climatic variables, however this has not been critically evaluated across these species using empirical allometric growth functions. We compared allometric equations derived from 590 individuals within and across nine broadly distributed sites at interspecific and intraspecific levels and explored the influence of climatic variables on allometric slopes and intercepts. Assessing variables that can be used to predict biomass in the field (height, diameter at breast height (DBH), canopy spread), we find interspecific root mean squared errors similar to or smaller than most intraspecific or site‐specific equations, particularly when examining sites with sample sizes above recommended values. We also find significant effects of several climatic variables on growth allometries with the strongest effects from minimum temperature followed by precipitation seasonality. Our results suggest that while climate has a clear influence on mangrove allometric growth, common equations may have utility in biomass prediction. Future methodological improvements, particularly larger sample sizes across the entire available size range, combined with data from a broader range of growth conditions will further inform which allometric relationships exhibit the most variability within and across sites and which variables best predict mangrove biomass.
Mitochondrial Genome Comparison and Phylogenetic Variety of Four Morphologically Similar Bamboo Pests
Authors: Ying Yue , Wang Wenhao , Li Yan , Li Zhihong , Zhao Xinkang , Zhang Shouke , Shu Jinping , Shen Zhenming , Zhang Wei 
Published: November 2024

ABSTRACTBamboo snout moths (Lepidoptera, Crambidae) comprise the four species: Eumorphobotys obscuralis, Circobotys aurealis, Demobotys pervulgalis, and Crypsiptya coclesalis. These economically important insect pests of bamboo are widely distributed in tropical and subtropical regions. The lack of precise mitochondrial genetic data has impeded the development of effective identification techniques, accurate classification strategies, and targeted prevention and treatment strategies. In this study, we obtained the complete mitochondrial genome sequences of four bamboo snout moth species using high‐throughput sequencing. The mitogenomes were 15,103–15,349 bp in length and contained 13 protein‐coding genes, 22 transfer RNA genes (tRNAs), two ribosomal RNA genes (rRNAs), and a noncoding region (A + T rich element), consistent with previously studied Crambidae mitogenomes. We reconstructed the phylogenetic relationships among the four species using Bayesian inference and maximum likelihood methods. The moths that fed on bamboo were well clustered in a single clade. Crypsiptya coclesalis was most closely related to D. pervulgalis, while E. obscuralis was most closely related to C. aurealis. The divergence among the main lineages of 97 Lepidoptera species was reconstructed using an uncorrelated relaxed molecular clock. Analyses of the phylogenetic relationships and divergence times showed that the evolution of lepidopteran species has been closely related to that of their hosts. The data support the development of molecular identification techniques for the four species of bamboo snout moth, and our results provide a basis for targeted control strategies.
Development of a Tetraplex Digital PCR Assay for the Detection of Invasive Snake Species in Florida, USA
Authors: Miller Melissa A. , Bloch Melody , Balaguera‐Reina Sergio A. , Olejniczak Kevin A. , Fussell Persaud Cynthia A. , Helmick Ericka E. , Mazzotti Frank J. , Bahder Brian W. 
Published: November 2024

ABSTRACTFlorida, USA is a hotspot of biological invasions with over 500 non‐native species reported. Reptiles encompass most of the non‐native wildlife with over 50 species established, many of which are sympatric and are identified as invasive due to their impacts to the environment, economy, and human health and safety. Reports of new non‐native reptiles occur, and many established non‐native reptiles continue to expand their ranges in Florida, increasing the need for multitaxa detection and monitoring capabilities. Invasive constrictor snakes are a primary focus of management efforts due to life history traits that favor successful establishment and dispersal in Florida as well as their impacts to native wildlife and Everglades restoration efforts. While traditional survey methods that rely on visual detections fail to reliably detect invasive constrictors, environmental DNA (eDNA) has proven to be a promising method for detection of cryptic and rare species across the landscape. To address emerging needs for multispecies detection and monitoring in Florida, we developed the first tetraplex dPCR assay designed for detection of four species of invasive constrictor snakes, including Burmese pythons (Python bivittatus), northern African pythons (P. sebae), boa constrictors (Boa constrictor), and rainbow boas (Epicrates cenchria). In this tetraplex assay, no cross‐amplification across species was documented. This assay serves as a valuable tool for faster and more accurate monitoring efforts of these invasive species in South Florida. Additionally, eDNA samples comprised of soil and water both tested positive for Burmese python DNA under controlled and semicontrolled conditions with DNA being detectable up to 2‐weeks post removal in soil samples. Water samples yielded positive detection as quickly as 5 min after exposure to the organism. These data highlight the utility and sensitivity of this protocol for eDNA monitoring.
THz‐EPR‐Based Direct Spectroscopic Determination of the Anisotropy Barrier of a Heteroleptic Bis‐Chelate Cobalt(II) Complex with Bis(sulfonamido)benzene Ligand and its Dynamic Magnetic Properties
Authors: Pohle Maximilian H. , Konrad Anne , Görls Helmar , Plass Winfried 
Published: November 2024

AbstractA new mononuclear, four‐coordinate heteroleptic cobalt(II) complex 1 was synthesised utilising N,N′‐1,2‐Phenylenebis‐(4‐methylbenzenesulfonamide) and 6,6′‐Dimethyl‐2,2′‐bipyridine as ligands and structurally characterised. Magnetic susceptibility and magnetisation measurements, along with ab initio calculations, revealed a large easy‐axis type magnetic anisotropy of the cobalt(II) centre. Frequency‐dependent ac susceptibility measurements revealed out‐of‐phase signals, indicating a slow relaxation of magnetisation, even in the absence of an additional static magnetic field. The corresponding relaxation behaviour can be attributed to a combination of Orbach and phonon‐assisted processes within the observable temperature range. Using FD‐FT THz‐EPR spectroscopy, the magnetic anisotropy barrier was determined to be unexpectedly large with a value of 146.4
. The deviation from the expected barrier, based on correlations with the elongation parameter
, is attributed to the charge distribution in the coordination environment.
Genetic neonatal seizures in the neonatal intensive care unit: Diagnostic and prognostic implications for three families
Authors: Chen Rongrong , Wu Huiming , Lu Yi , Yin Honggang , Wang Xueqian , Zhang Xiaohua 
Published: November 2024

AbstractObjectiveWe investigated neonatal seizures in three probands admitted to the neonatal intensive care units and their affected family members.MethodsWhole exome sequencing (WES) was performed along with confirmation by Sanger sequencing and segregation analysis. Copy number variant (CNV) analysis was also conducted. Neuroimaging, electroencephalography, and metabolic analysis revealed clinical phenotypes.ResultsBi‐allelic variants c.1025T>C and c.1150G>A in MOCS1 were found in twin girls with molybdenum cofactor deficiency. The c.1025T>C variant was novel. A c.877C>T variant in KCNQ2 co‐segregated with seizures in a family. A de novo 6.25 Mb duplication on 2q24.3 encompassing SCN1A, SCN2A, and SCN3A was identified in a proband who demonstrated normal development without seizures on follow‐up.SignificanceWES facilitated the molecular diagnosis of neonatal seizures in the study participants. Variants in the KCNQ2 and MOCS1 genes were classified as likely pathogenic based on our findings. The individual with a duplication of the sodium channel gene cluster on 2q24.3 exhibited additional phenotypes. Our investigation expanded the genotype–phenotype spectrum.
Symptomatic vigabatrin‐associated MRI toxicity is associated with simultaneous hormonal therapy among patients with infantile spasms
Authors: Sathe Rujuta , Shrestha Gyaneshwar , Terango Aria , Tabibzadeh David , Rajaraman Rajsekar R. , Nariai Hiroki , Hussain Shaun A. 
Published: November 2024

AbstractVigabatrin‐associated brain abnormalities on MRI (VABAM) are observed in approximately 20% of children who receive vigabatrin for treatment of infantile epileptic spasms syndrome. Although usually reversible and asymptomatic, VABAM is occasionally symptomatic. Whereas asymptomatic VABAM appears to be dose‐dependent, symptomatic VABAM is possibly associated with co‐administration of vigabatrin and hormonal therapy (i.e., corticosteroids or adrenocorticotropic hormone). With retrospective study of a cohort of vigabatrin‐treated children, we evaluated candidate risk factors for VABAM. Among 108 children with detailed vigabatrin exposure data, we identified VABAM in 17 children (11 symptomatic). Symptomatic VABAM was strongly associated with simultaneous exposure to hormonal therapy (p = 0.001). Neither symptomatic nor asymptomatic VABAM were associated with peak vigabatrin dose. Although these data support the hypothesis that symptomatic VABAM risk is higher with coadministration of vigabatrin and hormonal therapy, this study does not establish a causal link. Further study is warranted to better understand the pathogenesis of VABAM and devise strategies to mitigate risk. Clinicians should carefully weigh the potential risk of symptomatic vigabatrin toxicity against the known benefit of vigabatrin and hormonal therapy coadministration.Plain Language SummarySeveral case reports suggest that the combination of vigabatrin and hormonal therapy for treatment of infantile spasms may provoke an adverse reaction known as symptomatic vigabatrin MRI toxicity (sVABAM, which includes characteristic changes on MRI images and associated symptoms). In response to these reports, we studied a large single‐center cohort of children with infantile spasms and determined that combination therapy is indeed statistically associated with sVABAM. However, we have not proven that combination therapy actually causes sVABAM. Further study is needed to clarify the nature of sVABAM and risk factors thereof.
Predicting flow resistance in rough‐bed rivers from topographic roughness: Review and open questions
Authors: Ferguson Robert I. , Hardy Richard J. , Hodge Rebecca A. , Houseago Robert C. , Yager Elowyn M. , Yamasaki Taís N. 
Published: November 2024

AbstractMost ways of predicting flow resistance in shallow rivers with a partial or complete cover of coarse sediment use a bed‐sediment grain diameter as a roughness length scale. However, beds with the same grain size distribution differ in roughness and flow resistance depending on how the larger grains are arranged, the nature of any bedforms and the possible complications of bedrock or rough banks. This has led to interest in predicting flow resistance using metrics of the topographic roughness of the bed. Some researchers have used the standard deviation of bed elevation as a roughness length scale. An alternative for channels containing boulders is to regard the bed as an array of large roughness elements. Fluvial research to date using these two approaches is limited and inconclusive. We review potentially relevant findings from the much more extensive literature in boundary‐layer meteorology and various branches of engineering and note links between the distribution‐statistics and element‐array approaches. The skewness of the elevation distribution is widely seen as important but it is unclear how best to use it for flow prediction. Other open questions include the scale dependence of topographic metrics, and what type of flow resistance equation to use them in. Calibration and testing of new prediction methods require flow data from reaches with known roughness statistics. This need should be met partly by measurements at field sites or in flume models of them, but also by flume experiments and numerical simulations using synthetic roughness.