bluuebunny/crossref_metadata_2025_split huggingface dataset:
Direkte Katalytische C‐Glykosylierung von Arenen: beschleunigte Synthese des Remdesivir‐Nucleosids**
Authors: Obradors Carla , Mitschke Benjamin , Aukland Miles H. , Leutzsch Markus , Grossmann Oleg , Brunen Sebastian , Schwengers Sebastian A. , List Benjamin 
Published: December 2021

AbstractSeit Beginn des Jahres 2020 wird nach einer effektiven Lösung im Kampf gegen SARS‐CoV‐2 gesucht, vor allem durch Entwicklung verlässlicher Impfstoffe, welche die Verbreitung des Virus verhindern, und durch die Untersuchung bereits für andere Indikationen zugelassener Wirkstoffe. Diesbezüglich ist die Anwendung der antiviralen Prodrug Remdesivir immer noch am weitesten verbreitet, allerdings beschränkt sich die Synthese auf Schutzgruppen, sauerstoffsensitive Reagenzien und kryogene Temperaturen, weshalb eine kosteneffiziente Herstellung nicht immer gewährleistet werden kann. Um zur Lösung dieses Problems beizutragen, konzentrierten wir uns auf die Entwicklung einer direkten Addition von (Hetero)arenen an ungeschützte Zucker. Hier berichten wir von einer silyliumkatalysierten und vollkommen stereoselektiven C‐Glykosylierung, die zunächst offenkettige Polyole liefert, welche schließlich durch Cyclisierung unter kinetischer oder thermodynamischer Kontrolle zur α‐ oder β‐Furanose umgesetzt werden. Die Methode ermöglicht raschen Zugang zu Remdesivir‐Intermediat GS‐441524 nach anschließender Mn‐katalysierter C−H‐Oxidation sowie Deoxycyanierung.
A Hydrogen‐Bonded Ravel Assembled by Anion Coordination
Authors: Zhao Xiaotong , Wang Heng , Li Boyang , Zhang Wenyao , Li Xiaopeng , Zhao Wei , Janiak Christoph , Heard Andrew W. , Yang Xiao‐Juan , Wu Biao 
Published: December 2021

AbstractAnion‐coordination‐driven assembly (ACDA) is showing increasing power in the construction of anionic supramolecular architectures. Herein, by expanding the anion centers from oxoanion (phosphate or sulfate) to organic tris‐carboxylates, an Archimedean solid (truncated tetrahedron) and a highly entangled, double‐walled tetrahedron featuring a ravel topology have been assembled with tris‐bis(urea) ligands. The results demonstrate the promising ability of tris‐carboxylates as new anion coordination centers in constructing novel topologies with increasing complexity and diversity compared to phosphate or sulfate ions on account of the modifiable size and easy functionalization character of these organic anions.
Proton/Electron Donors Enhancing Electrocatalytic Activity of Supported Conjugated Microporous Polymers for CO2Reduction
Authors: Wang Rong , Wang Xinyue , Weng Weijun , Yao Ying , Kidkhunthod Pinit , Wang Changchun , Hou Yang , Guo Jia 
Published: December 2021

AbstractMetal phthalocyanines (MePc) hold great promise in electrochemical reduction of CO2to value‐added chemicals, whereas the catalytic activity of MePc‐containing polymers often suffers from a limited molecular modulation strategy. Herein, we synthesize an ultrathin conjugated microporous polymer sheath around carbon nanotubes by an ionothermal copolymerization of CoPc and H2Pc via the Scholl reaction. Given the H2Pc‐mediated regulation in the synthesis, CoIImetal is well preserved in the form of single atoms on the polymer sheath of the carbon nanotubes. With the synergistic effect of H2Pc moieties as proton/electron donors, the composites can selectively reduce CO2to CO with a high Faradaic efficiency (max. 97 % at −0.9 V) in broad potential windows, exceptional turnover frequency (97 592 h−1at −0.65 V) and large current density (>200 mA cm−2). It is thus desirable to develop a family of heterogeneous polymerized MePc with molecularly regulating electrocatalytic activity.
Dynamic three‐dimensional virtual environment to improve learning of anatomical structures
Authors: Duraes Martha , Akkari Mohamed , Jeandel Clément , Moreno Benjamin , Subsol Gérard , Duflos Claire , Captier Guillaume 
Published: December 2021

AbstractIncreasing number of medical students and limited availability of cadavers have led to a reduction in anatomy teaching through human cadaveric dissection. These changes triggered the emergence of innovative teaching and learning strategies in order to maximize students learning of anatomy. An alternative approach to traditional dissection was presented in an effort to improve content delivery and student satisfaction. The objective of this study is to acquire three‐dimensional (3D) anatomical data using structured‐light surface scanning to create a dynamic four‐dimensional (4D) dissection tool of four regions: neck, male inguinal and femoral areas, female perineum, and brachial plexus. At each dissection step, identified anatomical structures were scanned using a 3D surface scanner (Artec Spider™). Resulting 3D color meshes were overlaid to create a 4D (3D+time) environment. An educational interface was created for neck dissection. Its implementation in the visualization platform allowed 4D virtual dissection by navigating from surface to deep layers and vice versa. A group of 28 second‐year medical students and 17 first‐year surgery residents completed a satisfaction survey. A majority of medical students (96.4%) and 100% of surgery residents said that they would recommend this tool to their colleagues. According to surgery residents, the main elements of this virtual tool were the realistic high‐quality of 3D acquisitions and possibility to focus on each anatomical structure. As for medical students, major elements were the interactivity and entertainment aspect, precision, and accuracy of anatomical structures. This approach proves that innovative solutions to anatomy education can be found to help to maintain critical content and student satisfaction in anatomy curriculum.
Water‐Involved Ring‐Opening of 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione for “Photo‐Clicked” Access to Carbamoyl Formazan Photoswitches In Situ
Authors: Zheng Yuanqin , Zhou Yuqiao , Zhang Yan , Deng Pengchi , Zhao Xiaohu , Jiang Shichao , Du Guangxi , Shen Xin , Xie Xinyu , Su Zhishan , Yu Zhipeng 
Published: December 2021

AbstractCyclic azodicarbonyl derivatives, particularly 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione (PTAD), commonly serve as arenophile, dienophile, enophile and electrophile. Perplexed by its instability in aqueous environment, there are few studies focused on the transient intermediate produced by hydrolysis of PTAD to achieve synthetic significance. Herein, we describe a “photo‐click” method that involves nitrile imine (NI) from diarylsydnone to capture the diazenecarbonyl‐phenyl‐carbamic acid (DACPA) generated by water‐promoted ring‐opening of PTAD. DFT calculation reveal that H‐bonding interactions between PTAD and water are vital to form DACPA which exhibited an umpolung effect during ligation by nature bond orbit (NBO) analysis. The ultra‐fast ligation resulted in carbamoyl formazans, as a unique Z↔E photo‐switchable linker on target molecules, including peptide and drugs, with excellent anti‐fatigue performance. This strategy is showcased to construct highly functionalized carbamoyl formazans in situ for photo‐pharmacology and material studies, which also expands the chemistry of PTAD in aqueous media.
Parsec‐scale view of CSS/GPS sources at 327 MHz
Authors: Dallacasa Daniele , Orienti Monica 
Published: December 2021

AbstractGlobal very long baseline interferometry (VLBI) observations at low frequencies are of great importance since they allow us to test the oldest part of the relativistic electron populations in young radio sources. At 327 MHz ( 92 cm), the most compact regions are self‐absorbed, and the number of cores detected is very small. This could provide useful measurements of the magnetic field in the relativistic plasma, to be compared with the equipartition field derived from minimum energy arguments. Partial self‐absorption takes place also in hot‐spots. However, disentangling the hot‐spot emission from that of the lobe turned out to be rather difficult. On the other hand, a clearer and more complete characterization of the volumes occupied by the magnetized relativistic plasma and its total energy content can be obtained at 327 MHz. In turn, an independent estimate of the source age can be inferred, on the basis of simple assumptions on the jet power. Here, we show that the ages derived in this way (between and year) are consistent with the radiative ages determined from the break frequency in the radio spectrum.
Therapeutics studies and biological properties of Teucrium polium (Lamiaceae)
Authors: Rahmouni Fatma , Saoudi Mongi , Rebai Tarek 
Published: December 2021

AbstractTeucrium polium has been used in traditional medicine as antifungal, antipyretic, antispasmodic, and antibacterial. It is consumed by many jordanians for the treatment of many diseases. The effects of this plant have been investigated in kidney, liver, and brain. Its antidiabetic, antimicrobial, antioxidant, and anticancer effects have been introduced. Polyphenolic compound, flavonoids, monoterpenes, alkanoides, and essential oils were identified. Several studies revealed that this plant has a hypoglycemic effect and can help to control blood sugar. It was reported that plants containing flavonoids and phenolics compounds exhibit a large array of biological activities like genotoxicity (chromosomal aberrations and sister chromatid exchange) and oxidative stress damage. These phytochemicals are found in herbal and vegetables plants, as well as being reliably protective against oxidative stress damage and lipid peroxidation. In addition, T. polium has secondary effects on different organs, namely liver, kidney and at high doses this plant becomes toxic. In conclusion, this review investigates many pharmacologicals properties and side effects of T. polium.
BRAFV600E mutation test on fine‐needle aspiration specimens of thyroid nodules: Clinical correlations for 4600 patients
Authors: Chen Huang , Song Aiping , Wang Ye , He Yifan , Tong Jie , Di Jinxi , Li Chun , Zhou Zhongren , Cai Xiaopin , Zhong Dingrong , Da Jiping 
Published: December 2021

AbstractBackgroundThe BRAFV600E mutation is valuable for the diagnosis, prognosis, and therapy of papillary thyroid cancer (PTC). However, studies related to this mutation have involved only a small number of patients. Therefore, we performed a large‐scale analysis from a single institute to evaluate the accuracy of combined fine‐needle aspiration (FNA) and BRAFV600E mutation tests for PTC diagnosis.MethodsA total of 4600 patients with thyroid nodules who underwent both FNA cytology and BRAFV600E mutation analysis on FNA specimens were enrolled. The association between the BRAFV600E mutation and clinicopathological features was analyzed. A separate analysis was performed for the 311 patients who underwent repeated FNA for comparison of cytological evaluation and BRAFV600E mutation results. The diagnostic efficacy of the BRAFV600E mutation test and cytologic diagnoses was evaluated for 516 patients who underwent preoperative FNA tests in comparison with conclusive postoperative histopathologic results.ResultsThe cytology results of all 4600 FNA samples were categorized according to The Bethesda System for Reporting Thyroid Cytology (TBSRTC) stages I–VI, which accounted for 11.76%, 60.02%, 6.46%, 3.61%, 6.71%, and 11.43% of the samples, respectively. The BRAFV600E mutation was detected in 762 (16.57%) FNA samples, with rates of 1.48%, 0.87%, 20.20%, 3.01%, 66.02%, and 87.81% for TBSRTC I–VI lesions, respectively. Among the 311 repeat FNA cases, 81.0% of the BRAFV600E‐positive and 4.3% of the BRAFV600E‐negative specimens with an initial indication of cytological non‐malignancy were ultimately diagnosed as malignant by repeat FNA (p < 0.001). Among the 516 patients who underwent thyroidectomy, the sensitivity and specificity of the BRAFV600E mutation test alone for PTC diagnosis were 76.71% and 100.0%, respectively, which increased to 96.62% and 88.03%, respectively, when combining the BRAFV600E mutation test with cytology. BRAFV600E mutation was significantly associated with lymph node metastasis (p < 0.001), but not with age, gender, or tumor size.ConclusionsThe BRAFV600E mutation test in FNA samples has potential to reduce false negatives in PTC diagnosis, and therefore plays an important role in the diagnosis of thyroid nodules, especially those with an indeterminate or nondiagnostic cytology, which should be considered for repeat FNA.
Tailoring Enzyme Stringency Masks the Multispecificity of a Lyngbyatoxin (Indolactam Alkaloid) Nonribosomal Peptide Synthetase
Authors: Soeriyadi Angela H. , Ongley Sarah E. , Kehr Jan‐Christoph , Pickford Russel , Dittmann Elke , Neilan Brett A. 
Published: December 2021

AbstractIndolactam alkaloids are activators of protein kinase C (PKC) and are of pharmacological interest for the treatment of pathologies involving PKC dysregulation. The marine cyanobacterial nonribosomal peptide synthetase (NRPS) pathway for lyngbyatoxin biosynthesis, which we previously expressed in E. coli, was studied for its amenability towards the biosynthesis of indolactam variants. Modification of culture conditions for our E. coli heterologous expression host and analysis of pathway products suggested the native lyngbyatoxin pathway NRPS does possess a degree of relaxed specificity. Site‐directed mutagenesis of two positions within the adenylation domain (A‐domain) substrate‐binding pocket was performed, resulting in an alteration of substrate preference between valine, isoleucine, and leucine. We observed relative congruence of in vitro substrate activation by the LtxA NRPS to in vivo product formation. While there was a preference for isoleucine over leucine, the substitution of alternative tailoring domains may unveil the true in vivo effects of the mutations introduced herein.
A Conformationally Stable Acyclic β‐Hairpin Scaffold Tolerating the Incorporation of Poorly β‐Sheet‐Prone Amino Acids
Authors: Stanojlovic Vesna , Müller Anna , Moazzam Ali , Hinterholzer Arthur , Ożga Katarzyna , Berlicki Łukasz , Schubert Mario , Cabrele Chiara 
Published: December 2021

AbstractThe β‐hairpin is a structural element of native proteins, but it is also a useful artificial scaffold for finding lead compounds to convert into peptidomimetics or non‐peptide structures for drug discovery. Since linear peptides are synthetically more easily accessible than cyclic ones, but are structurally less well‐defined, we propose XWXWXpPXK(/R)X(R) as an acyclic but still rigid β‐hairpin scaffold that is robust enough to accommodate different types of side chains, regardless of the secondary‐structure propensity of the X residues. The high conformational stability of the scaffold results from tight contacts between cross‐strand cationic and aromatic side chains, combined with the strong tendency of the d‐Pro‐l‐Pro dipeptide to induce a type II′ β‐turn. To demonstrate the robustness of the scaffold, we elucidated the NMR structures and performed molecular dynamics (MD) simulations of a series of peptides displaying mainly non‐β‐branched, poorly β‐sheet‐prone residues at the X positions. Both the NMR and MD data confirm that our acyclic β‐hairpin scaffold is highly versatile as regards the amino‐acid composition of the β‐sheet face opposite to the cationic−aromatic one.
Transcatheter edge‐to‐edge mitral valve repair: Should we stay tied to COAPT tiers?
Authors: Saia Francesco 
Published: December 2021

Key Points
What the article teaches. Patients with secondary mitral regurgitation (SMR) undergoing transcatheter edge‐to‐edge mitral valve repair (TEER) have different prognosis based on eligibility criteria in the COAPT trial and on different echocardiographic tiers for enrollment in the same trial.
How it will impact practice. Patient selection for TEER should be based on an integrative approach rather than on a single parameter, and largely guided by the COAPT trial enrollment criteria.
What new research/study would help answer the question posed. Further studies are needed to clearly identify patients subgroups that could benefit from TEER and, within them, to identify parameters that may help stratifying patients with different outcomes.
Outflow graft obstruction in patients with left ventricular assist devices: Stenting the kink
Authors: Postalian Alexander , Krajcer Zvonimir 
Published: December 2021

Key Points
Outflow graft obstruction (OGO) is a feared complication in patients with left ventricular assist devices.
It can be caused by graft kinking or twisting, external compression, or internal material deposition.
The best endovascular approach for treating this complication is not well established.
The authors report their institutional experience treating OGO in patients with HeartMate 3 devices, describing a straightforward approach that appears safe and feasible for a large proportion of patients.
Sterically Crowded Tris(2‐(trimethylsilyl)phenyl)phosphine – Is it Still a Ligand?
Authors: Gildenast Hans , Garg Felix , Englert Ulli 
Published: December 2021

AbstractTris(2‐(trimethylsilyl)phenyl)phosphine, P(o‐TMSC6H4)3, was synthesised and characterised in solution and in the solid state. The large steric bulk prevents most reactions of the phosphorus donor and makes the compound air stable both in the solid state as well as in solution. This shielded phosphine can still undergo three reactions, namely protonation, oxidation to the phosphine oxide under harsh conditions and complexation to AuI, thus forming a complex with linear coordination. Unexpectedly, complexation was unsuccessful with a range of other metal cations. Neither PdII, PtII, ZnII nor HgII reacted and even the remaining coinage metal cations CuI and AgI could not be coordinated. Both the parent molecule as well as the reaction products were structurally characterised by single crystal X‐ray diffraction, and the conformational change of geometry required to accommodate the additional atoms was analysed in detail. Apart from chemical oxidation with H2O2, P(o‐TMSC6H4)3 displays reversible electrochemical oxidation with a potential not unlike the one of sterically unencumbered phosphines for which the oxidation is usually not reversible. P(o‐TMSC6H4)3 can thus be considered a model compound for the investigation of the electronic properties of sterically unencumbered phosphines.
Two Faces of the Same Coin: Coupling X‐Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes
Authors: Del Giudice Daniele , Tavani Francesco , Di Berto Mancini Marika , Frateloreto Federico , Busato Matteo , Oliveira De Souza Danilo , Cenesi Flavia , Lanzalunga Osvaldo , Di Stefano Stefano , D'Angelo Paola 
Published: December 2021

AbstractThe satisfactory rationalization of complex reactive pathways in solution chemistry may greatly benefit from the combined use of advanced experimental and theoretical complementary methods of analysis. In this work, we combine X‐Ray Absorption and 1H NMR spectroscopies with state‐of‐the‐art Multivariate Curve Resolution and theoretical analyses to gain a comprehensive view on a prototypical reaction involving the variation of the oxidation state and local structure environment of a selected metal ion coordinated by organic ligands. Specifically, we investigate the 2‐cyano‐2‐phenylpropanoic acid reduction of the octahedral complex established by the Cu2+ ion with terpyridine to the tetrahedral complex formed by Cu+ and neocuproine. Through our interdisciplinary approach we gain insights into the nature, concentration time evolution and structures of the key metal (XAS measurements) and organic (1H NMR measurements) species under reaction. We believe our method may prove to be useful in the toolbox necessary to understand the mechanisms of reactive processes of interest in solution.
Isolation of Cyclic Aluminium Polysulfides by Stepwise Sulfurization
Authors: Xu Huihui , Weetman Catherine , Hanusch Franziska , Inoue Shigeyoshi 
Published: December 2021

AbstractDespite the notable progress in aluminium chalcogenides, their sulfur congeners have rarely been isolated under mild conditions owing to limited synthetic precursors and methods. Herein, facile isolation of diverse molecular aluminium sulfides is achievable, by the reaction of N‐heterocyclic carbene‐stabilized terphenyl dihydridoaluminium (1) with various thiation reagents. Different to the known dihydridoaluminium 1Tipp, 1 features balanced stability and reactivity at the Al center. It is this balance that enables the first monomeric aluminium hydride hydrogensulfide 2, the six‐membered cyclic aluminium polysulfide 4 and the five‐membered cyclic aluminium polysulfide 6 to be isolated, by reaction with various equivalents of elemental sulfur. Moreover, a rare aluminium heterocyclic sulfide with Al−S−P five‐membered ring (7) was obtained in a controlled manner. All new compounds were fully characterized by multinuclear NMR spectroscopy and elemental analysis. Their structures were confirmed by single‐crystal X‐ray diffraction studies.
Energy Efficient and Reliable K Best Detection Approach with Hybrid Decomposition for WiMAX Applications
Authors: K.B. Bavithra , R Siva Kumar 
Published: December 2021

SummaryK‐best detection algorithm placed a vital role for best signal detection in multi‐input multi‐output (MIMO) systems. The major challenge in K‐best approach is that, if the number of users increases, the preprocessing complexity also increases. To mitigate this limitations, CLD (Cholesky factorization + LDLT factorization)‐based decomposition process is proposed with sorted integer Gauss transformation (SIGT) to design 4 × 4 MIMO system. It limits the processing complexity by reducing the number of pipelining stages. Experimental results exhibit that the novel CLD‐based K‐best detector reduces power consumption by 33.52%, 16.29%, 25.65%, 9.6%, and 6.61% and increases the throughput by 69.62%, 68.84%, 62.61%, 4.73%, and 66.04% when compared with K‐best detector, modified K‐best detector, variable K‐best detector, low‐complexity K‐best, and K‐best with hybrid merge network. The proposed K‐best detection scheme increases the energy efficiency by 79.80%, 73.92%, 72.21%, 13.72%, and 68.28% when compared with the existing techniques such as K‐best detection, modified K‐best detection, variable K‐best, low‐complexity K‐best, and K‐best with hybrid merge network.
Archäologisches Haus am Petriplatz – massive Außenwandkonstruktion
Authors: Schermer Detleff , Nagler Florian , Schwabe Almut 
Published: December 2021

AbstractDer Petriplatz in Berlin zählt zu einem der frühesten Besiedelungsorte Berlins aus dem 12. Jh. In diesem Bereich wird im Auftrag des Berliner Senats aktuell das Archäologische Haus errichtet, welches die mit dem Ort verbundenen Funde integrieren und den Besuchern direkt zugänglich machen soll. Die oberirdischen Geschosse werden als archäologische Werkstätten und Sammlungsräume dienen und einen Vortragssaal aufweisen. Die gewählte Konstruktion des siebengeschossigen Gebäudes passt sich den örtlichen Randbedingungen an: So erfolgt die Gründung auf Bohrpfählen, um den Eingriff in die Fundstätte zu minimieren und gleichzeitig Elemente für die Geothermie zu schaffen. Aus der statischen Funktion sowie den Brandschutzanforderungen und dem Schutz gegen Außenlärm ergab sich die Notwendigkeit, die Tragkonstruktion massiv in Stahlbeton auszuführen. Als quasi monolithischer Außenwandaufbau im Regelbereich wurde eine neue Systematik mittels tragender Stahlbetoninnenschale und nicht tragender Ausfachung aus hochwärmedämmendem Planziegelmauerwerk entwickelt. Neben dem Lastabtrag waren insbesondere die Themen der Rissesicherheit, der Ausführung und des Zusammenwirkens von Beton und Mauerwerk zu beachten.