bluuebunny/crossref_metadata_2025 huggingface dataset:
Voyage sur les rives du Mississippi : diversité culturelle et influence atlantique dans la Louisiane antebellum
Authors: Piché Geneviève
Published: November 2014

Au début du XIXe siècle, la Louisiane est une région agricole fort prospère, qui connaît un essor spectaculaire. La population servile augmente considérablement, alors que le système esclavagiste se développe et se radicalise. La Louisiane antebellum1 est ainsi le théâtre parfait pour étudier la rencontre entre religion et esclavage. Comment les esclaves parviennent-ils à se forger une culture religieuse bien distincte de celle de leurs maîtres ? Comment cette culture apparaît-elle aux yeux des voyageurs qui atteignent la Nouvelle-Orléans au XIXe siècle ? En quoi les pratiques religieuses des esclaves des Antilles, qui arrivent en grand nombre au tournant du siècle, ont-elles influencé la religion des esclaves louisianais ? En se basant sur les récits de voyage du XIXe siècle, cet article nous permettra de partir à la découverte de la culture religieuse des esclaves de Louisiane.
High-resolution structures of kinesin on microtubules provide a basis for nucleotide-gated force-generation
Authors: Shang Zhiguo , Zhou Kaifeng , Xu Chen , Csencsits Roseann , Cochran Jared C , Sindelar Charles V
Published: November 2014

Microtubule-based transport by the kinesin motors, powered by ATP hydrolysis, is essential for a wide range of vital processes in eukaryotes. We obtained insight into this process by developing atomic models for no-nucleotide and ATP states of the monomeric kinesin motor domain on microtubules from cryo-EM reconstructions at 5–6 Å resolution. By comparing these models with existing X-ray structures of ADP-bound kinesin, we infer a mechanistic scheme in which microtubule attachment, mediated by a universally conserved ‘linchpin’ residue in kinesin (N255), triggers a clamshell opening of the nucleotide cleft and accompanying release of ADP. Binding of ATP re-closes the cleft in a manner that tightly couples to translocation of cargo, via kinesin's ‘neck linker’ element. These structural transitions are reminiscent of the analogous nucleotide-exchange steps in the myosin and F1-ATPase motors and inform how the two heads of a kinesin dimer ‘gate’ each other to promote coordinated stepping along microtubules.
The national policy of primary care in municipal centers of health from programmatic area 1.0
Authors: Gomes Ana Leticia Monteiro , Soares Ana Carolina Mendes , Antunes Marília Almeida , Da Silva Luiziane de Oliveira Geraldo , De Souza Lugão Nátale Carvalho , Tyrrell Maria Antonieta Rubio
Published: November 2014

Objetivo: Discutir a política nacional de atenção básica do Sistema Único de Saúde junto aos profissionais de saúde de três centros municipais de saúde. Método: Qualitativo, descritivo-reflexivo e pesquisa-ação. A população foi os profissionais de saúde que atendem mulheres e crianças. Foram selecionados todos os profissionais dos centros municipais de saúde da área programática 1.0. Para coleta de dados foram realizados três seminários que foram gravados, transcritos e lavrados com atas. A pesquisa foi aprovada pelo Comitê de Ética em Pesquisa da Escola de Enfermagem Anna Nery sob protocolo 37/08. Resultados: Os dados foram submetidos à análise temática, seguida da construção de quatro categorias. Conclusão: Os sujeitos acreditam que a maior dificuldade de realizar os princípios da atenção básica é por falta de recursos humanos para realizar ações educativas no âmbito coletivo já que no individual é realizado. Descritores: Políticas públicas, atenção básica à saúde, capacitação profissional, enfermagem.
Seeking the meaning of reaching adolescence in a shelter institution
Authors: Soares Moreira Elisama Naara , Oliveira dos Santos Kamyla Félix , Pinto Costa Isabelle Cristinne , De Andrade Cristiani Garrido , Melo Fernandes Maria das Graças , De Brito Fabiana Medeiros
Published: November 2014

Objetivo: Revelar o significado de adolescer em uma instituição de abrigo, mediante os principais motivos que os levaram a essa experiência; averiguar acerca da representação da família e do cuidado diante do viver institucionalizado e identificar quais são as expectativas de vida dos adolescentes em relação ao futuro. Métodos:Trata-se de um estudo descritivo e exploratório com abordagem qualitativa, em que se utilizou a técnica de grupo focal. Os dados foram analisados conforme o Discurso do Sujeito Coletivo. Resultados: A pesquisa revelou as seguintes ideias centrais: 1) O mundo privado das instituições de abrigo; 2) Representação da família X cuidado sob o olhar dos adolescentes e 3) Perspectivas, sonhos e desejos em relação ao futuro. Conclusão: Evidencia-se a necessidade de novos debates acerca da vivência dos adolescentes frente às dificuldades em relação ao universo com o qual se defrontam. Descritores: Adolescente, Cuidador, Abrigo.
Is the residual vertical velocity a good proxy for stratosphere‐troposphere exchange of ozone?
Authors: Hsu Juno , Prather Michael J.
Published: November 2014

Stratosphere‐troposphere exchange (STE) of ozone (O3) is key in the budget of tropospheric O3, in turn affecting climate forcing and global air quality. We compare three commonly used diagnostics meant to quantify cross‐tropopause O3 fluxes with a Chemistry‐Transport Model driven by two distinct European Centre forecast fields. Our reference case calculates accurate, geographically resolved net transport across an isosurface in artificial tracer e90 representing the tropopause. Hemispheric fluxes derived from the ozone mass budget of the lowermost stratosphere yield similar results. Use of the Brewer‐Dobson residual vertical velocity as a scaled proxy for ozone flux, however, fails to capture the interannual variability. Thus, the common notion that the strength of stratospheric overturning circulation is a good measure for global STE does not apply to O3. Climatic variability in the modeled O3 flux needs to be diagnosed directly rather than indirectly through the overturning circulation.
The seasonal evolution of sea ice floe size distribution
Authors: Perovich Donald K. , Jones Kathleen F.
Published: November 2014

The Arctic sea ice cover undergoes large changes over an annual cycle. In winter and spring, the ice cover consists of large, snow‐covered plate‐like ice floes, with very little open water. By the end of summer, the snow cover is gone and the large floes have broken into a complex mosaic of smaller, rounded floes surrounded by a lace of open water. This evolution strongly affects the distribution and fate of the solar radiation deposited in the ice‐ocean system and consequently the heat budget of the ice cover. In particular, increased floe perimeter can result in enhanced lateral melting. We attempt to quantify the floe evolution process through the concept of a floe size distribution that is modified by lateral melting and floe breaking. A time series of aerial photographic surveys made during the SHEBA field experiment is analyzed to determine evolution of the floe size distribution from spring through summer. Based on earlier studies, we assume the floe size cumulative distribution could be represented by a power law D−α, where D is the floe diameter. The exponent α as well as the number density of floes Ntot are estimated from measurements of total ice area and perimeter. As summer progressed, there was an increase in α as the size distribution shifted toward smaller floes and the number of floes increased. Lateral melting causes the distribution to deviate from a power law for small floe sizes.
Models of fluorescence and photosynthesis for interpreting measurements of solar‐induced chlorophyll fluorescence
Authors: van der Tol C. , Berry J. A. , Campbell P. K. E. , Rascher U.
Published: November 2014

We have extended a conventional photosynthesis model to simulate field and laboratory measurements of chlorophyll fluorescence at the leaf scale. The fluorescence paramaterization is based on a close nonlinear relationship between the relative light saturation of photosynthesis and nonradiative energy dissipation in plants of different species. This relationship diverged only among examined data sets under stressed (strongly light saturated) conditions, possibly caused by differences in xanthophyll pigment concentrations. The relationship was quantified after analyzing data sets of pulse amplitude modulated measurements of chlorophyll fluorescence and gas exchange of leaves of different species exposed to different levels of light, CO2, temperature, nitrogen fertilization treatments, and drought. We used this relationship in a photosynthesis model. The coupled model enabled us to quantify the relationships between steady state chlorophyll fluorescence yield, electron transport rate, and photosynthesis in leaves under different environmental conditions.
A mixed‐layer model study of the stratocumulus response to changes in large‐scale conditions
Authors: De Roode Stephan R. , Siebesma A. Pier , Dal Gesso Sara , Jonker Harm J. J. , Schalkwijk Jerôme , Sival Jasper
Published: November 2014

A mixed‐layer model is used to study the response of stratocumulus equilibrium state solutions to perturbations of cloud controlling factors which include the sea surface temperature, the specific humidity and temperature in the free troposphere, as well as the large‐scale divergence and horizontal wind speed. In the first set of experiments, we assess the effect of a change in a single forcing condition while keeping the entrainment rate fixed, while in the second set, the entrainment rate is allowed to respond. The role of the entrainment rate is exemplified from an experiment in which the sea surface temperature is increased. An analysis of the budget equation for heat and moisture demonstrates that for a fixed entrainment rate, the stratocumulus liquid water path (LWP) will increase since the moistening from the surface evaporation dominates the warming effect. By contrast, if the response of the entrainment rate to the change in the surface forcing is sufficiently strong, enhanced mixing of dry and warm inversion air will cause a thinning of the cloud layer. If the entrainment warming effect is sufficiently strong, the surface sensible heat flux will decrease, as opposed to an increase which will occur for a fixed entrainment rate. It is argued that the surface evaporation will always increase for an increase in the sea surface temperature, and this change will be enlarged if the entrainment rate increases. These experiments aid the interpretation of results of similar simulations with single‐column model versions of climate models carried out in the framework of the CFMIP‐GCSS Intercomparison of Large‐Eddy and Single‐Column Models (CGILS) project. Because in a large‐scale models, the entrainment response to changes in the large‐scale forcing conditions depends on the details of the parameterization of turbulent and convective transport, intermodel differences in the sign of the LWP response may be well attributable to differences in the entrainment response.
Global Assimilation of Ionospheric Measurements‐Gauss Markov model: Improved specifications with multiple data types
Authors: Gardner L. C. , Schunk R. W. , Scherliess L. , Sojka J. J. , Zhu L.
Published: November 2014

The Earth's ionosphere is a highly dynamic region that is almost constantly in a state of flux. Solar radiation, geomagnetic activity, chemical reactions, and natural dynamics all act to perturb the state of the ionosphere. The ionosphere changes on time scales of hours to days, with the fine‐scale ionospheric structures that are frequently observed lacking in global physics‐based models due to time step and spatial resolution constraints. To properly specify the ionosphere, data are needed, thus data assimilation. The Utah State University Global Assimilation of Ionospheric Measurements‐Gauss Markov (GAIM‐GM) model uses a data assimilation method to correct a physics‐based model of the ionosphere using five different data types, divided into nine different data sources. Multiple data types are necessary because the data from any individual data source will not be sufficient for global reconstructions. The GAIM‐GM specification (in real time) can then be used to correct for ionospheric propagation delays, thereby improving geolocation and communications. The focus here is to show the quantitative effects that multiple data types have on GAIM‐GM ionospheric specifications for a relatively quiet day (19 April) in 2012.
Using Participant Choice to Enhance Memory Performance
Authors: Weger Ulrich W. , Loughnan Stephen
Published: November 2014

When patients are involved in deciding the course of treatment for their ailment and are given a chance to choose between different treatment options, the success of the intervention typically increases. In our study we transferred this approach to a cognitive psychology task and investigated whether treatment choice can enhance participants' memory performance. Participants who were free to choose one out of a selection of alleged cognitive enhancers showed better performance than those who were assigned an enhancer. We also found that performance‐expectations have a stronger impact when triggered prior to the encoding as opposed to the retrieval stage and thus appear to be more effective at a point when participants exercise a greater degree of cognitive control. The findings are of relevance in contexts where it can be assumed that participants have knowledge about their own needs and can in turn capitalize on this knowledge when given the opportunity. Copyright © 2014 John Wiley & Sons, Ltd.
Self‐Assembled Recyclable Hierarchical Bucky Aerogels
Authors: Karakaya Mehmet , Saini Deepika , Podila Ramakrishna , Skove Malcolm J. , Rao Apparao M. , Thevamaran Ramathasan , Daraio Chiara
Published: November 2014

We describe a simple method for the scalable synthesis of three‐dimensional, elastic, and recyclable multi‐wall carbon nanotube (MWCNT) based light weight (density <1 g cm−3) bucky‐aerogels (BAGs) that are capable of efficiently absorbing non‐polar solvents and separating oil‐in‐water emulsions. Our facile synthesis involves the self‐assembly of MWCNTs and carbon fibers into a multi‐layered, highly porous, and hierarchical structure that can be easily flexed, compressed, or burnt without any noticeable changes in its structure and absorption capacity. The BAG surface absorbs non‐polar solvents efficiently up to ≈20 times its own weight due to its superhydrophobic nature arising from the presence of MWCNTs. Furthermore, BAGs exhibit excellent resilience to impact by recovering more than 70% of the deformation. The energy dissipated by BAGs at 80% compressive strain is in the order of 500 kJ m−3, which is nearly 50 times more than the energy dissipated by commercial foams with similar densities.
Gadolinium‐Doped Persistent Nanophosphors as Versatile Tool for Multimodal In Vivo Imaging
Authors: Maldiney Thomas , Doan Bich‐Thuy , Alloyeau Damien , Bessodes Michel , Scherman Daniel , Richard Cyrille
Published: November 2014

Recent breakthroughs in the rational development of multifunctional nanocarriers have highlightened the advantage of combining the complementary forces of several imaging modalities into one single nanotool fully dedicated to the biomedical field and diagnosis applications. A novel multimodal optical‐magnetic resonance imaging nanoprobe is introduced. Designed on the basis of a spinel zinc gallate structure doped with trivalent chromium and gadolinium, this nanocrystal bears the ability to serve as both a highly sensitive persistent luminescence nanoprobe for optical imaging, and a negative contrast agent for highly resolved magnetic resonance imaging (MRI). Additional proof is given that surface coverage can be modified in order to obtain stealth nanoparticles highly suitable for real‐time in vivo application in mice, showing delayed reticulo‐endothelial uptake and longer circulation time after systemic injection.
Building Three‐Dimensional Graphene Frameworks for Energy Storage and Catalysis
Authors: Yu Minghao , Huang Yongchao , Li Cheng , Zeng Yinxiang , Wang Wang , Li Yao , Fang Pingping , Lu Xihong , Tong Yexiang
Published: November 2014

Due to their unique architectures and outstanding electrical properties, three dimensional graphene‐based frameworks (3DGFs) have attracted extensive attention in wide fields. However, recently reported techniques always require complex processes and high cost, which severely limit their large‐scale application. In this study, the massive preparation of macroscopically porous 3DGFs from the inherently inexpensive graphite paper is for the first time realized by simply combining the modified Hummer's method with freezing technique. The as‐prepared 3DGFs that consist of well exfoliated, high‐quality reduced graphene oxide (RGO) exhibit a mesoporous structure and superior conductivity. Such unique features enable the 3DGFs to be directly used as a supercapacitor electrode and as ideal 3D scaffolds to create PANI@3DGFs, Pd@3DGFs, and Pt@3DGFs composites, which hold great potential applications in supercapacitors and catalysts.
Iron Nitrate/TEMPO: a Superior Homogeneous Catalyst for Oxidation of Primary Alcohols to Nitriles in Air
Authors: Dighe Shashikant U. , Chowdhury Deepan , Batra Sanjay
Published: November 2014

A highly practical, one‐step, facile synthesis of aromatic, heteroaromatic, allylic and aliphatic nitriles from primary alcohols catalyzed by ferric nitrate [Fe(NO3)3⋅9H2O] in the presence of TEMPO, aqueous ammonia and air at room temperature is described.

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Mosaicism for trisomy 21: A review
Authors: Papavassiliou Paulie , Charalsawadi Chariyawan , Rafferty Kelly , Jackson‐Cook Colleen
Published: November 2014

The clinical and cytogenetic findings associated with mosaicism for trisomy 21/Down syndrome are the focus of this review. The primary topics discussed in this overview of the extant literature include the history of this condition and its diagnosis, the incidence of mosaicism, the meiotic and/or mitotic chromosomal malsegregation events resulting in mosaicism, the observation of mosaicism in the parents of children with the non‐mosaic form of Down syndrome, and the variation in phenotypic outcome for both constitutional and acquired traits present in people with mosaicism for trisomy 21/Down syndrome, including cognition, fertility, and overall phenotypic findings. Additional topics reviewed include the social conditions of people with mosaicism, as well as age‐related and epigenetic alterations observed in people with mosaicism for trisomy 21/Down syndrome. © 2014 Wiley Periodicals, Inc.
Variations of lamina papyracea position from the endoscopic view: a retrospective computed tomography analysis
Authors: Herzallah Islam R. , Marglani Osama A. , Shaikh Ahmed M.
Published: November 2014

Background

Accidental injury of lamina papyracea (LP) remains one of the most common complications reported in endoscopic sinus surgery (ESS) even in most recent studies. The purpose of this study was to categorize the LP position radiologically and from an endoscopic perspective.

Methods

A total of 207 computed tomography (CT) scans (414 sides) including both diseased and control groups were retrospectively reviewed by 2 examiners. Inferior turbinate attachment to the lateral nasal wall and the inferior margin of the planned middle meatal antrostomy (MMA) were identified anteriorly. Position of LP in relation to the vertical line passing through MMA inferior margin was reported. LP was categorized to lie either within 2 mm on either side of the MMA inferior margin (type I), more than 2 mm medial to the MMA line (type IIa: 2 to 4 mm; type IIb: >4 mm), or more than 2 mm lateral to the MMA line (type IIIa: 2 to 4 mm; type IIIb: >4 mm).

Results

Of the 221 sides in the control group, 69.7% were classified as type I, 24.9% as type II, and 5.5% as type III. Among the 193 diseased operated sides examined, 60.1% were classified as type I, 20.2% as type II, and 13.5% as type III. Weighted kappa coefficient showed good interexaminer reliability. Five sides (2.6%) in the case group had accidental LP penetration intraoperatively, 4 of them were type II and type III LP.

Conclusion

This study improves surgeons’ awareness of LP variations in the endoscopic field and can be of help for residents in training.
Terminal Phosphanido Rhodium Complexes Mediating Catalytic PP and PC Bond Formation
Authors: Geer Ana M. , Serrano Ángel L. , de Bruin Bas , Ciriano Miguel A. , Tejel Cristina
Published: November 2014

Complexes with terminal phosphanido (MPR2) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of PP and PC bonds. We showcase here the isolation and characterization of mononuclear phosphanide rhodium complexes ([RhTp(H)(PR2)L]) that result from the oxidative addition of secondary phosphanes, a reaction that was also explored computationally. These compounds are active catalysts for the dehydrocoupling of PHPh2 to Ph2PPPh2. The hydrophosphination of dimethyl maleate and the unactivated olefin ethylene is also reported. Reliable evidence for the prominent role of mononuclear phosphanido rhodium species in these reactions is also provided.
Metal‐Free Radical 5‐exo‐dig Cyclizations of Phenol‐Linked 1,6‐Enynes for the Synthesis of Carbonylated Benzofurans
Authors: Hu Ming , Song Ren‐Jie , Li Jin‐Heng
Published: November 2014

A new metal‐free radical 5‐exo‐dig cyclization of phenol‐linked 1,6‐enynes with O2, 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO), and tBuONO is described. With this general method, carbonylated benzofurans can be accessed through incorporation of two oxygen atoms into the product from O2 and TEMPO through dioxygen activation and oxidative cleavage of the NO bond, respectively.
Enantiotopos‐Selective CH Oxygenation Catalyzed by a Supramolecular Ruthenium Complex
Authors: Frost James R. , Huber Stefan M. , Breitenlechner Stefan , Bannwarth Christoph , Bach Thorsten
Published: November 2014

Spirocyclic oxindoles undergo an enantioselective oxygenation reaction (nine examples; e.r. up to 97:3) upon catalysis by a chiral ruthenium porphyrin complex (1 mol %). The catalyst exhibits a lactam ring, which is responsible for substrate association through hydrogen bonds, and an active ruthenium center, which is in a defined spatial relationship to the oxygenation substrate. DFT calculations illustrate the perfect alignment of the active site with the reactive CH bond and suggest—in line with the kinetic isotope effect—an oxygen rebound mechanism for the reaction.
Synthesis of a Stable Selenoaldehyde by Self‐Catalyzed Thermal Dehydration of a Primary‐Alkyl‐Substituted Selenenic Acid
Authors: Sase Shohei , Kakimoto Ryo , Goto Kei
Published: November 2014

The unprecedented dehydration of a selenenic acid (RCH2SeOH) to a selenoaldehyde (RCHSe) has been demonstrated. A primary‐alkyl‐substituted selenenic acid was synthesized for the first time by taking advantage of a bulky cavity‐shaped substituent. Upon heating in solution, the selenenic acid underwent thermal dehydration to produce a stable selenoaldehyde, which was isolated as stable crystals and crystallographically characterized. Investigation of the reaction mechanism revealed that this β dehydration reaction involves two processes, both of which reflect the characteristics of a selenenic acid: 1) dehydrative condensation of two molecules of selenenic acid to generate a selenoseleninate intermediate [RCH2SeSe(O)CH2R], an isomer of a selenenic anhydride, and 2) subsequent β elimination of the selenenic acid from this intermediate to form a CSe double bond, which establishes the self‐catalyzed β dehydration of the selenenic acid.
Chemical Assembly Systems: Layered Control for Divergent, Continuous, Multistep Syntheses of Active Pharmaceutical Ingredients
Authors: Ghislieri Diego , Gilmore Kerry , Seeberger Peter H.
Published: November 2014

While continuous chemical processes have attracted both academic and industrial interest, virtually all active pharmaceutical ingredients (APIs) are still produced by using multiple distinct batch processes. To date, methods for the divergent multistep continuous production of customizable small molecules are not available. A chemical assembly system was developed, in which flow‐reaction modules are linked together in an interchangeable fashion to give access to a wide breadth of chemical space. Control at three different levels—choice of starting material, reagent, or order of reaction modules—enables the synthesis of five APIs that represent three different structural classes (γ‐amino acids, γ‐lactams, β‐amino acids), including the blockbuster drugs Lyrica and Gabapentin, in good overall yields (49–75 %).
Ultrathin Cerium Orthovanadate Nanobelts for High‐Performance Flexible All‐Solid‐State Asymmetric Supercapacitors
Authors: He Junzhi , Zhao Junhong , Run Zhen , Sun Mengjun , Pang Huan
Published: November 2014

Ultrathin CeVO4 nanobelts were successfully synthesized by a hydrothermal method. The thickness of a single nanobelt is about 2.4 nm, which can effectively shorten the ion diffusion and fasten the charge pathway. More importantly, ultrathin CeVO4 nanobelts and graphene are easily assembled as a flexible all‐solid‐state asymmetric device, which shows a highly flexible property and achieves a maximum energy density of 0.78 mW h cm−3 and a high life cycle of >6000 cycles.
Chebulin: Terminalia chebula Retz. fruit‐derived peptide with angiotensin‐I–converting enzyme inhibitory activity
Authors: Sornwatana Thakorn , Bangphoomi Kunan , Roytrakul Sittiruk , Wetprasit Nuanchawee , Choowongkomon Kiattawee , Ratanapo Sunanta
Published: November 2014

Angiotensin‐I–converting enzyme (ACE) plays an important role in blood pressure regulation. In this study, an ACE–hexapeptide inhibitor (Asp–Glu–Asn–Ser–Lys–Phe) designated as chebulin was produced from the fruit protein of Terminalia chebula Retz. by pepsin digestion, ultrafiltrated through a 3 KDa cut‐off membrane, a reverse‐phase high‐performance liquid chromatography, and nano‐liquid chromatography tandem mass spectrometry analysis. Chebulin was found to inhibit ACE in a noncompetitive manner, as supported by the structural model. It bounds to ACE by the hydrogen bond, hydrophobic and ionic interactions via the interactions of C‐terminal Phe (Phe‐6), and N‐terminal residues (Asp‐1 and Glu‐2) with the amino acid residues on noncatalytic sites of the ACE. The results showed that chebulin derived from fruits of T. chebula Retz. is a potential ACE–peptide inhibitor that could be used as a functional food additive for the prevention of hypertension and as an alternative to ACE inhibitor drug.
Possible involvement of cationic‐drug sensitive transport systems in the blood‐to‐brain influx and brain‐to‐blood efflux of amantadine across the blood–brain barrier
Authors: Suzuki Toyofumi , Fukami Toshiro , Tomono Kazuo
Published: November 2014

The purpose of this study was to characterize the brain‐to‐blood efflux transport of amantadine across the blood–brain barrier (BBB). The apparentin vivoefflux rate constant for [3H]amantadine from the rat brain (keff) was found to be 1.53 × 10‐2 min‐1after intracerebral microinjection using the brain efflux index method. The efflux of [3H]amantadine was inhibited by 1‐methyl‐4‐phenylpyridinium (MPP+), a cationic neurotoxin, suggesting that amantadine transport from the brain to the blood across the BBB potentially involves the rat plasma membrane monoamine transporter (rPMAT). On the other hand, other selected substrates for organic cation transporters (OCTs) and organic anion transporters (OATs), as well as inhibitors of P‐glycoprotein (P‐gp), did not affect the efflux transport of [3H]amantadine. In addition,in vitrostudies using an immortalized rat brain endothelial cell line (GPNT) showed that the uptake and retention of [3H]amantadine by the cells was not changed by the addition of cyclosporin, which is an inhibitor of P‐gp. However, cyclosporin affected the uptake and retention of rhodamine123. Finally, the initial brain uptake of [3H]amantadine was determined using anin situmouse brain perfusion technique. Notably, the brain uptake clearance for [3H]amantadine was significantly decreased with the co‐perfusion of quinidine or verapamil, which are cationic P‐gp inhibitors, while MPP+did not have a significant effect. It is thus concluded that while P‐gp is not involved, it is possible that rPMAT and the cationic drug‐sensitive transport system participate in the brain‐to‐blood efflux and the blood‐to‐brain influx of amantadine across the BBB, respectively. Copyright © 2014 John Wiley & Sons, Ltd.
Simultaneous evaluation of human CYP3A4 and ABCB1 induction by reporter assay in LS174T cells, stably expressing their reporter genes
Authors: Inami Keita , Sasaki Takamitsu , Kumagai Takeshi , Nagata Kiyoshi
Published: November 2014

The bioavailability of orally administered therapies are often significantly limited in the human intestine by the metabolic activities of cytochrome P450 3A4 (CYP3A4) and P‐glycoprotein (P‐gp). Predicting whether candidate compounds induce CYP3A4 and P‐gp is a crucial stage in the drug development process, as drug–drug interactions may result in the induction of intestinal CYP3A4 and P‐gp. However, the assay systems needed to evaluate both CYP3A4 and P‐gp induction in the intestine are yet to be established. To address this urgent requirement, LS174T cells were used to create two stable cell lines expressing the CYP3A4 or ATP‐binding cassette subfamily B member 1 (ABCB1, encoding P‐gp) reporter genes. First, these stable cells were tested by treatment with 1α,25‐dihydroxyvitamin D3 (1,25(OH)2D3), all‐trans‐retinoic acid (ATRA) and 9‐cis‐retinoic acid (9‐cis RA) that induce CYP3A4 and P‐gp in the intestines. All these compounds significantly increased both CYP3A4 and ABCB1 reporter activities in the stable cell lines. To simultaneously assess the induction of CYP3A4 and ABCB1, both stable cells were co‐cultivated to measure their reporter activities. The mixed cells showed a significant increase in the CYP3A4 and ABCB1 reporter activities following treatment with 1,25(OH)2D3, ATRA, and 9‐cis RA. These activity levels were maintained after passaging more than 20 times and following multiple freeze–thaw cycles. These results demonstrate that our established cell lines can be used to evaluate simultaneously CYP3A4 and ABCB1 induction in the intestines, providing a valuable in vitro model for the evaluation of future drug candidates. Copyright © 2014 John Wiley & Sons, Ltd.
Novel insights on the DNA interaction of calicheamicin γ1I
Authors: Sissi Claudia , Moro Stefano , Crothers Donald M.
Published: November 2014

Calicheamicin γ1I (Cal) is a unique molecule in which a DNA binding motif (aryl‐tetrasaccharide) is linked to a DNA cleaving moiety (calicheamicinone). The hallmark of this natural product rests in the impressive optimization of these two mechanisms leading to a drug that is extremely efficient in cleaving DNA at well‐defined sites. However, the relative contributions of these two structurally distinct domains to the overall process have not been fully elucidated yet. Here, we used different experimental approaches to better dissect the role of the aryl‐tetrasaccharide and the enediyne moieties in the DNA sequence selective binding step as well as the in the cleavage reaction. Our results highlight the remarkable cooperation of the two components in producing an amazing molecular machine. The herein presented molecular details of this concerted mechanism of action can be further applied to rationally design more druggable compounds. © 2014 Wiley Periodicals, Inc. Biopolymers 103: 449–459, 2015.
Five Key Words for Effective Governance
Authors: Hull Ted
Published: November 2014

Policy Governance® consultant and practitioner Ted Hull applies his love of analogies (while recognizing that they can never be perfect) to help us understand the basics of good governance.
Threat assessment and management model required out‐of‐the‐box thinking
Authors: Gomez Cynthia
Published: November 2014

Individuals who become active shooters or commit other violent acts typically display concerning behavior prior to erupting into violence. The problem is often that those signs aren't reported, or if they are, reports live as discrete pieces of a puzzle that never get put together to create a clear picture of the imminent danger in time to stop it.
Senate report pinpoints problems with institutions' handling of sexual assaults
Authors: Gomez Cynthia
Published: November 2014

“Sexual Violence on Campus: How Too Many Institutions of Higher Education Are Failing to Protect Students,” is the newest assessment by federal legislators of how colleges and universities address reports of sexual violence. The report, which is based on a survey of 440 four‐year institutions across the country, was prepared by the U.S. Senate Subcommittee on Financial & Contracting Oversight at the request of U.S. Sen. Claire McCaskill of Missouri.
Rationale, development, implementation, and initial results of a fast track protocol for transfemoral transcatheter aortic valve replacement (TAVR)
Authors: Marcantuono Rebecca , Gutsche Jacob , Burke‐Julien Maureen , Anwaruddin Saif , Augoustides John G. , Jones David , Mangino – Blanchard Lisa , Hoke Nicole , Houseman Stephanie , Li Robert , Patel Prakash , Stetson Robert , Walsh Elizabeth , Szeto Wilson Y. , Herrmann Howard C.
Published: November 2014

Background

The care pathway for patients undergoing transcatheter aortic valve replacement (TAVR), particularly in the US, was initially based on open surgical techniques and often includes general anesthesia, transesophageal echocardiographic monitoring, and cardiothoracic intensive care unit (ICU) stays. Whether a subgroup of patients could benefit from early extubation, fewer days in the ICU, and early ambulation in terms of both cost and effectiveness is unknown.

Methods and Results

A fast track (FT) protocol was initiated at two institutions in our health system with specific inclusion criteria. Patients with complications or morbidity post procedure deemed ineligible to continue on the FT pathway were designated as deviations. Baseline characteristics, success and deviations, subsequent course, and direct costs were compared for FT eligible and ineligible patients over a 6‐month study period. Among 99 patients undergoing Transfemoral TAVR, 39 (39%) met FT inclusion criteria. The mean age of eligible and ineligible patients was similar at 85 years, but by design, eligible patients had fewer co‐morbid conditions. Successful completion of the FT protocol was achieved in 28 patients (72%). Patients on the FT had shorter ICU stays (28 ± 103 vs 45 ± 46 hours, P < 0.0001) and post‐operative length of stay (4.3 ± 4.4 vs 7.2 ± 5.3 days, P < 0.0001), and incurred lower direct costs ($44,923 ± $14,187 vs $56, 339 ± 17,808, P < 0.0001).

Conclusions

It is feasible to identify a large percentage of suitable patients preprocedure who are eligible for a FT postprocedure care pathway. There was no evidence for compromise of care and successful completion of the pathway was associated with shorter length of stay and fewer direct costs. © 2014 Wiley Periodicals, Inc.
The incremental impact of residual SYNTAX score on long‐term clinical outcomes in patients with multivessel coronary artery disease treated by percutaneous coronary interventions
Authors: Witberg Guy , Lavi Ifat , Assali Abid , Vaknin‐Assa Hana , Lev Eli , Kornowski Ran
Published: November 2014

Objective

To broaden the data supporting the use of the residual SYNTAX score (rSS) to define “reasonable” incomplete coronary revascularization (ICR) in order to improve the allocation of patients with severe coronary artery disease (CAD) to surgical/percutaneous revascularization and long‐term clinical outcomes.

Introduction

ICR is associated with a worse prognosis in patients with severe CAD, yet no consensus exists regarding its definition.

Methods

We studied 148 consecutive patients with triple vessel/left main (3VD/LM) CVD treated by percutaneous coronary interventions (PCI). Clinical outcomes at 3 years were collected; the SS and rSS were calculated. We used various definitions of “reasonable” ICR:no post‐PCI total occlusion, single vs. mutivessel residual post‐PCI disease, and the rSS at a cutoff value determined according to ROC curve fitted for 3 years major adverse cardiovascular and cerebrovascular adverse events (MACCE) in order to determine which definition has the strongest correlation with long‐term outcomes.

Results

rSS ≤ 8 was associated with significant reductions in 3 year MACCE (19.4 vs. 51.1%, HR = 3.62, P = 0.014) Death/MI/CVA (13.7 vs. 28.8%, HR = 6.01, P = 0.030) and repeat revascularization (8.6 vs. 28.9%, HR = 3.44, P = 0.033) using a Cox proportional hazard ratio model adjusted to baseline characteristics, whereas single vessel residual disease and absence of total occlusion were not.

Conclusions

“Reasonable” ICR as determined by rSS carries better long‐term prognosis in terms of clinical outcomes vs. more extensive residual coronary disease in patients with 3VD/LM coronary artery disease treated by PCI. The rSS may improve the allocation of coronary patients to the optimal mode of revascularization. © 2015 Wiley Periodicals, Inc.
Predictors of outcomes following catheter‐based therapy for acute stroke
Authors: Htyte Nay , Parto Parham , Ragbir Shawn , Jaffe Leeor , White Christopher J.
Published: November 2014

Background

Timely reperfusion directly impacts favorable neurologic outcomes in acute ischemic stroke (AIS) patients. Most strokes present outside the 3–4.5 h window for intravenous thrombolysis (IV‐tPA). Catheter‐based therapy (CBT) is commonly used in patients not eligible for timely IV‐tPa, but variables that predict good neurologic outcomes are poorly understood.

Methods

Results of 124 consecutive AIS patients who received CBT at Ochsner Medical Center from 2006 and 2012 are reported. A modified Rankin score (mRs) of ≤ 2 at 90 day post‐CBT was used as the primary measurement of a good neurologic outcome. All‐cause mortality during the index hospitalization, ≤30 days from treatment, and at 1 year were reported. Results are reported as those treated by Interventional Cardiologists (IC) or by Neurointerventionalists (NI).

Results

The mean age was 65 ± 16 years of which 48% (n = 52) were male. The mean NIHSS was 15.0 ± 7.5. Thrombolysis in cerebral infarction (TICI) ≥2 flow was achieved in 80% (n = 100). Good neurologic outcome was observed in 64% (n = 37 of 58) of patients 65 years or younger while in those older than 65, only 36% (n = 24 of 66) had the same outcome (P = 0.002). Mortality at 30 days for the two age groups were 21% (n = 12) vs. 50% (n = 33) (P = <0.001) respectively. A good neurologic outcome at 90 days was seen in 57% of patients with restoration of TICI ≥ 2 flow compared to 17% with TICI < 2 flow (P = <0.001). Those with failed reperfusion (TICI<2 flow) had 30‐day mortality rate of 54% (13 of 24) vs. 20% (19 of 97) in those with TICI ≥ 2 flow (P = <0.001). At 90 days, there was no significant differences in patient outcomes between IC (n = 58) and NI (n = 66) treated patients.

Conclusion

Successful revascularization with CBT leads to a good neurologic outcome in selected stroke patients. Medical co‐morbidities and increased age > 65 years contributed to poor outcomes. To support broadening the number of physicians qualified to perform catheter‐based stroke interventions, this study demonstrates that IC participating on a stroke team achieve comparable outcomes to NI. © 2014 Wiley Periodicals, Inc.
Alternating Donor–Acceptor Arrays from Hexa‐peri‐hexabenzocoronene and Benzothiadiazole: Synthesis, Optical Properties, and Self‐Assembly
Authors: Hinkel Felix , Cho Don , Pisula Wojciech , Baumgarten Martin , Müllen Klaus
Published: November 2014

Donor–acceptor (D–A) structures were obtained by alternating arrays of hexa‐peri‐hexabenzocoronene (HBC) and benzo[c][1,2,5]thiadiazole (BTZ). Optoelectronic investigations revealed a charge transfer due to strong push–pull interactions. 2 D wide‐angle X‐ray scattering (WAXS) data indicated an arrangement in liquid‐crystalline columnar assemblies, in which the π‐stacking distances and molecular orientation depend on the number of HBC units in the molecules.
4‐Aryl‐3,5‐bis(arylethynyl)aryl‐4H‐1,2,4‐triazoles: Multitasking Skeleton as a Self‐Assembling Unit
Authors: Pastor M. Jesús , Torres Iván , Cebrián Cristina , Carrillo José Ramón , Díaz‐Ortiz Ángel , Matesanz Emilio , Buendía Julia , García Fátima , Barberá Joaquín , Prieto Pilar , Sánchez Luis
Published: November 2014

The synthesis of a series of 4‐aryl‐3,5‐bis(arylethynyl)aryl‐4H‐1,2,4‐triazoles derivatives is reported and the influence exerted by peripheral substitution on the morphology of the aggregates generated from these 1,2,4‐triazoles is investigated by SEM imaging. The presence of paraffinic side chains results in long fibrillar supramolecular structures, but unsubstituted triazoles self‐assemble into thinner ribbons and needle‐like aggregates. The crystals obtained from methoxy‐substituted triazoles have been utilised to elaborate a model that helps to justify aggregation of the investigated 1,2,4‐triazoles, in which the operation of arrays of CH⋅⋅⋅π non‐covalent interactions plays a significant role. The results presented herein demonstrate the ability of simple molecules to behave as multitasking scaffolds with different properties, depending on peripheral substitution. Thus, although 1,2,4‐triazoles without long paraffinic side chains exhibit optical waveguiding behaviour, triazoles endowed with peripheral paraffinic side chains exhibit hexagonal columnar mesomorphism.
Substituent and Solvent Effects on the Excited State Deactivation Channels in Anils and Boranils
Authors: Dobkowski Jacek , Wnuk Paweł , Buczyńska Joanna , Pszona Maria , Orzanowska Grażyna , Frath Denis , Ulrich Gilles , Massue Julien , Mosquera‐Vázquez Sandra , Vauthey Eric , Radzewicz Czesław , Ziessel Raymond , Waluk Jacek
Published: November 2014

Differently substituted anils (Schiff bases) and their boranil counterparts lacking the proton‐transfer functionality have been studied using stationary and femtosecond time‐resolved absorption, fluorescence, and IR techniques, combined with quantum mechanical modelling. Dual fluorescence observed in anils was attributed to excited state intramolecular proton transfer. The rate of this process varies upon changing solvent polarity. In the nitro‐substituted anil, proton translocation is accompanied by intramolecular electron transfer coupled with twisting of the nitrophenyl group. The same type of structure is responsible for the emission of the corresponding boranil. A general model was proposed to explain different photophysical responses to different substitution patterns in anils and boranils. It is based on the analysis of changes in the lengths of CN and CC bonds linking the phenyl moieties. The model allows predicting the contributions of different channels that involve torsional dynamics to excited state depopulation.
Aminocatalysis: Beyond Steric Shielding and Hydrogen‐Bonding
Authors: Matos Paz Bruno , Jiang Hao , Jørgensen Karl Anker
Published: November 2014

The stereochemical outcome of most aminocatalytic transformations is determined by the steric‐shielding or hydrogen‐directing approach. However, in recent years several reactions have appeared in which the stereochemical outcome is beyond these two approaches. This Concept article will highlight such reactions and postulate that the stereochemical outcome can be accounted for by electrostatic interactions between the catalyst‐bound substrate and the reagent in the transition state.
Highly Enantioselective Hydrogenation of N‐Aryl Imines Derived from Acetophenones by Using Ru–Pybox Complexes under Hydrogenation or Transfer Hydrogenation Conditions in Isopropanol
Authors: Menéndez‐Pedregal Estefanía , Vaquero Mónica , Lastra Elena , Gamasa Pilar , Pizzano Antonio
Published: November 2014

The asymmetric reduction of N‐aryl imines derived from acetophenones by using Ru complexes bearing both a pybox (2,6‐bis(oxazoline)pyridine) and a monodentate phosphite ligand has been described. The catalysts show good activity with a diverse range of substrates, and deliver the amine products in very high levels of enantioselectivity (up to 99 %) under both hydrogenation and transfer hydrogenation conditions in isopropanol. From deuteration studies, a very different labeling is observed under hydrogenation and transfer hydrogenation conditions, which demonstrates the different nature of the hydrogen source in both reactions.
Reaction of an N‐Heterocyclic Carbene‐Stabilized Silicon(II) Monohydride with Alkynes: [2+2+1] Cycloaddition versus Hydrogen Abstraction
Authors: Eisenhut Carsten , Szilvási Tibor , Breit Nora C. , Inoue Shigeyoshi
Published: November 2014

An in depth study of the reactivity of an N‐heterocyclic carbene (NHC)‐stabilized silylene monohydride with alkynes is reported. The reaction of silylene monohydride 1, tBu3Si(H)Si←NHC, with diphenylacetylene afforded silole 2, tBu3Si(H)Si(C4Ph4). The density functional theory (DFT) calculations for the reaction mechanism of the [2+2+1] cycloaddition revealed that the NHC played a major part stabilizing zwitterionic transition states and intermediates to assist the cyclization pathway. A significantly different outcome was observed, when silylene monohydride 1 was treated with phenylacetylene, which gave rise to supersilyl substituted 1‐alkenyl‐1‐alkynylsilane 3, tBu3Si(H)Si(CHCHPh)(CCPh). Mechanistic investigations using an isotope labelling technique and DFT calculations suggest that this reaction occurs through a similar zwitterionic intermediate and subsequent hydrogen abstraction from a second molecule of phenylacetylene.
Long‐Lived Excited States of Zwitterionic Copper(I) Complexes for Photoinduced Cross‐Dehydrogenative Coupling Reactions
Authors: Wang Bin , Shelar Deepak Prakash , Han Xian‐Zhu , Li Ting‐Ting , Guan Xiangguo , Lu Wei , Liu Kun , Chen Yong , Fu Wen‐Fu , Che Chi‐Ming
Published: November 2014

Four heteroleptic copper(I) complexes containing phenanthroline and monoanionic nido‐carborane‐diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X‐ray diffraction. These complexes exhibit intense absorptions in the visible range and excited‐state lifetimes on the microsecond scale. Their application in visible‐light‐induced cross‐dehydrogenative coupling reactions was investigated. Preliminary studies showed that one of the four copper(I) complexes is an efficient catalyst for photoinduced oxidative CH functionalization using oxygen as oxidant. Furthermore, α‐functionalized tertiary amines were obtained in good‐to‐excellent yields by light irradiation (λ>420 nm) of a mixture of our CuI complex, tertiary amines, and a variety of nucleophiles (nitroalkane, acetone, or indoles) under aerobic conditions. Electron paramagnetic resonance measurements provided evidence for the formation of superoxide radical anions (O2−⋅) rather than singlet oxygen (1O2) during these photocatalytic reactions.
Graphitic Carbon Nitride Polymer as a Recyclable Photoredox Catalyst for Fluoroalkylation of Arenes
Authors: Baar Moritz , Blechert Siegfried
Published: November 2014

Heterogeneous catalysis for trifluoromethylations and perfluoroalkylations has been performed. Through the usage of cheap, metal‐free and recyclable mesoporous graphitic carbon nitride (mpg‐CN) it was possible to fluoroalkylate various arenes by the reductive activation of sulfonyl chlorides with visible light. Thus, we were able to demonstrate the robustness and versatility of mpg‐CN as a photoredox catalyst beyond water splitting and the activation of oxygen.
ChemInform Abstract: Formic Acid Derivatives as Practical Carbon Monoxide Surrogates for Metal‐Catalyzed Carbonylation Reactions
Authors: Konishi Hideyuki , Manabe Kei
Published: November 2014

Review: [40 refs.
ChemInform Abstract: Current Perspective on Bacterial Pigments: Emerging Sustainable Compounds with Coloring and Biological Properties for the Industry — An Incisive Evaluation
Authors: Venil Chidambaram Kulandaisamy , Aruldass Claira Arul , Dufosse Laurent , Zakaria Zainul Akmar , Ahmad Wan Azlina
Published: November 2014

Review: 52 refs.