bluuebunny/crossref_metadata_2025 huggingface dataset:
A inclusão escolar e o movimento Todos Pela Educação
Authors: Hattge Morgana Domênica , Lopes Maura Corcini
Published: March 2016

Este texto analisa a inclusão a partir de uma das cinco metas previstas em um dos mais profícuos movimentos da sociedade civil brasileira para assegurar que até o ano de 2022 todas as crianças e jovens tenham garantido o direito de acesso à escola básica de qualidade: o Todos Pela Educação, criado em 2006. Partindo de uma perspectiva genealógica no sentido que lhe atribui Michel Foucault, a pesquisa analisa a proveniência e emergência do Movimento no cenário educacional brasileiro neste início de século e suas implicações na política educacional. A referida análise genealógica visibiliza a instauração da performatividade no cenário educacional contemporâneo, entendendo-se esse conceito com base nas teorizações de Stephen Ball. A partir da análise de excertos retirados de publicações de divulgação e de relatórios de monitoramento das metas produzidos pelo Movimento Todos Pela Educação, conclui-se que a inclusão escolar no Movimento assume um caráter de minimização do risco social e que a relação da performatividade com a inclusão se constitui em um paradoxo. Se, por um lado, num sistema escolar pautado pelas exigências da performatividade, a inclusão de todos é uma condição inegociável, absolutamente necessária para reduzir o risco social e elevar o Brasil nos rankings internacionais na Educação, por outro lado, esses ditos “incluídos” ameaçam a performatividade escolar, uma vez que seus desempenhos nas avaliações de larga escala, muitas vezes, não são considerados satisfatórios para atender às metas estabelecidas pelo Movimento Todos Pela Educação.
Patterns on a Calendar
Authors: Cady Jo Ann , Wells Pamela J.
Published: March 2016

To elicit creative thinking, this open-ended problem asks students to analyze pattern found on a calendar.
Five Steps to Zero: A Game for Number Sense and Reasoning
Authors: Wieman Rob
Published: March 2016

A game called Five Steps to Zero and its variations are meant to help students with mathematical reasoning.
Reverse and Add to 100: Explorations in Place Value
Authors: Edwards Michael Todd , Quinlan James , Strayer Jeremy F.
Published: March 2016

A collaborative number quest challenges third graders to strengthen their understanding of patterns, multidigit addition, and number operations
Downregulation of Melanoma Cell Adhesion Molecule (MCAM/CD146) Accelerates Cellular Senescence in Human Umbilical Cord Blood-Derived Mesenchymal Stem Cells
Authors: Jin Hye Jin , Kwon Ji Hye , Kim Miyeon , Bae Yun Kyung , Choi Soo Jin , Oh Wonil , Yang Yoon Sun , Jeon Hong Bae
Published: March 2016

Therapeutic applications of mesenchymal stem cells (MSCs) for treating various diseases have increased in recent years. To ensure that treatment is effective, an adequate MSC dosage should be determined before these cells are used for therapeutic purposes. To obtain a sufficient number of cells for therapeutic applications, MSCs must be expanded in long-term cell culture, which inevitably triggers cellular senescence. In this study, we investigated the surface markers of human umbilical cord blood-derived MSCs (hUCB-MSCs) associated with cellular senescence using fluorescence-activated cell sorting analysis and 242 cell surface-marker antibodies. Among these surface proteins, we selected the melanoma cell adhesion molecule (MCAM/CD146) for further study with the aim of validating observed expression differences and investigating the associated implications in hUCB-MSCs during cellular senescence. We observed that CD146 expression markedly decreased in hUCB-MSCs following prolonged in vitro expansion. Using preparative sorting, we found that hUCB-MSCs with high CD146 expression displayed high growth rates, multilineage differentiation, expression of stemness markers, and telomerase activity, as well as significantly lower expression of the senescence markers p16, p21, p53, and senescence-associated β-galactosidase, compared with that observed in hUCB-MSCs with low-level CD146 expression. In contrast, CD146 downregulation with small interfering RNAs enhanced the senescence phenotype. In addition, CD146 suppression in hUCB-MSCs caused downregulation of other cellular senescence regulators, including Bmi-1, Id1, and Twist1. Collectively, our results suggest that CD146 regulates cellular senescence; thus, it could be used as a therapeutic marker to identify senescent hUCB-MSCs.

Significance

One of the fundamental requirements for mesenchymal stem cell (MSC)-based therapies is the expansion of MSCs during long-term culture because a sufficient number of functional cells is required. However, long-term growth inevitably induces cellular senescence, which potentially causes poor clinical outcomes by inducing growth arrest and the loss of stem cell properties. Thus, the identification of markers for evaluating the status of MSC senescence during long-term culture may enhance the success of MSC-based therapy. This study provides strong evidence that CD146 is a novel and useful marker for predicting senescence in human umbilical cord blood-derived MSCs (hUCB-MSCs), and CD146 can potentially be applied in quality-control assessments of hUCB-MSC-based therapy.
Passively Q-switched erbium-doped fiber laser using Fe3O4-nanoparticle saturable absorber
Authors: Bai Xuekun , Mou Chengbo , Xu Luxi , Wang Shaofei , Pu Shengli , Zeng Xianglong
Published: March 2016

We experimentally demonstrate passively Q-switched erbium-doped fiber laser (EDFL) operation using a saturable absorber (SA) based on Fe3O4nanoparticles (FONPs). As a type of transition metal oxide, the FONPs have a large nonlinear optical response and fast response time. The FONP-based SA possesses a modulation depth of 8.2% and nonsaturable absorption of 56.6%. Stable passively Q-switched EDFL pulses with an output pulse energy of 23.76 nJ, a repetition rate of 33.3 kHz, and a pulse width of 3.2 µs were achieved when the input pump power was 110 mW. The laser features a low threshold pump power of ∼15 mW.
Rock magnetic expression of fluid infiltration in the Yingxiu‐Beichuan fault (Longmen Shan thrust belt, China)
Authors: Yang Tao , Yang Xiaosong , Duan Qingbao , Chen Jianye , Dekkers Mark J.
Published: March 2016

Fluid infiltration within fault zones is an important process in earthquake rupture. Magnetic properties of fault rocks convey essential clues pertaining to physicochemical processes in fault zones. In 2011, two shallow holes (134 and 54 m depth, respectively) were drilled into the Yingxiu‐Beichuan fault (Longmen Shan thrust belt, China), which accommodated most of the displacement of the 2008 Mw 7.9 Wenchuan earthquake. Fifty‐eight drill core samples, including granitic host rock and various fault rocks, were analyzed rock‐magnetically, mineralogically, and geochemically. The magnetic behavior of fault rocks appears to be dominated by paramagnetic clay minerals. Magnetite in trace amounts is identified as the predominant ferrimagnetic fraction in all samples, decreasing from the host rock, via fault breccia to (proto‐)cataclasite. Significant mass‐losses (10.7–45.6%) are determined for the latter two with the “isocon” method. Volatile contents and alteration products (i.e., chlorite) are enriched toward the fault core relative to the host rocks. These observations suggest that magnetite depletion occurred in these fault rocks—exhumed from the shallow crust—plumbed by fluid‐assisted processes. Chlorite, interpreted to result from hydrothermal activity, occurs throughout almost the entire fault core and shows high coefficients of determination (R2 > 0.6) with both low and high‐field magnetic susceptibility. Close relationships, with R2 > 0.70, are also observed between both low and high‐field magnetic susceptibility and the immobile elements (e.g., TiO2, P2O5, MnO), H2O+, and the calculated mass‐losses of fault rocks. Hence, magnetic properties of fault rocks can serve as proxy indicators of fluid infiltration within shallow fault zones.
Potential and limits of InSAR to characterize interseismic deformation independently of GPS data: Application to the southern San Andreas Fault system
Authors: Chaussard E. , Johnson C. W. , Fattahi H. , Bürgmann R.
Published: March 2016

The evaluation of long‐wavelength deformation associated with interseismic strain accumulation traditionally relies on spatially sparse GPS measurements, or on high spatial‐resolution InSAR velocity fields aligned to a GPS‐based model. In this approach the InSAR contributes only short‐wavelength deformation and the two data sets are dependent, thereby challenging the evaluation of the InSAR uncertainties and the justification of atmospheric corrections. Here we present an analysis using 7 years of Envisat InSAR data to characterize interseismic deformation along the southern San Andreas Fault (SAF) and the San Jacinto Fault (SJF) in southern California, where the SAF bifurcates onto the Mission Creek (MCF) and the Banning (BF) fault strands. We outline the processing steps for using InSAR alone to characterize both the short‐ and long‐wavelength deformation, and evaluate the velocity field uncertainties with independent continuous GPS data. InSAR line‐of‐sight (LOS) and continuous GPS velocities agree within ∼1–2 mm/yr in the study area, suggesting that multiyear InSAR time series can be used to characterize interseismic deformation with a higher spatial resolution than GPS. We investigate with dislocation models the ability of this mean LOS velocity field to constrain fault slip rates and show that a single viewing geometry can help distinguish between different slip‐rate scenarios on the SAF and SJF (∼35 km apart) but multiple viewing geometries are needed to differentiate slip on the MCF and BF (<12 km apart). Our results demonstrate that interseismic models of strain accumulation used for seismic hazards assessment would benefit from the consideration of InSAR mean velocity maps.
On the ordinary mode Weibel instability in space plasmas: A comparison of three‐particle distributions
Authors: Rubab Nazish , Chian Abraham C.‐L. , Jatenco‐Pereira Vera
Published: March 2016

Electromagnetic wave fluctuations driven by temperature anisotropy in plasmas are of interest for solar flare, solar corona, and solar wind studies. We investigate the dispersion characteristics of electromagnetic wave propagating perpendicular to the uniform magnetic field which is derived by using multiple particle distribution functions: Maxwellian, bi‐kappa, and product bi‐kappa. The presence of temperature anisotropy in which the parallel plasma kinetic energy density exceeding by a sufficient amount can lead to Weibel‐like electromagnetic instability. A general description is made to calculate the growth/damping rates of Weibel‐like modes when the temperature anisotropy and nonthermal features are associated with these distributions. We demonstrate that for the zeroth cyclotron harmonic, our results for bi‐Maxwellian and bi‐kappa overlap with each other, while the product bi‐kappa distribution shows some dependence on parallel kappa index. For higher harmonics, the growth rates vanish and the damping prevails.
Optics of the offshore Columbia River plume from glider observations and satellite imagery
Authors: Saldías Gonzalo. S. , Kipp Shearman R. , Barth John A. , Tufillaro Nicholas
Published: March 2016

The Columbia River (CR) is the largest source of freshwater along the U.S. Pacific coast. The resultant plume is often transported southward and offshore forming a large buoyant feature off Oregon and northern California in spring‐summer—the offshore CR plume. Observations from autonomous underwater gliders and Moderate Resolution Imaging Spectroradiometer (MODIS) satellite imagery are used to characterize the optics of the offshore CR plume off Newport, Oregon. Vertical sections, under contrasting river flow conditions, reveal a low‐salinity and warm surface layer of ∼20–25 m (fresher in spring and warmer in summer), high Colored Dissolved Organic Matter (CDOM) concentration, and backscatter, and associated with the base of the plume high chlorophyll fluorescence. Plume characteristics vary in the offshore direction as the warm and fresh surface layer thickens progressively to an average 30–40 m of depth 270–310 km offshore; CDOM, backscatter, and chlorophyll fluorescence decrease in the upper 20 m and increase at subsurface levels (30–50 m depth). MODIS normalized water‐leaving radiance (nLw(λ)) spectra for CR plume cases show enhanced water‐leaving radiance at green bands (as compared to no‐CR plume cases) up to ∼154 km from shore. Farther offshore, the spectral shapes for both cases are very similar, and consequently, a contrasting color signature of low‐salinity plume water is practically imperceptible from ocean color remote sensing. Empirical algorithms based on multivariate regression analyses of nLw(λ) plus SST data produce more accurate results detecting offshore plume waters than previous studies using single visible bands (e.g., adg(412) or nLw(555)).
Reference aquaplanet climate in the Community Atmosphere Model, Version 5
Authors: Medeiros Brian , Williamson David L. , Olson Jerry G.
Published: March 2016

Fundamental characteristics of the aquaplanet climate simulated by the Community Atmosphere Model, Version 5.3 (CAM5.3) are presented. The assumptions and simplifications of the configuration are described. A 16 year long, perpetual equinox integration with prescribed SST using the model's standard 1° grid spacing is presented as a reference simulation. Statistical analysis is presented that shows similar aquaplanet configurations can be run for about 2 years to obtain robust climatological structures, including global and zonal means, eddy statistics, and precipitation distributions. Such a simulation can be compared to the reference simulation to discern differences in the climate, including an assessment of confidence in the differences. To aid such comparisons, the reference simulation has been made available via earthsystemgrid.org. Examples are shown comparing the reference simulation with simulations from the CAM5 series that make different microphysical assumptions and use a different dynamical core.
Describing the catchment‐averaged precipitation as a stochastic process improves parameter and input estimation
Authors: Del Giudice Dario , Albert Carlo , Rieckermann Jörg , Reichert Peter
Published: March 2016

Rainfall input uncertainty is one of the major concerns in hydrological modeling. Unfortunately, during inference, input errors are usually neglected, which can lead to biased parameters and implausible predictions. Rainfall multipliers can reduce this problem but still fail when the observed input (precipitation) has a different temporal pattern from the true one or if the true nonzero input is not detected. In this study, we propose an improved input error model which is able to overcome these challenges and to assess and reduce input uncertainty. We formulate the average precipitation over the watershed as a stochastic input process (SIP) and, together with a model of the hydrosystem, include it in the likelihood function. During statistical inference, we use “noisy” input (rainfall) and output (runoff) data to learn about the “true” rainfall, model parameters, and runoff. We test the methodology with the rainfall‐discharge dynamics of a small urban catchment. To assess its advantages, we compare SIP with simpler methods of describing uncertainty within statistical inference: (i) standard least squares (LS), (ii) bias description (BD), and (iii) rainfall multipliers (RM). We also compare two scenarios: accurate versus inaccurate forcing data. Results show that when inferring the input with SIP and using inaccurate forcing data, the whole‐catchment precipitation can still be realistically estimated and thus physical parameters can be “protected” from the corrupting impact of input errors. While correcting the output rather than the input, BD inferred similarly unbiased parameters. This is not the case with LS and RM. During validation, SIP also delivers realistic uncertainty intervals for both rainfall and runoff. Thus, the technique presented is a significant step toward better quantifying input uncertainty in hydrological inference. As a next step, SIP will have to be combined with a technique addressing model structure uncertainty.
Time‐series measurements of bubble plume variability and water column methane distribution above Southern Hydrate Ridge, Oregon
Authors: Philip Brendan T. , Denny Alden R. , Solomon Evan A. , Kelley Deborah S.
Published: March 2016

An estimated 500–2500 gigatons of methane carbon is sequestered in gas hydrate at continental margins and some of these deposits are associated with overlying methane seeps. To constrain the impact that seeps have on methane concentrations in overlying ocean waters and to characterize the bubble plumes that transport methane vertically into the ocean, water samples and time‐series acoustic images were collected above Southern Hydrate Ridge (SHR), a well‐studied hydrate‐bearing seep site ∼90 km west of Newport, Oregon. These data were coregistered with robotic vehicle observations to determine the origin of the seeps, the plume rise heights above the seafloor, and the temporal variability in bubble emissions. Results show that the locations of seep activity and bubble release remained unchanged over the 3 year time‐series investigation, however, the magnitude of gas release was highly variable on hourly time scales. Bubble plumes were detected to depths of 320–620 m below sea level (mbsl), in several cases exceeding the upper limit of hydrate stability by ∼190 m. For the first time, sustained gas release was imaged at the Pinnacle site and in‐between the Pinnacle and the Summit area of venting, indicating that the subseafloor transport of fluid and gas is not restricted to the Summit at SHR, requiring a revision of fluid‐flow models. Dissolved methane concentrations above background levels from 100 to 300 mbsl are consistent with long‐term seep gas transport into the upper water column, which may lead to the build‐up of seep‐derived carbon in regional subsurface waters and to increases in associated biological activity.
On the ratio of dynamic topography and gravity anomalies in a dynamic Earth
Authors: Colli L. , Ghelichkhan S. , Bunge H.‐P.
Published: March 2016

Growing evidence from a variety of geologic indicators points to significant topography maintained convectively by viscous stresses in the mantle. However, while gravity is sensitive to dynamically supported topography, there are only small free‐air gravity anomalies (<30 mGal) associated with Earth's long‐wavelength topography. This has been used to suggest that surface heights computed assuming a complete isostatic equilibrium provide a good approximation to observed topography. Here we show that the apparent paradox is resolved by the well‐established formalism of global, self‐gravitating, viscously stratified Earth models. The models predict a complex relation between dynamic topography, mass, and gravity anomalies that is not summarized by a constant admittance—i.e., ratio of gravity anomalies to surface deflections—as one would infer from analytic flow solutions formulated in a half‐space. Our results suggest that sizable dynamic topography may exist without a corresponding gravity signal.
Molecular Genetics of the Fibrillinopathies
Authors: Aubart Mélodie , Benarroch Louise , Arnaud Pauline , Collod‐Béroud Gwenaëlle , Jondeau Guillaume , Boileau Catherine
Published: March 2016

Fibrillins are major glycoprotein components of microfibrils in the extracellular matrix. They are polymerised in a complex beads‐on‐a‐string appearance and form isolated aggregates or are closely associated with elastin in elastic fibres. Fibrillins are critical actors of the biomechanical function of connective tissue and regulators of the bioavailability of signalling molecules, especially TGF‐β. Mutations in the
FBN1
and
FBN2
genes are associated with inherited diseases now termed fibrillinopathies. These diseases represent a wide spectrum of disorders including Marfan and neonatal Marfan syndrome, acromelic dysplasias, progeroid‐marfanoid syndrome, the stiff skin syndrome and congenital contractural arachnodactyly. Clinical symptoms are varied, thus highlighting the importance of fibrillins in tissue development and integrity. The identification of over 3000 mutations in
FBN1
and over 100 in
FBN2
has provided only a few instances of genotype–phenotype correlations but have provided clues in the functional role of fibrillin domains.

Key Concepts

Fibrillin is a structural component of the extracellular matrix but is involved in cytokine signalling through its role of a niche for inactive procytokines.

There are three fibrillin genes encoding fibrillins 1, 2 and 3 that all share a conserved modular domain organisation with various degrees of homology.

Marfan syndrome is a highly variable and rare autosomal dominant disease with plurisystemic features and life‐threatening vascular complications.

Marfan syndrome is mostly associated with mutations in the
FBN1
gene with no clear genotype/phenotype correlation, thus undescoring the existence of genetic modifiers that underlie clinical variability.

Acromelic and geleophysic dysplasias, stiff skin syndrome and progeroid syndrome also display mutations in the
FBN1
gene, constituting with Marfan syndrome the group of type 1 fibrillinopathies.

Contrary to Marfan syndrome, all other type 1 fibrillinopathies are associated with mutations in specific domains of the protein.

Mutations in the
FBN2
gene are found in congenital contractural arachnodactyly.

No disease‐related mutation has been reported yet in the
FBN3
gene.

Eighteen spontaneous, radiation‐induced or transgenic mice models with mutations in the
FBN1
and
FBN2
genes are available.
Invertible Nanocup Array Supporting Hybrid Plasmonic Resonances
Authors: Wang Limin , Ai Bin , Möhwald Helmuth , Yu Ye , Zhang Gang
Published: March 2016

Continuous inverse nanocup array films are fabricated utilizing a simple and efficient colloidal lithography method. The structured films further can be easily transferred to arbitrary substrates and laid upside down during transfer. The topologically continuous film consisted of a frustum‐like void core surrounded by a concentric metal shell. The unique structure with a cavity element provides hybrid plasmonic resonances coupling between frustum‐like mode and void‐like surface plasmon (SP) mode, leading to a greatly enhanced SP energy, which largely improves plasmonic sensing and surface enhanced Raman scattering performance. Moreover, the existence of hybrid modes induces distinct electric field distributions inside and outside the nanocup, allowing the structured film to act as a spatial selective sensor.
Catalytic and Enantioselective Synthesis of Chiral Multisubstituted Tribenzothiepins by Intermolecular Cycloadditions
Authors: Tahara Yu‐ki , Matsubara Riku , Mitake Akihito , Sato Tatsuki , Kanyiva Kyalo Stephen , Shibata Takanori
Published: March 2016

The first catalytic and highly enantioselective synthesis of tribenzothiepin derivatives was achieved. Two types of intermolecular cycloadditions using either diphenyl‐sulfide‐tethered diynes or 2‐phenyl sulfanylbenzene‐tethered diynes with a monoalkyne successfully gave chiral multisubstituted tribenzothiepins in good to excellent ee values under mild conditions. The inversion energy of this saddle‐shaped molecule was calculated by measurement of the racemization rate of chiral tribenzothiepins using the Eyring kinetic equation under heating conditions. The present protocol could also be used to prepare a chiral tribenzoselenepin.
Enantiospecific Alkynylation of Alkylboronic Esters
Authors: Wang Yahui , Noble Adam , Myers Eddie L. , Aggarwal Varinder K.
Published: March 2016

Enantioenriched secondary and tertiary alkyl pinacolboronic esters undergo enantiospecific deborylative alkynylation through a Zweifel‐type alkenylation followed by a 1,2‐elimination reaction. The process involves use of α‐lithio vinyl bromide or vinyl carbamate species, for which application to Zweifel‐type reactions has not previously been explored. The resulting functionalized 1,1‐disubstituted alkenes undergo facile base‐mediated elimination to generate terminal alkyne products in high yield and excellent levels of enantiospecificity over a wide range of pinacolboronic ester substrates. Furthermore, along with terminal alkynes, internal and silyl‐protected alkynes can be formed by simply introducing a suitable carbon‐ or silicon‐based electrophile after the base‐mediated 1,2‐elimination reaction.
A Tissue‐Penetrating Double Network Restores the Mechanical Properties of Degenerated Articular Cartilage
Authors: Cooper Benjamin G. , Stewart Rachel C. , Burstein Deborah , Snyder Brian D. , Grinstaff Mark W.
Published: March 2016

Incorporation of an interpenetrating polymer network into an existing single polymer network enables augmentation of the original substrate's mechanical properties, and translation of this concept from purely synthetic materials to natural–synthetic hybrid systems provides the opportunity to reinforce mechanical properties of bulk biological substrates. In many disease states, the mechanical properties of bodily tissues deteriorate rendering them prone to further material failure. Herein, a tissue‐supplementing technique is described in which an interpenetrating biomimetic hydrogel is polymerized in situ throughout cartilage tissue. The treatment restores the inferior compressive properties of osteoarthritic cartilage to that of healthy cartilage, preferentially localizing to weaker regions of tissue. Furthermore, the treatment technique preserves cartilage under harsh articulation conditions, showing promise as a materials‐based treatment for early‐stage osteoarthritis.
Rhodium‐Catalyzed Synthesis of 4‐Bromo‐1,2‐dihydroisoquinolines: Access to Bromonium Ylides by the Intramolecular Reaction of a Benzyl Bromide and an α‐Imino Carbene
Authors: He Jun , Shi Yinping , Cheng Wanli , Man Zengming , Yang Dongdong , Li Chuan‐Ying
Published: March 2016

Highly functionalized 4‐bromo‐1,2‐dihydroisoquinolines were synthesized from readily available 4‐(2‐(bromomethyl)phenyl)‐1‐sulfonyl‐1,2,3‐triazoles. A bromonium ylide is proposed as the key intermediate, which can be formed by the intramolecular nucleophilic attack of the benzyl bromide on the α‐imino rhodium carbene formed in the presence of the rhodium catalyst.
Chemoselective Reduction of Tertiary Amides under Thermal Control: Formation of either Aldehydes or Amines
Authors: Tinnis Fredrik , Volkov Alexey , Slagbrand Tove , Adolfsson Hans
Published: March 2016

The chemoselective reduction of amides in the presence of other more reactive reducible functional groups is a highly challenging transformation, and successful examples thereof are most valuable in synthetic organic chemistry. Only a limited number of systems have demonstrated the chemoselective reduction of amides over ketones. Until now, the aldehyde functionality has not been shown to be compatible in any catalytic reduction protocol. Described herein is a [Mo(CO)6]‐catalyzed protocol with an unprecedented chemoselectivity and allows for the reduction of amides in the presence of aldehydes and imines. Furthermore, the system proved to be tunable by variation of the temperature, which enabled for either C−O or C−N bond cleavage that ultimately led to the isolation of both amines and aldehydes, respectively, in high chemical yields.
Nanostructured star‐shaped polythiophene with tannic acid core: Synthesis, characterization, and its physicochemical properties
Authors: Massoumi Bakhshali , Jaymand Mehdi
Published: March 2016

For the first time, synthesis and characterization of a nanostructured star‐shaped polythiophene (PTh) with tannic acid core by both chemical and electrochemical oxidation polymerization methods through a “core‐first” method is reported. The chemical structures of all samples as representatives were characterized by means of Fourier transform infrared (FTIR), and1H nuclear magnetic resonance (NMR) spectroscopies. The electroactivity behaviors of the synthesized samples were verified under cyclic voltammetric conditions, and their conductivities were determined using the four‐probe technique. The synthesized star‐shaped PTh showed higher electrical conductivity and electroactivity than those of the PTh in both chemical and electrochemical polymerized samples, due to its large surface area, spherical, and three‐dimensional structure. Moreover, the thermal behaviors, optical properties, and morphologies of the synthesized samples were investigated by means of thermogravimetric analysis (TGA), ultraviolet–visible (UV–Vis) spectroscopy, and field emission scanning electron microscopy (FE‐SEM), respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43513.
Factors motivating, demotivating, or impeding information seeking and use by people with type 2 diabetes: A call to work toward preventing, identifying, and addressing incognizance
Authors: St. Jean Beth
Published: March 2016

Type 2 diabetes has grown increasingly prevalent over recent decades, now affecting nearly 400 million people worldwide; however, nearly half of these individuals have no idea they have it. Consumer health information behavior (CHIB), which encompasses people's health‐related information needs as well as the ways in which they interact (or do not interact) with health‐related information, plays an important role in people's ability to prevent, cope with, and successfully manage a serious chronic disease across time. In this mixed‐method longitudinal study, the CHIB of 34 people with type 2 diabetes is explored with the goal of identifying the factors that motivate, demotivate, or impede their diabetes‐related information seeking and use. The findings reveal that while these processes can be motivated by many different factors and can lead to important benefits, there are significant barriers (such as “incognizance,” defined herein as having an information need that one is not aware of) that may demotivate or impede their information seeking and use. The implications of these findings are discussed, focusing on how we might work toward preventing, identifying, and addressing incognizance among this population, ensuring they have the information they need when it can be of the most use to them.
Prevalence, characteristics, and survival of children with esophageal atresia: A 32‐year population‐based study including 1,417,724 consecutive newborns
Authors: Cassina Matteo , Ruol Michele , Pertile Riccardo , Midrio Paola , Piffer Silvano , Vicenzi Virginia , Saugo Mario , Stocco Carmen Fiorella , Gamba Piergiorgio , Clementi Maurizio
Published: March 2016

Background

Esophageal atresia (EA) is a congenital malformation of the upper gastrointestinal tract with an estimated prevalence varying from 1 in 2500 to 1 in 4500 births. The aim of this study was to describe the epidemiology of EA between 1981 and 2012 and evaluate patients' survival.

Methods

This study used data from a population‐based Italian Congenital Malformation Registry. The survival status was ascertained by linking the registry records, vital records and the regional registries of patients. Kaplan‐Meier methods were used to estimate survival probabilities up to 25 years and Cox proportional hazards regression was used to evaluate factors that affected survival.

Results

A total of 407 cases of EA were identified among 1,417,724 total births. After the exclusion of cases with chromosomal anomalies, 49.9% of the patients presented with at least one associated congenital anomaly. The 25‐year survival probability was 85.1% (95% confidence interval [CI], 80.8–89.4), with most deaths occurring during the first months of life. Patients' characteristics associated with decreased survival probability were low birth weight (hazard ratio, 3.7; 95% CI, 1.7–8.3) and presence of additional major defects (hazard ratio, 2.8; 95% CI, 1.3–6.0). A significant improvement in survival over the decades was observed for patients with nonisolated EA.

Conclusion

This study detected a significant improvement in survival of individuals with EA over the past decades and identified the strongest predictors of mortality. These results will be important for the planning of the clinical management and formulation of prognosis when EA is diagnosed in a newborn. Birth Defects Research (Part A) 106:542–548, 2016. © 2016 Wiley Periodicals, Inc.
Impact of multimodal therapy in locally recurrent rectal cancer
Authors: You Y N , Skibber J M , Hu C-Y , Crane C H , Das P , Kopetz E S , Eng C , Feig B W , Rodriguez-Bigas M A , Chang G J
Published: March 2016

Background

The practice of salvaging recurrent rectal cancer has evolved. The aim of this study was to define the evolving salvage potential over time among patients with locally recurrent disease, and to identify durable determinants of long-term success.

Methods

The study included consecutive patients with recurrent rectal cancer undergoing multimodal salvage with curative intent between 1988 and 2012. Predictors of long-term survival were defined by Cox regression analysis and compared over time. Re-recurrence and subsequent treatments were evaluated.

Results

After multidisciplinary evaluation of 229 patients, salvage therapy with curative intent included preoperative chemotherapy and/or radiotherapy (73·4 per cent; with 41·3 per cent undergoing repeat pelvic irradiation), surgical salvage resection with or without intraoperative irradiation (36·2 per cent), followed by postoperative adjuvant chemotherapy (38·0 per cent). Multivisceral resection was undertaken in 47·2 per cent and bone resection in 29·7 per cent. The R0 resection rate was 80·3 per cent. After a median follow-up of 56·5 months, the 5-year overall survival rate was 50 per cent in 2005–2012, markedly increased from 32 per cent in 1988–1996 (P = 0·044). Long-term success was associated with R0 resection (P = 0·017) and lack of secondary failure (P = 0·003). Some 125 patients (54·6 per cent) developed further recurrence at a median of 19·4 months after salvage surgery. Repeat operative rescue was feasible in 21 of 48 patients with local re-recurrence alone and in 17 of 77 with distant re-recurrence, with a median survival of 19·8 months after further recurrence.

Conclusion

The long-term salvage potential for recurrent rectal cancer improved significantly over time, with the introduction of an individualized treatment algorithm of multimodal treatments and surgical salvage. Durable predictors of long-term success were R0 resection at salvage operation, avoidance of secondary failure, and feasibility of repeat rescue after re-recurrence.
Outcome of hypocalcaemia after thyroidectomy treated only in symptomatic patients
Authors: Järhult J , Landerholm K
Published: March 2016

Background

Calcium supplementation has been proposed after bilateral thyroid surgery, either to all patients or to those with biochemical hypocalcaemia. It has also been suggested that supplementation aids parathyroid recovery and prevents permanent hypoparathyroidism. This single-centre study investigated the feasibility of a restrictive management of post-thyroidectomy hypocalcaemia.

Methods

Serum calcium was checked before surgery, on postoperative day 1 (POD) 1, at a follow-up visit 6–8 weeks after surgery and after a minimum of 12 months in all patients. Regardless of serum calcium levels, patients with symptoms of hypocalcaemia were prescribed oral calcium supplementation (0·5–1·0 g twice daily) and asymptomatic patients were not. Asymptomatic patients were informed about hypocalcaemic symptoms and instructed to contact the surgical ward should symptoms appear.

Results

Some 640 patients underwent bilateral thyroid surgery without previous or intentional simultaneous parathyroidectomy. A subnormal serum calcium level (below 2·15 mmol/l) was observed in 412 patients (64·4 per cent) on POD 1. By comparison, only 63 patients (9·8 per cent) experienced symptoms of hypocalcaemia in the postoperative period, all but one with a corresponding biochemical hypocalcaemia on POD 1. Calcium levels in all patients with asymptomatic postoperative hypocalcaemia recovered to normal without supplementation. Serum calcium was also normalized during follow-up in all symptomatic patients, except 22 (3·4 per cent) who became permanently hypoparathyroid. No patient without early hypocalcaemic symptoms developed permanent hypoparathyroidism.

Conclusion

The proposed restrictive management of postoperative hypocalcaemia after bilateral thyroid surgery avoids unnecessary supplementation for most patients.
A transient awakening of a patient with Alzheimer's disease that questions our practice
Authors: Bloch Frédéric
Published: March 2016

Key Clinical Message

Improvements are not usually described in the natural history of degenerative dementia. It seems possible to find the normal workings of impaired learning and lost long‐term memories that appeared to be permanently altered after severe neurodegeneration and synaptic loss. The activation of these programs seems to represent the basis of the dysfunction, rather than the program itself.
Olmesartan‐induced enteropathy associated with cutaneous lesions
Authors: Hammoudi Nassim , Dior Marie , Giraud Vincent , Coffin Benoit
Published: March 2016

Key Clinical Message

Olmesartan is an angiotensin II receptor antagonist which may cause severe sprue‐like enteropathy with duodenal villous atrophy. Skin lesions may be associated as reported for the first time in our case. Clinicians should be informed of this side effect and its reversibility after suspension of the drug.
Synthesis and Characterization of New Conjugated Fluorenyl‐Porphyrin Dendrimers for Optics
Authors: Yao Dandan , Zhang Xu , Mongin Olivier , Paul Frédéric , Paul‐Roth Christine O.
Published: March 2016

A new family of conjugated meso‐tetraphenylporphyrin‐based dendrimers with four (TPP1, TPP2), eight (TPP3, TPP4, TPP5) and up to sixteen (TPP6) fluorenyl groups has been synthesized and fully characterized. These tetraphenylporphyrin‐cored dendrimers present peripheral alkynyl π‐conjugated dendrons with fluorenyl termini. The meso‐aryl rings of these porphyrins are functionalized either in para‐ (TPP1, TPP2, and TPP3) or meta‐positions (TPP4, TPP5, and TPP6). Their detailed luminescence properties are discussed in reference to two porphyrins lacking fluorenyl dendrons (TPP‐H1,2,3 and TPP‐H4,5,6). A strong dependence of their luminescence quantum yield and lifetime on their structures is stated, their nonlinear optical properties were also discussed.
Rhodium(II)‐Catalyzed and Thermally Induced Intramolecular Migration of N‐Sulfonyl‐1,2,3‐triazoles: New Approaches to 1,2‐Dihydroisoquinolines and 1‐Indanones
Authors: Sun Run , Jiang Yu , Tang Xiang‐Ying , Shi Min
Published: March 2016

New rhodium(II)‐catalyzed or thermally induced intramolecular alkoxy group migration of N‐sulfonyl‐1,2,3‐triazoles has been developed, affording divergent synthesis of 1,2‐dihydroisoquinoline and 1‐indanone derivatives according to different conditions. N‐Sulfonyl keteneimine is the key intermediate for the synthesis of dihydroisoquinoline, whereas the aza‐vinyl carbene intermediate results in the formation of 1‐indanone.
Spontaneous Double Hydrometallation Induced by N→M Coordination in Organometallic Hydrides of Group 14 Elements
Authors: Novák Miroslav , Dostál Libor , Turek Jan , Alonso Mercedes , De Proft Frank , Růžička Aleš , Jambor Roman
Published: March 2016

Our attempts to synthesise N→M intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si (4), Ge (5), Sn (6)] containing the CH=N imine group (in which L is C,N‐chelating ligand {2‐[(2,6‐iPr2C6H3)N=CH]C6H4}−) yielded 1,1′‐bis(2,6‐diisopropylphenyl)‐2,2′‐spriobi[benzo[c][1,2]azasilole] (7), 1,1′‐bis(2,6‐diisopropylphenyl)‐2,2′‐spriobi[benzo[c][1,2]azagermole] (8) and C,N‐chelated homoleptic stannylene L2Sn (10), respectively. Compounds 7 and 8 are an outcome of a spontaneous double hydrometallation of the two CH=N imine moieties induced by N→M intramolecular coordination (M=Si, Ge) in the absence of any catalyst. In contrast, the diorganotin hydride L2SnH2 (6) is redox‐unstable and the reduction of the tin centre with the elimination of H2 provided the C,N‐chelated homoleptic stannylene L2Sn (10). Compounds 7 and 8 were characterised by NMR spectroscopy and X‐ray diffraction analysis. Because the proposed N→M intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si (4), Ge (5), Sn (6)] revealed two different types of reduction reactions, DFT calculations were performed to gain an insight into the structures and bonding of the non‐isolable diorganometallic hydrides as well as the products of their subsequent reactions. Furthermore, the thermodynamic profiles of the different reaction pathways with respect to the central metal atom were also investigated.
Expansion of the Concept of Nonlinear Effects in Catalytic Reactions Beyond Asymmetric Catalysis
Authors: Pollice Robert , Schnürch Michael
Published: March 2016

The observation and investigation of nonlinear effects in catalytic reactions provides valuable mechanistic insight. However, the applicability of this method was, until now, limited to molecules possessing chirality and therefore to asymmetric synthesis. The concept of nonlinear effects is expanded to catalytic reactions beyond asymmetric catalysis by using derivatives instead of enantiomers and by considering rates instead of enantiomeric excess. Additionally, its systematic application to investigate the mechanism of catalytic reactions is presented. By exceeding the limitation to asymmetric reactions, the study of nonlinear effects can become a general tool to elucidate reaction mechanisms.
The Double‐Bond Configuration of Corynanthean Alkaloids and Its Impact on Monoterpenoid Indole Alkaloid Biosynthesis
Authors: Eckermann Ruben , Gaich Tanja
Published: March 2016

Experimental evidence is provided for the coherence of the double‐bond geometry and the occurrence of “secondary cyclizations” in the biosynthesis of monoterpenoid indole alkaloids. Biosynthetically, akuammiline, C‐mavacurine, and Strychnos alkaloids are proposed to be derived from the corynanthean alkaloid geissoschizine, a key intermediate in the biosynthetic pathway of these monoterpenoid indole alkaloids. This process occurs by so‐called “secondary cyclizations” from geissoschizine or its derivatives. Although corynanthean alkaloids like geissoschizine incorporate E or Z double bonds located at C19–C20, the alkaloids downstream in the biosynthesis exclusively exhibit the E double bond. This study shows that secondary cyclizations preferentially occur with the E isomer of geissoschizine or its derivatives. This is attributed to the flexibility of the quinolizidine system of the corynanthean alkaloids, which can adopt a cis or trans conformation. For the secondary cyclization to take place, the cis‐quinolizidine conformation is required. Experimental evidence supports the hypothesis that the E double bond of geissoschizine induces the cis conformation, whereas the Z double bond induces the trans conformation, which prohibits secondary cyclization of the Z compounds.
Enhancing Metal–Support Interactions by Molybdenum Carbide: An Efficient Strategy toward the Chemoselective Hydrogenation of α,β‐Unsaturated Aldehydes
Authors: He Sina , Shao Zheng‐Jiang , Shu Yijin , Shi Zhangping , Cao Xiao‐Ming , Gao Qingsheng , Hu Peijun , Tang Yi
Published: March 2016

Metal–support interactions are desired to optimize the catalytic turnover on metals. Herein, the enhanced interactions by using a Mo2C nanowires support were utilized to modify the charge density of an Ir surface, accomplishing the selective hydrogenation of α,β‐unsaturated aldehydes on negatively charged Irδ− species. The combined experimental and theoretical investigations showed that the Irδ− species derive from the higher work function of Ir (vs. Mo2C) and the consequently electron transfer. In crotonaldehyde hydrogenation, Ir/Mo2C delivered a crotyl alcohol selectivity as high as 80 %, outperforming those of counterparts (<30 %) on silica. Moreover, such electronic metal–support interactions were also confirmed for Pt and Au, as compared with which, Ir/Mo2C was highlighted by its higher selectivity as well as the better activity. Additionally, the efficacy for various substrates further verified our Ir/Mo2C system to be competitive for chemoselective hydrogenation.
Spatially Directional Resorcin[4]arene Cavitand Glycoconjugates for Organic Catalysis
Authors: Husain Ali A. , Maknenko Arthur M. , Bisht Kirpal S.
Published: March 2016

The synthesis of novel spatially directional multivalent resorcin[4]arene cavitand glycoconjugates (RCGs) and their ability to catalyze organic reactions is reported. The β‐d‐glucopyranoside moieties on the upper rim of the “bowl”‐shaped resorcin[4]arene cavitand core are capable of multiple hydrogen‐bond interactions resulting in a pseudo‐cavity, which has been investigated for organic transformations in aqueous media. The RCGs have been demonstrated to catalyze thiazole formation, thiocyanation, copper(I)‐catalyzed azide alkyne cycloaddition (CuAAC), and Mannich reactions; they impart stereoselectivity in the three‐component Mannich reaction. Thermodynamic values obtained from 1H diffusion‐ordered spectroscopy (DOSY) experiments suggest that the upper saccharide cavity of the RCG and not the resorcin[4]arene cavity is the site of the complexation event.
A Convenient Palladium‐Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid
Authors: Qi Xinxin , Li Chong‐Liang , Wu Xiao‐Feng
Published: March 2016

Palladium‐catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium‐catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source.
Catalytic Asymmetric Prins Bicyclization for the endo‐Selective Formation of 2,6‐dioxabicyclo[2.2.2]octanes
Authors: Liu Jie , Zhou Lijun , Wang Chao , Liang Demin , Li Zhiming , Zou Yue , Wang Quanrui , Goeke Andreas
Published: March 2016

A new Lewis acid‐catalyzed endo‐selective Prins bicyclization of γ,δ‐unsaturated aldehydes or ketones with a broad range of aldehydes to dioxabicyclo[2.2.2]octanes is disclosed. When using a chiral BINOL‐derived N‐triflylphosphoramide (NTPA) as catalyst and glyoxylate esters as substrates, the cross‐dimerization afford functionalized bicyclic acetals with excellent diastereo‐ and enantioselectivities.
Hydrierung von Diethylsuccinat zu γ‐Butyrolacton, 1,4‐Butandiol und Tetrahydrofuran
Authors: Stein Jürgen , Kabasci Stephan
Published: March 2016

Die Verknappung der fossilen Ressourcen erfordert die Suche nach alternativen Edukten für die Produktion von wichtigen Grundchemikalien. Diethylsuccinat auf Basis von biobasierter Bernsteinsäure kann als erneuerbare Alternative zu fossilen Rohstoffen für die Herstellung von γ‐Butyrolacton, 1,4‐Butandiol und Tetrahydrofuran eingesetzt werden. Kommerziell erhältliche ZnO‐freie Kupferkatalysatoren in einem Festbettreaktor zeigen eine vielversprechende Selektivität zu C4‐Produkten, wobei 1,4‐Butandiol an sauren Katalysatorbestandteilen wie Aluminium‐ und Zirconiumoxid zu Tetrahydrofuran dehydratisiert wird.