bluuebunny/crossref_metadata_2025_split huggingface dataset:
Os cidadãos-professores e a formação para a cidadania na construção de escolas democráticas
Authors: Stürmer Arthur Breno , Ferreira Liliana Soares 
Published: July 2018

O presente artigo discute a formação para a cidadania em escolas públicas estaduais de Santa Catarina, com foco na atuação dos cidadãos-professores e nas Instâncias de Gestão Escolar Democrática (IGEDs).Trata dos pressupostos históricos e legais da escola democrática, aborda as condições de formação dos cidadãos e até chegar ao papel dos cidadãos-professores diante da construção de escolas democráticas. Os dados procedem de pesquisa desenvolvida no Curso de Especialização em Gestão Educacional da Universidade Federal de Santa Maria/UAB. A partir do questionamento de dezessete professores, salienta-se que os cidadãos-professores pouco participam das principais IGEDs — Conselho Escolar e a Associação de Pais e Professores —, as quais não funcionam como núcleos de formação para a cidadania. Logo, a experiência de construção de escolas democráticas necessita de maior empenho e estimulo à participação direta, seja dos professores, seja da comunidade como um todo.Palavras-chave: gestão escolar, democracia, cidadania.
Controlling Cells with Light and LOV
Authors: Hoffmann Mareike Daniela , Bubeck Felix , Eils Roland , Niopek Dominik 
Published: July 2018

AbstractOptogenetics is a powerful method for studying dynamic processes in living cells and has advanced cell biology research over the recent past. Key to the successful application of optogenetics is the careful design of the light‐sensing module, typically employing a natural or engineered photoreceptor that links the exogenous light input to the cellular process under investigation. Light–oxygen–voltage (LOV) domains, a highly diverse class of small blue light sensors, have proven to be particularly versatile for engineering optogenetic input modules. These can function via diverse modalities, including inducible allostery, protein recruitment, dimerization, or dissociation. This study reviews recent advances in the development of LOV domain‐based optogenetic tools and their application for studying and controlling selected cellular functions. Focusing on the widely employed LOV2 domain from Avena sativa phototropin‐1, this review highlights the broad spectrum of engineering opportunities that can be explored to achieve customized optogenetic regulation. Finally, major bottlenecks in the development of optogenetic methods are discussed and strategies to overcome these with recent synthetic biology approaches are pointed out.
Dynamic Covalent Chemistry at Interfaces: Development of Tougher, Healable Composites through Stress Relaxation at the Resin–Silica Nanoparticles Interface
Authors: Sowan Nancy , Cox Lewis M. , Shah Parag K. , Song Han Byul , Stansbury Jeffrey W. , Bowman Christopher N. 
Published: July 2018

AbstractThe interfacial region in composites that incorporate filler materials of dramatically different modulus relative to the resin phase acts as a stress concentrator and becomes a primary locus for composite failure. A novel adaptive interface (AI) platform formed by coupling moieties capable of dynamic covalent chemistry (DCC) is introduced to the resin–filler interface to promote stress relaxation. Specifically, silica nanoparticles (SNP) are functionalized with a silane capable of addition fragmentation chain transfer (AFT), a process by which DCC‐active bonds are reversibly exchanged upon light exposure and concomitant radical generation, and copolymerized with a thiol‐ene resin. At a fixed SNP loading of 25 wt%, the toughness (2.3 MJ m−3) is more than doubled and polymerization shrinkage stress (0.4 MPa) is cut in half in the AI composite relative to otherwise identical composites that possess a passive interface (PI) with similar silane structure, but without the AFT moiety. In situ activation of the AI during mechanical loading results in 70% stress relaxation and three times higher fracture toughness than the PI control. When interfacial DCC was combined with resin‐based DCC, the toughness was improved by 10 times relative to the composite without DCC in either the resin or at the resin–filler interface.
Development of Novel Chloramphenicol Scaffold‐Based Chiral Hydroxyl Oxazoline Ligands and Their Application to the Asymmetric Alkynylation of Isatins
Authors: Chen Lei , Huang Guanxin , Liu Minjie , Huang Zedu , Chen Fen‐Er 
Published: July 2018

AbstractThe synthesis of new chloramphenicol base‐derived chiral hydroxyl oxazoline ligands, and their use in the first Zn(OTf)2‐catalyzed enantioselective alkynylation of isatins are described. This transformation features mild reaction conditions, a remarkably broad substrate scope, and excellent functional group tolerance, affording the corresponding tertiary propargylic alcohols in high yields and with high enantioselectivities. The application of chiral hydroxyl oxazolines as ligands in Zn(II)‐catalyzed asymmetric alkynylation reactions is unprecedented.magnified image
Ru (II)‐Catalyzed Coupling‐Cyclization of Sulfoximines with alpha‐Carbonyl Sulfoxonium Ylides as an Approach to 1,2‐Benzothiazines
Authors: Xie Haisheng , Lan Jianyong , Gui Jiao , Chen Fengjuan , Jiang Huangfeng , Zeng Wei 
Published: July 2018

AbstractA Ru(II)‐catalyzed approach for the rapid assembly of 1,2‐benzothiazines has been developed to enable the coupling‐cyclization of aryl Csp2−H bonds with α‐carbonyl sulfoxonium ylides via Csp2−H activation process. The present method could be further applied to the construction of the 4‐substituted 1,2‐benzothiazine skeletons.magnified image
Assembly of a Wheel‐Like Eu24Ti8 Cluster under the Guidance of High‐Resolution Electrospray Ionization Mass Spectrometry
Authors: Zheng Hao , Du Ming‐Hao , Lin Shui‐Chao , Tang Zi‐Chao , Kong Xiang‐Jian , Long La‐Sheng , Zheng Lan‐Sun 
Published: July 2018

AbstractA building blocks strategy is an effective approach for constructing the large molecular systems. Herein, we demonstrate that high‐resolution electro‐spray ionization mass spectrometry (HRESI‐MS) provides an effective chance to insight the assemble process of the building blocks and guides the construction of high‐nuclearity metal clusters on the basis of the reaction of Ti(OiPr)4, Eu(acac)3, and salicylic acid. The time‐dependent HRESI‐MS indicates that not only a Eu3Ti building block can be formed, but that it can further assemble into a Eu24Ti8 compound. Temperature‐dependent HRESI‐MS reveals that increase of the reaction temperature favors the formation and crystallization of the stable Eu24Ti8 structure. Single‐crystal structural analysis demonstrates that the Eu24Ti8 has a wheel‐like structure with diameter of ca. 4.1 nm and is the highest nuclearity lanthanide‐titanium oxo cluster reported to date.
Chiral Phosphoric Acid Catalyzed Asymmetric Synthesis of Hetero‐triarylmethanes from Racemic Indolyl Alcohols
Authors: Yue Caizhen , Na Fei , Fang Xiantao , Cao Yang , Antilla Jon C. 
Published: July 2018

AbstractThe direct enantioselective 1,4‐ and 1,8‐arylations of 7‐methide‐7H‐indoles and 6‐methide‐6H‐indoles, respectively, generated in situ from diarylmethanols, with electron‐rich arenes as nucleophiles, has been achieved in the presence of chiral phosphoric acids (CPAs). These two remote activation protocols provide an efficient approach for the construction of diverse hetero‐triarylmethanes in high yields (up to 97 %) and with excellent enantioselectivities (up to 96 %). Mechanistically inspired experiments tentatively indicate that the catalytic enantioselective 1,4‐addition as well as the formal SN1 substitution could proceed efficiently in the similar catalytic systems. Furthermore, the modification of the catalytic system and diarylmethanol structure successfully deviates the reactivity toward a remote, highly enantioselective 1,8‐arylation reaction. This flexible activation mode and novel reactivity of diarylmethanols expand the synthetic potential of chiral phosphoric acids.
γ‐, Diastereo‐, and Enantioselective Addition of MEMO‐Substituted Allylboron Compounds to Aldimines Catalyzed by Organoboron–Ammonium Complexes
Authors: Morrison Ryan J. , Hoveyda Amir H. 
Published: July 2018

AbstractThe first catalytic, broadly applicable, efficient, γ‐, diastereo‐, and enantioselective method for addition of O‐substituted allyl‐B(pin) compounds to phosphinoylimines (MEM=methoxyethoxymethyl, pin=pinacolato) is presented. The identity of the most effective catalyst and the optimal protecting group for the organoboron reagent were determined by consideration of the steric and electronic requirements at different stages of the catalytic cycle, namely, the generation of the chiral allylboronate, the subsequent 1,3‐borotropic shift, and the addition step. Aryl‐, heteroaryl‐, alkenyl‐ and alkyl‐substituted vicinal phosphinoylamido MEM‐ethers were thus accessed in 57–92 % yield, 89:11 to >98:2 γ:α selectivity, 76:24–97:3 diastereomeric ratio, and 90:10–99:1 enantiomeric ratio. The method is scalable, and the phosphinoyl and MEM groups may be removed selectively or simultaneously. Utility is highlighted by enantioselective synthesis of an NK‐1 receptor antagonist.
Nickel‐Catalyzed Asymmetric [2+2] Cycloaddition Reaction of Hetero‐Bicyclic Alkenes with Internal Alkynes
Authors: Qin Hongyu , Chen Jingchao , Li Kangkui , He Zhenxiu , Zhou Yongyun , Fan Baomin 
Published: July 2018

AbstractEnantioselective [2+2] cycloaddition reaction of azabenzonorbornadienes and oxabenzonorbornadienes with internal alkynes has been enabled by a catalyst system comprising Ni(COD)2 and (R)‐SIPHOS‐Ph‐Mor. This transformation represents the first asymmetric [2+2] cycloaddition reaction of azabenzonorbornadienes with internal alkynes, providing a straightforward method to prepare four‐membered carbocycles.
Phosphorescence Resulting from Interaction between Two Non‐equivalent Metals on a Helical π‐Conjugated Surface
Authors: Akiyama Midori , Tsuchiya Yuto , Ishii Ayumi , Hasegawa Miki , Kurashige Yuki , Nozaki Kyoko 
Published: July 2018

AbstractA [7]helicene bis‐ruthenium complex, with one ruthenium atom bound to the cyclopentadienyl (Cp) ring and the other coordinated to the arene ring at the edge of the helicene, was synthesized. This complex showed phosphorescence both in butyronitrile (Φ=31 %, 77 K) and in the solid state (Φ=18 %, 77 K). The two non‐equivalent ruthenium metal atoms, attached to the helicene ligand, interact with each other upon photoabsorption and emission.
Azopyridine‐Containing Three‐arm Star Compounds with Aggregation‐induced Fluorescence
Authors: Chen Yinjie , Feng Xing , Sun Zhicheng , Wang Dan , Yang Tao , Zhao Ziyuan , Li Luhai , Wang Xiaogong , Yu Haifeng 
Published: July 2018

AbstractThree‐arm star azopyridinium salts self‐organize into various morphologies in water/organic mixed solvents. Interesting AIE and self‐assembling features are observed due to the strong interaction of the azopyridinium moieties with the highly polar H2O molecules causing the salts to aggregate, which restricts the molecular motion and induces the fluorescence.
Design of a phosphinate‐based bioluminescent probe for superoxide radical anion imaging in living cells
Authors: Liu Xinda , Tian Xiaodong , Xu Xu , Lu Jianzhong 
Published: July 2018

AbstractSuperoxide radical anion (O2˙−) as an important member of reactive oxygen species (ROS) plays a vital role both in physiology and pathology. Herein we designed and synthesized a novel phosphinate‐based bioluminescence probe for O2˙− detection in living cells, which exhibited good sensitivity for capturing O2˙− at the nanomole level and high selectivity against other ROS. The probe was further found to be of low toxicity for living cells and was then successfully employed for sensing endogenous O2˙− by using phorbol‐12‐myristate‐13‐acetate (PMA) as a traditional O2˙− stimulator in Huh7 cells. Moreover, the increasing production and use of nanoparticles, has given rise to many concerns and debates among the public and scientific authorities regarding their safety and final fate in biological systems. Herein it was found that mondisperse polystyrene particles could stimulate O2˙− generation in Huh7 cells. Overall, the probe was demonstrated to have a great potential as a novel bioluminescent sensor for detecting O2˙− in living cells. To our knowledge, this is the first small‐molecule phosphinate‐based bioluminescence probe that will open up great opportunities for unlocking the mystery of O2˙− in human health and disease.
Corporate culture, environmental innovation and financial performance
Authors: Liao Zhongju 
Published: July 2018

AbstractBased on the logic of culture‐behaviour performance, this study constructs a theoretical model to examine the effect of four types of corporate culture (clan, adhocracy, hierarchy and market) on the three dimensions of a firm's environmental innovation (eco‐organizational, eco‐process and eco‐product) and whether environmental innovation affects a firm's financial performance. Three hundred and sixty‐six firms in the manufacturing and service industries are selected as a valid research sample, and a structural equation model is used for empirical analysis. The results show that adhocracy and market cultures are positively related to a firm's eco‐organizational, eco‐process and eco‐product innovation; clan culture has a positive effect, and hierarchy culture a negative effect, on eco‐organizational innovation; and the three dimensions of environmental innovation all promote a firm's financial performance. Based on these conclusions, this study discusses managerial implications and suggests future research directions.
Alternative access for transcatheter aortic valve replacement in older adults: A collaborative study from France and United States
Authors: Damluji Abdulla A. , Murman Magdalena , Byun Seunghwan , Moscucci Mauro , Resar Jon R , Hasan Rani K. , Alfonso Carlos E. , Carrillo Roger G. , Williams Donald B. , Kwon Christopher C. , Cho Peter W. , Dijos Marina , Peltan Julien , Heldman Alan W. , Cohen Mauricio G. , Leroux Lionel 
Published: July 2018

AbstractBackgroundWe examined the outcomes of older adults undergoing nontrans‐femoral (non‐TF) transcatheter aortic valve replacement (TAVR) procedures including trans‐apical (TA), trans‐aortic (TAo), trans‐subclavian (TSub), and trans‐carotid (TCa) techniques.Methods and ResultsThis is an observational study of all consecutive older patients who underwent non‐TF TAVR for symptomatic severe AS with Edwards Sapien (ES), Medtronic CoreValve, ES3 or Lotus Valve at three centers in France and the United States from 04/2008 to 02/2017. Baseline characteristics and clinical outcomes were defined according to VARC‐2 criteria. Of 857 patients who received TAVR, 172 (20%) had an alternative access procedure. Of these, 45 (26%) were TA, 67 (39%) TAo, 17 (10%) TSub, and 43 (25%) TCa procedures. The preference for non‐TF access site was different between the two countries (US: TA 39%, TAo 52%, TSub 9%; TCa 0% vs. France: TA 9%, TAo 23%, TSub 11%, and TCa 57%, P‐value < .001). Most patients who underwent TAo TAVR were older women (median age: TA 82, TAo 84, TSub 81, TCa 81, P‐value = 0.043; female gender: TA 32 (27%), TAo 30 (55%), TSub 10 (41%), TCa 27 (37%), P‐value = .021). The predicted Society of Thoracic Surgery risk of mortality was similar among groups (TA 7%, TAo 7%, TSub 6%, TCa 7%, P‐value= .738). No differences were observed in the frequency of para‐valvular leak, intra‐procedural bleeding, vascular complications, conversion to open‐heart surgery, or development of acute kidney injury. The highest in‐hospital mortality was observed in the TAo group (TA 2%, TAo 15%, TSub 0%, TCa 2%, P‐value = .014). However, hospital length of stay, one‐month, and one‐year mortality were similar among non‐TF techniques.ConclusionAlthough regional differences exist in the choice of alternative access techniques, centers with high technical expertise can provide a safe alternative to traditional TF TAVR. TAo TAVR was associated with higher in‐hospital mortality than other non‐TF approaches, and this may have reflected patient rather than procedural factors. All alternative access techniques had similar mortality rates and clinical outcomes at one‐year follow‐up. Trans‐carotid access is safe and feasible compared to other non‐TF access techniques.
A novel FBN2 mutation cosegregates with congenital contractural arachnodactyly in a five‐generation Chinese family
Authors: Zhou Shiyuan , Wang Fengyu , Dou Yongheng , Zhou Jiping , Hao Gefang , Xu Chengqi , Wang Qing K. , Wang Haili , Wang Pengyun 
Published: July 2018

Key Clinical MessageWe identified a novel heterozygous mutation (c.4177T>G and p.Cys1393Gly) in FBN2 that cosegregated with congenital contractural arachnodactyly (CCA) in a five‐generation Chinese family. This mutation may cause the loss of the disulfide bond between Cys 1393 and Cys 1378 residues of fibrillin‐2. Our study expands the genetic profile of CCA.
HypervirulentKlebsiella pneumoniaeK1 liver abscess and endogenous endophthalmitis in a Caucasian man
Authors: Baekby Martin , Hegedüs Nicolas , Sandahl Thomas Damgaard , Krogfelt Karen Angeliki , Struve Carsten 
Published: July 2018

Key Clinical MessageInvasive Liver Abscess Syndrome is the most frequent of a number of infectious syndromes caused by hypervirulentKlebsiella pneumoniaeclones. While incidences peak in Southeast Asia, travels to Asia and Asian ethnicity are independent risk factors for infection in the western countries, although non‐Asians are infected as well. Although challenging, a prompt diagnosis is of utmost importance to ensure adequate treatment and improve overall survival and visual outcome in cases with ocular involvement.
Electronic and Steric Effects on the Reductive Elimination of Anionic Arylferrate(III) Complexes
Authors: Parchomyk Tobias , Koszinowski Konrad 
Published: July 2018

AbstractArylferrate(III) complexes Ph3FeR− (R=para‐ and ortho‐substituted aryl) are proposed as model systems for the in‐depth investigation of reductive eliminations from organoiron(III) species. Electrospray ionization transfers the arylferrate complexes prepared in situ from solution into the gas phase, where mass selection ensures a well‐defined population of reactant ions. Upon gas‐phase fragmentation, the arylferrate complexes undergo reductive elimination of the cross‐coupling product PhR as well as the homo‐coupling product Ph2. The measured branching ratios between the two competing reaction channels are used to construct a Hammett plot, which shows that electron‐donating aryl groups R favor the formation of the cross‐coupling product. In this way, the complexes avoid the build‐up of too much electron density at the iron center during the reductive elimination. ortho Substitution in R increases the fraction of the homo‐coupling product, presumably by hindering the approach between the two aryl groups participating in the reductive elimination. The obtained mechanistic insight substantially advances our understanding of one of the central elementary steps of transition‐metal‐catalyzed cross‐coupling reactions.
Normal, Abnormal, and Cascade Wittig Olefinations of α‐Oxoketenes
Authors: Pierrot David , Presset Marc , Rodriguez Jean , Bonne Damien , Coquerel Yoann 
Published: July 2018

Abstractα‐Oxoketenes generated in situ by a thermal Wolff rearrangement have been found to participate as 1,2‐ and 1,4‐ambident C‐electrophilic/O‐nucleophilic reagents towards donor/acceptor carbonyl‐stabilized Wittig ylides. This resulted in the very direct and practical syntheses of functionalized allenes by a normal Wittig olefination, 4H‐pyran‐4‐ones by an abnormal Wittig olefination, or 4H‐pyranylidenes following a Wittig/abnormal Wittig cascade sequence as a function of the substrates combination employed. Mechanistic experimental and computational studies provided a full rational for these reactivity switches. Some unusual mechanistic features for Lewis acid‐free Wittig olefinations were identified in this series such as the involvement of betaine intermediates and some degree of reversibility in the normal Wittig olefination. The abnormal Wittig olefination was fully uncovered.
A Polymerization‐Cutting Strategy: Self‐Protection Synthesis of Thiol‐Based Nanoporous Adsorbents for Efficient Mercury Removal
Authors: Xu Yang , Wang Tianqi , He Zidong , Zhou Minghong , Yu Wei , Shi Buyin , Huang Kun 
Published: July 2018

AbstractHighly toxic heavy metal ions such as mercury ions (Hg2+) are a great threat to human life and the environment. Developing new strategies and materials to remove the toxic heavy metal ions has attracted more and more attentions. Herein a facile self‐protection synthesis of thiol‐based nanoporous adsorbents for efficient mercury removal via a polymerization‐cutting strategy is reported. The direct free‐radical polymerization of divinyl disulfide derivative and subsequently cutting off the disulfide linkage, without post‐synthesis or modification, can give rise to an exceptionally high density of thiol chelating sites. Moreover, the resultant thiol‐based nanoporous adsorbents (NAs‐SH) exhibit a high saturation uptake capacity (1240 mg g−1) and reused ability for mercury removal from water solution. The proposed polymerization‐cutting strategy may provide an alternative and cost‐effective method for the design and synthesis of various efficient nanoporous adsorbents at large scale in the future.
Immobilized Poly(aryleneethynylene) pH Strips Discriminate Different Brands of Cola
Authors: Bender Markus , Bojanowski N. Maximilian , Seehafer Kai , Bunz Uwe H. F. 
Published: July 2018

AbstractFluorescent, water‐soluble poly(p‐aryleneethynylene)s (PAE) were immobilized on commercially available nylon membranes by using a slot plotter, creating fluorescent, barcode‐like sensor strips. Digital imaging by using a standard digital camera, before and after immersion of the strips in buffers of different pH, displays a unique color for each pH value. Statistical evaluation, multivariate analysis of variance (MANOVA) and principal component analysis (PCA), of the acquired data revealed that the immobilized PAEs are superior to the identical fluorophores when dissolved. The pH sensor array discriminates 20 different brands of commercial‐cola soft drinks through differences in pH and colorant–PAE interactions.
Stereoselective and Modular Assembly Method for Heterocycle‐Fused Daucane Sesquiterpenoids
Authors: Christiaens Mien , Hullaert Jan , Van Hecke Kristof , Laplace Duchan , Winne Johan M. 
Published: July 2018

AbstractA stereoselective synthetic method is reported for the molecular framework found in common daucane and isodaucane sesquiterpenoid natural products. The synthetic method constitutes a scalable, modular, and also asymmetric access to a complex natural product scaffold, wherein the substitution pattern and the stereochemistry can be adjusted simply by choosing different starting materials. The method allows the rapid introduction of diverse heterocyclic substructures such as (benzo)furans, (benzo)thiophenes, dithiins, thiazoles, and indoles, which actually also facilitate and direct the key intramolecular annulation step.