bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fluctuating asymmetry, a marker of poor growth quality, is associated with adult male metabolic rate
Authors: Longman Daniel P. , Oyama Sakura , Cracknell James , Thompson Nathan , Gordon Dan , Stock Jay T. , Wells Jonathan C. K. 
Published: March 2021

AbstractObjectivesLife history theory, a branch of evolutionary theory, predicts the existence of trade‐offs in energetic allocation between competing physiological functions. The core metabolic cost of self‐maintenance, measured by resting metabolic rate (RMR), represents a large component of human daily energy expenditure. Despite strong selective pressures for energetic frugality and high observed interindividual variation in RMR, the link between RMR and energetic allocation to life‐history traits remains understudied in humans.MaterialsIn a sample of 105 (m = 57, f = 48), we investigated the relationship between adult RMR and investment in growth quality, as measured by fluctuating asymmetry (FA).ResultsMeasurement of RMR and FA in university rowers revealed a significant positive correlation amongst males (n= 57,r= 0.344,p= 0.005, 1‐tailed; standardized 95% CI, 0.090 to 0.598). Convincing evidence for a correlation among females was not found (n= 48,r= 0.142,p= 0.169, 1‐tailed, standardized 95% CI, −0.152 to 0.435).DiscussionThe data suggest that low‐quality asymmetrical growth is associated with later‐life metabolic inefficiencies in males. Energetic investment in processes (likely concerning the stress‐response) unrelated to growth during childhood may thereby trade‐off against adult metabolic efficiency. We suggest that the presence of a relationship between RMR and FA in males but not females may be explained by the additional metabolic strain associated with larger body size and increased male muscularity, which may amplify the inefficiencies arising from low‐quality growth.
Usefulness of intraoperative frozen section for diagnosing acute invasive fungal rhinosinusitis: A systematic review and meta‐analysis
Authors: Kim Do Hyun , Kim Sung Won , Hwang Se Hwan 
Published: March 2021

AbstractBackgroundThe accuracy of diagnoses of acute invasive fungal rhinosinusitis (AIFRS) based on frozen sections has been questioned.MethodsPubMed, the Cochrane Central Register of Controlled Trials, Embase, Web of Science, SCOPUS, and Google Scholar were used for data sources. True‐positive, true‐negative, false‐positive, and false‐negative data were extracted for each study. Methodological quality was evaluated using the Quality Assessment of Diagnostic Accuracy Studies 2 (QUADAS‐2) Tool.ResultsNine prospective and retrospective studies were included. The diagnostic odds ratio of intraoperative frozen section in AIFRS was 124.4717 (95% confidence interval [CI], 75.5168–205.1623). The area under the summary receiver operating characteristic curve was 0.906. The sensitivity, specificity, and positive predictive value were 0.8337 (95% CI, 0.7962–0.8655), 0.9858 (95% CI, 0.9330–0.9971), and 0.9822 (95% CI, 0.8905–0.9973), respectively. The correlation between sensitivity and the false‐positive rate was 0.437, indicating a lack of heterogeneity. In subgroup analysis, the “per patient” subgroup tended to show higher diagnostic accuracy than the “per specimen” subgroup. Regarding fungal species, the frozen biopsy of aspergillus showed higher sensitivity than that of mucor (0.8103 vs. 0.7544).ConclusionPositive frozen sections are reliable and facilitate early intervention in AIFRS. Collecting multiple specimens during surgery will decrease the rate of false‐negative results.
Photochemical Probe Identification of a Small‐Molecule Inhibitor Binding Site in Hedgehog Acyltransferase (HHAT)**
Authors: Lanyon‐Hogg Thomas , Ritzefeld Markus , Zhang Leran , Andrei Sebastian A. , Pogranyi Balazs , Mondal Milon , Sefer Lea , Johnston Callum D. , Coupland Claire E. , Greenfield Jake L. , Newington Joshua , Fuchter Matthew J. , Magee Anthony I. , Siebold Christian , Tate Edward W. 
Published: March 2021

AbstractThe mammalian membrane‐bound O‐acyltransferase (MBOAT) superfamily is involved in biological processes including growth, development and appetite sensing. MBOATs are attractive drug targets in cancer and obesity; however, information on the binding site and molecular mechanisms underlying small‐molecule inhibition is elusive. This study reports rational development of a photochemical probe to interrogate a novel small‐molecule inhibitor binding site in the human MBOAT Hedgehog acyltransferase (HHAT). Structure‐activity relationship investigation identified single enantiomer IMP‐1575, the most potent HHAT inhibitor reported to‐date, and guided design of photocrosslinking probes that maintained HHAT‐inhibitory potency. Photocrosslinking and proteomic sequencing of HHAT delivered identification of the first small‐molecule binding site in a mammalian MBOAT. Topology and homology data suggested a potential mechanism for HHAT inhibition which was confirmed by kinetic analysis. Our results provide an optimal HHAT tool inhibitor IMP‐1575 (Ki=38 nM) and a strategy for mapping small molecule interaction sites in MBOATs.
A Cavity‐Tailored Metal‐Organic Cage Entraps Gases Selectively in Solution and the Amorphous Solid State
Authors: Zhu Jun‐Long , Zhang Dawei , Ronson Tanya K. , Wang Wenjing , Xu Lin , Yang Hai‐Bo , Nitschke Jonathan R. 
Published: March 2021

AbstractHere we report the subcomponent self‐assembly of a truxene‐faced Zn4L4tetrahedron, which is capable of binding the smallest hydrocarbons in solution. By deliberately incorporating inward‐facing ethyl groups on the truxene faces, the resulting partially‐filled cage cavity was tailored to encapsulate methane, ethane, and ethene via van der Waals interactions at atmospheric pressure in acetonitrile, and also in the amorphous solid state. Interestingly, gas capture showed divergent selectivities in solution and the amorphous solid state. The selective binding may prove useful in designing new processes for the purification of methane and ethane as feedstocks for chemical synthesis.
Biosynthesis and Mechanism of Action of the Cell Wall Targeting Antibiotic Hypeptin
Authors: Wirtz Daniel A. , Ludwig Kevin C. , Arts Melina , Marx Carina E. , Krannich Sebastian , Barac Paul , Kehraus Stefan , Josten Michaele , Henrichfreise Beate , Müller Anna , König Gabriele M. , Peoples Aaron J. , Nitti Anthony , Spoering Amy L. , Ling Losee L. , Lewis Kim , Crüsemann Max , Schneider Tanja 
Published: March 2021

AbstractHypeptin is a cyclodepsipeptide antibiotic produced by Lysobacter sp. K5869, isolated from an environmental sample by the iChip technology, dedicated to the cultivation of previously uncultured microorganisms. Hypeptin shares structural features with teixobactin and exhibits potent activity against a broad spectrum of gram‐positive pathogens. Using comprehensive in vivo and in vitro analyses, we show that hypeptin blocks bacterial cell wall biosynthesis by binding to multiple undecaprenyl pyrophosphate‐containing biosynthesis intermediates, forming a stoichiometric 2:1 complex. Resistance to hypeptin did not readily develop in vitro. Analysis of the hypeptin biosynthetic gene cluster (BGC) supported a model for the synthesis of the octapeptide. Within the BGC, two hydroxylases were identified and characterized, responsible for the stereoselective β‐hydroxylation of four building blocks when bound to peptidyl carrier proteins. In vitro hydroxylation assays corroborate the biosynthetic hypothesis and lead to the proposal of a refined structure for hypeptin.
Asymmetric Core–Shell Gold Nanoparticles and Controllable Assemblies for SERS Ratiometric Detection of MicroRNA
Authors: Zhu Rong , Feng Hongjuan , Li Qingqing , Su Lichao , Fu Qinrui , Li Juan , Song Jibin , Yang Huanghao 
Published: March 2021

AbstractJanus nanogap gold nanoparticles (JAuNNPs) with varying proportions of Au shell coverage of (ca. 100/75/50/25 %) are presented. The internal nanogap between the partial Au shell and core caused asymmetric optical behavior; tunability depends on the degree of Au shell coverage and structural asymmetry. The shell‐to‐shell or core‐to‐core JAuNNDs(50 %) were self‐assembled from amphiphilic JAuNNPs(50 %) by tuning the hydrophilic and hydrophobic polymer brushes on the Au core or shell. The positions of electromagnetic field enhancement of JAuNNDs varied with geometrical configurations because of hybridized plasmonic coupling effects. Furthermore, DNA linkers were utilized to form JAuNND12(50 %). By combining with Raman molecules, ratiometric SERS signals could be generated, enabling JAuNND12(50 %) to image the distribution of miR‐21 in living cells and tumors. Asymmetric JAuNNPs allowed facile conjugation of various linkage molecules to fabricate dimeric nanostructures.
Rekombinante Spinnenseidengele aus wässrig‐organischen Mischphasen als Wirkstoffdepots
Authors: Neubauer Vanessa J. , Trossmann Vanessa T. , Jacobi Sofia , Döbl Annika , Scheibel Thomas 
Published: March 2021

AbstractHydrogele finden weitreichend Anwendung in der Biomedizin, wo sie nicht nur als Material in der Biofabrikation, sondern u. a. auch als Wirkstoffdepots verwendet werden. Die Möglichkeiten, wasserunlösliche Wirkstoffe in Hydrogelen zu formulieren, sind jedoch begrenzt. In dieser Studie konnten rekombinante Spinnenseidenproteine durch ein neuartiges Herstellungsverfahren in wässrig‐organischen Mischphasen zu Gelen selbstassemblieren. Deren Eigenschaften konnten dabei durch die Wahl der Lösungsmittel kontrolliert werden. Die Gegenwart einer organischen Phase erlaubte das Einbringen hydrophober Wirkstoffe, was exemplarisch anhand von 6‐Mercaptopurin gezeigt wurde. Die entwickelten Gele zeigten scherverdünnende Eigenschaften und konnten injiziert (zum Beispiel für Anwendungen als Wirkstoffdepot) und sogar 3D‐verdruckt werden, um Gerüste für die Geweberegeneration herzustellen. Mithilfe dieser neuen Herstellungsroute können nun wasserunlösliche Wirkstoffe in Spinnenseidendepots formuliert und damit gängige pharmazeutische Löslichkeitsgrenzen überwunden werden.
Ligand Controls the Activity of Light‐Driven Water Oxidation Catalyzed by Nickel(II) Porphyrin Complexes in Neutral Homogeneous Aqueous Solutions
Authors: Liu Chengyu , van den Bos Daan , den Hartog Barthold , van der Meij Dennis , Ramakrishnan Ashok , Bonnet Sylvestre 
Published: March 2021

AbstractFinding photostable, first‐row transition metal‐based molecular systems for photocatalytic water oxidation is a step towards sustainable solar fuel production. Herein, we discovered that nickel(II) hydrophilic porphyrins are molecular catalysts for photocatalytic water oxidation in neutral to acidic aqueous solutions using [Ru(bpy)3]2+ as photosensitizer and [S2O8]2− as sacrificial electron acceptor. Electron‐poorer Ni‐porphyrins bearing 8 fluorine or 4 methylpyridinium substituents as electron‐poorer porphyrins afforded 6‐fold higher turnover frequencies (TOFs; ca. 0.65 min−1) than electron‐richer analogues. However, the electron‐poorest Ni‐porphyrin bearing 16 fluorine substituents was photocatalytically inactive under such conditions, because the potential at which catalytic O2 evolution starts was too high (+1.23 V vs. NHE) to be driven by the photochemically generated [Ru(bpy)3]3+. Critically, these Ni‐porphyrin catalysts showed excellent stability in photocatalytic conditions, as a second photocatalytic run replenished with a new dose of photosensitizer, afforded only 1–3 % less O2 than during the first photocatalytic run.
Covalent Bisfunctionalization of Two‐Dimensional Molybdenum Disulfide
Authors: Chen Xin , Bartlam Cian , Lloret Vicent , Moses Badlyan Narine , Wolff Stefan , Gillen Roland , Stimpel‐Lindner Tanja , Maultzsch Janina , Duesberg Georg S. , Knirsch Kathrin C. , Hirsch Andreas 
Published: March 2021

AbstractCovalent functionalization of two‐dimensional molybdenum disulfide (2D MoS2) holds great promise in developing robust organic‐MoS2 hybrid structures. Herein, for the first time, we demonstrate an approach to building up a bisfunctionalized MoS2 hybrid structure through successively reacting activated MoS2 with alkyl iodide and aryl diazonium salts. This approach can be utilized to modify both colloidal and substrate supported MoS2 nanosheets. We have discovered that compared to the adducts formed through the reactions of MoS2 with diazonium salts, those formed through the reactions of MoS2 with alkyl iodides display higher reactivity towards further reactions with electrophiles. We are convinced that our systematic study on the formation and reactivity of covalently functionalized MoS2 hybrids will provide some practical guidance on multi‐angle tailoring of the properties of 2D MoS2 for various potential applications.
Versatile Direct Cyclization Constructs Spiro‐acridan Derivatives for Highly Efficient TADF emitters
Authors: Liu He , Liu Zhiwen , Li Ganggang , Huang Huaina , Zhou Changjiang , Wang Zhiming , Yang Chuluo 
Published: March 2021

AbstractSpiro‐acridan (SpA) derivatives possess a great potential in preparing efficient thermally activated delayed fluorescent (TADF) emitters. However, the conventional synthetic routes are cost‐expensive and time‐consuming. The development of a simple procedure to synthesize SpAs is still in urgent pursuing appreciated by academic and industrial communities. In this contribution, we present a feasible acid‐catalyzed solvent‐free metal‐free cyclization between diarylamines and ketones to construct SpAs. The as‐constructed moieties provide a wide possibility to assemble efficient TADF emitters. As an example, D2T‐TR with high photoluminescent quantum yield and proper TADF character is applied in organic light emitting diodes (OLEDs) which achieves a maximum external quantum efficiency (EQE) of 27.1 %. This work shows us a bright inspiration on developing excellent organic optoelectronic materials and an effective tool to realize it.
Self‐doped sulfonated polyaniline ultrafiltration membranes with enhanced chlorine resistance and antifouling properties
Authors: Alhweij Hassan , Amura Ida , Wenk Jannis , Emanuelsson Emma Anna Carolina , Shahid Salman 
Published: March 2021

AbstractMembranes heavily rely on chlorination to diminish (bio)fouling, but chlorination can also lead to membrane degradation. We developed sulfonated polyaniline (S‐PANI) ultrafiltration (UF) membranes with improved chlorine resistance and intrinsic antifouling properties. The S‐PANI membranes were synthesized through Non‐solvent Induced Phase Separation (NIPS). Membrane performance was evaluated under harsh chlorine conditions (250 ppm sodium hypochlorite for 3 days under different pH conditions). The S‐PANI membranes showed improved chlorine resistance including a stable performance without changes in model foulant BSA rejection. In contrast, PANI membranes suffered critical structural damage with complete leakage and commercial PES membranes showed a 76% increase in pure water flux and a noticeable change in BSA rejection. Small changes in S‐PANI membrane performance could be linked to membrane structural changes with pH, as confirmed by SEM, IR spectroscopy, and contact angle measurements. Additionally, the S‐PANI membranes showed better antifouling properties with a high flux recovery ratio in comparison to PANI membranes using alginic acid, humic acid, and BSA model foulants. Chemical cleaning by sodium hypochlorite re‐instated the transport properties to its initial condition. Overall, the developed S‐PANI membranes have a high chlorine tolerance and enhanced antifouling properties making them promising for a range of UF membrane applications.
Photoactive mussels inspired polymer coatings: Preparation and antibacterial activity
Authors: Bryaskova Rayna , Philipova Nikoleta , Georgiev Nikolay , Lalov Ivo , Bojinov Vladimir , Detrembleur Christophe 
Published: March 2021

AbstractIn this article we report on the facile preparation of photoactive antibacterial mussel inspired polymer coatings deposited on a stainless steel (SS) substrate from water based precursors. The coating is prepared by the sequential deposition of aqueous based solutions of an anchoring layer based on bio‐inspired glue, a cationic polymer bearing pendent catechols, a nanogel decorated by ortho‐quinones and a photosensitizer of the aminoacridine type. This latter is grafted to the coating by reaction of its amino group with the o‐quinone of the deposited nanogel. The deposition of all layers is followed in‐line by Quartz crystal microbalance coupled with dissipation (QCM‐D) and AFM shows that the thin polymer film repeated the roughness of the SS substrate. The prepared coatings show good mechanical properties applying nanoindentation techniques. The established antibacterial activity of the prepared photoactive polymer coatings on SS against Gram‐negative E. coli strain demonstrate their potential as a power tool for medical applications.
Harnessing the potential for otolith microchemistry to foster the conservation of Amazonian fishes
Authors: Hermann Theodore W. , Duponchelle Fabrice , Castello Leandro , Limburg Karin E. , Pereira Luciana A. , Hauser Marília 
Published: March 2021

Abstract

Freshwater environments host roughly half of the world’s fish diversity, much of which is concentrated in large, tropical river systems such as the Amazon. Fishes are critical to ecosystem functioning in the Amazon River basin but face increasing human threats. The basic biology of these species, and particularly migratory behaviour, remains poorly studied, in part owing to the difficulty associated with conducting tagging studies in remote tropical regions.
Otolith microchemistry can circumvent logistical issues and is an increasingly important tool for studying fish life histories. However, this approach is still new in the Amazon, and its potential and limitations to inform fish conservation strategies remain unclear.
Here, otolith microchemistry studies in the Amazon are reviewed, highlighting current possibilities, and several key factors that limit its use as a conservation tool in the Amazon are discussed. These include the dearth of spatiotemporal elemental data, poor understanding of environment–fish–otolith pathways, and insufficient funding, facilities, and equipment.
A research initiative is proposed to harness the potential of this technique to support conservation in the Amazon. Key aspects of the proposal include recommendations for internal and external funding, which are critical to acquiring and maintaining technical staff, cutting‐edge equipment, and facilities, as well as fostering regular scientific meetings and working groups. Meetings can facilitate a systematic approach to investigating environment–otolith pathways, broadening the chemical baseline for most Amazonian tributaries, and exploring potential valuable elements.
These outcomes are urgently needed to conserve biodiversity and ecosystem functioning in the Amazon, especially given threats such as widespread hydroelectric damming. The initiative proposed here could make otolith microchemistry an important, cost‐effective tool to inform and foster conservation in the Amazon, and act as a template for other imperilled tropical river basins, such as the Mekong and the Congo.
Cytolytic activity score as a biomarker for antitumor immunity and clinical outcome in patients with gastric cancer
Authors: Hu Qingjiang , Nonaka Kentaro , Wakiyama Hiroaki , Miyashita Yu , Fujimoto Yoshiaki , Jogo Tomoko , Hokonohara Kentaro , Nakanishi Ryota , Hisamatsu Yuichi , Ando Koji , Kimura Yasue , Masuda Takaaki , Oki Eiji , Mimori Koshi , Oda Yoshinao , Mori Masaki 
Published: March 2021

AbstractBackgroundA simple measure of immune cytolytic activity (CYT) base on mRNA expression levels of two genes, GZMA and PRF1, was recently reported. Here, we aimed to evaluate the CYT score's potential as a measure of antitumor immunity and predictor of clinical outcome in gastric cancer (GC) patients.Materials and MethodsWe evaluated the correlations between tumor‐infiltrating immune cells and the CYT score in 238 GC samples from The Cancer Genome Atlas (TCGA). Next, we investigated CYT score associations with molecular subtypes, somatic mutation load, and immune checkpoint molecules in GC samples from TCGA and Asian Cancer Research Group (ACRG). Moreover, we evaluated the clinical significance of the CYT score calculated by reverse transcription (RT)‐quantitative PCR (qPCR) data in 123 GC samples and the association of the CYT score with the response to anti‐PD‐1 therapy in 7 GC samples from Kyushu University Hospital.ResultsThe CYT score positively correlated with the proportions of tumor‐infiltrating CD8+ T cells and macrophages and negatively correlated with the proportion of regulatory T cells in GC tissues. A high CYT score was associated with common immune checkpoint molecules, a high mutation, the Epstein–Barr virus subtype, and the microsatellite instability subtype in GC. Moreover, a low CYT score was a poor prognosis factor in patients with GC. Finally, the CYT score was higher in a responder to anti‐PD‐1 therapy compared to nonresponders.ConclusionThe CYT score reflects antitumor immunity and predicts clinical outcome in GC patients.
When the context rows against. Voicing parents of transgender children and teenagers in Italy: A qualitative study
Authors: Lorusso Maric , Albanesi Cinzia 
Published: March 2021

AbstractHaving a supportive family with a non‐binary vision of gender differences is a protective factor for transgender and gender‐variant (TGV) children and teenagers; however, the parents of TGV children find themselves alone when dealing with doubts and challenges, and this may hamper their capacity to provide support to their children. This study aimed to map/describe the needs of the parents of TGV children in Italy, their relationship with the health care and educational systems, and how they cope with the challenges of the context they live in. We used a qualitative approach based on thematic interviews with respondent validation, involving 13 parents of TGV children and teenagers. Our participants reported difficulties in accessing information, obstacles in finding adequate support from mental health professionals and in interactions with educational professionals, recognizing that these challenges are strongly embedded in the Italian socio‐cultural context and its widespread homobitransphobic culture. Nevertheless, they are personally committed to changing this situation through advocacy and affirmative action for their children, engaged in knowledge production on gender variance, and with parent support groups. Please refer to the Supplementary Material section to find this article'sCommunity and Social Impact Statement.
Beyond the Active Site. Cp*ZrMe3/Sulfated Alumina‐Catalyzed Olefin Polymerization Tacticity via Catalyst⋅⋅⋅Surface Ion‐Pairing
Authors: Zhang Jialong , Mason Alexander H. , Wang Yang , Motta Alessandro , Kobayashi Takeshi , Pruski Marek , Gao Yanshan , Marks Tobin J. 
Published: March 2021

AbstractSurface‐bound organometallic molecules have recently enabled the development of single‐site heterogeneous catalysts, advancing the atomic scale understanding and diversity of heterogeneous catalysis. Here we report that supporting Cp*ZrMe3 (Cat1) on acidic sulfated‐alumina (AlS) affords the surface catalyst Cat1/AlS, which was characterized by multi‐dimensional solid‐state NMR spectroscopies, and is active in ethylene homo‐ and copolymerizations, as well as propylene and 1‐hexene homopolymerizations. In contrast to propylene (or 1‐hexene) polymerization by homogeneous Cp*ZrMe2+ B(C6F5)4− which yields atactic polyolefins, Cat1/AlS promotes remarkable isotacticity with mmmm >95 %. Complementary DFT analysis argues that the restrictive local Cat1/AlS C1‐symmetry favors activation and enchainment at the propylene re enantioface, promoting isotactic polymerization via a “back‐skip‐like” mechanism.