bluuebunny/crossref_metadata_2025 huggingface dataset:
Selected music education textbooks for the grades I–III from the perspective of educational reforms in 1997–2011
Authors: Sowik Rafał
Published: October 2017

The article examines music education textbooks for the 1st–3rd primary school grades.
The author presents the main objectives of successive educational reforms. He describes chosen textbooks, used by pupils at different times – before and after successive educational reforms.
He also presents an original interactive textbook, focusing on its musical content.
“Podemos tirar, se achar melhor”: a relação entre notícia e público no jornalismo online brasileiro
Authors: Santos Lucas Demeda dos , Acker Ana Maria
Published: October 2017

Este artigo busca avaliar até que ponto a internet modifica a relação entre os grandes veículos de comunicação e seu público. Para isso, se parte de uma analise descritiva de caso com base em Wolton (2003 e 2010) e bibliografia selecionada. Os resultados apontam que a internet não é preponderante na modificação nas relações comunicacionais estabelecidas, mas reforça a autonomia do receptor diante dos meios de massa.“Podemos sacarlo, si prefieres”: la relación entre noticia y público en el periodismo en línea brasileñoResumen: Ese ensayo busca evaluar hasta qué punto el internet modifica la relación entre los grandes vehículos de comunicación y su público. Para eso, partiese de un análisis descriptiva de caso con base en Wolton (2003 y 2010) y bibliografía seleccionada. Los resultados indican que el internet no es preponderante en la modificación de las relaciones comunicacionales establecidas, pero refuerza la autonomía del receptor ante los medios masivos.Palabras-llave: Internet; Periodismo en línea; Dominique Wolton; Redes sociales; Medios de comunicación de masas.“We can take it out, if you prefer”: The relation between news and public in Brazilian online journalismAbstract: This article seeks to evaluate to witch extent the internet changes the relationship between the mass media press and their audience. To achieve this, it begins with a descriptive case analysis based on Wolton (2003 and 2010) and selected bibliography. The results imply that the internet is not relevant to the changes in the process of the established communicational relations, but it strengthens the autonomy of the receptor.   Keywords: Internet; Online journalism; Dominique Wolton; Social media; mass media.
La vulgarisation radiophonique de la littérature et de l’histoire canadiennes-françaises par l’Université du Manitoba, 1940-1949
Authors: Keller Michelle
Published: October 2017

Cet article évalue la contribution d’animateurs radiophoniques à la définition du statut de la littérature et à la perception de l’histoire canadienne-française au Manitoba. Nous commençons par un survol historique de la radio à l’Université du Manitoba et de la participation de membres du Département de français à sa programmation des années 1920 et 1930. Nous analysons ensuite des causeries littéraires et historico-culturelles animées par des membres du Département de français, du Collège de Saint-Boniface et de la population franco-manitobaine dans les années 1940 au cours de l’émission University on the Air de l’Université du Manitoba. Quoique les animateurs universitaires et communautaires contribuent peu à l’autonomisation de la littérature canadienne-française, ils valorisent l’histoire et la culture canadiennes-françaises de l’Ouest canadien, grâce à des institutions comme la Société historique de Saint-Boniface. Notre conclusion souligne ce qui fait l’originalité des causeries étudiées, notamment le support radiophonique, la collaboration communautaire et la présence pendant une dizaine d’années de la langue française à la radio anglophone pendant une période pourtant pas encore favorable à l’éducation en français au Manitoba.
Réflexion sur les perceptions, conceptions, représentations et affections, ou la quadrature des approches qualitatives en géographie 1
Authors: BÉDARD Mario
Published: October 2017

Les chercheurs en géographie humaine tentent de saisir le plus finement possible la nature des relations que nous entretenons avec la Nature et le Territoire à partir de ce qu’en « pensent » les divers acteurs ou groupes d’acteurs concernés. Or, ces « pensées » émanent de registres de signification fort distincts selon que ceux-ci résultent de la perception, de la représentation, de la conception ou de l’affection. Soit quatre processus souvent confondus, par suite du manque d’amplitude et d’acuité du regard exercé et, surtout, parce qu’ils ne sont pas abordés et examinés communément. Cela n’est pas sans conséquences sur la cohérence de toute démarche référant à l’un ou l’autre de ces modes relationnels pour saisir les « opinions » des acteurs, puis sur la validité des résultats obtenus. Et c’est pour tenter de résoudre quelque peu ces difficultés dans notre compréhension des relations subjectives que l’être humain entretient avec son environnement naturel ou bâti que nous cherchons, dans ce texte, à dégager et articuler les principales modalités et finalités à l’oeuvre au sein de la perception, de la représentation, de la conception et de l’affection.
Sharing the Land at Moose Factory in 1763
Authors: Long John S. , Preston Richard J. , Srigley Katrina , Sutherland Lorraine
Published: October 2017

In the 18th century the Indigenous peoples of the James Bay region shared land near the coast, a few resources, and furs from a vast hinterland with European newcomers. The Royal Proclamation of 1763 excluded Rupert’s Land – an appropriate decision for it was quite distinct from lands in the south where settlers were acquiring Indigenous land on the fee simple real estate model. What were the James Bay indigenous people’s conditions for sharing their land? It was arguably their principles, and not King George’s edict, that characterized the year 1763 at Moose Fort (Moose Factory). This paper draws on Hudson’s Bay Co. records to examine what was being shared with the newcomers in this northern region. Unlike in the southern regions, the newcomers had no intention of displacing Indigenous peoples. A modest sharing of land and a generous sharing of food and fur resources, on terms congenial to its first inhabitants, characterizes 1763 in this northern region.
Validity and Reliability of Four Clinical Gait Measures in Patients with Multiple Sclerosis
Authors: Bennett Susan E. , Bromley Lacey E. , Fisher Nadine M. , Tomita Machiko R. , Niewczyk Paulette
Published: October 2017

Background:

The gold standards for assessing ambulation are the Expanded Disability Status Scale (EDSS) and the Timed 25-Foot Walk (T25FW) test. In relation with these measures, we assessed the reliability and validity of four clinical gait measures: the Timed Up and Go (TUG) test, the Dynamic Gait Index (DGI), the 2-Minute Walk Test (2MWT), and the 6-Minute Walk Test (6MWT). Patient self-report of gait was also assessed using the 12-item Multiple Sclerosis Walking Scale (MSWS-12).

Methods:

Individuals 20 years or older with a diagnosis of multiple sclerosis (MS) and an EDSS score of 2.0 to 6.5 completed the MSWS-12, T25FW test, TUG test, DGI, 2MWT, and 6MWT. All the tests were repeated 2 weeks later at the same time of day to establish their reliability and concurrent validity. Predictive validity was established using the EDSS.

Results:

Forty-two patients with MS were included. All measures showed high test-retest reliability. The TUG test, 2MWT, and 6MWT were significantly correlated with the T25FW test (Spearman ρ = −0.902, −0.919, and −0.905, respectively). The EDSS was also significantly correlated with all the walking tests. The MSWS-12 demonstrated the highest correlation to the EDSS (ρ = 0.788).

Conclusions:

The TUG test, the DGI, the 2MWT, and the 6MWT exhibited strong psychometric properties and were found to be significant predictors of the EDSS score. Use of these tests to prospectively monitor the effects of medical and rehabilitation treatment should be considered in the comprehensive care of patients with MS.
Proteomic analysis of cell cycle progression in asynchronous cultures, including mitotic subphases, using PRIMMUS
Authors: Ly Tony , Whigham Arlene , Clarke Rosemary , Brenes-Murillo Alejandro J , Estes Brett , Madhessian Diana , Lundberg Emma , Wadsworth Patricia , Lamond Angus I
Published: October 2017

The temporal regulation of protein abundance and post-translational modifications is a key feature of cell division. Recently, we analysed gene expression and protein abundance changes during interphase under minimally perturbed conditions (Ly et al., 2014, 2015). Here, we show that by using specific intracellular immunolabelling protocols, FACS separation of interphase and mitotic cells, including mitotic subphases, can be combined with proteomic analysis by mass spectrometry. Using this PRIMMUS (PRoteomic analysis of Intracellular iMMUnolabelled cell Subsets) approach, we now compare protein abundance and phosphorylation changes in interphase and mitotic fractions from asynchronously growing human cells. We identify a set of 115 phosphorylation sites increased during G2, termed ‘early risers’. This set includes phosphorylation of S738 on TPX2, which we show is important for TPX2 function and mitotic progression. Further, we use PRIMMUS to provide the first a proteome-wide analysis of protein abundance remodeling between prophase, prometaphase and anaphase.
The enigmatic xenopsins
Authors: Arendt Detlev
Published: October 2017

A new member of the family of light-sensitive proteins called opsins has stirred up our view of photoreceptors.
The future of graduate and postdoctoral training in the biosciences
Authors: Hitchcock Peter , Mathur Ambika , Bennett Jabbar , Cameron Patricia , Chow Christine , Clifford Philip , Duvoisin Robert , Feig Andrew , Finneran Kevin , Klotz Diane M , McGee Richard , O'Riordan Mary , Pfund Christine , Pickett Christopher , Schwartz Nancy , Street Nancy E , Watkins Elizabeth , Wiest Jonathan , Engelke David
Published: October 2017

This article summarizes the outcomes of the second national conference on the Future of Bioscience Graduate and Postdoctoral Training. Five topics were addressed during the conference: diversity in leadership positions; mentoring; modernizing the curriculum; experiential learning; and the need for better data on trainees. The goal of the conference was to develop a consensus around these five topics and to recommend policies that can be implemented by academic and research institutions and federal funding agencies in the United States.
Ongoing removals of invasive lionfish in Honduras and their effect on native Caribbean prey fishes
Authors: Peiffer Friederike , Bejarano Sonia , Palavicini de Witte Giacomo , Wild Christian
Published: October 2017

The invasion of Indo-Pacific lionfish is one of the most pressing concerns in the context of coral reef conservation throughout the Caribbean. Invasive lionfish threaten Caribbean fish communities by feeding on a wide range of native prey species, some of which have high ecological and economic value. In Roatan (Honduras) a local non-governmental organisation (i.e. Roatan Marine Park) trains residents and tourists in the use of spears to remove invasive lionfish. Here, we assess the effectiveness of local removal efforts in reducing lionfish populations. We ask whether reefs subject to relatively frequent removals support more diverse and abundant native fish assemblages compared to sites were no removals take place. Lionfish biomass, as well as density and diversity of native prey species were quantified on reefs subject to regular and no removal efforts. Reefs subject to regular lionfish removals (two to three removals month−1) with a mean catch per unit effort of 2.76 ± 1.72 lionfish fisher−1 h−1 had 95% lower lionfish biomass compared to non-removal sites. Sites subject to lionfish removals supported 30% higher densities of native prey-sized fishes compared to sites subject to no removal efforts. We found no evidence that species richness and diversity of native fish communities differ between removal and non-removal sites. We conclude that opportunistic voluntary removals are an effective management intervention to reduce lionfish populations locally and might alleviate negative impacts of lionfish predation. We recommend that local management and the diving industry cooperate to cost-effectively extend the spatial scale at which removal regimes are currently sustained.
Range expansion of a fouling species indirectly impacts local species interactions
Authors: Speights Cori J. , McCoy Michael W.
Published: October 2017

We investigated how recent changes in the distribution and abundance of a fouling organism affected the strength of interactions between a commercially important foundation species and a common predator. Increases in the abundance of boring sponges that bioerode the calcified shells of oysters and other shelled organisms have been attributed to increased salinization of estuarine ecosystems. We tested the hypothesis that fouling by boring sponges will change the interaction strength between oysters and a common predator (stone crabs). We generated five oyster density treatments crossed with two sponge treatments (sponge and no sponge). We contrasted the interaction strength between stone crabs and fouled and non-fouled oysters by comparing the parameters of fitted functional response curves based on Rogers random predation model. We found that fouled oysters suffered higher predation from stone crabs, and that the increased predation risk stemmed from a reduction in the handling time needed to consume the fouled oysters. These findings highlight the importance of understanding the effects of abiotic changes on both the composition of ecological communities, and on the strengths of direct and indirect interactions among species. Global climate change is altering local ecosystems in complex ways, and the success of restoration, management, and mitigation strategies for important species requires a better appreciation for how these effects cascade through ecosystems.
The neuroprotective effect of nicotine in Parkinson’s disease models is associated with inhibiting PARP-1 and caspase-3 cleavage
Authors: Lu Justin Y.D. , Su Ping , Barber James E.M. , Nash Joanne E. , Le Anh D. , Liu Fang , Wong Albert H.C.
Published: October 2017

Clinical evidence points to neuroprotective effects of smoking in Parkinson’s disease (PD), but the molecular mechanisms remain unclear. We investigated the pharmacological pathways involved in these neuroprotective effects, which could provide novel ideas for developing targeted neuroprotective treatments for PD. We used the ETC complex I inhibitor methylpyridinium ion (MPP+) to induce cell death in SH-SY5Y cells as a cellular model for PD and found that nicotine inhibits cell death. Using choline as a nicotinic acetylcholine receptor (nAChR) agonist, we found that nAChR stimulation was sufficient to protect SH-SY5Y cells against cell death from MPP+. Blocking α7 nAChR with methyllycaconitine (MLA) prevented the protective effects of nicotine, demonstrating that these receptors are necessary for the neuroprotective effects of nicotine. The neuroprotective effect of nicotine involves other pathways relevant to PD. Cleaved Poly (ADP-ribose) polymerase-1 (PARP-1) and cleaved caspase-3 were decreased by nicotine in 6-hydroxydopamine (6-OHDA) lesioned mice and in MPP+-treated SH-SY5Y cells. In conclusion, our data indicate that nicotine likely exerts neuroprotective effects in PD through the α7 nAChR and downstream pathways including PARP-1 and caspase-3. This knowledge could be pursued in future research to develop neuroprotective treatments for PD.
Lithologic Effects on Landscape Response to Base Level Changes: A Modeling Study in the Context of the Eastern Jura Mountains, Switzerland
Authors: Yanites Brian J. , Becker Jens K. , Madritsch Herfried , Schnellmann Michael , Ehlers Todd A.
Published: October 2017

Landscape evolution is a product of the forces that drive geomorphic processes (e.g., tectonics and climate) and the resistance to those processes. The underlying lithology and structural setting in many landscapes set the resistance to erosion. This study uses a modified version of the Channel‐Hillslope Integrated Landscape Development (CHILD) landscape evolution model to determine the effect of a spatially and temporally changing erodibility in a terrain with a complex base level history. Specifically, our focus is to quantify how the effects of variable lithology influence transient base level signals. We set up a series of numerical landscape evolution models with increasing levels of complexity based on the lithologic variability and base level history of the Jura Mountains of northern Switzerland. The models are consistent with lithology (and therewith erodibility) playing an important role in the transient evolution of the landscape. The results show that the erosion rate history at a location depends on the rock uplift and base level history, the range of erodibilities of the different lithologies, and the history of the surface geology downstream from the analyzed location. Near the model boundary, the history of erosion is dominated by the base level history. The transient wave of incision, however, is quite variable in the different model runs and depends on the geometric structure of lithology used. It is thus important to constrain the spatiotemporal erodibility patterns downstream of any given point of interest to understand the evolution of a landscape subject to variable base level in a quantitative framework.
Two‐step continuous production of monodisperse colloidal ellipsoids at rates of one gram per day
Authors: Ferrar Joseph A. , Pavlovsky Leonid , Viges Eric , Liu Yanliang , Solomon Michael J.
Published: October 2017

We report a two‐step process for the continuous production of monodisperse polystyrene colloidal ellipsoids of aspect ratios up to 6.8 at rates that exceed 1.0 g per day, an improvement on previously reported synthetic batch processing rates of nearly a factor of 20. This scale up is accomplished by continuous evaporative processing of a polymer solution into an elastomeric film embedded with colloidal spheres. Subsequently, the film is continuously elongated at a temperature that stretches the embedded spheres into ellipsoids. The method is used to deform initially 1.0 μm diameter spheres into ellipsoids of aspect ratio 1.27 ± 0.15, 3.31 ± 0.44, 3.91 ± 0.72, 4.14 ± 0.47, and 6.77 ± 1.01. The particle production rate reported here opens new possibilities for applications of monodisperse ellipsoids, such as self‐assembly and optical characterization of complex crystalline unit cells, as well as rheological characterization of dilute gels and dense suspensions. © 2017 American Institute of Chemical Engineers AIChE J, 64: 697–707, 2018
Liquid–liquid two‐phase flow in ultrasonic microreactors: Cavitation, emulsification, and mass transfer enhancement
Authors: Zhao Shuainan , Dong Zhengya , Yao Chaoqun , Wen Zhenghui , Chen Guangwen , Yuan Quan
Published: October 2017

The effects of ultrasound on the hydrodynamic and mass transfer behaviors of immiscible liquid–liquid two‐phase flow was investigated in a domestic ultrasonic microreactor. Under ultrasonic irradiation, cavitation bubble was generated and underwent violent oscillation. Emulsification of immiscible phases was initiated by virtue of oscillating bubbles shuttling through the water/oil interface. The pressure drop was found to decrease with increasing ultrasound power, with a maximum decrement ratio of 12% obtained at power 30 W. The mass transfer behavior was characterized by extraction of Rhodamine B from water to 1‐octanol. An enhancement factor of 1.3–2.2 on the overall mass‐transfer coefficient was achieved under sonication. The mass transfer performance was comparable to passive microreactor at similar energy dissipation rate (61–184 W/kg). The extraction equilibrium was reached under a total flow velocity 0.01 m/s and input power 20 and 30 W, exhibiting its potential use in liquid‐liquid extraction process. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1412–1423, 2018
A randomized controlled trial comparing two vaso‐occlusive episode (VOE) protocols in sickle cell disease (SCD)
Authors: Tanabe Paula , Silva Susan , Bosworth Hayden B. , Crawford Regina , Paice Judith A. , Richardson Lynne D. , Miller Christopher N. , Glassberg Jeffrey
Published: October 2017

Limited evidence guides opioid dosing strategies for acute Sickle Cell (SCD) pain. We compared two National Heart, Lung and Blood (NHBLI) recommended opioid dosing strategies (weight‐based vs. patient‐specific) for ED treatment of acute vaso‐occlusive episodes (VOE).

A prospective randomized controlled trial (RCT) was conducted in two ED's. Adults ≥ 21 years of age with SCD disease were eligible. Among the 155 eligible patients, 106 consented and 52 had eligible visits. Patients were pre‐enrolled in the outpatient setting and randomized to one of two opioid dosing strategies for a future ED visit. ED providers accessed protocols through the electronic medical record. Change in pain score (0‐100 mm VAS) from arrival to ED disposition, as well as side effects were assessed. 52 patients (median age was 27 years, 42% were female, and 89% black) had one or more ED visits for a VOE (total of 126 ED study visits, up to 5 visits/patient were included). Participants randomized to the patient‐specific protocol experienced a mean reduction in pain score that was 16.6 points greater than patients randomized to the weight‐based group (mean difference 95% CI = 11.3 to 21.9, P = 0.03). Naloxone was not required for either protocol and nausea and/or vomiting was observed less often in the patient‐specific protocol (25.8% vs 59.4%, P = 0.0001). The hospital admission rate for VOE was lower for patients in the patient‐specific protocol (40.3% vs 57.8% P = 0.05). NHLBI guideline‐based analgesia with patient‐specific opioid dosing resulted in greater improvements in the pain experience compared to a weight‐based strategy, without increased side effects.
Novel recessive PDZD7 biallelic mutations in two Chinese families with non‐syndromic hearing loss
Authors: Guan Jing , Wang Hongyang , Lan Lan , Wang Li , Yang Ju , Xie Linyi , Yin Zifang , Xiong Wenping , Zhao Lidong , Wang Dayong , Wang Qiuju
Published: October 2017

Autosomal recessive non‐syndromic hearing loss (ARNSHL) is a highly heterogeneous genetic condition. PDZD7 has emerged as a new genetic etiology of ARNSHL. Biallelic mutations in the PDZD7 gene have been reported in two German families, four Iranian families, and a Pakistani family with ARNSHL. The effect of PDZD7 on ARNSHL in other population has yet to be elucidated. Two Chinese ARNSHL families, each of which had two affected siblings, were included in this study. The families underwent target region capture and high‐throughput sequencing to analyze the exonic, splice‐site, and intronic sequences of 128 genes. Furthermore, 1751 normal Chinese individuals served as controls, and 122 Chinese families segregating with apparent ARNSHL, who had been previously excluded for variants in the common deafness genes GJB2 and SLC26A4, were subjected to screening for candidate mutations. We identified a novel homozygous missense mutation (p.Arg66Leu) and novel compound heterozygous frameshift mutations (p.Arg56fsTer24 and p.His403fsTer36) in Chinese families with ARNSHL. This is the first report to identify PDZD7 as an ARNSHL‐associated gene in the Chinese population. Our finding could expand the pathogenic spectrum and strengthens the clinical diagnostic role of the PDZD7 gene in ARNSHL patients.
Longitudinal perspectives on the psychosis spectrum in 22q11.2 deletion syndrome
Authors: Tang Sunny X. , Gur Raquel E.
Published: October 2017

The prevalence of psychotic disorders in individuals with 22q11.2 Deletion Syndrome (22q11DS) reaches 25–35% in young adulthood and may provide a neurogenetic model for clinical risk of psychotic disorders in the general population. This review focuses on prospective longitudinal studies in 22q11DS, which capture fluctuations in psychosis symptoms over time and may provide insights into potential demographic, clinical, cognitive, and neuroimaging predictors of psychosis‐spectrum outcomes in the general population. Findings are compared and contrasted with those from idiopathic psychosis‐spectrum populations. Onset of psychotic disorders in 22q11DS can occur over a wide range of ages, peaking in late adolescence. Symptoms may be gradually progressive or episodic in nature, highlighting the importance and challenge of risk and resilience prediction models. Converging results suggest that psychosis‐spectrum outcomes in 22q11DS are predicted by lower baseline functioning, higher baseline psychosis‐spectrum symptoms, presence of mood disturbance or anxiety, and lower baseline and subsequent decline in global measures of cognition. Predictors of transition to threshold psychotic disorders and ages of onset are similar in idiopathic clinical risk. They also share similarly global cognitive deficits, but not to the same extent as in 22q11DS. While neuroimaging studies in idiopathic clinical risk suggest loss of prefrontal gray matter, there is no consistent evidence yet emerging in the limited literature in 22q11DS. Interventional efforts in 22q11DS aimed at halting progression to psychosis or mitigating outcomes in early psychosis may be best implemented during the adolescent age range. Collaborative longitudinal efforts may help to address existing gaps in our understanding.
Thyroid hormone fluctuations indicate a thermoregulatory function in both a tropical (Alouatta palliata) and seasonally cold‐habitat (Macaca fuscata) primate
Authors: Thompson Cynthia L. , Powell Brianna L. , Williams Susan H. , Hanya Goro , Glander Kenneth E. , Vinyard Christopher J.
Published: October 2017

Thyroid hormones boost animals’ basal metabolic rate and represent an important thermoregulatory pathway for mammals that face cold temperatures. Whereas the cold thermal pressures experienced by primates in seasonal habitats at high latitudes and elevations are often apparent, tropical habitats also display distinct wet and dry seasons with modest changes in thermal environment. We assessed seasonal and temperature‐related changes in thyroid hormone levels for two primate species in disparate thermal environments, tropical mantled howlers (Alouatta palliata), and seasonally cold‐habitat Japanese macaques (Macaca fuscata). We collected urine and feces from animals and used ELISA to quantify levels of the thyroid hormone triiodothyronine (fT3). For both species, fT3 levels were significantly higher during the cooler season (wet/winter), consistent with a thermoregulatory role. Likewise, both species displayed greater temperature deficits (i.e., the degree to which animals warm their body temperature relative to ambient) during the cooler season, indicating greater thermoregulatory pressures during this time. Independently of season, Japanese macaques displayed increasing fT3 levels with decreasing recently experienced maximum temperatures, but no relationship between fT3 and recently experienced minimum temperatures. Howlers increased fT3 levels as recently experienced minimum temperatures decreased, although demonstrated the opposite relationship with maximum temperatures. This may reflect natural thermal variation in howlers’ habitat: wet seasons had cooler minimum and mean temperatures than the dry season, but similar maximum temperatures. Overall, our findings support the hypothesis that both tropical howlers and seasonally cold‐habitat Japanese macaques utilize thyroid hormones as a mechanism to boost metabolism in response to thermoregulatory pressures. This implies that cool thermal pressures faced by tropical primates are sufficient to invoke an energetically costly and relatively longer‐term thermoregulatory pathway. The well‐established relationship between thyroid hormones and energetics suggests that the seasonal hormonal changes we observed could influence many commonly studied behaviors including food choice, range use, and activity patterns.
Cucurbit[7]uril as a Supramolecular Artificial Enzyme for Diels–Alder Reactions
Authors: Palma Aniello , Artelsmair Markus , Wu Guanglu , Lu Xiaoyong , Barrow Steven J. , Uddin Najib , Rosta Edina , Masson Eric , Scherman Oren A.
Published: October 2017

The ability to mimic the activity of natural enzymes using supramolecular constructs (artificial enzymes) is a vibrant scientific research field. Herein, we demonstrate that cucurbit[7]uril (CB[7]) can catalyse Diels–Alder reactions for a number of substituted and unreactive N‐allyl‐2‐furfurylamines under biomimetic conditions, without the need for protecting groups, yielding powerful synthons in previously unreported mild conditions. CB[7] rearranges the substrate in a highly reactive conformation and shields it from the aqueous environment, thereby mimicking the mode of action of a natural Diels–Alderase. These findings can be directly applied to the phenomenon of product inhibition observed in natural Diels–Alderase enzymes, and pave the way toward the development of novel, supramolecular‐based green catalysts.
Eine Bor‐Tellur‐Doppelbindung: direkte Insertion in eine Mn=B‐Doppelbindung
Authors: Liu Siyuan , Légaré Marc‐André , Auerhammer Dominic , Hofmann Alexander , Braunschweig Holger
Published: October 2017

Das basenstabilisierte Borylen [Cp(OC)2Mn=BtBu(IMe)] reagiert direkt mit elementaren Chalkogenen in einer Insertionsreaktion unter Bildung von Borachalkonkomplexen [Cp(OC)2Mn‐E=BtBu(IMe)] (E=S, Se, Te). Die Tellurverbindung enthält hierbei die erste charakterisierte Doppelbindung zwischen den Elementen Bor und Tellur. Des Weiteren ist Tellur das bislang schwerste Hauptgruppenelement, von dem eine Mehrfachbindung mit Bor bekannt ist. Diese beispiellose Wechselwirkung wurde durch theoretische und experimentelle Studien vollständig untersucht.
Isoquinoline‐1‐Carboxylate as a Traceless Leaving Group for Chelation‐Assisted Glycosylation under Mild and Neutral Reaction Conditions
Authors: Wang Hao‐Yuan , Simmons Christopher J. , Blaszczyk Stephanie A. , Balzer Paul G. , Luo Renshi , Duan Xiyan , Tang Weiping
Published: October 2017

Glycosyl isoquinoline‐1‐carboxylate was developed as a novel benchtop stable and readily available glycosyl donor. The glycosylation reaction was promoted by the inexpensive Cu(OTf)2 salt under mild reaction conditions. The copper isoquinoline‐1‐carboxylate salt was precipitated from the solution and thus rendered a traceless leaving group. Surprisingly, the proton from the acceptor was absorbed by the precipitated metal complex and the reaction mixture remained at neutral pH. The copper‐promoted glycosylation was also proven to be completely orthogonal to the gold‐promoted glycosylation, and an iterative synthesis of oligosaccharides from benchtop stable anomeric ester building blocks becomes possible under mild reaction conditions.
Multi‐Step Crystallization of Barium Carbonate: Rapid Interconversion of Amorphous and Crystalline Precursors
Authors: Whittaker Michael L. , Smeets Paul J. M. , Asayesh‐Ardakani Hasti , Shahbazian‐Yassar Reza , Joester Derk
Published: October 2017

The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X‐ray scattering, cryo‐, and low‐dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds. We describe a bulk synthesis and report a first assessment of the composition, vibrational spectra, and structure of gortatowskite. Our findings indicate that transient amorphous and crystalline precursors can play a role in aqueous precipitation pathways that may often be overlooked owing to their extremely short lifetimes and small dimensions. However, such transient precursors may be integral to the formation of more stable phases.
Controllable Modular Growth of Hierarchical MOF‐on‐MOF Architectures
Authors: Gu Yifan , Wu Yi‐nan , Li Liangchun , Chen Wei , Li Fengting , Kitagawa Susumu
Published: October 2017

Fabrication of hybrid MOF‐on‐MOF heteroarchitectures can create novel and multifunctional platforms to achieve desired properties. However, only MOFs with similar crystallographic parameters can be hybridized by the classical epitaxial growth method (EGM), which largely suppressed its applications. A general strategy, called internal extended growth method (IEGM), is demonstrated for the feasible assembly of MOFs with distinct crystallographic parameters in an MOF matrix. Various MOFs with diverse functions could be introduced in a modular MOF matrix to form 3D core–satellite pluralistic hybrid system. The number of different MOF crystals interspersed could be varied on demand. More importantly, the different MOF crystals distributed in individual domains could be used to further incorporate functional units or enhance target functions.
The First Boron–Tellurium Double Bond: Direct Insertion of Heavy Chalcogens into a Mn=B Double Bond
Authors: Liu Siyuan , Légaré Marc‐André , Auerhammer Dominic , Hofmann Alexander , Braunschweig Holger
Published: October 2017

The base‐stabilized borylene [Cp(OC)2Mn=BtBu(IMe)] readily reacts with elemental chalcogens in an insertion reaction that yields borachalcone complexes [Cp(OC)2Mn‐E=BtBu(IMe)] (E=S, Se, Te). The tellurium example features the first double bond between boron and tellurium, making Te the heaviest main‐group element to make multiple bonds with boron. This unprecedented interaction has been fully investigated both experimentally and computationally.
A Review on Detection and Abatement of Heavy Metals
Authors: Sikdar Sayantani , Kundu Madhusree
Published: October 2017

Heavy metal contamination is one of the major concerns in today's world. Trace elements like arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc are released from natural and anthropogenic activities and considered highly hazardous. Therefore, the continuous monitoring, detection, and remediation of heavy metals in groundwater and soil are of utmost importance. In this article, the detection technologies available together with their working principles and the remediation processes that are used until today are presented. The basic abatement technologies used fall into 3 categories: chemical, biological, and physico‐chemical. General approaches like isolation, immobilization, toxicity reduction, physical separation, and extraction can also be used for remediation of heavy metals. For large scale operations, chemical treatment technologies have proven to be the best option. Physico‐chemical treatment technologies can exclude all the possibilities of auxiliary toxic effects that may be produced by the treating chemical agents, hence, approaching a green remediation process.
A novel HIF1AN substrate KANK3 plays a tumor‐suppressive role in hepatocellular carcinoma
Authors: Kim Iljin , Kang Jengmin , Gee Heon Yung , Park Jong‐Wan
Published: October 2017

The KN motif and ankyrin repeat domain‐containing protein (KANK) family is involved in actin cytoskeleton organization and cell motility. Compared with other KANK members, the biological function of KANK3 is not clear. Here, we identified KANK3 as a new substrate for the oxygen sensor hypoxia‐inducible factor 1‐alpha inhibitor (HIF1AN), which hydroxylates HIF‐1/2α and other ankyrin repeat domain‐containing proteins at asparagine residues. An in vitro hydroxylation assay clearly demonstrated asparaginyl hydroxylation of KANK3 by HIF1AN, and mass spectroscopic analysis revealed that KANK3 is hydroxylated at three asparagine residues within the ankyrin repeat domain. Bioinformatics analysis revealed that KANK3 downregulation is correlated with a poor prognosis in several types of cancers, including hepatocellular carcinoma (HCC). In HCC cells, KANK3 knockdown enhanced cell migration and invasion, while its overexpression inhibited these cell behaviors. Interestingly, such effects of KANK3 were not observed under hypoxic conditions, suggesting oxygen‐dependent activity of KANK3. Based on these data, we propose that KANK3 acts as a tumor suppressor to control cancer behavior in an oxygen‐dependent manner.
Controllable Hierarchical Surface Patterns of Supramolecular Hydrogels: Harnessing Buckling Instability by Confinement
Authors: Li Xiaohui , Guo Mingyu , Wang Fang , Shen Xuezhen , Weng Yuyan , Hu Zhijun
Published: October 2017

Patterned surfaces of responsive polymers find applications in diverse fields. However, it is still a great challenge to fabricate hierarchical patterns with long‐range orders. Herein controllable hierarchical surface patterns that can be fabricated by combining nanoembossing techniques with the surface instability of supramolecular hydrogels are presented. Nanoembossed nanostripe arrays of polyethylene glycol (PEG)‐based polyurethane–urea supramolecular hydrogels are fabricated and exposed to water, whereby the lateral expansion of nanostripes is confined and leads to the formation of folded in‐plane or out‐of‐plane patterns depending on the aspect ratios. The direction of folds is perpendicular to the nanostripes. Both the amplitude and the wavelength of out‐of‐plane folds are proportional to the thickness of nanostripes. Therefore, hierarchical structures, in which one periodicity is defined by the nanoembossing processes and the other is determined by surface buckling, can be quickly fabricated in supramolecular hydrogel thin films.
Metal‐Free, Site‐Selective Peptide Modification by Conversion of “Customizable” Units into β‐Substituted Dehydroamino Acids
Authors: Saavedra Carlos J. , Hernández Dácil , Boto Alicia
Published: October 2017

Our site‐selective modification of serine or threonine units in peptides allows the generation of β‐substituted dehydroamino acids, which increase peptide resistance to hydrolysis and may improve their biological properties. Both the terminal and internal positions can be modified, and different customizable units can be activated separately. Remarkably, high Z selectivity is achieved, even at internal positions. The conversion involves a one‐pot oxidative radical scission/phosphorylation process by using the low‐toxicity (diacetoxyiodo)benzene/iodine system as the scission reagent. The resulting α‐amino phosphonates undergo a Horner‐Wadsworth‐Emmons reaction to produce the dehydroamino acid derivatives (in a Z/E ratio of usually >98:2) under mild and metal‐free conditions.
A Rotaxane Scaffold for the Construction of Multiporphyrinic Light‐Harvesting Devices
Authors: Delavaux‐Nicot Béatrice , Ben Aziza Haifa , Nierengarten Iwona , Minh Nguyet Trinh Thi , Meichsner Eric , Chessé Matthieu , Holler Michel , Abidi Rym , Maisonhaute Emmanuel , Nierengarten Jean‐François
Published: October 2017

A sophisticated photoactive molecular device has been prepared by combining recent concepts for the preparation of multifunctional nanomolecules (click chemistry on multifunctional scaffolds) with supramolecular chemistry (self‐assembly to prepare rotaxanes). Specifically, a clickable [2]rotaxane scaffold incorporating a free‐base porphyrin stopper has been prepared and functionalized with ten peripheral Zn(II)‐porphyrin moieties. Electrochemical investigations of the final compound revealed a peculiar behavior resulting from the intramolecular coordination of the Zn(II) porphyrin moieties to 1,2,3‐triazole units. Finally, steady state investigations of the compound combining Zn(II) and free‐base porphyrin moieties have shown that this compound is a light‐harvesting device capable of channeling the light energy from the peripheral Zn(II)‐porphyrin subunits to the core by singlet–singlet energy transfer.
Oligonucleotides with Cationic Backbone and Their Hybridization with DNA: Interplay of Base Pairing and Electrostatic Attraction
Authors: Schmidtgall Boris , Kuepper Arne , Meng Melissa , Grossmann Tom N. , Ducho Christian
Published: October 2017

Non‐natural oligonucleotides represent important (bio)chemical tools and potential therapeutic agents. Backbone modifications altering hybridization properties and biostability can provide useful analogues. Here, we employ an artificial nucleosyl amino acid (NAA) motif for the synthesis of oligonucleotides containing a backbone decorated with primary amines. An oligo‐T sequence of this cationic DNA analogue shows significantly increased affinity for complementary DNA. Notably, hybridization with DNA is still governed by Watson–Crick base pairing. However, single base pair mismatches are tolerated and some degree of sequence‐independent interactions between the cationic NAA backbone and fully mismatched DNA are observed. These findings demonstrate that a high density of positive charges directly connected to the oligonucleotide backbone can affect Watson–Crick base pairing. This provides a paradigm for the design of therapeutic oligonucleotides with altered backbone charge patterns.
Cubane Cross‐Coupling and Cubane–Porphyrin Arrays
Authors: Bernhard Stefan S. R. , Locke Gemma M. , Plunkett Shane , Meindl Alina , Flanagan Keith J. , Senge Mathias O.
Published: October 2017

Herein, an improved methodology for aryl‐cubane cross‐coupling is reported. The peculiarities of the cubane core and its behavior during cross‐coupling conditions were analyzed, while the versatility of this adapted Baran cross‐coupling methodology was demonstrated by the synthesis of various aryl‐cubane systems, including coupling products of cubanes and porphyrins. Furthermore, arm extension of alkynyl‐cubanes by Sonogashira reactions is demonstrated, showcasing the first proof of the stability of the cubane core in the presence of palladium catalysts.
Supramolecular Storage and Controlled Photorelease of an Oxidizing Agent using a Bambusuril Macrocycle
Authors: Torti Edoardo , Havel Václav , Yawer Mirza A. , Ludvíková Lucie , Babiak Michal , Klán Petr , Sindelar Vladimir
Published: October 2017

The oxidizing ability of peroxodisulfate upon complexation inside the Bambusuril macrocycle cavity is inhibited. This dianionic agent can be released on demand from its stable 1:1 complex in water (log Ka=6.9 m−1) by addition of a more strongly bound anion, such as iodide (log Ka=7.1 m−1), which can also be delivered in situ upon irradiation from a 4‐hydroxyphenacyl iodide derivative with spatial and temporal precision. The oxidizing properties of peroxodisulfate ions liberated from the complex recover and can take part in subsequent chemical transformations.
Unexpected Crystallization Patterns of Zinc Boron Imidazolate Framework ZBIF‐1: NMR Crystallography of Integrated Metal–Organic Frameworks
Authors: Kobera Libor , Rohlicek Jan , Czernek Jiri , Abbrent Sabina , Streckova Magdalena , Sopcak Tibor , Brus Jiri
Published: October 2017

Framework materials, that is, metal–organic frameworks (MOFs) and inorganic frameworks (zeolites), are porous systems with regular structures that provide valuable properties suitable for sorption, catalysis, molecular sieving, and so on. Herein, an efficient, experimental/computational strategy is presented that allows detailed characterization of a polycrystalline MOF system, namely, zinc boron imidazolate framework ZBIF‐1, with two integrated unit cells on the atomic‐resolution level. Although high‐resolution 1H, 11B, 13C, and 15N MAS NMR spectra provide valuable structural information on the coexistence of two distinct asymmetric units in the investigated system, an NMR crystallography approach combining X‐ray powder diffraction, solid‐state NMR spectroscopy, and DFT calculations allowed the exact structure of the secondary crystalline phase to be firmly defined and, furthermore, the mutual interconnectivity of the two crystalline frameworks to be resolved. Thus, this study shows the versatility and efficiency of solid‐state NMR crystallography for the investigation of the wide family of MOF materials with their extensive structural complexity.
Vacuum‐Deposited versus Spin‐Coated Emissive Layers for Fabricating High‐Performance Blue–Green‐Emitting Diodes
Authors: Ma Dongxin , Qiu Yong , Duan Lian
Published: October 2017

The electroluminescent characteristics of two sublimable cationic iridium(III) complexes that bear the same coordinated iridium(III) cation but different tetraphenylborate‐type negative counterions have been investigated. Blue–green‐emitting devices were successfully fabricated from these complexes using various preparation processes, namely, spin‐coating and vacuum evaporation deposition. Experiments indicated that devices with vacuum‐deposited emissive layers showed superior photoelectric properties relative to devices with spin‐coated emissive layers, including a maximum current efficiency of 27.91 cd A−1, an external quantum efficiency of 10.48 %, a power efficiency of 27.73 lm W−1 and the highest luminance of up to 25.34×103 cd m−2, whereas the turn‐on voltages were quite low. The overall device performance surely ranks among the best of phosphorescent organic light‐emitting diodes based on ionic transition‐metal complexes.
A Comparative Study of Structurally Related Homogeneous Ruthenium and Iron Catalysts for the Hydrogenation of Levulinic Acid to γ‐Valerolactone
Authors: van Slagmaat Christian A. M. R. , De Wildeman Stefaan M. A.
Published: October 2017

The conversion of levulinic acid (LA) to γ‐valerolactone (GVL) was investigated by employing the homogeneous Shvo catalyst (Ru‐1) and iron Knölker‐type catalysts, in order to evaluate the possibility to replace ruthenium with cheap, earth‐abundant iron for this catalytic reaction. While the ruthenium‐catalyzed reactions readily proceed, the activating agent required for the iron complex was found to interfere with the LA. This problem could be circumvented by pre‐activating the original Knölker complex (Fe‐1) into the corresponding dicarbonyl mono‐acetonitrile iron species (Fe‐3). The pre‐activated iron catalyst deactivated after a few turn‐overs in transfer hydrogenation reactions with isopropyl alcohol; however, highly improved GVL yields were achieved under H2 pressure to a notable maximum of 570 turn‐overs for Fe‐3. Nevertheless, comparative screening experiments with various solvents and kinetic studies showed that Ru‐1 is still superior over Fe‐3 in terms of catalytic activity.
Executive attention at 8 years: Concurrent and longitudinal predictors and individual differences
Authors: Joyce Amanda W. , Friedman Denise R. , Wolfe Christy D. , Bell Martha Ann
Published: October 2017

Executive attention, the attention necessary to reconcile conflict among simultaneous attentional demands, is vital to children's daily lives. This attention develops rapidly as the anterior cingulate cortex and prefrontal areas mature during early and middle childhood. However, the developmental course of executive attention is not uniform among children. Therefore, the purpose of this investigation was to examine the role of individual differences in the development of executive attention by exploring the concurrent and longitudinal contributions to its development at 8 years of age. Executive attention was predicted by concurrent measures of frontal electroencephalography, laboratory‐based performance on a conflict task, and parent report of attention. Longitudinally, 8‐year‐old executive attention was significantly predicted by a combination of 4‐year‐old frontal activity, conflict task performance, and parent report of attention focusing, but not with an analogous equation replacing attention focusing with attention shifting. Together, data demonstrate individual differences in executive attention.

Highlights

This research examines the role of individual differences in executive attention by exploring concurrent and longitudinal contributions to its development.

Executive attention was predicted by concurrent frontal electroencephalographic, conflict task performance, and parent‐reported attention as well as some longitudinal measures.

Together, data demonstrate individual differences in executive attention.