bluuebunny/crossref_metadata_2025 huggingface dataset:
Photocatalytic Abstraction of Hydrogen Atoms from Water Using Hydroxylated Graphitic Carbon Nitride for Hydrogenative Coupling Reactions
Authors: Zhang Dongsheng , Ren Pengju , Liu Wuwen , Li Yaru , Salli Sofia , Han Feiyu , Qiao Wei , Liu Yu , Fan Yingzhu , Cui Yi , Shen Yanbin , Richards Emma , Wen Xiaodong , Rummeli Mark H. , Li Yongwang , Besenbacher Flemming , Niemantsverdriet Hans , Lim Tingbin , Su Ren
Published: March 2022

Employing pure water, the ultimate green source of hydrogen donor to initiate chemical reactions that involve a hydrogen atom transfer (HAT) step is fascinating but challenging due to its large H−O bond dissociation energy (BDEH‐O=5.1 eV). Many approaches have been explored to stimulate water for hydrogenative reactions, but the efficiency and productivity still require significant enhancement. Here, we show that the surface hydroxylated graphitic carbon nitride (gCN−OH) only requires 2.25 eV to activate H−O bonds in water, enabling abstraction of hydrogen atoms via dehydrogenation of pure water into hydrogen peroxide under visible light irradiation. The gCN−OH presents a stable catalytic performance for hydrogenative N−N coupling, pinacol‐type coupling and dehalogenative C−C coupling, all with high yield and efficiency, even under solar radiation, featuring extensive impacts in using renewable energy for a cleaner process in dye, electronic, and pharmaceutical industries.
A General Strategy for Kilogram‐Scale Preparation of Highly Crystal‐line Covalent Triazine Frameworks
Authors: Sun Tian , Liang Yan , Luo Wenjia , Zhang Lei , Cao Xiaofeng , Xu Yuxi
Published: March 2022

Scalable and eco‐friendly synthesis of crystalline porous covalent triazine frameworks (CTFs) is essential to realize their broad industrial applications but remains a great challenge, which requires the fundamental understanding of the two‐dimensional polymerization mechanism. Herein, we report a universal polyphosphoric acid (H6P4O13)‐catalyzed nitrile trimerization route to synthesize a series of highly crystalline CTFs with high specific surface areas. This new strategy enables the cost‐effective large‐scale fabrication of crystalline CTFs at kilogram level for the first time. Through density functional theory calculation and detailed controlled experiments, we reveal that the polyphosphate acid show much higher catalytic activity for trimerization reaction than its analogues such as P2O5and H3PO4. Furthermore, the crystalline CTFs with regular porosity and abundant triazine groups exhibit ultrahigh removal efficiency of micropollutants, indicating its great potential in environment remediation.
Experimental and theoretical approaches on structural, spectroscopic (FT‐IR and UV‐Vis), nonlinear optical, and molecular docking analyses for Zn (II) and Cu (II) complexes of 6‐chloropyridine‐2‐carboxylic acid
Authors: Dege Necmi , Tamer Ömer , Şimşek Merve , Avcı Davut , Yaman Mavişe , Başoğlu Adil , Atalay Yusuf
Published: March 2022

Novel transition metal‐based complexes that may be of value as biological agents and/or nonlinear optical materials, Zn (II) and Cu (II) transition metal complexes of 6‐chloropyridine‐2‐carboxylic acid (LH), were successfully synthesized. The chemical structure of each complex was characterized using X‐ray diffraction (XRD) method and FT‐IR spectroscopy. XRD and FT‐IR demonstrated that L ligand coordinate to central metal ions through the donor N and O atoms. By coordinating two H2O ligand to Zn (II) ion, a distorted octahedral complex geometry was constructed for 1. As for 2, a distorted trigonal bipyramidal coordination geometry was obtained by a H2O ligand coordination to Cu (II) ion. Theoretical studies using B3LYP/6‐311++G(d,p)‐LanL2DZ were performed to further validate the proposed structures. The molecular docking of 1 to SARS‐CoV‐2 main protease (PDB: 6LU7) gives a binding energy of −5.24 kcal/mol and inhibition constant of 144.6 μM, demonstrating that 1 is a more promising candidate to biologically active complexes than 2. The first‐order hyperpolarizability (β) parameter for 1 and 2 was calculated as 0.88 × 10−30 and 10.40 × 10−30 esu, respectively. These β values also demonstrated that 2 exhibits more effective NLO character than 1 due to the electronic configuration and coordination geometry.
Transamidation‐based vitrimers from renewable sources
Authors: Pettazzoni Luca , Leonelli Francesca , Martinelli Andrea , Migneco Luisa Maria , Alfano Sara , Di Luca Daniele , Celio Lorenzo , Di Lisio Valerio
Published: March 2022

Vitrimers are polymeric materials that behave as thermosets at room temperature but, when heated, they exhibit a plastic flow similar to thermoplastics, enabling their reprocessability. A series of new bio‐based polyamide‐polyamine vitrimers are synthetized starting from tris(2‐aminoethyl)amine and epoxidized methyl oleate, a material that can be easily prepared from renewable resources obtainable both from natural products and waste. The incorporation of free amine groups in the network enables the transamidation exchange reaction with the crosslinking amide functions; this reaction, if appropriately catalyzed, donates a full reprocessability to the material. Boric acid, which is known to be a green, cheap and non‐toxic catalyst for transamidation reactions, is employed in this work. Once that the optimal condition for the transamidation reaction is found, different catalyst loadings are tested and the obtained materials are subjected to thermal and mechanical characterization. The obtained materials possess good thermal stability up to 300°C and a Tg value ranging between 7 and 21°C depending on the B(OH)3 content. Furthermore it is possible to observe how the introduction of boric acid in the materials reduces the Ea (inferred from stress‐relaxation experiments) of the transamidation reaction from 130 ± 8 KJ mol−1 to a mean value of 63 ± 4 KJ mol−1.
Copper chelation therapy inhibits renal fibrosis by modulating copper transport proteins
Authors: Saifi Mohd Aslam , Godugu Chandraiah
Published: March 2022

The copper (Cu) transporter proteins play an important role in the maintenance of the Cu homeostasis in the body. Lysyl oxidase (LOX) proteins are involved in crosslinking of collagens and elastin molecules resulting in the establishment of extracellular matrix (ECM) and require Cu for their functional activity. Although there are few reports showing the protective effects of Cu chelators, the mechanism behind protection remains unknown. The present study investigated the role of Cu transporter proteins in renal fibrosis. We used tubular epithelial cells and three different animal models of renal injury to investigate the induction of Cu transporter proteins in renal injury with different etiology. We used disulfiram, clioquinol as two Cu chelators and ammonium tetrathiomolybdate as a standard Cu chelator. In addition, β‐aminopropionitrile (BAPN) was used as a standard LOX inhibitor. We demonstrated that renal fibrosis is associated with the induction of Cu transporter proteins such as ATP7A and Copper Transporter 1 (CTR1) but the Cu overload did not induce renal fibrosis. In addition, the Cu chelators inhibited renal fibrosis by inhibiting the Cu transporter proteins.
Molecular mechanisms involved in the effects of morin in experimental hepatic encephalopathy
Authors: Shafey Ghada M. , Rashed Engy R. , Zaki Hala F. , Attia Amina S. , El‐Ghazaly Mona A.
Published: March 2022

This study aimed to investigate the possible usefulness of morin flavonoid in comparison to silymarin as a hepatic/neuronal‐supportive agent with similar effects and higher bioavailability in a rat model of hepatic encephalopathy (HE). Morin effects on rat liver and brain were evaluated post‐induction of HE by thioacetamide (TAA; 200 mg/kg/day for 3 successive days). Then, the serum activities of aspartate transaminase (AST) and alanine transaminase (ALT) together with ammonia concentration were estimated to assess the liver function. Also, the degree of brain effects was evaluated via the assessment of brain contents of reduced glutathione (GSH), malondialdehyde (MDA), tumor necrosis factor‐alpha (TNF‐α), and interleukin (IL‐1β) together with glutathione peroxidase (GPx) activity. In addition, the apoptotic and inflammatory changes in brain and liver tissues were also assessed via immunohistochemical examination. Our findings revealed a promising effect of morin against HE complications; as it corrected the liver functions, attenuated the brain/liver tissue injuries, and reduced the apoptotic and inflammatory insults of HE on both organs. These effects are comparable to those of silymarin. Morin could be introduced as a promising hepato‐ and neuro‐therapeutic adjuvant in HE‐associated neuronal complications especially in cases like silymarin intolerance.
Anatomy of the vesicovaginal fascia and its relation to branches of the inferior hypogastric plexus
Authors: Stupart Douglas , Pickles Kylie , Briggs Chris
Published: March 2022

The inferior hypogastric plexus (IHP) lies in the extraperitoneal pelvis, and supplies branches to pelvic and perineal viscera. In men, the rectoprostatic fascia (Denonvillier's fascia) forms a distinct double fascial layer between the seminal glands and the rectum. The hypogastric nerve projections to the prostate and seminal glands run anterior to this. An analagous fascial layer in women between the vagina and cervix posteriorly and the urinary bladder anteriorly has recently been described. The purpose of this study was to examine the anatomy of the vesicovaginal fascia (VVF) and to determine its relationship to the anterior branches of the IHP. This dissection study examined the fascial layers between the posterior urinary bladder and anterior vagina/cervix (VVF) in 15 female embalmed cadavers and three fresh specimens. Anterior branches of the IHP were identified and followed distally. The relationship between these nerve projections and the VVF was examined. In 16 dissection, the VVF was identified as a complete fascial plane extending beneath the vesicouterine pouch to the neck of the bladder inferiorly and to the endopelvic fascia laterally. Anterior projections from the hypogastric nerves and IHP maintained an extraperitoneal course passing anteriorly to the VVF towards the urinary bladder The VVF is a distinct fascial structure and projections of the hypogastric nerves pass anterior to this. This may have implications for nerve sparing hysterectomy.
Sexual function of transgender women after gender affirming surgery: A mini review
Authors: Barcelos Thays Marina Roncato , Ferreira Cristine Homsi Jorge , Lerri Maria Rita , Brito Luiz Gustavo Oliveira , de Sá Marcos Felipe Silva , de Sá Ana Carolina Silva , da Silva Lara Lucia Alves
Published: March 2022

A transgender person has a gender identity opposite to the sex assigned at birth. Transgender individuals may have altered sexual function (SF) due to psychosocial factors related to body image distortion, shame, and dissatisfaction with genital appearance, and these conditions can increase the risk of sexual dysfunction. This study aimed to characterize the SF of trans‐women after gender affirming surgery (GAS). We reviewed the Pubmed database for studies published between January 2008 and December 2021. 17 studies were included, four were cross‐sectional studies, one prospective study, four prospective cohort studies, five retrospective studies. The instruments used to evaluate the SF were female sexual function index, semistructured questionnaires, patients' opinion, Sexual Desire Inventory, Maudsley Marital Questionnaire‐S, WHOQOL‐100. The results of our review indicate there is weak evidence that GAS improves the SF of trans‐women. We thus recommend that future studies use questionnaires that are validated for the assessment of the SF of trans‐women to better determine the impact of genital surgery in this population.
Biomass and Active Compounds Accumulation of the Medicinal Orchid Pleione bulbocodioides in Response to Light Intensity and Irrigation Frequency
Authors: Shi Yu‐Cen , Zhang Wei , Zhang Shi‐Bao
Published: March 2022

Pseudobulbs of Pleione species are widely used as traditional medicine in Asian countries, but the mechanism of active compound accumulation remains unclear. In the present study, we investigated the accumulation of biomass and three active compounds (dactylorhin A, militarine and batatasin III) of Pleione bulbocodioides in response to different light intensities and irrigation frequencies. We found that single high light (65 % of full sunlight) or drought stress (14‐day irrigation interval) increased active compounds accumulation but the combined effect of these two treatments decreased the total content of these three active compounds. This decrease was due to the plants under combined stress having a significantly lower photosynthetic rate, leaf area and longevity, leading to a dramatic decrease in pseudobulb biomass. Among all treatments, the highest total content of active compounds was observed in plants subjected to the high light level with a high water level (3‐day irrigation interval), and plants under medium light intensity (30 % of full sunlight) also had considerable content of active compounds accumulation. To balance the quality and quantity of Pleione pseudobulbs during artificial cultivation, 30∼65 % of full sunlight with the avoidance of drought stress is recommended. Our results suggest the accumulation of the three active compounds is significantly influenced by light intensity and irrigation frequency, which may contribute to the artificial cultivation and quality control of medicinal Pleione.
Artificial Fusions between P450 BM3 and an Alcohol Dehydrogenase for Efficient (+)‐Nootkatone Production
Authors: Kokorin Arsenij , Urlacher Vlada B.
Published: March 2022

Multi‐enzyme cascades enable the production of valuable chemical compounds, and fusion of the enzymes that catalyze these reactions can improve the reaction outcome. In this work, P450 BM3 from Bacillus megaterium and an alcohol dehydrogenase from Sphingomonas yanoikuyae were fused to bifunctional constructs to enable cofactor regeneration and improve the in vitro two‐step oxidation of (+)‐valencene to (+)‐nootkatone. An up to 1.5‐fold increased activity of P450 BM3 was achieved with the fusion constructs compared to the individual enzyme. Conversion of (+)‐valencene coupled to cofactor regeneration and performed in the presence of the solubilizing agent cyclodextrin resulted in up to 1080 mg L−1 (+)‐nootkatone produced by the fusion constructs as opposed to 620 mg L−1 produced by a mixture of the separate enzymes. Thus, a two‐step (+)‐valencene oxidation was considerably improved through the simple method of enzyme fusion.
Primary large B‐cell lymphoma of the cervix: A case report and review of literature
Authors: Aminimoghaddam Soheila , Salarifar Elnaz , Noei Teymoordash Somayyeh
Published: March 2022

The primary diffuse large B‐cell lymphoma (DLBCL) of the uterine cervix is extremely rare. In the present study, we described two cases of DLBCL of the uterine cervix in reproductive‐aged women complaining of postcoital bleeding, recurrent vaginal discharge, and abnormal uterine bleeding.
Constructing Atomic Fe and N Co‐doped Hollow Carbon Nanospheres with a Polymer Encapsulation Strategy for High‐Performance Lithium‐Sulfur Batteries with Accelerated Polysulfide Conversion
Authors: Zhang Ting‐Ting , Yang Cheng‐Ye , Qu Jin , Chang Wei , Liu Yu‐Hao , Zhai Xian‐Zhi , Liu Hong‐Jun , Jiang Zhi‐Guo , Yu Zhong‐Zhen
Published: March 2022

As competitive next‐generation rechargeable batteries, lithium‐sulfur batteries (LSBs) suffer from the shuttle effect and the sluggish kinetics of intermediate polysulfides during charge and discharge processes, adversely affecting their electrochemical performances and actual applications. Herein, we demonstrate a polymer encapsulation strategy to synthesize atomic Fe and N co‐doped hollow carbon nanospheres (Fe−NHC) with Fe−Nx sites for modifying commercial PP separator of LSBs to suppress the shuttle effect and promote the kinetics of intermediate polysulfides. Benefiting from the excellent structural design, the doped‐N with positive charges could effectively adsorb negatively charged soluble polysulfides, help attract the soluble polysulfides to the Fe atoms and boost the catalytic transformation of the soluble polysulfides. Additionally, such a thin carbon shell could provide a short mass diffusion pathway and hence promote the adsorption and the catalytic conversion. Therefore, the battery with the Fe−NHC/PP separator delivers outstanding cycling and rate performances. At the large current density of 1 C, the specific capacity is 1079 mA h g−1 and maintains a low loss of 0.076 % per cycle within 500 cycles. Even at a harsh current density of 4 C, a high capacity of 824 mA h g−1 is still achieved, indicating the advantage of the Fe−NHC/PP separator in LSBs.
Generalizing the Aromatic δ‐Amino Acid Foldamer Helix
Authors: Bindl Daniel , Mandal Pradeep K. , Huc Ivan
Published: March 2022

A series of aromatic oligoamide foldamer sequences containing different proportions of three δ‐amino acids derived from quinoline, pyridine, and benzene and possessing varying flexibility, for example due to methylene bridges, were synthesized. Crystallographic structures of two key sequences and 1H NMR data in water concur to show that a canonical aromatic helix fold prevails in almost all cases and that helix stability critically depends on the ratio between rigid and flexible units. Notwithstanding subtle variations of curvature, i. e. the numbers of units per turn, the aromatic δ‐peptide helix is therefore shown to be general and tolerant of a great number of sp3 centers. We also demonstrate canonical helical folding upon alternating two monomers that do not promote folding when taken separately: folding occurs with two methylenes between every other unit, not with one methylene between every unit. These findings highlight that a fine‐tuning of helix handedness inversion kinetics, curvature, and side chain positioning in aromatic δ‐peptidic foldamers can be realized by systematically combining different yet compatible δ‐amino acids.
Influence of rivaroxaban compared to vitamin K antagonist treatment upon development of cardiovascular calcification in patients with atrial fibrillation and/or pulmonary embolism
Authors: Stöhr Robert , Dirrichs Timm , Kneizeh Kinan , Reinartz Sebastian , Frank Dario , Brachmann Johannes , Schroeder Joerg , Schurgers Leon , Göttsch Claudia , Keszei Andras , Floege Jürgen , Marx Nikolaus , Brandenburg Vincent , Schuh Alexander
Published: March 2022

Background

Vitamin K antagonists (VKA) such as warfarin or phenprocoumon have been the mainstay of therapy for long‐term oral anticoagulant therapy (OAT) in patients with atrial fibrillation or with pulmonary embolism. Due to interferences with matrix Gla‐protein, an important vitamin K‐dependent local calcification inhibitor in cardiovascular structures, VKA antagonists stimulate cardiovascular calcification (CVC). In contrast, rivaroxaban, a nonvitamin K‐dependent oral anticoagulant (NOAC), should be neutral in terms of CVC. We seek to investigate these potential differences in CVC development between VKA versus NOACs in a randomized controlled trial (RCT).

Methods

The influence of rivaroxaban compared to vitamin K antagonist treatment upon development of cardiovascular calcification in patients with atrial fibrillation and/or pulmonary embolism trial (NCT02066662) is a multicenter, prospective RCT with a two‐arm, open‐label study design. The primary endpoint is the progression of coronary and aortic valve calcification (quantified as calcification volume score) as assessed by cardiac computed tomography (CT) at 24 months in patients either treated by rivaroxaban or VKA. A total of 192 patients were randomized in a 1:1 fashion. The main inclusion criteria were the presence of atrial fibrillation and/or pulmonary embolism with the indication for OAT and pre‐existent coronary calcification. The development of CVC will be assessed by follow‐up CT at 12 and 24 months.

Results

In total 192 patients (median age 70, 72% male) were enrolled over a period of 5 years and followed up for 2 years.
Total IgE in tears accurately reflects the severity and predicts the prognosis of seasonal allergic conjunctivitis
Authors: Bao Jiayu , Tian Lei , Meng Yifan , Wu Binge , Wang Jingyi , He Jing , Shao Qiyan , Wang Chengshuo , Jie Ying , Zhang Luo
Published: March 2022

Background

Although immunoglobulin E (IgE) increases significantly in tears and serum during seasonal allergic conjunctivitis (SAC), it is unclear whether tear total IgE can reflect the severity and prognosis of SAC more accurately than serum total IgE. We aimed to investigate the usefulness of measuring the total IgE in tears to evaluate the severity and determine the treatment of SAC.

Methods

This prospective, nonrandomized study involved 55 patients with SAC and 10 age‐ and sex‐matched healthy controls. Serum and tears were collected before and after treatment to analyze the total IgE. SAC patients received the same topical anti‐allergy treatment and were followed‐up every 2 weeks for 1 month. The relationship of tear and serum total IgE concentrations with pollen concentrations and symptom severity before and after treatment was assessed.

Results

The total IgE concentration in tears was higher in SAC patients than in healthy participants with significant correlations between tear and serum total IgE concentrations. The total IgE concentration in tears, but not in serum, correlated with the pollen concentration and severity of ocular symptoms and reactions in SAC. Treatment‐associated improvements in symptoms and reactions in SAC correlated with decreased concentrations of the tear total IgE. Patients with disease recurrence following treatment demonstrated significantly higher tear total IgE concentrations than patients with no recurrence.

Conclusion

The total tear IgE level can indicate the severity and predict the prognosis of SAC more accurately than the serum total IgE.
A 1,2‐Dioxetane‐Based Chemiluminescent Probe for Highly Selective and Sensitive Detection of Superoxide Anions in Vitro and in Vivo
Authors: Gong Yuanyuan , Yang Mingyan , Lv Jiajia , Li Hongyu , Gao Jie , Yuan Zeli
Published: March 2022

Superoxide anion (O2.−), a short‐lived, highly active reactive oxygen species, participates in many physiological processes. This work reports the design of a chemiluminescent probe (CLO) based on 1,2‐dioxetane‐phenol with a selective and sensitive response to O2.−. The CLO consisted of a 1,2‐dioxetane‐phenol as a chemiluminophore core bearing a trifluoromethanesulfonate (Tf) moiety and methyl acrylate group. Upon reacting with O2.−, the Tf was specifically cleaved from the CLO, resulting in chemiluminescence generation. The CLO emits chemiluminescence at 450–650 nm (λmax=540 nm), representing visible and red chemiluminescent molecules, responsive to O2.−. The CLO processes high sensitivity (Limit of detection=66 nM) and selectivity for O2.− with and has been applied to track O2.− fluctuations in living cells and animals. In addition, CLO successfully detected and visualized O2.−‐related biochemical processes, making it promising as an important imaging tool for studying redox in biology and medicine.
Exploring the Interface of Porous Cathode/Bipolar Membrane for Mitigation of Inorganic Precipitates in Direct Seawater Electrolysis
Authors: Han Ji‐Hyung
Published: March 2022

Direct seawater electrolysis utilizes natural seawater as the electrolyte. Hydroxide ions generated from the hydrogen evolution reaction at the cathode induce the precipitation of inorganic compounds, which block the active sites of the catalysts, leading to high cell voltage. To mitigate inorganic scaling, herein, an optimized interface between a porous electrode and a bipolar membrane (BPM, as a separator) was suggested in zero‐gap seawater electrolyzers. Despite the formation of inorganic deposits at the front side (facing bulk seawater) of the porous cathode due to the water reduction reaction, the back side facing the cation exchange layer of the BPM remained free from thick inorganic deposits. This was ascribed to the locally acidic environment generated by proton flux from water dissociation at the BPM, enabling stable hydrogen production via the proton reduction at low overpotential. This asymmetric hydrogen evolution reaction at the porous cathode led to a considerably lower cell voltage and higher stability than that achieved with the mesh electrode. Moreover, precipitation at the front side of the porous cathode was further mitigated through acidification of the seawater by introducing an open area of the BPM that was not in contact with the porous cathode, allowing free protons that were not involved in the electron transfer reaction to diffuse out into the bulk seawater. These findings may provide critical guidance for the investigation of interfacial phenomena for the complete mitigation of inorganic scaling in the direct electrolytic splitting of seawater.
Timely stimulation of early embryo promotes the acquisition of pluripotency
Authors: Zhang Fengying , Pang Changmiao , Zhu Haoyun , Chen Yanglin
Published: March 2022

Mouse embryonic stem cells (ESCs) and epiblast stem cells (EpiSCs) are both pluripotent stem cells from early embryos. Another type of pluripotent stem cells, which are similar with EpiSCs and derive from pre‐implantation embryos in feeder‐free and chemically defined medium containing Activin A and basic fibroblast growth factors (bFGF), is termed as AFSCs. The pluripotency and self‐renewal maintenance of ESCs rely on Leukemia inhibitory factor (LIF)/STAT/BMP4/SMAD signaling, while the pluripotency and self‐renewal maintenance of EpiSCs and AFSCs rely on bFGF and Activin/Nodal signaling. However, the establishment efficiency of AFSCs lines is low. In this study, we stimulated early embryos by 2i/LIF (CHIR99021 + PD0325901 + LIF) and Activin A + bFGF respectively, to change the cell fate in inner cell mass (ICM). The “fate changed embryos” by 2i/LIF can efficiently produce AFSCs in feeder‐free and chemically defined medium, but the efficiency of embryos treated with Activin A + bFGF were poor. The AFSCs from fate‐changed embryos share similar molecular characteristics with conventional AFSCs and EpiSCs. Our results suggest that the advanced stimulation of 2i/LIF and the premature stimulation of Activin A + bFGF contribute to capturing the pluripotent stem cells in early embryos, and the FGF/MAPK signaling dominate early embryo development. Our study provides a new approach to capturing pluripotency from pre‐implantation embryos.
Predator–prey landscapes of large sharks and game fishes in the Florida Keys
Authors: Griffin Lucas P. , Casselberry Grace A. , Lowerre‐Barbieri Susan K. , Acosta Alejandro , Adams Aaron J. , Cooke Steven J. , Filous Alex , Friess Claudia , Guttridge Tristan L. , Hammerschlag Neil , Heim Vital , Morley Danielle , Rider Mitchell J. , Skomal Gregory B. , Smukall Matthew J. , Danylchuk Andy J. , Brownscombe Jacob W.
Published: March 2022

Interspecific interactions can play an essential role in shaping wildlife populations and communities. To date, assessments of interspecific interactions, and more specifically predator–prey dynamics, in aquatic systems over broad spatial and temporal scales (i.e., hundreds of kilometers and multiple years) are rare due to constraints on our abilities to measure effectively at those scales. We applied new methods to identify space‐use overlap and potential predation risk to Atlantic tarpon (Megalops atlanticus) and permit (Trachinotus falcatus) from two known predators, great hammerhead (Sphyrna mokarran) and bull (Carcharhinus leucas) sharks, over a 3‐year period using acoustic telemetry in the coastal region of the Florida Keys (USA). By examining spatiotemporal overlap, as well as the timing and order of arrival at specific locations compared to random chance, we show that potential predation risk from great hammerhead and bull sharks to Atlantic tarpon and permit are heterogeneous across the Florida Keys. Additionally, we find that predator encounter rates with these game fishes are elevated at specific locations and times, including a prespawning aggregation site in the case of Atlantic tarpon. Further, using machine learning algorithms, we identify environmental variability in overlap between predators and their potential prey, including location, habitat, time of year, lunar cycle, depth, and water temperature. These predator–prey landscapes provide insights into fundamental ecosystem function and biological conservation, especially in the context of emerging fishery‐related depredation issues in coastal marine ecosystems.
Species‐level tree crown maps improve predictions of tree recruit abundance in a tropical landscape
Authors: Barber Cristina , Graves Sarah J. , Hall Jefferson S. , Zuidema Pieter A. , Brandt Jodi , Bohlman Stephanie A. , Asner Gregory P. , Bailón Mario , Caughlin T. Trevor
Published: March 2022

Predicting forest recovery at landscape scales will aid forest restoration efforts. The first step in successful forest recovery is tree recruitment. Forecasts of tree recruit abundance, derived from the landscape‐scale distribution of seed sources (i.e., adult trees), could assist efforts to identify sites with high potential for natural regeneration. However, previous work revealed wide variation in the effect of seed sources on seedling abundance, from positive to no effect. We quantified the relationship between adult tree seed sources and tree recruits and predicted where natural recruitment would occur in a fragmented, tropical, agricultural landscape. We integrated species‐specific tree crown maps generated from hyperspectral imagery and property ownership data with field data on the spatial distribution of tree recruits from five species. We then developed hierarchical Bayesian models to predict landscape‐scale recruit abundance. Our models revealed that species‐specific maps of tree crowns improved recruit abundance predictions. Conspecific crown area had a much stronger impact on recruitment abundance (8.00% increase in recruit abundance when conspecific tree density increases from zero to one tree; 95% credible interval (CI): 0.80% to 11.57%) than heterospecific crown area (0.03% increase with the addition of a single heterospecific tree, 95% CI: −0.60% to 0.68%). Individual property ownership was also an important predictor of recruit abundance: The best performing model had varying effects of conspecific and heterospecific crown area on recruit abundance, depending on individual property ownership. We demonstrate how novel remote sensing approaches and cadastral data can be used to generate high‐resolution and landscape‐level maps of tree recruit abundance. Spatial models parameterized with field, cadastral, and remote sensing data are poised to assist decision support for forest landscape restoration.
Avian species richness and tropical urbanization gradients: Effects of woodland retention and human disturbance
Authors: Thaweepworadej Phakhawat , Evans Karl L.
Published: March 2022

Urbanization is a major driver of tropical biodiversity loss. In temperate regions avian species richness–urbanization intensity relationships typically exhibit unimodal patterns, with peak richness at intermediate urbanization levels. In tropical regions, the form of such relationships and the extent to which they are moderated by patches of seminatural habitat are unclear. We address these questions in Bangkok, Thailand (one of the largest and most rapidly expanding tropical mega‐cities) and generate conservation recommendations for tropical biodiversity in urban locations. We use repeated point count surveys at a random location, and the largest available woodland patch, in 150 1 km × 1 km grid cells selected along the urbanization gradient. Woodland patches support higher species richness compared with randomized locations (except for non‐natives), and avian species richness declines linearly with increasing urbanization. The contrast with unimodal patterns in temperate regions is probably driven by divergent patterns of habitat heterogeneity along tropical and temperate urbanization gradients. Moreover, we provide novel evidence that retaining patches of urban woodland moderates adverse impacts of urbanization on avian species richness. For most species groups, the benefits of woodland increase as urbanization intensifies, despite such woodland patches being very small (mean of 0.38 ha). Avian species richness in woodland patches is maximized, and community composition less similar to that in randomized locations, when woodland patches are larger and visited by fewer people. Assemblages of forest‐dependent species (which provide additional ecological functions) have higher richness, and are less similar to those in randomized locations, in patches of woodland with higher tree species richness and biomass. Finally, species richness in randomized sites is greatest when they are closer to woodland patches, and such assemblages more closely resemble those of woodland sites. Our work highlights four strategies for tropical urban bird conservation: (1) conserving woodland patches across the urbanization gradient regardless of patch size, (2) improving the quality of existing woodland by increasing tree biomass and diversity, (3) creating additional woodland that is well distributed throughout the urban area to minimize effects of habitat isolation and (4) reducing human disturbance, especially in areas of the highest habitat quality, while ensuring that the benefits of connecting people to nature are realized in other locations.
Livestock grazing to maintain habitat of a critically endangered grassland bird: Is grazer species important?
Authors: Nugent Daniel T. , Baker‐Gabb David J. , Leonard Steve W. J. , Morgan John W.
Published: March 2022

Livestock grazing is an important management tool for biodiversity conservation in many native grasslands across the globe. Understanding how different grazing species interact with their environment is integral to achieving conservation goals. In the semiarid grasslands of Australia, grazing by sheep or cattle is used to manipulate vegetation structure to suit the habitat needs of a globally unique, critically endangered grassland bird, the plains‐wandererPedionomus torquatus. However, there has been no investigation of whether sheep and cattle differ in their effects on plains‐wanderer habitat and, therefore, it is unknown if these grazers are substitutable as a management tool. Using a grazing experiment in native grasslands over 3 years, we determined the effects of grazer type (sheep, cattle) on occurrence and vocal activity of plains‐wanderer, vegetation structure and composition, and food availability. We also examined grazer effects on encounter rates of other grassland birds. Plains‐wanderer breeding activity was inferred from vocalization rates captured by bioacoustic recorders. Spotlighting was used to measure encounter rates of other grassland birds. We found that different grazers altered the structure of the habitat. Grasslands grazed by cattle were typically more open, less variable, and lacked patches of dense vegetation relative to those grazed by sheep. Grazer type did not influence the likelihood of plains‐wanderer occurrence, but it did interact with year of survey to affect breeding activity. The number of days with one or more calls significantly increased at sheep grazed sites in year‐3, which coincided with enduring drought conditions. Similarly, grazer effects on encounter rate of all birds, bird species richness, and Australasian pipitAnthus novaeseelandiaewere different between years. Dense vegetation specialists (such as stubble quailCoturnix pectoralis) were positively associated with grasslands grazed by sheep. As a habitat management tool, sheep or cattle grazing are useful when the goal is to support an open grassland structure for the plains‐wanderer. However, their substitutability is likely to be dependent upon climate. We caution that a loss of dense vegetation in grasslands grazed by cattle during drought could limit the availability of optimal habitat for the plains‐wanderer and habitat for other grassland birds.
Wild, tamed, and domesticated: Three fire macroregimes for global pyrogeography in the Anthropocene
Authors: Pereira José M. C. , Oom Duarte , Silva Pedro C. , Benali Akli
Published: March 2022

Climate and natural vegetation dynamics are key drivers of global vegetation fire, but anthropogenic burning now prevails over vast areas of the planet. Fire regime classification and mapping may contribute towards improved understanding of relationships between those fire drivers. We used 15 years of daily active fire data from the MODIS fire product (MCD14ML, collection 6) to create global maps of six fire descriptors (incidence, size inequality, season length, interannual variability, intensity, and fire season modality). Using multiple correspondence analysis (MCA) and hierarchical agglomerative clustering, we identified three fire macroregimes: Wild, Tamed, and Domesticated, each of which splitting into prototypical and transitional regimes. Interpretation of the six fire regimes in terms of their main drivers relied on the global maps of anthromes and Köppen climate types. The analysis yielded a two‐dimensional space where the principal dimension of variability is primarily defined by interannual variability in fire activity and fire season length, and the secondary axis is based mainly on fire incidence. The Wild fire macroregime occurs mostly in cold wildlands, where burning is sporadic and fire seasons are short. Tamed fires predominate in seasonally dry tropical rangelands and croplands with high fire incidence. Domesticated fires are characteristic of humid, warm temperate and tropical croplands and villages with low fire incidence. The Tamed and Domesticated fire macroregimes, representing managed burning, account for 86% of all active fires in our dataset and for 70% of the global burnable area. Fourteen percent of active fires were found in the cold wildlands, and in the rangelands and forests of steppe and desert climates of the Wild macroregime. These results highlight the extent of human control over global pyrogeography in the Anthropocene.
Novel mitochondrial gene rearrangements pattern in the millipede Polydesmus sp. GZCS‐2019 and phylogenetic analysis of the Myriapoda
Authors: Zuo Qing , Zhang Zhisheng , Shen Yanjun
Published: March 2022

The subphylum Myriapoda included four extant classes (Chilopoda, Symphyla, Diplopoda, and Pauropoda). Due to the limitation of taxon sampling, the phylogenetic relationships within Myriapoda remained contentious, especially for Diplopoda. Herein, we determined the complete mitochondrial genome of Polydesmus sp. GZCS‐2019 (Myriapoda: Polydesmida) and the mitochondrial genomes are circular molecules of 15,036 bp, with all genes encoded on + strand. The A+T content is 66.1%, making the chain asymmetric, and exhibits negative AT‐skew (−0.236). Several genes rearrangements were detected and we propose a new rearrangement model: “TD (N\R) L + C” based on the genome‐scale duplication + (non‐random/random) loss + recombination. Phylogenetic analyses demonstrated that Chilopoda and Symphyla both were monophyletic group, whereas Pauropoda was embedded in Diplopoda to form the Dignatha. Divergence time showed the first split of Myriapoda occurred between the Chilopoda and other classes (Wenlock period of Silurian). We combine phylogenetic analysis, divergence time, and gene arrangement to yield valuable insights into the evolutionary history and classification relationship of Myriapoda and these results support a monophyletic Progoneata and the relationship (Chilopoda + (Symphyla + (Diplopoda + Pauropoda))) within myriapod. Our results help to better explain the gene rearrangement events of the invertebrate mitogenome and lay the foundation for further phylogenetic study of Myriapoda.
Environmental DNA captures elasmobranch diversity in a temperate marine ecosystem
Authors: Liu Zifang , Collins Rupert A. , Baillie Charles , Rainbird Sophie , Brittain Rachel , Griffiths Andrew M. , Sims David W. , Mariani Stefano , Genner Martin J.
Published: March 2022

Many sharks, skates, and rays (elasmobranchs) are highly threatened by the activities of commercial fisheries, and a clear understanding of their distributions, diversity, and abundance can guide protective measures. However, surveying and monitoring elasmobranch species can be highly invasive or resource‐intensive, and utilization of non‐invasive environmental DNA‐based methods may overcome these problems. Here, we studied spatial and seasonal variation in the elasmobranch community of the Western English Channel using environmental DNA (eDNA) collected from surface and bottom waters periodically over an annual cycle (2017–2018). In total we recovered 13 elasmobranch species within eDNA samples, and the number of transformed eDNA reads was positively associated with species (hourly) catch data resolved from 105‐year time series trawl data (1914–2018). These results demonstrate the ability of eDNA to detect and semi‐quantitatively reflect the prevalence of historically dominant and rare elasmobranch species in this region. Notably, eDNA recorded a greater number of species per sampling event than a conventional trawl survey in the same area over the same sampling years (2017–2018). Several threatened species were recovered within the eDNA, including undulate ray, porbeagle shark, and thresher shark. Using eDNA, we found differences in elasmobranch communities among sampling stations and between seasons, but not between sampling depths. Collectively, our results suggest that non‐invasive eDNA‐based methods can be used to study the spatial and seasonal changes in the diversity and abundance of whole elasmobranch communities within temperate shelf habitats. Given the threatened status of many elasmobranchs in human‐impacted marine environments, eDNA analysis is poised to provide key information on their diversity and distributions to inform conservation‐focused monitoring and management.
High‐Performance 3D Li‐B‐C‐Al Alloy Anode and its Twofold Li Electrostripping and Plating Mechanism Revealed by Synchrotron X‐Ray Tomography
Authors: Tang Fengcheng , Zhang Xia , Osenberg Markus , Yang Chao , Huang Haifeng , Hilger André , Uesugi Masyuki , Uesug Kentaro , Takeuchi Akihisa , Manke Ingo , Sun Fu , Chen Libao
Published: March 2022

The uncontrollable Li electrostripping and plating process that results in dendritic Li growth and huge volume change of Li anode limits the practicality of Li metal batteries (LMBs). To simultaneously address these issues, designing three‐dimensional (3D), lithiophilic and mechanically robust electrodes seems to be one of the cost‐effective strategies. Herein, a new 3D Li‐B‐C‐Al alloy anode is designed and fabricated. The prepared 3D alloy anode exhibits not only superior lithiophilicity that facilitates uniform Li nucleation and growth but also sufficient mechanical stability that maintains its structural integrity. Superior performance of the prepared 3D alloy is demonstrated through comprehensive electrochemical tests. In addition, non‐destructive and 3D synchrotron X‐ray computed tomography (SX‐CT) technique is employed to investigate the underlying working mechanisms of the prepared alloy anode. A unique twofold Li electrostripping and plating mechanism under different electrochemical cycling conditions is revealed. Lastly, improved performance of the full cells built with the 3D alloy anode and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode corroborate its potential application capability. Overall, the current work not only showcases the superiority of the 3D alloy as potential anode material for LMBs but also provides fundamental insights into its underlying working mechanisms that may further propel its research and development.
Neighboring Group Participation of Benzoyl Protecting Groups in C3‐ and C6‐Fluorinated Glucose
Authors: Greis Kim , Kirschbaum Carla , Fittolani Giulio , Mucha Eike , Chang Rayoon , von Helden Gert , Meijer Gerard , Delbianco Martina , Seeberger Peter H. , Pagel Kevin
Published: March 2022

Fluorination is a potent method to modulate chemical properties of glycans. Here, we study how C3‐ and C6‐fluorination of glucosyl building blocks influence the structure of the intermediate of the glycosylation reaction, the glycosyl cation. Using a combination of gas‐phase infrared spectroscopy and first‐principles theory, glycosyl cations generated from fluorinated and non‐fluorinated monosaccharides are structurally characterized. The results indicate that neighboring group participation of the C2‐benzoyl protecting group is the dominant structural motif for all building blocks, correlating with the β‐selectivity observed in glycosylation reactions. The infrared signatures indicate that participation of the benzoyl group in enhanced by resonance effects. Participation of remote acyl groups such as Fmoc or benzyl on the other hand is unfavored. The introduction of the less bulky fluorine leads to a change in the conformation of the ring pucker, whereas the structure of the active dioxolenium site remains unchanged.
A numerical study on smoke back‐layering length in V‐shaped tunnels under natural ventilation
Authors: Xie En , Zhao Wangda , Xu Zhisheng , Zhang Xiaochun , Xu Weiku , Wang Tianxiong , He Lu
Published: March 2022

When a fire occurs at the lowest point of a V‐shaped tunnel, the stack effects on both sides have different directions and will compete with each other. The smoke back‐layering can be observed in the side with a smaller angle. In this work, the smoke back‐layering length in the V‐shaped tunnel was investigated by theoretical analyses and numerical simulations. The different inclination combinations of the V‐shaped tunnel and the heat release rates (HRRs) were concerned. The HRRs were set at 3, 5, 8, and 10 MW, respectively. An equivalent longitudinal velocity of the V‐shaped tunnel was proposed in this study. Different from the horizontal tunnel fire, the smoke back‐layering length decreased with the increase of the HRR in the V‐shaped tunnel due to the special smoke movement, and a prediction function was proposed to describe the relationship. After that, the effect of the different inclination combinations on the smoke back‐layering length was researched under the same HRR. The dimensionless smoke back‐layering length decreased with the rise of the sine difference between the two angles of the V‐shaped tunnel. In addition, when the smaller angle was fixed, the dimensionless smoke back‐layering length decreases logarithmically with the increase of the sine difference of the tunnel angles on both sides. At last, a semi‐empirical formula for smoke back‐layering length in V‐shaped tunnels was proposed.
Oral metastasis as the first indication of undiscovered malignancy at a distant site: A systematic review of 413 cases
Authors: de Carvalho Kimura Talita , Henschel Flávia Akemi Nakayama , Carneiro Mailon Cury , Santin Gabriela Cristina , Veltrini Vanessa Cristina
Published: March 2022

This systematic review is the first to provide evidence regarding demographic, clinical, and imaging characteristics, as well as information related to survival, of patients with oral and maxillofacial metastases of occult primary tumors. Case reports, case series, and cross‐sectional studies were included. Ten databases were searched. The risk of bias was assessed using the Joanna Briggs Institute appraisal tools. Overall, 353 articles (413 patients) were included. Statistically significant associations between survival and multiplicity of metastatic foci, and between each of the main primary sites and some features of the oral lesions were observed. Some clinical and imaging characteristics can help dentists in raising diagnostic suspicions and also in relating to plausible primary sites. Early diagnosis of oral and maxillofacial metastases can positively affect the survival rate when they are the only focus of dissemination, conferring an important role on the dentist.