bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cryptic Hybridization Dynamics in a Three‐Way Hybrid Zone of Dinopium Flamebacks on a Tropical Island
Authors: Ranasinghe Rashika W. , Seneviratne Sampath S. , Irwin Darren 
Published: December 2024

ABSTRACTIsland ecosystems have emerged as vital model systems for evolutionary and speciation studies due to their unique environmental conditions and biodiversity. This study investigates the population divergence, hybridization dynamics, and evolutionary history of hybridizing golden‐backed and red‐backed Dinopium flameback woodpeckers on the island of Sri Lanka, providing insights into speciation processes within an island biogeographic context. Utilizing genomic analysis based on next‐generation sequencing, we revealed that the Dinopium hybrid zone on this island is a complex three‐way hybrid zone involving three genetically distinct populations: two cryptic populations of golden‐backed D. benghalense in the north and one island‐endemic red‐backed population of D. psarodes in the south of Sri Lanka. Our findings indicate asymmetric introgressive hybridization, where alleles from the southern D. psarodes introgress into the northern D. benghalense genome while phenotype remains adapted to their respective northern arid and southern wet habitats. The discovery of two genetically distinct but phenotypically similar D. benghalense populations in northern Sri Lanka highlights the process of cryptic population differentiation within island ecosystems. These populations trace their ancestry back to a common ancestor, similar to the Indian form D. b. tehminae, which colonized Sri Lanka from mainland India during the late Pleistocene. Subsequent divergence within the island, driven by selection, isolation by distance, and genetic drift, led to the current three populations. Our findings provide evidence of cryptic diversification and within‐island population divergence, highlighting the complexity of hybridization and speciation processes. These findings further emphasize the intricate nature of evolutionary dynamics in island ecosystems.
Agriculture and Water Availability Show Contrasting Effects on Bats in a Mediterranean Island of Outstanding Chiropteran Biogeographical Value
Authors: Cistrone Luca , Augusto Ana Margarida , Fichera Gaetano , Rebelo Hugo , Russo Danilo 
Published: December 2024

ABSTRACTWith their unique ecosystems and evolutionary dynamics, small islands offer fascinating contexts to explore animal diversity. Island bats are key players in maintaining ecological balance. However, their populations are threatened worldwide, necessitating comprehensive research and conservation strategies. Pantelleria, a small Mediterranean island and a biogeographic crossroad between Europe and Africa, offers an excellent model to exemplify the challenges to bat conservation in such geographic contexts. We tested three hypotheses: (1) bats would show weak preference patterns for landscape composition due to the island's heterogeneous landscapes, (2) farmland (especially vineyards) would strongly affect bat activity, and (3) distance from water sources would highly influence bat richness and activity. We surveyed bats acoustically using Audiomoth recorders covering most of the island's surface. We recorded seven bat species, including endangered Plecotus gaisleri, Myotis punicus and Rhinolophus mehelyi. Bats showed weak preferences for specific landscape composition, but the dominant species (Pipistrellus kuhlii) decreased its activity for increasing portions of vineyards within the landscape. Moreover, distance to water critically influenced bat richness and activity. Agricultural expansion, pesticide use and human activities pose significant threats to bats on Pantelleria. We advocate for sustainable farming practices and careful water resource management to safeguard bat habitats and mitigate these threats. Conservation should target vineyards, a key economic resource to produce world‐renowned wine ‘Passito di Pantelleria’ by reducing pesticide use and adopting organic management. Water might be supplemented in critical dry habitats. We urge the preservation of bat diversity to support ecosystem health and resilience on small islands like Pantelleria.
Ecofriendly Synthesis of Titanium Dioxide for Glyphosate Adsorption
Authors: Marconi Eleonora , Lopez Alberto , Bertelà Federica , Meneghini Carlo , Battocchio Chiara , Mirabile Gattia Daniele , Vanga Giuseppina , Centomo Paolo , Zecca Marco , Rizzotto Valentina , Pettenuzzo Silvia , Roverso Marco , Bogialli Sara , Simon Ulrich , Chen Peirong , Tortora Luca 
Published: December 2024

AbstractThe widespread use of glyphosate for weed control in agricultural, silvicultural, and urban areas worldwide is causing concerns about its potential toxicity and mobility in environment. Consequently, there is a pressing need to develop treatment processes to mitigate the effects of glyphosate, its metabolites, and/or coadjutants on the environment. Titanium dioxide nanoparticles (TNPs), among the most widely used engineered NPs, have recently attracted significant attention for glyphosate adsorption. In this study, TNPs were obtained through two synthesis procedures working at low temperatures and with a reduced amount of organic solvent. The first involves a polycondensation reaction of alkoxide precursors at 70 °C in a water‐in‐oil (W/O) microemulsion with a 1 : 1 volume ratio, employing cetylpyridinium bromide (CPB) as a cationic surfactant to obtain crystalline TNPs. In the second method, two resins characterized by different morphologies were used as a template, to grow amorphous TNPs. Glyphosate adsorption tests performed at different pH values, i.e. 4.0 and 8.5, revealed that the analyte is more effectively retained by the TNPs at pH 4.0, at which TiO2 surfaces are positively charged and better interact with anionic glyphosate species. TNPs obtained via microemulsion using titanium alkoxide as the precursor and calcined at 450 °C showed excellent performance, removing from the solution nearly 99% of glyphosate, even at pH 8.5. Similarly, resin composites work efficiently in eliminating a high percentage of glyphosate, taking advantage of a better dispersion of amorphous TiO2 and a higher surface‐to‐volume ratio. This study demonstrates the effective capture of glyphosate by titanium dioxide nanoparticles, highlighting some factors contributing to the adsorption ability, and their potential as a unique tool for adsorbing glyphosate in a one‐pot process.
Tailoring the Multi‐Protolytic Equilibrium of Tin Porphyrins as Promising Molecular Catalyst for the Two‐Electron Oxidation of Water in Artificial Photosynthesis
Authors: Joseph Reshma , Baby Haritha , Kaiprampattuparambil Gopi Aswathy , Kanjirathingal Ibrahim Shabna , Kallattil Aparna , Thomas Arun , Mathew Siby , Haridas Suja , Kuttassery Fazalurahman , Tachibana Hiroshi , Inoue Haruo , Nybin Remello Sebastian 
Published: December 2024

AbstractTwo‐electron oxidation of water to form hydrogen peroxide is an alternative approach to overcome the photon‐flux density problem as the bottleneck subject in artificial photosynthesis associated with molecular systems for photochemical water splitting. Tin‐porphyrin complexes show promising activity and selectivity for the two‐electron water‐oxidation pathway. A key aspect of the reaction mechanism of these systems is the attack of OH−/H2O to the activated axial oxygen atom as the reaction center of the one‐electron oxidized species to form O−O bond, which is feasible when an odd electron is localized on axial oxygen. DFT calculations show that the spin of the odd electron is mostly localized on the axial oxygen atoms when they are in deprotonated states; hence, their pKa determine the applicability of these systems under the pH conditions adopted. The milder pH conditions are most preferable. To explore the conditions the effect of various porphyrin ring substituents on the pKa of the protonation–deprotonation process in A4 and A3B tin‐porphyrin complexes have been studied here by spectrophotometric titration. Tetra‐fluorophenyl (Sn−F4), tetra‐chlorophenyl (Sn−Cl4), and tetra‐methoxycarbonylphenyl (SnTCPPMester)‐substituted Sn−A4 porphyrins have pKa1 values of 10.1 (Sn−F4), 9.8 (Sn−Cl4), and 6.7 (SnTCPPMester), which are in the increasing order of the electron‐withdrawing effect, ‐F (σp=0.06)<‐Cl (0.23)<‐COOMe (0.45). For A3B (A=fluorophenyl or chlorophenyl, B=methoxycarbonylphenyl) Sn‐porphyrins, pKa1 shifts to the smaller value (Sn−F3Mester: 9.4, Sn−Cl3Mester: 6.6), improving the pH range of the active species from basic to ambient pH. This study shows how the pH range of the active species can be effectively tailored by choosing the meso‐substituents.
Mechanistic Studies on the Michael‐type Addition of Amines to 2‐Arylvinylidenebisphosphonates: Bisphosphonate Elimination via a Retro‐Aza‐Michael‐type Reaction
Authors: Sonego Juan M. , Beviglia Martina E. , Stortz Carlos A. , Rodriguez Juan B. 
Published: December 2024

AbstractEncouraged by the potent inhibitory effect exhibited by long chain 2‐alkylaminoethyl‐1,1‐bisphosphonates against proliferation of the clinically more relevant form of Trypanosoma cruzi, the etiologic agent of American trypanosomiasis (Chagas disease), and against tachyzoites of Toxoplasma gondii, the responsible agent of toxoplasmosis, it was conceived a new series of structurally related 1,1‐bisphosphonates bearing a phenyl group at the C‐2 position of the title compounds. The synthetic approach to access these compounds employed a Michael‐type addition by reaction of tetraethyl 2‐phenylvinylidenebisphosphonate or substituted phenyl group with a suitable amine. To our surprise the reaction experienced a retro‐Michael type reaction resulting in an imine formation instead of the hypothetical and expected Michael‐type adduct. Obtainment of the imine derivatives was observed regardless of the nature of the substituent at the phenyl moiety. The source of the alkyl chain was the alkyl group of the amine substrate. Interestingly, when mercaptans were used as soft nucleophiles, the Michael‐type adducts were obtained in all cases.
Recent Advances in Allylic Fluoride Synthesis
Authors: Tomon Daiki , Arimitsu Satoru 
Published: December 2024

AbstractThe recent decades have witnessed considerable progress in the development of fluorinated‐building‐block strategies and direct‐fluorination techniques selectively affording allylic monofluorides and gem‐difluorides. For allylic monofluorides, high enantioselectivities were achieved, even for fluorinated tertiary carbons, with expanded substitution patterns on vinylic moieties enabling precise structural control over di‐, tri‐, and tetrasubstituted fluorides. Advances in defluorofunctionalization and direct C−H fluorination have addressed the limitations of raw materials and made these species more accessible. Additionally, considerable progress has been achieved in the related photoredox reactions, and electrochemistry has emerged as a valuable tool for allylic fluoride synthesis. This review summarizes the recent advances in the synthesis of allylic fluorides, focusing on transition metal catalysis, organocatalysis, and noncatalytic methodologies.
Chiral Sulfoxide Ligands in Asymmetric Allylic Substitution
Authors: Li Xiao , Zheng Sheng‐Cai , Zhao Xiao‐Ming 
Published: December 2024

AbstractChiral nitrogen‐, and phosphorus‐based ligands have been extensively investigated in the asymmetric allylic reactions. However, chiral sulfoxides have not been deemed as a class of practical chiral ligands until last decade, despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination. This perspective collects the recent development of chiral sulfoxide ligands for asymmetric allylation since the beginning of 2013. In addition, insights into the future development of this type of promising ligand are discussed.
Alkynyl Phenyl Selenides as Intermediates in the Metal‐Free Cyclisation of N‐Tosyl Homopropargyl Amides to γ‐Lactams
Authors: Temperini Andrea , Brufani Giulia , Santoro Stefano , Vaccaro Luigi 
Published: December 2024

AbstractIn this work, we present an efficient Brønsted acid‐catalysed intramolecular hydroamination reaction of homopropargyl N‐tosyl amides to produce synthetically useful substituted γ‐lactams through the corresponding alkynyl phenyl selenide intermediates. Our focus on optimising the cyclisation protocol under flow conditions has led to a significant enhancement in efficiency, thereby reducing the time and resources required for the process. DFT calculations of the reaction mechanism for the catalytic transformation of a model alkynyl phenyl selenide were also conducted.
Use of Real‐Time In‐Situ UV‐vis Spectrophotometry as a Tool for Monitoring Electrochemically‐Mediated Organic Synthesis
Authors: Schroeder Chelsea M. , Leadbeater Nicholas E. 
Published: December 2024

AbstractA real‐time in‐situ UV‐vis reaction monitoring tool is used for the optimization and substrate screening of two electrochemically‐mediated reactions, namely the dehydrogenation of 1,2‐diphenylhydrazines, and the hydrogenation of azobenzenes. Key reaction parameters were assayed easily and effectively, this enabling rapid optimization and substrate screening.
Research on Fire Smoke Characteristics and Key Factor Evaluation in High‐Altitude Traffic Tunnels
Authors: Yang Keqing , Sun Jianchun , Xiang Fen , Yang Shiyong , Ling Weihao 
Published: December 2024

ABSTRACTGiven the seriousness of fire safety issues in high‐altitude traffic tunnels, it is essential to investigate the spatial temperature characteristics under the coupling of multiple factors and their correlation with fire safety elements. This study systematically conducted full‐scale simulation analyses of highway tunnels to reveal the distribution of transverse and longitudinal spatial temperature as well as the longitudinal smoke diffusion patterns. Based on the simulation data, an integrated approach utilizing orthogonal test analysis, deviation analysis, and sensitivity analysis was employed to explore the impacts of various factors, including altitude, the transverse position of the fire source, fire scale, and wind speed, on tunnel fire safety. The results indicate that the influence of altitude on the longitudinal temperature along the arch and the position of spatial cross‐section characteristic points varies. Longitudinal ventilation speed is a relatively key factor affecting tunnel fire safety, particularly in terms of arch temperature and smoke backflow length, where its impact is significant. Additionally, fire scale has a notable impact on evacuation safety, with its overall influence ranking just below that of wind speed. In contrast, altitude and fire source position have relatively minor effects on tunnel fire safety. Inadequate longitudinal ventilation hinders the escape of personnel during tunnel fires, indicating that the design and operation of ventilation systems should be prioritized in fire prevention and control strategies. The findings of this study have significant practical implications for optimizing fire prevention and response capabilities in high‐altitude tunnels.
The Submental Artery Island Flap for Reconstruction of Acquired Maxillary and Palatal Defects After Tumor Ablation: Reversed Flow Versus the Extended Antegrade Design
Authors: Amin Ayman A. , Jamali Omer M. , Farid Ramez , Zedan Mohamed H. , Ghobrial Romany Esshak , Zakka Reem , Rifaat Mohammed A. 
Published: December 2024

ABSTRACTBackgroundThe submental artery island flap (SIF) is a valid option for palatal reconstruction. However, the main limitation for its application for palatal defects is the arc of rotation. A novel modification for tunneling of the antegrade design of SIF that allows a compliant easy reach to the defect is described.MethodsEighteen patients with Brown class II maxillectomy defects were included. Reconstruction started using reversed flow SIF in five patients then shifted to the modified antegrade technique in the remaining patients. Speech, swallowing, chewing, other parameters, and oncological outcomes were assessed.ResultsThe reversed flow group has high complications. In the antegrade SIF group, all flaps survived. One developed marginal flap necrosis that healed spontaneously. The follow‐up period ranged from 1 to 4.2 years with favorable functional outcome and with no evidence of recurrence.ConclusionThe modified SIF antegrade design is a reliable option for palate reconstruction that allows favorable functional and oncological outcome.
Vitamin C Ameliorates Potassium Dichromate‐Induced Oxidative Stress and Mitochondrial Dysfunction via PGC‐1α/Nrf‐2/TFAM Pathway
Authors: Fatima Sabiha , Alrashoudi Reem H. , Alqarni Sana S. , Alshehri Samiyah , Alsaigh Sara M. , Malik Abdul , Siddiqi Nikhat J. , Umrani Arbila 
Published: December 2024

ABSTRACTExposure to potassium dichromate (K2Cr2O7) is well known for its nephrotoxic effects on humans and animals. This study investigated the protective effects of vitamin C against K2Cr2O7‐induced nephrotoxicity, focusing on its impact on altered carbohydrate metabolism, mitochondrial dysfunction, and associated molecular mechanisms in the cortical and medullary kidney segments. Male Wistar rats (n = 8) were divided into four groups: Group I received saline, Group II received a single 250 mg/kg body weight (bwt) intraperitoneal (i.p.) injection of vitamin C, Group III received K2Cr2O7 (15 mg/kg bwt, i.p.), and Group IV received vitamin C 6 h before K2Cr2O7 administration. Vitamin C significantly mitigated K2Cr2O7‐induced nephrotoxic effects, restoring normal renal function and histological architecture. It preserved the activities of glycolytic and gluconeogenic enzymes altered by K2Cr2O7. Additionally, vitamin C mitigated K2Cr2O7‐induced mitochondrial dysfunction by maintaining tricarboxylic acid (TCA) cycle enzymes, electron transport chain proteins, mitochondrial DNA copy number, and ATP content. It also reduced oxidative stress markers and enhanced antioxidant enzyme activity. The protective mechanism of vitamin C against K2Cr2O7‐induced renal damage involved upregulation of the protein expression of peroxisome proliferation‐activated receptor‐γ coactivator‐1α (PGC‐1α), which further elevated the protein expression of nuclear factor erythroid 2‐related factor‐2 (Nrf‐2) and transcription factor A, mitochondrial (TFAM), crucial for protecting cells from oxidative stress, enhancing mitochondrial function, and promoting cellular health. Overall, this study highlights the significant protective role of vitamin C against K2Cr2O7‐induced renal damage by preserving carbohydrate metabolism and mitigating mitochondrial dysfunction through the PGC‐1α/Nrf‐2/TFAM pathway, offering valuable insights into its protective mechanisms in nephrotoxicity.
MicroRNAs as Biomarker in Rheumatoid Arthritis: Pathogenesis to Clinical Relevance
Authors: Qamar Tooba , Ansari Md. Samsuddin , Masihuddin  , Mukherjee Sayali 
Published: December 2024

ABSTRACTMicroRNAs (miRNAs) have emerged as intricate players in rheumatoid arthritis (RA), holding promise as discerning biomarkers for diagnostic and prognostic purposes. The lack of sensitivity and specificity in current diagnostic techniques, such as rheumatoid factor (RF) and anti‐citrullinated protein antibodies (ACPA), causes diagnosis delays in RA. The miR‐146a and miR‐155 act in inflammatory cascades and reduce joint deterioration, and miR‐223 is paradoxical, acting differently in different illness scenarios. The microenvironment of RA is shaped by the complex modulation of gene expression and cytokine dynamics by miR‐126 and miR‐24. miRNAs serve as a promising candidate for precision medicine in the management of RA. There are obstacles encountered in validation, delivery optimization, and off‐target effect mitigation before miRNA‐based biomarkers may be applied in clinical settings. Machine learning (ML) and artificial intelligence (AI) have been used to integrate miRNA expression patterns with clinical data to greatly advance the treatment of RA. Because of the disease's inherent complexity and variability, these state‐of‐the‐art models provide accurate predictions regarding the onset, development, and response to treatment of RA. By using clinical information and miRNA expression data, ML algorithms are revolutionizing the treatment of RA by predicting the onset and course of the disease with remarkably high accuracy. The development of therapeutic modalities and miRNA profiling has great potential to transform the diagnosis, prognosis, and treatment of RA, providing fresh hope for better patient outcomes.
CT‐Based Body Composition and Frailty as Predictors of Survival Among Older Adults With Gastrointestinal Malignancies
Authors: Giri Smith , Harmon Christian , Hess Daniel , Cespedes Feliciano Elizabeth M. , Fumagalli Ijeamaka Anyene , Caan Bette , Lenchik Leon , Popuri Karteek , Chow Vincent , Beg Mirza Faisal , Bhatia Smita , Williams Grant R. 
Published: December 2024

ABSTRACTBackgroundOlder adults with cancer are at an increased risk of treatment related toxicities and early death. Routinely collected clinico‐demographic characteristics inadequately explain this increased risk limiting accurate prognostication. Prior studies have suggested that altered body composition and frailty are independently associated with worse survival among older adults with cancer; however, their combined influence remains unclear.MethodsWe used data from a single‐institution prospective cohort study of older adults (≥ 60 years) who underwent geriatric assessment (GA) at the time of initial consultation with a medical oncologist from September 2017 to December 2020 and available baseline abdominal computed tomography within 60 days of GA. Using multi‐slice CT images from T12 to L5 level, we assessed volumetric measures of skeletal muscle (SMV), visceral adipose tissue (VATV), subcutaneous adipose tissue (SATV) and averaged skeletal muscle density (SMD), computing sex‐specific z for each measure. Frailty was measured using a 44‐item frailty index using the deficit accumulation approach. Primary outcome of interest was overall survival (OS) defined as time from GA to death or last follow up. We used multivariable Cox regression model to study the independent association between the above four body composition measurements and OS adjusted for baseline confounders and frailty.ResultsWe included 459 patients with a mean age of 69.7 ± 7.5 years, 60% males and 77% non‐Hispanic Whites. Most had colorectal (27%) or pancreatic cancer (20%) and 48% had stage IV disease. Over a median follow up of 39.4 months, 209 patients (46%) died. In multivariable Cox regression models adjusted for age, sex, race, cancer type, cancer stage and frailty, skeletal muscle volume (HR 0.74; 95% CI 0.58–0.96; p = 0.02, per 1 SD increment) was independently associated with OS. The addition of body composition variables to baseline clinico‐demographic variables and frailty led to a slightly improved model discrimination.ConclusionsSMV is independently associated with OS among older adults with newly diagnosed gastrointestinal cancers. Capturing body composition measurements in oncology practice may provide additional prognostic information for older adults with cancer above and beyond what is captured in routine clinical assessment including frailty.