bluuebunny/crossref_metadata_2025_split huggingface dataset:
Assessing The Key Photophysical Properties of Triangulenium Dyes for DNA Binding by Alteration of the Fluorescent Core
Authors: Lewis Benjamin W. , Bisballe Niels , Santella Marco , Summers Peter A. , Vannier Jean‐Baptiste , Kuimova Marina K. , Laursen Bo W. , Vilar Ramon 
Published: October 2020

AbstractFour‐stranded G‐quadruplex (G4) DNA is a non‐canonical DNA topology that has been proposed to form in cells and play key roles in how the genome is read and used by the cellular machinery. Previously, a fluorescent triangulenium probe (DAOTA‐M2) was used to visualise G4s in cellulo, thanks to its distinct fluorescence lifetimes when bound to different DNA topologies. Herein, the library of available triangulenium probes is expanded to explore how modifications to the fluorescent core of the molecule affect its photophysical characteristics, interaction with DNA and cellular localisation. The benzo‐bridged and isopropyl‐bridged diazatriangulenium dyes, BDATA‐M2 and CDATA‐M2 respectively, featuring ethyl‐morpholino substituents, were synthesised and characterised. The interactions of these molecules with different DNA topologies were studied to determine their binding affinity, fluorescence enhancement and fluorescence lifetime response. Finally, the cellular uptake and localisation of these optical probes were investigated. Whilst structural modifications to the triangulenium core only slightly alter the binding affinity to DNA, BDATA‐M2 and CDATA‐M2 cannot distinguish between DNA topologies through their fluorescence lifetime. It is argued theoretically and experimentally that this is due to reduced effectiveness of photoinduced electron transfer (PET) quenching. This work presents valuable new evidence into the critical role of PET quenching when using the fluorescence lifetime of triangulenium dyes to discriminate G4 DNA from duplex DNA, highlighting the importance of fine tuning redox and spectral properties when developing new triangulenium‐based G4 probes.
Generation and Identification of the Linear OCBNO and OBNCO Molecules with 24 Valence Electrons
Authors: Deng Guohai , Pan Sudip , Jin Jiaye , Wang Guanjun , Zhao Lili , Zhou Mingfei , Frenking Gernot 
Published: October 2020

AbstractTwo structural isomers containing five second‐row element atoms with 24 valence electrons were generated and identified by matrix‐isolation IR spectroscopy and quantum chemical calculations. The OCBNO complex, which is produced by the reaction of boron atoms with mixtures of carbon monoxide and nitric oxide in solid neon, rearranges to the more stable OBNCO isomer on UV excitation. Bonding analysis indicates that the OCBNO complex is best described by the bonding interactions between a triplet‐state boron cation with an electron configuration of (2s)0(2pσ)0(2pπ)2 and the CO/NO− ligands in the triplet state forming two degenerate electron‐sharing π bonds and two ligand‐to‐boron dative σ bonds.
Planar Tetracoordinate Silicon in Organic Molecules As Carbenoid‐Type Amphoteric Centers: A Computational Study
Authors: Zhang Yuwei , Zhang Caiyun , Mo Yirong , Cao Zexing 
Published: October 2020

AbstractDesigning and synthesizing a stable compound with a planar tetracoordinate silicon (ptSi) center is a challenging goal for chemists. Here, a series of potential aromatic ptSi compounds composed of four conjugated rings shared by a centrally embedded Si atom are theoretically designed and computationally verified. Both Born–Oppenheimer molecular dynamics (BOMD) simulations and potential energy surface scannings verify the high stability and likely existence of these compounds, particularly Si‐16‐5555 (SiN4C8H8) with 16 π electrons, under standard ambient temperature and pressure. Notably, the Hückel aromaticity rule, which works well for single rings, is inconsistent with the high stability of Si‐16‐5555 where the 16 p electrons are spread over four five‐membered rings fused together. Bonding analyses show that the strong electron donation from the peripheral 12‐membered conjugated ring with 16 π electrons to the vacant central atomic orbital Si 3pz leads to the stabilization for both the ptSi coordination and planar aromaticity. The partial occupation of Si 3pz results in the peculiar carbenoid‐type behaviors for the amphoteric center. By modulating the electron density on the ring with substituent groups, we can regulate the nucleophilic and electrophilic properties of the central Si.
Synthesis and Coordination Ability of a Donor‐Stabilised Bis‐Phosphinidene
Authors: Hadlington Terrance J. , Kostenko Arseni , Driess Matthias 
Published: October 2020

AbstractChelating phosphines have long been a mainstay as efficient directing ligands in transition‐metal catalysis. Low‐valent derivatives, namely chelating phosphinidenes, are to date unknown, and could lead to chelating complexes containing more than one metal centre due to the intrisic capacity of phosphinidenes to bind two metal fragments at one P‐centre. Here we describe the synthesis of the first such chelating bis‐phosphinidene ligand, XantP2 (2), generated by the reduction of a diphosphino xanthene derivative, Xant(PH2)2 (1) with iPrNHC (iPrNHC=[:C{N(iPr)C(H)}2]). Initial studies have shown that this novel chelating ligand can act as a bidentate ligand towards element dihalides (i.e. FeCl2, ZnI2, GeCl2, SnBr2), forming cationic complexes with the tetryl elements. In contrast, XantP2 demonstrates an ability to bind multiple metal centres in the reaction with CuCl, leading to a cationic Cu3P3 ring complex, with Cu centres bridged by phosphinidene arms. Density Functional Theory calculations show that 2 indeed holds 4 lone pairs of electrons, shedding further light on the coordination capacity for this novel ligand class through observation of directionality and hybridisation of these electron pairs.
Ion Exchange Membrane “ABC” – A Key Material for Upgrading Process Industries
Authors: Wang Yaoming , Yang Zhengjin , Wu Liang , Ge Liang , Xu Tongwen 
Published: October 2020

AbstractIon exchange membrane plays a crucial role in transforming and upgrading traditional chemical manufacturing procedures and boosting a multitude of new applications. Due to the strict regulations on wastewater discharge and increasing demands of renewable energy, anion exchange membrane (“A” membrane), bipolar membrane (“B” membrane) and cation exchange membrane (“C” membrane) have become a key material for upgrading various process industries. Herein, we summarized several novel synthetic routes for “ABC” membranes fabrication from the viewpoints of designing novel membrane synthetic routes, regulating the ionic transport channels, imparting dynamic transfer regions, introducing intrinsic micro‐porosity into the membrane and among others. The account includes a brief introduction to membrane structure designs and fabrications, emerging and industrial applications, and perspectives on ion exchange membranes.
Who is the most influenced person in your academic career?My supervisor academician Binglin He.How do you get into the field of ion exchange membrane?I got in contact with ion exchange membranes during my postdoc research in Nankai University under the guidance of Prof. Binglin He. My supervisor is known as “father of China's ion exchange resin”. But in the synthesis of ion exchange resin, the resin pellets larger than 6 mm or smaller than 4 mm cannot be used and are directly discarded. Therefore, Prof. He asked me to explore how to convert them into membrane shape so as to reuse the wasted resin. Since then I entered the field of ion exchange membrane.In your opinion, what is the most promising ion exchange membrane in the next couple years?Alkaline stable anion‐exchange membranes that can be used for hydrogen production from electrolytic water splitting, fuel cells, and electrochemical ammonia synthesis, etc.Besides the fundamental research, why do you spend a lot time andenergy to industrialize the ion exchange membrane?Ion exchange membrane is relatively a narrow product in the field of separation membrane materials. Nowadays, there are tremendous demands of these kind of membranes due to the stricter regulations on wastewater disposal. However, the development of ion exchange membranes in China lags far behind that in other developed countries. As a scientist in this filed, I believe that I have the responsibility to promote the development and advancement of our domestic ion exchange membrane. For this reason, four licensed patents of us have been transferred for industrialization and more than 400000 m2 of membranes were used per year in various industries.What is the greatest honor for your academic achievement?My students are my greatest honor. I am proud of more and more students being graduated from my lab, who have played/will play important roles in making our country stronger.What's your hobbies?Walking, playing basketball and cards.
Cilium axoneme internalization and degradation in chytrid fungi
Authors: Venard Claire M , Vasudevan Krishna Kumar , Stearns Tim 
Published: October 2020

AbstractLoss of the cilium is important for cell cycle progression and certain developmental transitions. Chytrid fungi are a group of basal fungi that have retained centrioles and cilia, and they can disassemble their cilia via axoneme internalization as part of the transition from free‐swimming spores to sessile sporangia. While this type of cilium disassembly has been observed in many single‐celled eukaryotes, it has not been well characterized because it is not observed in common model organisms. To better characterize cilium disassembly via axoneme internalization, we focused on chytrids Rhizoclosmatium globosum and Spizellomyces punctatus to represent two lineages of chytrids with different motility characteristics. Our results show that each chytrid species can reel in its axoneme into the cell body along its cortex on the order of minutes, while S. punctatus has additional faster ciliary compartment loss and lash‐around mechanisms. S. punctatus retraction can also occur away from the cell cortex and is partially actin dependent. Post‐internalization, the tubulin of the axoneme is degraded in both chytrids over the course of about 2 hr. Axoneme disassembly and axonemal tubulin degradation are both partially proteasome dependent. Overall, chytrid cilium disassembly is a fast process that separates axoneme internalization and degradation.
Camellia Pollen‐Derived Carbon with Controllable N Content for High‐Performance Supercapacitors by Ammonium Chloride Activation and Dual N‐Doping
Authors: Cao Lihua , Li Huiling , Xu Zhaoxiu , Gao Ruirui , Wang Suqing , Zhang Guoying , Jiang Shaohua , Xu Wenhui , Hou Haoqing 
Published: October 2020

AbstractBiomass‐derived carbon materials are an amazing electrode material for supercapacitor, owing to their abundant, porous structure and composition. Herein, a controllable N content carbon material with hierarchical porous structure was fabricated via an integrated carbonization, activation and nitrogen‐doping process. N‐rich camellia pollen is used as carbon precursor, while NH4Cl is employed as both activation agent and dopant. The optimal N‐doped carbon with higher N content (3.82 at%), suitable pore size distribution and larger specific surface area (810 m2 g−1), provides abundant ion transport channels and exposes more accessible active sites. Thus, a high specific capacitance of 280 F g−1 (1 A g−1) in 6 M KOH (three‐electrode system) can be obtained with making full use of N−HPC‐1. Moreover, the assembled symmetrical supercapacitor delivers high energy densities both in 6 M KOH (13.3 Wh kg−1) and 1 M Na2SO4 (20 Wh kg−1) that can be used for LED lighting. More than that, it is also demonstrates excellent cycle stability in 6 M KOH (85.4% after 20000 cycles at 20 A g−1). In view of the above‐mentioned merits, this N‐doped hierarchical porous carbon is anticipated to be a promising material for application in supercapacitors and other fields.
Spatial Distribution and Location of Natural Organic Matter on Sediment Particles by Scanning Electron Microscopic Analysis and the Development of a New Persistent Organic Pollutant–Sediment Kinetic Desorption Model
Authors: Clay Marra M. , Morgan Jack A. , Dunnivant Frank M. 
Published: October 2020

Abstract
Natural organic matter (NOM) has long been shown to be the dominant factor in determining equilibrium and kinetic processes during sorption and desorption phenomena in sediment and soil experiments. Although several models have been suggested for predicting these processes, few offer mechanistic interpretations because the spatial location of organic matter on sediment particles is unknown. This investigation manually examined sediment particles from multiple locations, containing varying concentrations of NOM, using scanning electron microscopy with energy dispersive X-ray spectroscopy to determine the types of particles present by categorizing them as individual particles, aggregates, and “other” (detritus, algae, etc.). These types of particles were subsequently analyzed for their elemental composition, specifically the spatial location of carbon. By creating a carbon map of each particle, this investigation has determined that organic matter tends to occur in 2 forms: large aggregates or dispersed across individual sediment particles. These findings were then used to propose a more mechanistically sound mathematical model for pollutant desorption phenomena, assigning the traditional labile kinetic release component to the dispersed NOM spread randomly across sediment particles and the nonlabile kinetic release component to diffusion from densely packed NOM aggregates. Environ Toxicol Chem 2021;40:323–332. © 2020 SETAC
Reconstructing prehistoric demography: What role for extant hunter‐gatherers?
Authors: Page Abigail E. , French Jennifer C. 
Published: October 2020

AbstractDemography is central to biological, behavioral, and cultural evolution. Knowledge of the demography of prehistoric populations of both Homo sapiens and earlier members of the genus Homo is, therefore, key to the study of human evolution. Unfortunately, demographic processes (fertility, mortality, migration) leave little mark on the archeological and paleoanthropological records. One common solution to this issue is the application of demographic data from extant hunter‐gatherers to prehistory. With the aim of strengthening this line of enquiry, here we outline some pitfalls and their interpretative implications. In doing so, we provide recommendations about the application of hunter‐gatherer data to the study of demographic trends throughout human evolution. We use published demographic data from extant hunter‐gatherers to show that it is the diversity seen among extant hunter‐gatherers—both intra‐ and inter‐population variability—that is most relevant and useful for understanding past hunter‐gatherer demography.
Aflatoxin exposure among lactating women in southern Ethiopia
Authors: Boshe Bergene , Gebremedhin Samson , Alemayehu Fikadu , Eshete Mesfin , Taye Mestawet , Stoecker Barbara J. 
Published: October 2020

AbstractIn Ethiopia and many other low‐income countries, little is known about the exposure of lactating women to aflatoxin, which is a major health concern to the mother and her nursing infant. We determined the aflatoxin B1 contamination of family foods (AFB1) and urinary aflatoxin M1 (AFM1) of lactating women in Sidama, southern Ethiopia, and compared the levels across agroecological settings (lowland, midland, highland) and two seasons. We conducted two surveys (n = 360) that represented the dry and wet seasons of the locality. AFM1 and AFB1 were determined using enzyme‐linked immunosorbent assay (ELISA). Statistical analysis was made using Mann–Whitney U test and Kruskal–Wallis test. The median (interquartile range) AFB1 was 0.94 (0.63–1.58) ppb. AFB1 was detected in 95.6% of the food samples, and 13.6% exceeded the 2.0 ppb threshold. We observed an increasing trend for aflatoxin exposure from highland to lowland (p < .001), but there was no difference between seasons (p = .743). The median (interquartile range) urinary AFM1 was 214 (undetectable to 2,582) ppt, and AFM1 was detectable in 53.3% of the samples. Urinary AFM1 showed significant difference among agroecological zones (p < .001) but not between seasons (p = .275). A significant but weak correlation was observed between AFB1 and urinary AFM1 (rs = 0.177, p = .001). We concluded that lactating women in Sidama, especially those in the lowland area, have unsafe exposure to aflatoxin.
Disease aggressiveness signatures of amyotrophic lateral sclerosis in white matter tracts revealed by the D50 disease progression model
Authors: Steinbach Robert , Gaur Nayana , Roediger Annekathrin , Mayer Thomas E. , Witte Otto W. , Prell Tino , Grosskreutz Julian 
Published: October 2020

AbstractNumerous neuroimaging studies in amyotrophic lateral sclerosis (ALS) have reported links between structural changes and clinical data; however phenotypic and disease course heterogeneity have occluded robust associations. The present study used the novel D50 model, which distinguishes between disease accumulation and aggressiveness, to probe correlations with measures of diffusion tensor imaging (DTI). DTI scans of 145 ALS patients and 69 controls were analyzed using tract‐based‐spatial‐statistics of fractional anisotropy (FA), mean‐ (MD), radial (RD), and axial diffusivity (AD) maps. Intergroup contrasts were calculated between patients and controls, and between ALS subgroups: based on (a) the individual disease covered (Phase I vs. II) or b) patients' disease aggressiveness (D50 value). Regression analyses were used to probe correlations with model‐derived parameters. Case–control comparisons revealed widespread ALS‐related white matter pathology with decreased FA and increased MD/RD. These affected pathways showed also correlations with the accumulated disease for increased MD/RD, driven by the subgroup of Phase I patients. No significant differences were noted between patients in Phase I and II for any of the contrasts. Patients with high disease aggressiveness (D50 < 30 months) displayed increased AD/MD in bifrontal and biparietal pathways, which was corroborated by significant voxel‐wise regressions with D50. Application of the D50 model revealed associations between DTI measures and ALS pathology in Phase I, representing individual disease accumulation early in disease. Patients' overall disease aggressiveness correlated robustly with the extent of DTI changes. We recommend the D50 model for studies developing/validating neuroimaging or other biomarkers for ALS.
Reply to the Letter to the Editor regarding “Early oral hydration protects against pharyngocutaneous fistula after total laryngectomy or total pharyngolaryngectomy”
Authors: Le Flem Matthieu , Santini Laure , Boulze Carole , Alshukry Abdallah , Giovanni Antoine , Dessi Patrick , Fakhry Nicolas 
Published: October 2020

see page 716–717.
Real‐world, population‐based cohort study of toxicity and resource utilization of second‐line ipilimumab for metastatic melanoma in Ontario, Canada
Authors: Dai Wei Fang , Beca Jaclyn , Croxford Ruth , Isaranuwatchai Wanrudee , Menjak Ines B. , Petrella Teresa M. , Mittmann Nicole , Earle Craig C. , Gavura Scott , Mercer Rebecca E. , Hanna Timothy P. , Chan Kelvin K. W. 
Published: October 2020

AbstractSecond‐line ipilimumab has been publicly funded in Ontario for metastatic melanoma (MM) since September 2012. We examined real‐world toxicity of second‐line ipilimumab compared to standard second‐line treatments prior to funding. MM patients who received systemic treatment from April 2005 to March 2015 were included. Patients receiving second‐line ipilimumab after September 2012 were considered as cases, and those who received second‐line treatment prior to the funding date were included as historical controls. Outcomes assessed include treatment‐related mortality, any‐cause hospital visits, ipilimumab‐related hospital visits and specialist visits (eg, endocrinologists, ophthalmologists, gastroenterologists, rheumatologists and respirologists), which were captured from up to 30 and/or 90 days after end of second‐line treatment. Inverse probability of treatment weighting was used to adjust for baseline differences between groups. Odds ratios (ORs) from logistic regressions and rate ratios (RRs) from rate regressions were used to assess differences between groups. We identified 329 MM patients who received second‐line treatments (ipilimumab: 189; controls: 140). Ipilimumab was associated greater any‐cause (60.1% vs 45.7%; OR = 1.81; P value = .019) and ipilimumab‐related (47.2% vs 31.9%; OR = 1.91; P value = .011) hospital visits. Adjusting for different follow‐up days, ipilimumab was associated with higher rates of all‐cause (RR = 1.56 [95%CI: 1.12‐2.16]), and ipilimumab‐related (RR = 2.18 [95% CI: 1.45‐3.27]) hospital visits. Patients receiving ipilimumab were more likely to visit specialist involved in immunotherapy toxicity management (23.5% vs 13.7%; P value = .04). Compared to historical second‐line treatments, second‐line ipilimumab was associated with more health service utilization (specifically hospital visits and specialist visits), suggestive of potentially increased toxicity in the real world.
Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families
Authors: Feldt Milica , Brown Alex 
Published: October 2020

AbstractIt was previously reported that Laplace transformed local CC2 (LCC2*) provided the best agreement (MAE = 0.145 eV) when comparing vertical excitation energies to experimental λmax for a benchmark set of 17 BODIPY/Aza‐BODIPY molecules. However, these energies did not agree with values obtained from canonical CC2. Here we report LCC2* computations of vertical excitation energies on the same benchmark set of molecules using a newly implemented treatment of the ground state. Comparison with resolution‐of‐identity approximate coupled cluster to second‐order (RI‐CC2) results demonstrate that the new LCC2* results agree quantitatively. Furthermore, these values can easily be corrected empirically to also provide excellent agreement with the experiment. We show that the local algebraic diagrammatic construction to second‐order (LADC(2)) method exhibits the same differences between implementations as seen for LCC2. The source of the difference is traced to an improved treatment of the ground state in the local methods, which decreases agreement with the experiment (as attributed to a fortuitous cancellation of errors) but significantly improves agreement with RI‐CC2. While the absolute vertical excitation energies now show larger deviations, there remains a strong linear correlation between the LCC2* results and the experiment. For the 17 BODIPY/Aza‐BODIPY molecules vertical excitation energies are determined using DLPNO‐STEOM‐CCSD and shown to have excellent agreement with experimental λmax (MAE = 0.145 eV), which is the best of all the single‐reference methods. The vertical excitation energies are determined using LCC2*, empirically corrected LCC2*, and RI‐CC2 for a series of eight large BODIPYs and Aza‐BODIPYs.