bluuebunny/crossref_metadata_2025_split huggingface dataset:
General Approach to Single and Hybrid Metal Oxide Fiber Structures for High‐Performance Lithium‐Ion Batteries
Authors: Xie Ling , Yan Yan , Lin Huijuan , Rui Kun , Huang Aoming , Du Min , Shen Yu , Zhu Jixin 
Published: February 2020

AbstractOwing to the high specific capacity and energy density, metal oxides have become very promising electrodes for lithium‐ion batteries (LIBs). However, poor electrical conductivity accompanied with inferior cycling stability resulting from large volume changes are the main obstacles to achieve a high reversible capacity and stable cyclability. Herein, a facile and general approach to fabricate SnO2, Fe2O3 and Fe2O3/SnO2 fibers is proposed. The appealing structural features are favorable for offering a shortened lithium‐ion diffusion length, easy access for the electrolyte and reduced volume variation when used as anodes in LIBs. As a consequence, both single and hybrid oxides show satisfactory reversible capacities (1206 mAh g−1 for Fe2O3 and 1481 mAh g−1 for Fe2O3/SnO2 after 200 cycles at 200 mA g−1) and long lifespans.
Catalytic Approaches for the Direct Heterofunctionalization of Aliphatic Carboxylic Acids and Their Equivalents with Group 16 Elements
Authors: Kumar Jogendra , Rahaman Ajijur , Singh Anupam Kumar , Bhadra Sukalyan 
Published: February 2020

AbstractIn contrast to traditional multistep synthesis, modern organic synthesis extensively depends on the direct functionalization of unactivated C−H bonds for the construction of various C−C and C‐heteroatom bonds in atom‐ and step‐economic manner. Common aliphatic substrates, e. g. carboxylic acids and their synthetic equivalents, are regiospecifically functionalized based on either a directed approach, in which the polar directing group assists to functionalize a specific C−H bond positioned at β‐ and γ‐carbon centers, or a non‐directed approach typically leading to α‐functionalization. While numerous reviews on catalytic C−H functionalization have appeared, a concise review on the direct C(sp3)−H heterofunctionalization of carboxylic acid synthons with Group 16 elements has been awaited. The recent advances on the direct oxy‐functionalization and chalcogenation of aliphatic carboxylic acid synthons enabled by transition metal, organo‐ and photocatalysts are described herein.
Solubilization of poorly water‐soluble bioactive molecules in neutral aqueous media by complexation with renatured β‐1,3‐1,6‐glucan nanoparticles
Authors: Kodama Ayumu , Nakagawa Akifumi , Nonoguchi Yuki , Sakurai Haruka , Yano Chieko , Suzuki Toshio , Koumoto Kazuya 
Published: February 2020

AbstractThe design of scaffolds for solubilizing/dispersing poorly water‐soluble bioactive molecules in neutral aqueous media is a major challenge of functional food, pharmaceuticals, and cosmetics development, as highlighted by the plethora of corresponding solubilization/dispersion strategies. Herein, renatured β‐1,3‐1,6‐glucan (r‐glucan) nanoparticles prepared by neutralization of alkali‐denatured β‐1,3‐1,6‐glucan and subsequent centrifugation are used as a host to disperse water‐insoluble bioactive molecules (curcumin, all‐trans‐retinoic acid, and rebamipide) by simple mixing of host and guest solutions. Curcumin in the r‐glucan cavity is found to be stacked in the form of J‐aggregates and twisted along the helix, and is demonstrated to be retained for significantly longer than curcumin in the corresponding γ‐cyclodextrin (γ‐CD) complex. Specifically, curcumin incorporated in γ‐CD is released within 5.5 hours, whereas that in the r‐glucan complex is released very slowly, with 12% of curcumin in the latter complex retained after 31‐day incubation at 37°C. Thus, inclusion protocol simplicity and slow release ability make r‐glucan nanoparticles a potential carrier scaffold for various applications.
Association of aspirin resistance with 4‐hydroxynonenal and its impact on recurrent cerebral infarction in patients with acute cerebral infarction
Authors: Guo Juan , Wang Jue , Guo Yanxia , Feng Juan 
Published: February 2020

AbstractObjectivesTo investigate the association of aspirin resistance (AR) with the plasma 4‐hydroxynonenal (4‐HNE) level and its impact on recurrent cerebral infarction (CI) in patients with acute cerebral infarction (ACI) who were receiving aspirin therapy.MethodsOne hundred and fifty‐four ACI patients who previously received aspirin therapy (100 mg/day) were enrolled. Whole urine (for measuring 11dhTXB2 and creatinine) along with blood (for measuring the plasma 4‐HNE level) were collected at least 7 days after the patients received aspirin. A cutoff of 1500 pg/mg of 11dhTXB2/ creatinine was used to determine AR. A follow‐up period to monitor recurrence CI events was 1 year. In addition, blood testing was performed when the patients were first admitted to hospital.ResultsForty‐six of the 154 enrolled patients (29.9%) were found to be AR. No statistical difference in age, sex, hypertension, diabetes mellitus, coronary disease, smoking status, NIHSS score, TOAST classification, platelet count, thrombocytocrit, LDL‐C, HDL‐C, TG, and TC was found between the AR and aspirin‐sensitive (AS) patients, but the plasma 4‐HNE level was found to be higher in the AR patients than AS patients (p < .05). Multiple logistic regression analysis showed that the 4‐HNE level was associated with a higher risk of AR (OR = 1.034; 95% CI = 1.011–1.058; p < .05). Moreover, 1‐year follow‐up showed that AR was more prevalent in patients with recurrent CI (26 (56.6%)) than those without (20/(43.5%)) (p < .001).ConclusionsThe plasma 4‐HNE level is strongly associated with AR and thus may be a factor contributing to AR. Patients with AR have a greater risk of recurrence CI.
Physical framework for a counselling environment in India: Thematic analysis of counsellors' perceptions
Authors: Dey Anjali Miriam , Kumar Aneesh 
Published: February 2020

AbstractThe influence of the physical environment on the counselling process is an inevitable part of a counselling session. However, there is little insight in Indian research into the desirable elements of the physical environment of the counselling room that helps facilitate a counselling session. Interviews were conducted with 10 professional counsellors in India. Thematic analysis of the data brought out various Basic and Organising themes under the following three Global themes: (a) Elements of the physical framework; (b) Counsellor's perspectives about the physical framework in counselling; and (c) Motivation to build a framework. The findings show how counsellors can systematise the physical framework to help construct the counselling session effectively.
A Pronucleotide Probe for Live‐Cell Imaging of Protein AMPylation
Authors: Kielkowski Pavel , Buchsbaum Isabel Y. , Becker Tobias , Bach Kathrin , Cappello Silvia , Sieber Stephan A. 
Published: February 2020

AbstractConjugation of proteins to AMP (AMPylation) is a prevalent post‐translational modification (PTM) in human cells, involved in the regulation of unfolded protein response and neural development. Here we present a tailored pronucleotide probe suitable for in situ imaging and chemical proteomics profiling of AMPylated proteins. Using straightforward strain‐promoted azide–alkyne click chemistry, the probe provides stable fluorescence labelling in living cells.
A New Cell‐Based AI‐2‐Mediated Quorum Sensing Interference Assay in Screening of LsrK‐Targeted Inhibitors
Authors: Gatta Viviana , Tomašič Tihomir , Ilaš Janez , Zidar Nace , Peterlin Mašič Lucija , Barančoková Michaela , Frlan Rok , Anderluh Marko , Kikelj Danijel , Tammela Päivi 
Published: February 2020

AbstractQuorum sensing (QS), a bacterial communication strategy, has been recognized as one of the control mechanisms of virulence in bacteria. Thus, targeting QS offers an interesting opportunity to impair bacterial pathogenicity and develop antivirulence agents. Aiming to enhance the discovery of QS inhibitors, we developed a bioreporter Escherichia coli JW5505 pET‐Plsrlux and set up a cell‐based assay for identifying inhibitors of autoinducer‐2 (AI‐2)‐mediated QS. A comparative study on the performance of target‐ versus cell‐based assays was performed, and 91 compounds selected with the potential to target the ATP binding pocket of LsrK, a key enzyme in AI‐2 processing, were tested in an LsrK inhibition assay, providing 36 hits. The same set of compounds was tested by the AI‐2‐mediated QS interference assay, resulting in 24 active compounds. Among those, six were also found to be active against LsrK, whereas 18 might target other components of the pathway. Thus, this AI‐2‐mediated QS interference cell‐based assay is an effective tool for complementing target‐based assays, yet also stands as an independent assay for primary screening.
Fatal outcome of malignant transformation of hidradenitis suppurativa: A case report and literature review
Authors: Nielsen Valdemar Wendelboe , Jørgensen Astrid‐Helene Ravn , Thomsen Simon Francis 
Published: February 2020

AbstractSquamous cell carcinoma arising in hidradenitis suppurativa (HS) is a rare albeit the most serious complication in HS, with a reported fatality of up to 42.9%. This calls for greater clinical awareness in patients with long‐standing chronic HS.
Perivascular epithelioid cell tumor (PEComa) of the pterygopalatine fossa
Authors: Dougherty Michael I. , Payne Spencer C. , Gupta Akriti , Mattos Jose L. 
Published: February 2020

AbstractPerivascular epithelioid cell tumors (PEComas) are a rare group of mesenchymal tumors associated with tuberous sclerosis. These tumors are typically treated with resection and rarely recur or exhibit malignant behavior. A 78‐year‐old woman presented with an incidentally discovered pterygopalatine fossa/retroantral mass. Excisional biopsy was performed and revealed pathology consistent with PEComa. Upon review of the literature, there have been 43 reported cases of PEComa of the head and neck. There is only one previously reported case of PEComa in the skull base, and none reported in the pterygopalatine fossa. Of note, the previously reported case of skull base PEComa involved an aggressive tumor with widespread metastasis. Here, we report the first case of a PEComa of the pterygopalatine fossa/retroantral region, which was treated conservatively. This rare pathology should be considered in the differential diagnosis for atypical skull base tumors.
Managing harvest of ‘Russell’ and ‘Tifton 44’ bermudagrass receiving broiler litter for nutritive value and phosphorus removal
Authors: Read John J. , Lang David J. , Adeli Ardeshir , Jenkins Johnie N. 
Published: February 2020

AbstractBermudagrass [Cynodon dactylon (L.) Pers.] hay fields receiving broiler litter offer a means to both produce high quality forage and export excess manure nutrients, for example P. This 3‐yr study determined the nutritive value, P removal, and soil P for ‘Russell’ and ‘Tifton 44’ bermudagrass receiving 4 ton ac−1 broiler litter and 98 lb ac−1 N (as NH4NO3) annually and cut at 21‐, 35‐, and 49‐d intervals with residual stubble heights of 1.2 and 3.5 inches. Forage cut every 49 d at 1.2‐inch stubble height had the greatest dry matter (DM) yield and low nutritive value; weighted‐sum crude protein (CP) ranged from 7.2 to 8.2% and weighted‐sum in vitro true DM digestibility (IVTDMD) ranged from 56.8 to 62.0%, depending on year. With a 35‐d interval, forage CP and IVTDMD amounts generally exceeded 9.6 and 62.0%, respectively. Forage IVTDMD was greater in Tifton 44 than Russell in 2006 and 2007, when values with a 35‐d interval were approximately 3.0 and 0.3% greater, respectively. Cutting at a 1.2‐inch height increased P removal by approximately 23% in Russell and 30% in Tifton 44 compared with a 3.5‐inch height. Phosphorus removal was maximized with a 49‐d interval and 1.2‐inch height in 2005 (29.8 lb ac−1) and 2006 (19.3 lb ac−1) and with a 35‐d interval and 1.2‐inch height in 2007 (29.3 lb ac−1). Managing the balance between high DM and nutritive value in both cultivars can be achieved with a 35‐d interval and 1.2‐inch height. A prolonged harvest interval of 49 d is a valuable consideration for P removal via biomass.
Competitive Reactivity of Tautomers in the Degradation of Organophosphates by Imidazole Derivatives
Authors: Campos Renan B. , Silva Valmir B. , Menezes Leociley R. A. , Ocampos Fernanda M. M. , Fernandes Juliano M. , Barison Andersson , Oliveira Alfredo R. M. , Tantillo Dean J. , Orth Elisa S. 
Published: February 2020

AbstractThe harmful impact caused by pesticides on human health and the environment necessitates the development of efficient degradation processes and control of prohibited stocks of such substances. Organophosphates (OPs) are among the most used agrochemicals in the world and their degradation can proceed through several possible pathways. Investigating the reactivity of OPs with nucleophilic species allows one to propose new and efficient catalyst scaffolds for use in detoxification. In light of the remarkable catalytic activity of imidazole (IMZ) at promoting dephosphorylation processes of OPs, the reactivity of 4(5)‐hydroxymethylimidazole (HMZ) with diethyl‐2,4‐dinitrophenylphosphate (DEDNPP) and Paraoxon are evaluated by combining experimental and theoretical approaches. It is observed that HMZ is an efficient and regiospecific catalyst with reactivity modulated by competing tautomers. To propose an optimal IMZ‐based catalyst, quantum chemical calculations were performed for monosubstituted 4(5)IMZ derivatives that might cleave DEDNPP. Both inductive effects and hydrogen bonding by the substituents are shown to influence barriers and mechanisms.
Scope and Limitations of the s‐Block Metal‐Mediated Pudovik Reaction
Authors: Fener Benjamin E. , Schüler Philipp , Ueberschaar Nico , Bellstedt Peter , Görls Helmar , Krieck Sven , Westerhausen Matthias 
Published: February 2020

AbstractThe hydrophosphorylation of phenylacetylene with di(aryl)phosphane oxides Ar2P(O)H (Pudovik reaction) yields E/Z‐isomer mixtures of phenylethenyl‐di(aryl)phosphane oxides (1). Alkali and alkaline‐earth metal di(aryl)phosphinites have been studied as catalysts for this reaction with increasing activity for the heavier s‐block metals. The Pudovik reaction can only be mediated for di(aryl)phosphane oxides whereas P‐bound alkyl and alcoholate substituents impede the P−H addition across alkynes. The demanding mesityl group favors the single‐hydrophosphorylated products 1‐Ar whereas smaller aryl substituents lead to the double‐hydrophosphorylated products 2‐Ar. Polar solvents are beneficial for an effective addition. Increasing concentration of the reactants and the catalyst accelerates the Pudovik reaction. Whereas Mes2P(O)H does not form the bis‐phosphorylated product 2‐Mes, activation of an ortho‐methyl group and cyclization occurs yielding 2‐benzyl‐1‐mesityl‐5,7‐dimethyl‐2,3‐dihydrophosphindole 1‐oxide (3).
Solution Conformations Explain the Chameleonic Behaviour of Macrocyclic Drugs
Authors: Danelius Emma , Poongavanam Vasanthanathan , Peintner Stefan , Wieske Lianne H. E. , Erdélyi Máté , Kihlberg Jan 
Published: February 2020

AbstractIt has been hypothesised that drugs in the chemical space “beyond the rule of 5” (bRo5) must behave as molecular chameleons to combine otherwise conflicting properties, including aqueous solubility, cell permeability and target binding. Evidence for this has, however, been limited to the cyclic peptide cyclosporine A. Herein, we show that the non‐peptidic and macrocyclic drugs roxithromycin, telithromycin and spiramycin behave as molecular chameleons, with rifampicin showing a less pronounced behaviour. In particular roxithromycin, telithromycin and spiramycin display a marked, yet limited flexibility and populate significantly less polar and more compact conformational ensembles in an apolar than in a polar environment. In addition to balancing of membrane permeability and aqueous solubility, this flexibility also allows binding to targets that vary in structure between species. The drugs’ passive cell permeability correlates to their 3D polar surface area and corroborate two theoretical models for permeability, developed for cyclic peptides. We conclude that molecular chameleonicity should be incorporated in the design of orally administered drugs in the bRo5 space.
Stereochemistry‐Controlled Supramolecular Architectures of New Tetrahydroxy‐Functionalised Amphiphilic Carbocyanine Dyes
Authors: Schade Boris , Singh Abhishek Kumar , Wycisk Virginia , Cuellar‐Camacho Jose Luis , von Berlepsch Hans , Haag Rainer , Böttcher Christoph 
Published: February 2020

AbstractThe syntheses of novel amphiphilic 5,5′,6,6′‐tetrachlorobenzimidacarbocyanine (TBC) dye derivatives with aminopropanediol head groups, which only differ in stereochemistry (chiral enantiomers, meso form and conformer), are reported. For the achiral meso form, a new synthetic route towards asymmetric cyanine dyes was established. All compounds form J aggregates in water, the optical properties of which were characterised by means of spectroscopic methods. The supramolecular structure of the aggregates is investigated by means of cryo‐transmission electron microscopy, cryo‐electron tomography and AFM, revealing extended sheet‐like aggregates for chiral enantiomers and nanotubes for the mesomer, respectively, whereas the conformer forms predominately needle‐like crystals. The experiments demonstrate that the aggregation behaviour of compounds can be controlled solely by head group stereochemistry, which in the case of enantiomers enables the formation of extended hydrogen‐bond chains by the hydroxyl functionalities. In case of the achiral meso form, however, such chains turned out to be sterically excluded.
One‐Step Synthesis of Janus Fluorographene Derivatives
Authors: Kouloumpis Antonios , Chronopoulos Demetrios D. , Potsi Georgia , Pykal Martin , Vlček Jakub , Scheibe Magdalena , Otyepka Michal 
Published: February 2020

AbstractFluorographene, a two‐dimensional derivative of graphene, is an excellent starting material for the synthesis of graphene derivatives. In this work, a one‐step, substrate‐free method for the asymmetric functionalization of fluorographene layers with hydroxyl groups by a facile nucleophilic substitution reaction is reported. Such a chemical modification occurs in a biphasic aqueous–organic system under mild conditions, leading to Janus graphene nanosheets functionalized by hydroxyl groups on one side and retaining fluorine atoms on the other. The reported experimental route paves the way for two‐dimensional bifacial graphene templates, thus broadening the application potential of graphene materials.
Iron Biomineral Growth from the Initial Nucleation Seed in L‐Ferritin
Authors: Ciambellotti Silvia , Pozzi Cecilia , Mangani Stefano , Turano Paola 
Published: February 2020

AbstractX‐ray structures of homopolymeric human L‐ferritin and horse spleen ferritin were solved by freezing protein crystals at different time intervals after exposure to a ferric salt and revealed the growth of an octa‐nuclear iron cluster on the inner surface of the protein cage with a key role played by some glutamate residues. An atomic resolution view of how the cluster formation develops starting from a (μ3‐oxo)tris[(μ2‐glutamato‐κO:κO’)](glutamato‐κO)(diaquo)triiron(III) seed is provided. The results support the idea that iron biomineralization in ferritin is a process initiating at the level of the protein surface, capable of contributing coordination bonds and electrostatic guidance.
Stereochemical analysis of chiral amines, diamines, and amino alcohols: Practical chiroptical sensing based on dynamic covalent chemistry
Authors: Hassan Diandra S. , Thanzeel F. Yushra , Wolf Christian 
Published: February 2020

AbstractPractical chiroptical sensing with a small group of commercially available aromatic aldehydes is demonstrated. Schiff base formation between the electron‐deficient 2,4‐dinitrobenzaldehyde probe and either primary amines, diamines, or amino alcohols proceeds smoothly in chloroform at room temperature and is completed in the presence of molecular sieves within 2.5 hours. The substrate binding coincides with a distinct circular dichroism signal induction at approximately 330 nm, which can be correlated to the absolute configuration and enantiomeric composition of the analyte. The usefulness of this sensing method is highlighted with the successful sensing of 18 aliphatic and aromatic amines and amino alcohols and five examples showing quantitative %ee determination with good accuracy.
Klärschlammverbrennung in einer stationären Wirbelschicht mit integrierter Phosphor‐Rückgewinnung
Authors: Schnell Matthias , Quicker Peter 
Published: February 2020

AbstractFür die zukünftig obligatorische Phosphorrückgewinnung aus Klärschlamm werden besonders nasschemische und thermochemische Verfahren diskutiert. Die Kopplung der Phosphorrückgewinnung mit der Verbrennung in stationären Wirbelschichtfeuerungen, der dominierenden Monoverbrennungstechnologie, bietet hinsichtlich des Nachbehandlungsaufwandes und der Wirtschaftlichkeit potenzielle Vorteile. In Versuchen konnte durch Einstellung der Verbrennungsbedingungen und Zugabe von Additiven eine Asche hergestellt werden, die der Düngemittelverordnung entspricht und somit potenziell als Phosphor‐Rezyklat einsetzbar ist.
Solid‐Phase Synthesis of Substrate‐Based Dipeptides and Heterocyclic Pseudo‐dipeptides as Potential NO Synthase Inhibitors
Authors: Touati‐Jallabe Youness , Tintillier Thibault , Mauchauffée Elodie , Boucher Jean‐Luc , Leroy Jérémy , Ramassamy Booma , Hamzé Abdallah , Mezghenna Karima , Bouzekrini Amine , Verna Claudia , Martinez Jean , Lajoix Anne‐Dominique , Hernandez Jean‐François 
Published: February 2020

AbstractMore than 160 arginine analogues modified on the C‐terminus via either an amide bond or a heterocyclic moiety (1,2,4‐oxadiazole, 1,3,4‐oxadiazole and 1,2,4‐triazole) were prepared as potential inhibitors of NO synthases (NOS). A methodology involving formation of a thiocitrulline intermediate linked through its side‐chain on a solid support followed by modification of its carboxylate group was developed. Finally, the side‐chain thiourea group was either let unchanged, S‐alkylated (Me, Et) or guanidinylated (Me, Et) to yield respectively after TFA treatment the corresponding thiocitrulline, S‐Me/Et‐isothiocitrulline and N‐Me/Et‐arginine substrate analogues. They all were tested against three recombinant NOS isoforms. Several compounds containing a S‐Et‐ or a S‐Me‐Itc moiety and mainly belonging to both the dipeptide‐like and 1,2,4‐oxadiazole series were shown to inhibit nNOS and iNOS with IC50 in the 1–50 μM range. Spectral studies confirmed that these new compounds interacted at the heme active site. The more active compounds were found to inhibit intra‐cellular iNOS expressed in RAW264.7 and INS‐1 cells with similar efficiency than the reference compounds L‐NIL and SEIT.
Using Complementary Ligand Denticity to Direct Metallosupramolecular Structure about Metal Ions with Square‐Planar Geometry
Authors: Preston Dan , Kruger Paul E. 
Published: February 2020

AbstractAn understanding of methods to control the structure of self‐assembled architectures is central to the efforts of chemists interested in self‐assembly synthesis. Metal ions with square‐planar geometry are a favorite of metallosupramolecular chemists, as there are only a limited number of possible ligand arrangements around the metal ion. Two such arrangements, firstly four monodentate donor sites (1,1,1,1), and secondly two monodentate donors and one bidentate donor (1,1,2) exemplify the symmetry interaction and ligand directed approaches, respectively. Symmetry interaction approaches using two bidentate sites (2,2) or a monodentate and tridentate site (1,3) have not received the same level of attention. In these arrangements, two complementary sites combine at the metal ion(s). This Minireview seeks to detail strategies employed to direct structure in systems with these arrangements, and is illustrated with key exemplars from the field.