bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Decarboxylative C−N Formation to Generate Alkyl, Alkenyl, and Aryl Amines
Authors: Zhang Yipin , Ge Xia , Lu Hongjian , Li Guigen 
Published: October 2020

AbstractTransition‐metal‐catalyzed sp2 C−N bond formation is a reliable method for the synthesis of aryl amines. Catalytic sp3 C−N formation reactions have been reported occasionally, and methods that can realize both sp2 and sp3 C−N formation are relatively unexplored. Herein, we address this challenge with a method of catalytic decarboxylative C−N formation that proceeds through a cascade carboxylic acid activation, acyl azide formation, Curtius rearrangement and nucleophilic addition reaction. The reaction uses naturally abundant organic carboxylic acids as carbon sources, readily prepared azidoformates as the nitrogen sources, and 4‐dimethylaminopyridine (DMAP) and Cu(OAc)2 as catalysts with as low as 0.1 mol % loading, providing protected alkyl, alkenyl and aryl amines in high yields with gaseous N2 and CO2 as the only byproducts. Examples are demonstrated of the late‐stage functionalization of natural products and drug molecules, stereospecific synthesis of useful α‐chiral alkyl amines, and rapid construction of different ureas and primary amines.
Series of Crystals with Giant Optical Anisotropy: A Targeted Strategic Research
Authors: Tong Tinghao , Zhang Wenyao , Yang Zhihua , Pan Shilie 
Published: October 2020

AbstractThe main commercially used birefringent oxides α‐BaB2O4 and YVO4 have the birefringences of 0.12 and 0.22. We propose a targeted high‐throughput screening system to search birefringence‐active functional modules (FMs) and large birefringent materials. A series of π‐conjugated C−O units [C2O4]2−, [C2O6]2−, [C4O4]2−, and [C6O6]2− are discovered to be birefringence‐active FMs. Theoretical and experimental studies on the crystals with C−O units confirm the feasibility of strategy. Based on this, the C−O containing compounds ranging from deep‐ultraviolet to near‐infrared region with large birefringence from 0.1 to 1.35 are found, and most of them break through the birefringent limit of oxides. The (NH4)2C2O4⋅H2O crystal is grown and its experimental birefringence is 0.248 at 546 nm, which is identified as a promising UV birefringent crystal. The A‐site cations play significant roles in optical properties by influencing the density and arrangement of the C−O units.
Approaching a “Naked” Boryl Anion: Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes
Authors: Protchenko Andrey V. , Vasko Petra , Fuentes M. Ángeles , Hicks Jamie , Vidovic Dragoslav , Aldridge Simon 
Published: October 2020

AbstractAmide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3Si)2N}M{B(NDippCH)2}(thf)n(M=Ca,n=2; M=Sr,n=3), through the reactions of the corresponding bis(amides), M{N(SiMe3)2}2(thf)2, with (thf)2Li‐ {B(NDippCH)2}. Most notably, this approach can also be applied to the analogous potassium amide K{N(SiMe3)2}, leading to the formation of the solvent‐free borylpotassium dimer [K{B(NDippCH)2}]2, which is stable in the solid state at room temperature for extended periods (48 h). A dimeric structure has been determined crystallographically in which the K+cations interact weakly with both the ipso‐carbons of the flanking Dipp groups and the boron centres of the diazaborolyl heterocycles, with K⋅⋅⋅B distances of >3.1 Å. These structural features, together with atoms in molecules (QTAIM) calculations imply that the boron‐containing fragment closely approaches a limiting description as a “free” boryl anion in the condensed phase.
1,1,2‐Trifunctionalization of Terminal Alkynes by Radical Addition–Translocation–Cyclization–Trapping for the Construction of Highly Substituted Cyclopentanes
Authors: Yang Youqing , Daniliuc Constantin G. , Studer Armido 
Published: October 2020

AbstractRadical 1,1,2‐trifunctionalization of terminal alkynes by an addition–translocation–cyclization–trapping sequence using readily available alkynyl triflones as trifluoromethyl radical precursors and trapping reagents is reported. Cascades occur by addition of the trifluoromethyl radical to a terminal alkyne, 1,5‐hydrogen atom transfer, 5‐exo‐cyclization, and subsequent alkynylation to provide (1‐trifluoromethyl)propargyl cyclopentanes. Reactions proceed with commercial dibenzoyl peroxide or α,α′‐azobisisobutyronitrile as the initiator at elevated temperature and provide the highly substituted cyclopentanes in good yields.
Chromium‐Catalyzed Selective Dimerization/Hydroboration of Allenes to Access Boryl‐Functionalized Skipped (E,Z)‐Dienes
Authors: Zhao Yinsong , Ge Shaozhong 
Published: October 2020

AbstractA chromium‐catalyzed dimerization/hydroboration of allenes is developed to access synthetically versatile boryl‐functionalized skipped dienes with a catalyst generated in situ from CrCl2 and a pyridine‐2,6‐diimine ligand mesPDI. A variety of allenes reacted with pinacolborane (HBpin) to afford the corresponding boryl‐functionalized (E,Z)‐1,4‐dienes in high yields and with excellent selectivity. Electron paramagnetic resonance (EPR) spectroscopic studies suggest that this chromium‐catalyzed reaction probably proceeds through a chromium(I) hydride intermediate.
A Homoleptic Beryllium Carbonyl Complex with an End‐On and Side‐On Bridging Carbonyl Ligand
Authors: Wang Guanjun , Zhou Yangyu , Jin Xiaoyang , Jin Jiaye , Zhou Mingfei 
Published: October 2020

AbstractHomoleptic dinuclear beryllium carbonyl cation complexes have been produced and characterized in the gas phase. Infrared photodissociation spectroscopic and theoretical results confirm that Be2(CO)5+ is a coordination saturated complex that can be assigned to a mixture of two almost isoenergetic structural isomers. Besides a beryllium–beryllium single‐bonded (OC)2Be‐Be(CO)3+ isomer, another structure involving an unusual end‐on and side‐on bridging carbonyl ligand with very low carbonyl stretching frequency is identified.
Interfacing High‐Energy Charge‐Transfer States to a Near‐IR Sensitizer for Efficient Electron Transfer upon Near‐IR Irradiation
Authors: Pinjari Dilip , Alsaleh Ajyal Z. , Patil Yuvraj , Misra Rajneesh , D'Souza Francis 
Published: October 2020

AbstractPush–pull systems comprising of triphenylamine–tetracyanobutadiene (TPA‐TCBD), a high‐energy charge‐transfer species, are linked to a near‐IR sensitizer, azaBODIPY, for promoting excited‐state CS. These systems revealed panchromatic absorption owing to intramolecular CT and near‐IR absorbing azaBODIPY. Using electrochemical and computational studies, energy levels were established to visualize excited state events. Fs‐TA studies were performed to monitor excited state CT events. From target analysis, the effect of solvent polarity, number of linked CT entities, and excitation wavelength dependence in governing the lifetime of CS states was established. Electron exchange between two TPA‐TCBD entities in 3 seem to prolong lifetime of the CS state. We have been successful in demonstrating efficient CS upon both high‐energy CT and low‐energy near‐IR excitations, signifying importance of these push–pull systems for optoelectronic applications operating in the wide optical window.
Leben unter Druck
Authors: Eitner Pascal 
Published: October 2020

ZusammenfassungDruck ist ein abiotischer Umweltfaktor, der Organismen auf vielen Ebenen beeinflusst. Gerade im marinen Milieu ist der hydrostatische Druck ein wesentlicher Grund für Anpassungen im Bereich von Morphologie und Physiologie: Makroskopisch wurden vor allem Gewichtseinsparung, Auftriebskörper und neue Jagdstrategien für das Überleben in der Tiefsee erforderlich. Auf zellulärer Ebene hemmt hoher Druck (>10 MPa) den Stoffwechsel aufgrund der Deformation der Biomoleküle, so dass sich Lebensmittel mit Druck bei Raumtemperatur sterilisieren lassen. Andererseits existieren auch extremophile Mikroben sowie höhere Tiere, die der starken mechanischen Beanspruchung z. B. mittels kompatibler Solute trotzen und oft nur unter Hochdruckbedingungen überleben können. Auch für die normale Entwicklung von belastbarem Gewebe wie Gelenkknorpel und Knochen ist die Anwendung von Druck unabdingbar.
Niedergang der Insekten
Authors: Reichholf Josef H. 
Published: October 2020

ZusammenfassungDie Auswertung von fünfzig Jahren standardisierter Untersuchungen zum Anflug von Insekten an UV‐Licht in Südostbayern und München ergab einen starken Rückgang der Häufigkeit nachtaktiver Schmetterlinge um über 80 Prozent und der übrigen (Klein)Insekten um 96 Prozent für die Ortsrandbereiche zur Flur, aber keine Abnahmen in München und lediglich moderate im Auwald, deren Verursachung in der Wuchsverdichtung nach Ende der Niederwaldnutzung zu sehen ist. Die Schmetterlingshäufigkeit am Rand der intensiv landwirtschaftlich genutzten Flur ist gegenwärtig unter das Großstadtniveau gesunken. Der Vergleich zweier Münchner Stadtbereiche mit normaler und so gut wie keiner Einwirkung von Straßenbeleuchtung ergab überraschenderweise keinen Unterschied. Als Hauptgrund für den Insektenrückgang ist die Überdüngung, verbunden mit dem Einsatz von Pestiziden zu sehen. An zweiter Stelle stehen aber die öffentlichen Pflegemaßnahmen von nicht landwirtschaftlich genutztem Gelände mit zumeist mehrfacher Radikalmahd im Jahreslauf. Die davon verursachten Verluste ließen sich vermeiden.
A survey of lifestyle factors in dystonia
Authors: Söderlund Jacob , Nyholm Dag 
Published: October 2020

AbstractBackgroundKnowledge about what causes dystonia is highly incomplete, especially about the impact of nongenetic factors.Aims of the StudyThis cross‐sectional survey‐based explorative study examined different nongenetic factors in patients with dystonia.MethodsInformation from both medical records and a questionnaire was collected. In total, 220 patients with dystonia were identified, of which 51 participated in the survey.ResultsWomen had a higher prevalence for cervical dystonia than men. Smoking was approximately twice as common in our studied population compared to the general Swedish population. Significantly more men than women met the criteria for low level of physical activity, yet the proportion of missing data was high in this category.ConclusionsConclusions on causality cannot be drawn in this preliminary study, further research is encouraged regarding the link between smoking and dystonia.
Directed Evolution of a Cp*RhIII‐Linked Biohybrid Catalyst Based on a Screening Platform with Affinity Purification
Authors: Kato Shunsuke , Onoda Akira , Taniguchi Naomasa , Schwaneberg Ulrich , Hayashi Takashi 
Published: October 2020

AbstractDirected evolution of Cp*RhIII‐linked nitrobindin (NB), a biohybrid catalyst, was performed based on an in vitro screening approach. A key aspect of this effort was the establishment of a high‐throughput screening (HTS) platform that involves an affinity purification step employing a starch‐agarose resin for a maltose binding protein (MBP) tag. The HTS platform enables efficient preparation of the purified MBP‐tagged biohybrid catalysts in a 96‐well format and eliminates background influence of the host E. coli cells. Three rounds of directed evolution and screening of more than 4000 clones yielded a Cp*RhIII‐linked NB(T98H/L100K/K127E) variant with a 4.9‐fold enhanced activity for the cycloaddition of acetophenone oximes with alkynes. It is confirmed that this HTS platform for directed evolution provides an efficient strategy for generating highly active biohybrid catalysts incorporating a synthetic metal cofactor.
Concentration‐Dependent Interactions of Amphiphilic PiB Derivative Metal Complexes with Amyloid Peptides Aβ and Amylin**
Authors: Majdoub Saida , Garda Zoltán , Oliveira Alexandre C. , Relich Inga , Pallier Agnès , Lacerda Sara , Hureau Christelle , Geraldes Carlos F. G. C. , Morfin Jean‐François , Tóth Éva 
Published: October 2020

AbstractMetal chelates targeted to amyloid peptides are widely explored as diagnostic tools or therapeutic agents. The attachment of a metal complex to amyloid recognition units typically leads to a decrease in peptide affinity. We show here that by separating a macrocyclic GdL chelate and a PiB targeting unit with a long hydrophobic C10 linker, it is possible to attain nanomolar affinities for both Aβ1‐40 (Kd=4.4 nm) and amylin (Kd=4.5 nm), implicated, respectively in Alzheimer's disease and diabetes. The Scatchard analysis of surface plasmon resonance data obtained for a series of amphiphilic, PiB derivative GdL complexes indicate that their Aβ1‐40 or amylin binding affinity varies with their concentration, thus micellar aggregation state. The GdL chelates also affect peptide aggregation kinetics, as probed by thioflavin‐T fluorescence assays. A 2D NMR study allowed identifying that the hydrophilic region of Aβ1‐40 is involved in the interaction between the monomer peptide and the Gd3+ complex. Finally, ex vivo biodistribution experiments were conducted in healthy mice by using 111In labeled analogues. Their pancreatic uptake, ∼3 %ID g−1, is promising to envisage amylin imaging in diabetic animals.
Guest Recognition Control Accompanied by Stepwise Gate Closing and Opening of a Macrocyclic Metallohost
Authors: Sakata Yoko , Okada Masahiro , Akine Shigehisa 
Published: October 2020

AbstractHost–guest binding behavior of macrocyclic hosts is significantly influenced by the shapes and sizes of the hosts. In particular, closing/opening the apertures of the hosts controls the guest uptake/release. A post‐metalation modification method was used to achieve the open/close conversions. The starting open complex, [LCo2(pip)4](OTf)2, was efficiently converted to the closed complex, [LCo2(hda)2](OTf)2, which has a doubly bridged structure. The conversion of this closed complex to the open complex [LCo2(hda)2(OAc)]+ was too slow to be completed, but this gate‐opening was dramatically accelerated by the addition of Na+. The Na+ binding was also significantly enhanced by the gate‐opening, that is, conversion of [LCo2(hda)2]2+ to [LCo2(hda)2(OAc)]+.
Breast metastasis from medullary thyroid carcinoma mimicking ductal carcinoma with neuroendocrine differentiation
Authors: Laforga Juan B. , Dominguez Eva , Aranda Francisco Ignacio 
Published: October 2020

AbstractBackgroundMedullary thyroid carcinoma very rarely metastasizes to the breast. Hematogenous spread to the liver, lungs, or mediastinum is more common.CaseWe describe the morphologic and immunohistochemical features of a 63‐year‐old woman who presented with a BIRADS‐5 category nodule in the right breast and enlarged axillary lymph nodes. Core biopsy showed suggested breast cancer with neuroendocrine or apocrine differentiation. The immunohistochemical profile showed (RE−/RP−/HER‐2−) and Ki67 10%. Chromogranin and synaptophysin were positive; AR and GCDFP‐15 were negative. On reviewing the patient's clinical history, it was discovered that she had been treated for medullary thyroid carcinoma 15 years earlier. Additional stains showed positivity for TTF‐1, CEA, and calcitonin. These findings were consistent with a diagnosis of breast metastasis from medullary thyroid carcinoma. We discuss briefly the morphologic features and the possible key features in order to make an accurate diagnosis.ConclusionThis case highlights the importance of investigating a history of cancer in patients with discordant or unusual histologic or immunohistochemical findings, as this can help avoid misdiagnosis and inappropriate treatment.
Lingual alveolar soft part sarcoma with absent TFE3 rearrangement
Authors: Alshahrani Saeed , Khan Abdullatif 
Published: October 2020

AbstractBackgroundLingual ASPS is extremely rare and aggressive tumor. rearrangement is typically detected in ASPS patients using FISH analysis.AimTo present the clinical, histopathological, and radiological features of lingual Alveolar Soft Part Sarcoma.MethodA 30‐year‐old male presented with a painless, slowly growing mass of the tongue. Initial impression was of benign vascular lesion. Later, the patient became symptomatic as the mass progressed in size, which necessitated further investigations.ResultA lip‐split, mandibulotomy was performed for the excision of the tumor and revealed an alveolar soft part sarcoma with PAS‐positive, diastase resistant intracytoplasmic granules. However, molecular analysis using FISH was negative for TFE3 rearrangement. Patient underwent partial glossectomy with postoperative radiotherapy.ConclusionClinical and pathological correlation of ASPS is very useful to reach a proper diagnosis.
Timeliness of cancer care in a regional Victorian health service: A comparison of high‐volume (Lung) and low‐volume (oesophagogastric) tumour streams
Authors: Kabwe Mwila , Robinson Amanda , Shethia Yachna , Parker Carol , Blum Robert , Solo Ilana , Leach Michael 
Published: October 2020

AbstractBackgroundTimeliness of cancer care is vital for improved survival and quality of life of patients. Service and care centralisation at larger‐volume centres has been associated with improved outcomes. However, there is a lack of systematic data on the impact of tumour stream volume on timeliness of care.AimsTo investigate and compare timeliness of care for lung cancer, a high‐volume (more commonly diagnosed) tumour stream, and oesophagogastric (OG) cancer, a low‐volume (less commonly diagnosed) tumour stream, at a regional health service in Victoria, Australia.MethodsA retrospective cohort study comprising random samples of 75 people newly diagnosed with lung cancer (International Classification of Diseases and Related Health Problems‐10 [ICD‐10] diagnosis codes C34 in the Victorian Cancer Registry [VCR]) and 50 people newly diagnosed with OG cancer (ICD‐10 diagnosis codes C15 or C16 in VCR) at one regional Victorian health service between 2016 and 2017. Binary logistic regression was used to calculate odds ratios (ORs) and 95% confidence intervals (CIs) for associations between patient factors and suboptimal timeliness of care.ResultsIn comparison to OG cancer patients, lung cancer patients had reduced odds of suboptimal timeliness of care in reference to times outside OCP for referral to diagnosis (OR [95% CI] = 0.34 [0.14 to 0.83]) but increased odds of suboptimal timeliness for diagnosis to treatment (OR [95% CI] = 2.48 [1.01 to 6.09]).ConclusionIn the low‐volume OG cancer stream, patients had longer wait times from referral to an MDM, where treatment decisions occur, but shorter time to commencement of first treatment. Conversely in the high‐volume lung cancer group, there was delayed initiation of first treatment following presentation at MDM. There is need to explore ways to fast‐track MDM presentation and commencement of therapy among people diagnosed with low‐volume and high‐volume cancers, respectively.
Being responsible for someone else: a shared duty for parents and heart failure specialists during the COVID‐19 pandemic
Authors: Mapelli Massimo 
Published: October 2020

AbstractA pandemic by a novel coronavirus disease (COVID‐19) has been declared by the World Health Organization. Lombardy, the region of our tertiary referral centre for heart diseases in Northern Italy, has been particularly hit by the pandemic. According to the government's prescriptions, all elective activities and procedures in the last months were suspended in order to concentrate our efforts on COVID‐19 patients' care. Entire departments have been turned into ‘COVID‐19 units’, where healthcare professionals are daily involved in supporting critically ill patients.On a personal level, this was a period of special feelings and peculiar unexpected events. People close to healthcare workers have been affected, and our lives have been turned upside down. Furthermore, right in this period, few colleagues (and friends) are facing entirely new events in their lives, such as fatherhood with its load of joy and concern.Through the case of a young woman recently admitted to our department with a severe heart failure due to a peripartum cardiomyopathy, described in narrative form, this manuscript would help all those involved in the front line in the fight against the pandemic in these difficult times.
A vegetable oil–based biopesticide with ovicidal activity against the two‐spotted spider mite, Tetranychus urticae Koch
Authors: Takeda Naoki , Takata Ayumi , Arai Yuka , Sasaya Kazuhiro , Noyama Shimpei , Wakisaka Shigekazu , Ghazy Noureldin Abuelfadl , Voigt Dagmar , Suzuki Takeshi 
Published: October 2020

AbstractA recently developed biopesticide made of safflower and cottonseed oils has excellent ovicidal activity against the hard‐to‐control spider mite Tetranychus urticae Koch (Acari: Tetranychidae). It has attracted attention as a sustainable treatment for controlling T. urticae because it has low potential for promoting resistance and little effect on the predatory mite Neoseiulus californicus (McGregor) (Acari: Phytoseiidae), which is an important natural enemy of spider mites. Here, we investigated the mechanism of its ovicidal activity against T. urticae. The oil droplets in the oil‐in‐water emulsion of the biopesticide strongly adhered to T. urticae eggs, seeped through the chorion being cut during hatching, and inhibited the embryonic rotational movement necessary for cutting and hatching. No adverse effect was observed on N. californicus eggs even in undiluted biopesticide. We conclude that this biopesticide and N. californicus can be used simultaneously in the integrated management of T. urticae in oily biopesticide‐tolerant plant species.
Rohtang Tunnel – NATM in the Indian Himalayas
Authors: Reichenspurner Peter , Riedel Thomas 
Published: October 2020

AbstractThe 8,900 m long Rohtang Tunnel lies in the Indian Himalayas north of the Manali tourist region. It avoids the dangerous route over the Rohtang Pass, which is at an elevation of almost 4,000 m, shortening the Manali‐Leh Highway by approx. 50 km and enabling access to the northern regions of the state of Himachal Pradesh and onto Jammu and Kashmir even during the winter.It was envisaged that the tunnel would be driven from two sides by drilling and blasting. The horseshoe‐shaped cross‐section with an excavation diameter of more than 13 m carries two lanes of vehicle traffic, two footpaths and an emergency egress beneath the carriageway.In addition to the extreme conditions that were a feature of this project – portals at an altitude of over 3,000 m, with corresponding severe winters, avalanches and mudslides, etc. – the NATM was also driven to its limits. Friable soils instead of blast rock, water ingress in excess of 250 l/s, high rock pressure with extreme deformations and rapid changes in rock formations presented major challenges to all involved. Tunnelling operations are now nearing completion and the road tunnel will be open to traffic later this year.
Full percutaneous intraoperative neuromonitoring technique in remote thyroid surgery: Porcine model feasibility study
Authors: Huang Tzu‐Yen , Lin Yi‐Chu , Tseng Hsin‐Yi , Kim Hoon Yub , Dionigi Gianlorenzo , Lu I‐Cheng , Chang Pi‐Ying , Chiang Feng‐Yu , Wu Che‐Wei 
Published: October 2020

AbstractBackgroundIn remote thyroid surgery, a reliable intraoperative neuromonitoring (IONM) procedure is an important tool for reducing injury to recurrent laryngeal nerve (RLN). This study proposes an alternative or adjunct technique for performing full percutaneous (PC) IONM and confirms its feasibility in animal experiments.MethodsThis prospective porcine model study enrolled four piglets with eight nerve sides. Evoked electromyography (EMG) was stimulated from PC ball‐tip probe, and recorded from EMG endotracheal tube (ETT) and from PC paired long‐needle electrodes on the perichondrium of the lateral aspect of thyroid cartilage.ResultsIn all RLNs and vagus nerves, typical laryngeal EMG waveforms were successfully evoked by PC probe stimulation and recorded by both ETT and PC needle electrodes.ConclusionsThis study confirms the feasibility of the full PC IONM techniques in porcine model. However, further clinical studies are needed to compare the practicality of different remote‐access approaches for thyroid surgery.