bluuebunny/crossref_metadata_2025 huggingface dataset:
Atenção domiciliar na atenção primária à saúde: uma síntese operacional
Authors: Gallassi Caio Vaciski , Ramos Daniel Felipe Herculano , Kinjo Juliana Yumi , Souto Bernardino Geraldo Alves
Published: February 2015

A institucionalização do sujeito adoecido privilegiou o modelo médico científico e subordinou a autonomia da família no cuidado à pessoa com necessidades de saúde ao hospital e ao saber médico. No entanto, esse modelo tem se mostrado pouco eficiente para o atendimento das demandas de saúde resultantes da transição demográfica e epidemiológica pelas quais a sociedade vem passando. Nesse contexto, a atenção domiciliar surge como alternativa ao cuidado hospitalar, possibilitando a retomada do lar como espaço para produção de cuidado, fundamentada nos princípios da humanização e da clínica ampliada, evitando hospitalizações desnecessárias e possibilitando um uso mais adequado dos recursos disponíveis. Esta revisão narrativa da literatura aborda o cuidado domiciliar no contexto da atenção básica de saúde. Contemplam suas definições, princípios, objetivos, aspectos organizacionais, elegibilidade de sujeitos para o cuidado domiciliar, classificação de risco familiar, função de cada membro da equipe de saúde da família, construção de tecnologias de cuidado e o desenvolvimento de um eficiente sistema de registro de dados.
Compulsão alimentar e obesidade no climatério: uma revisão de literatura
Authors: Conte Franciéli Aline , Franz Lígia Beatriz Bento , Idalêncio Vanessa Huber
Published: February 2015

O climatério é uma fase de mudanças distintas na vida das mulheres caracterizada principalmente pelo hipoestrogenismo, por muitas mudanças fisiológicas e sintomas diversos. Devido à importante relevância desse tema à sociedade, buscou-se abordar a relação entre a compulsão alimentar e a obesidade no climatério. Foi realizada uma revisão de literatura por meio de busca científica de meio eletrônico e livros, a partir do ano de 2003, nas fontes de dados: Scientific Electronic Library Online (SciELO), Biblioteca Regional de Medicina (BIREME), Literatura Latino-Americana em Ciências da Saúde (LILACS) e Google Acadêmico. O sobrepeso e a obesidade são mais prevalentes no climatério, sendo a alimentação e o estilo de vida diretamente ligados a esses fatores. A ansiedade e o estresse podem dar origem a um problema muito comum e que repercute diretamente na alimentação e na não adesão às intervenções nutricionais: a compulsão por alimentos, conhecida como transtorno da compulsão alimentar periódica (TCAP). O climatério provoca o aumento da ansiedade e labilidade emocional pelo hipoestrogenismo, e o alívio da ansiedade ou estresse se dá, na maioria das vezes, pelo consumo de comida, o que favorece a obesidade e o aparecimento do TCAP.
Errata - ABCShs v. 39, n. 2 (2014)
Authors: Congresso Médico Universitário do ABC COMUABC
Published: February 2015

Correção dos resumos EPI-09, RCI-21 e RCI-25 dos Anais do 39º COMUABC, publicados no volume 39 número 2 da ABCS Health Sciences.
Caracterización de la comunidad de mamíferos de un área remota del sur de Chile mediante el uso combinado de metodologías
Authors: Delibes-Mateos Miguel , Díaz-Ruiz Francisco , Caro Jesús , Ferreras Pablo
Published: February 2015

The presence and distribution of mammals in remote areas are currently poorly known, although these areas are usually rich in biodiversity. The main objective of this study was to characterize the terrestrial mammal community within the reserve of Huinay, southern Chile, using three methodologies: i) questionnaires to residents and visitors to the area (n=42); ii) transects of mammals’ presence (scats, tracks, etc; the total length of transects was 80 km); iii) camera-trapping (18 camera-traps were set with a total sampling effort of 590 trap-days). A total of 13 species of mammals were identified, and only three of them (pudu, Pudu puda, kodkod, Leopardus guigna and lesser grison, Galictis cuja) were recorded with all the methods employed. Our results suggest that different methodologies can complement each other for surveying species presence and distribution in remote areas.
Distribución de la musaraña canaria (Crocidura canariensis) en Fuerteventura, Islas Canarias
Authors: Schuster Claudia
Published: February 2015

The only endemic non-flying land mammal of the Canary Archipelago, the Canary Shrew, inhabits the two easternmost islands Lanzarote and Fuerteventura, and nearby islets. Based on the poor data available, this study aimed to add knowledge about its distribution using pitfall live-traps, as well as searches for remains in pellets of avian predators, and dead shrews in discarded bottles. In addition, population fluctuations were attempted to register by frequent pitfall live-trapping in three places. Prospection ran from December 2012 to April 2013, accumulating 900 trap-nights in 22 locations. With a global trapping success of 18,3 individuals/1000 trap-nights, 11 shrews were captured in lava fields and five on a mountain ridge, all quite barren areas. No captures occurred in richer habitats. Pellets of avian predators were very scarce. Searches of discarded bottles gave better results, with dead shrews present in three out of eight visited locations, and individuals encountered afterwards by live-trapping in all three. Shrews were missing in four protected areas formerly occupied by the species, but monitoring should take place regularly to confirm local extinctions and (re)colonizations. To ensure conservation of this endemism, investigations of interactions with alien species are needed, and introduction of vertebrates and invertebrates to the islands should be avoided.
The sheddase ADAM10 is a potent modulator of prion disease
Authors: Altmeppen Hermann C , Prox Johannes , Krasemann Susanne , Puig Berta , Kruszewski Katharina , Dohler Frank , Bernreuther Christian , Hoxha Ana , Linsenmeier Luise , Sikorska Beata , Liberski Pawel P , Bartsch Udo , Saftig Paul , Glatzel Markus
Published: February 2015

The prion protein (PrPC) is highly expressed in the nervous system and critically involved in prion diseases where it misfolds into pathogenic PrPSc. Moreover, it has been suggested as a receptor mediating neurotoxicity in common neurodegenerative proteinopathies such as Alzheimer's disease. PrPC is shed at the plasma membrane by the metalloprotease ADAM10, yet the impact of this on prion disease remains enigmatic. Employing conditional knockout mice, we show that depletion of ADAM10 in forebrain neurons leads to posttranslational increase of PrPC levels. Upon prion infection of these mice, clinical, biochemical, and morphological data reveal that lack of ADAM10 significantly reduces incubation times and increases PrPSc formation. In contrast, spatiotemporal analysis indicates that absence of shedding impairs spread of prion pathology. Our data support a dual role for ADAM10-mediated shedding and highlight the role of proteolytic processing in prion disease.
PRIMELT3 MEGA.XLSM software for primary magma calculation: Peridotite primary magma MgO contents from the liquidus to the solidus
Authors: Herzberg C. , Asimow P. D.
Published: February 2015

An upgrade of the PRIMELT algorithm for calculating primary magma composition is given together with its implementation in PRIMELT3 MEGA.xlsm software. It supersedes PRIMELT2.xls in correcting minor mistakes in melt fraction and computed Ni content of olivine, it identifies residuum mineralogy, and it provides a thorough analysis of uncertainties in mantle potential temperature and olivine liquidus temperature. The uncertainty analysis was made tractable by the computation of olivine liquidus temperatures as functions of pressure and partial melt MgO content between the liquidus and solidus. We present a computed anhydrous peridotite solidus in T‐P space using relations amongst MgO, T and P along the solidus; it compares well with experiments on the solidus. Results of the application of PRIMELT3 to a wide range of basalts shows that the mantle sources of ocean islands and large igneous provinces were hotter than oceanic spreading centers, consistent with earlier studies and expectations of the mantle plume model.
The emergence of volcanic oceanic islands on a slow‐moving plate: The example of Madeira Island, NE Atlantic
Authors: Ramalho Ricardo S. , Brum da Silveira António , Fonseca Paulo E. , Madeira José , Cosca Michael , Cachão Mário , Fonseca Maria M. , Prada Susana N.
Published: February 2015

The transition from seamount to oceanic island typically involves surtseyan volcanism. However, the geological record at many islands in the NE Atlantic—all located within the slow‐moving Nubian plate—does not exhibit evidence for an emergent surtseyan phase but rather an erosive unconformity between the submarine basement and the overlying subaerial shield sequences. This suggests that the transition between seamount and island may frequently occur by a relative fall of sea level through uplift, eustatic changes, or a combination of both, and may not involve summit volcanism. In this study, we explore the consequences for island evolutionary models using Madeira Island (Portugal) as a case study. We have examined the geologic record at Madeira using a combination of detailed fieldwork, biostratigraphy, and
geochronology in order to document the mode, timing, and duration of edifice emergence above sea level. Our study confirms that Madeira's subaerial shield volcano was built upon the eroded remains of an uplifted seamount, with shallow marine sediments found between the two eruptive sequences and presently located at 320–430 m above sea level. This study reveals that Madeira emerged around 7.0–5.6 Ma essentially through an uplift process and before volcanic activity resumed to form the subaerial shield volcano. Basal intrusions are a likely uplift mechanism, and their emplacement is possibly enhanced by the slow motion of the Nubian plate relative to the source of partial melting. Alternating uplift and subsidence episodes suggest that island edifice growth may be governed by competing dominantly volcanic and dominantly intrusive processes.
Observation of the simultaneous transport of Asian mineral dust aerosols with anthropogenic pollutants using a POPC during a long‐lasting dust event in late spring 2014
Authors: Pan Xiaole , Uno Itsushi , Hara Yukari , Kuribayashi Masatoshi , Kobayashi Hiroshi , Sugimoto Nobuo , Yamamoto Shigekazu , Shimohara Takaaki , Wang Zifa
Published: February 2015

We observed a long‐lasting dust event from 25 May to 2 June 2014, using a polarization optical particle counter (POPC). The transport of dust plumes over East Asia was verified on the basis of observations of Moderate Resolution Imaging Spectroradiometer, a lidar network, and surface synoptic observation stations. Mixing of dust and anthropogenic pollutants was investigated according to the variation in the depolarization ratio as a function of particle size. The nonsphericity of dust particles varied due to the impact of anthropogenic pollutants on their pathway. In the coarse mode, dust particles always had a clear nonspherical configuration, although large amounts of nitrate were also present. Supermicron particles are occasionally present in a spherical configuration, possibly due to the complex mixing of natural dust and anthropogenic particles. Statistically, ~64% of the total nitrate mass was deemed to be transported from outside of Japan due to a trapping effect in the dust plume.
Atmospheric initial conditions and the predictability of the Arctic Oscillation
Authors: Stockdale Timothy N. , Molteni Franco , Ferranti Laura
Published: February 2015

The Arctic Oscillation (AO) is the leading mode of variation in the northern hemisphere winter circulation. Despite its importance for winter temperatures, seasonal forecast models typically suggest that its predictability is low. Nonetheless, we show that an operational forecast model has high skill in predicting the AO, with a correlation of 0.61 for the period of 1981–2010. Experimentation covering a recent 8 year high‐skill period demonstrates the predictability of the model AO to be dominated by atmospheric initial conditions, although surface forcing does have increasing influence later in the winter. Results suggest that the stratosphere is an important carrier of model predictability during the early winter. These results challenge the conventional paradigm of surface forcing being the dominant source of predictability on seasonal time scales but are compatible with the results showing stratospheric influence on winter circulation. They also suggest that model representation of stratospheric to tropospheric coupling needs urgent improvement.
Effects of Kuroshio Intrusions on the atmosphere northeast of Taiwan Island
Authors: Chow Chun Hoe , Liu Qinyu , Xie Shang‐Ping
Published: February 2015

The Kuroshio loses bathymetric support off northeast Taiwan Island, causing large variability in its path. The resultant covariability of sea surface temperature (SST) and the lower atmosphere is investigated using satellite observations. In winter and spring off northeast Taiwan Island, the intrusions of warm Kuroshio water onto the continental shelf cause a large increase in local SST, intensify the northeasterly monsoonal winds, and lead to the increases in water vapor and rainfall. Key to this air‐sea interaction is the existence of anomalous heat advection by the Kuroshio intrusions. The Kuroshio intrusions are partly due to westward propagating ocean eddies east of Taiwan Island with a lead time of 3 weeks, hinting at the possibility of improved weather prediction near northeast Taiwan Island by considering ocean variability east of Taiwan Island.
Postmidnight depletion of the high‐energy tail of the quiet plasmasphere
Authors: Sarno‐Smith Lois K. , Liemohn Michael W. , Katus Roxanne M. , Skoug Ruth M. , Larsen Brian A. , Thomsen Michelle F. , Wygant John R. , Moldwin Mark B.
Published: February 2015

The Van Allen Probes Helium Oxygen Proton Electron (HOPE) instrument measures the high‐energy tail of the thermal plasmasphere allowing study of topside ionosphere and inner magnetosphere coupling. We statistically analyze a 22 month period of HOPE data, looking at quiet times with a Kp index of less than 3. We investigate the high‐energy range of the plasmasphere, which consists of ions at energies between 1 and 10 eV and contains approximately 5% of total plasmaspheric density. Both the fluxes and partial plasma densities over this energy range show H+ is depleted the most in the postmidnight sector (1–4 magnetic local time), followed by O+ and then He+. The relative depletion of each species across the postmidnight sector is not ordered by mass, which reveals ionospheric influence. We compare our results with keV energy electron data from HOPE and the Van Allen Probes Electric Fields and Waves instrument spacecraft potential to rule out spacecraft charging. Our conclusion is that the postmidnight ion disappearance is due to diurnal ionospheric temperature variation and charge exchange processes.
Intensities and spatiotemporal variability of equatorial noise emissions observed by the Cluster spacecraft
Authors: Němec F. , Santolík O. , Hrbáčková Z. , Cornilleau‐Wehrlin N.
Published: February 2015

Equatorial noise (EN) emissions are electromagnetic waves observed in the equatorial region of the inner magnetosphere at frequencies between the proton cyclotron frequency and the lower hybrid frequency. We present the analysis of 2229 EN events identified in the Spatio‐Temporal Analysis of Field Fluctuations (STAFF) experiment data of the Cluster spacecraft during the years 2001–2010. EN emissions are distinguished using the polarization analysis, and their intensity is determined based on the evaluation of the Poynting flux rather than on the evaluation of only the electric/magnetic field intensity. The intensity of EN events is analyzed as a function of the frequency, the position of the spacecraft inside/outside the plasmasphere, magnetic local time, and the geomagnetic activity. The emissions have higher frequencies and are more intense in the plasma trough than in the plasmasphere. EN events observed in the plasma trough are most intense close to the local noon, while EN events observed in the plasmasphere are nearly independent on magnetic local time (MLT). The intensity of EN events is enhanced during disturbed periods, both inside the plasmasphere and in the plasma trough. Observations of the same events by several Cluster spacecraft allow us to estimate their spatiotemporal variability. EN emissions observed in the plasmasphere do not change on the analyzed spatial scales (ΔMLT<0.2h, Δr<0.2 RE), but they change significantly on time scales of about an hour. The same appears to be the case also for EN events observed in the plasma trough, although the plasma trough dependencies are less clear.
On the use of drift echoes to characterize on‐orbit sensor discrepancies
Authors: O'Brien T. P. , Claudepierre S. G. , Looper M. D. , Blake J. B. , Fennell J. F. , Clemmons J. H. , Roeder J. L. , Kanekal S. G. , Manweiler J. W. , Mitchell D. G. , Gkioulidou M. , Lanzerotti L. J. , Spence H. E. , Reeves G. D. , Baker D. N.
Published: February 2015

We describe a method for using drift echo signatures in on‐orbit data to resolve discrepancies between different measurements of particle flux. The drift period has a well‐defined energy dependence, which gives rise to time dispersion of the echoes. The dispersion can then be used to determine the effective energy for one or more channels given each channel's drift period and the known energy for a reference channel. We demonstrate this technique on multiple instruments from the Van Allen Probes mission. Drift echoes are only easily observed at high energies (100 s keV to multiple MeV), where several drift periods occur before the observing satellite has moved on or the global magnetic conditions have changed. We describe a first‐order correction for spacecraft motion. The drift echo technique has provided a significant clue in resolving substantial flux discrepancies between two instruments measuring fluxes near 2 MeV.
Two‐phase dynamics of volcanic eruptions: Particle size distribution and the conditions for choking
Authors: Yarushina Viktoriya M. , Bercovici David , Michaut Chloé
Published: February 2015

Explosive volcanic eruptions are studied using a two‐phase model of polydisperse suspensions of solid particles in gas. Eruption velocities depend on choking conditions in the volcanic conduit, which depend on acoustic wave propagation that is, in turn, influenced by the particle size distribution in the two‐phase mixture. The acoustic wave spectrum is divided into three regions of superfast short waves moving at the pure gas sound speed, purely attenuated domain at intermediate wavelengths, and slower long waves for a dusty pseudogas. The addition of solid phases with differing particle sizes qualitatively preserves the features of two‐phase acoustic wave dispersion, although it narrows the regions of short‐fast and intermediate‐blocked waves. Choking conditions, however, strongly depend on the number and size distribution of solid phases. Changes in particle sizes lead to variations in the choking conditions, which determine the eruption velocities and the resulting height of the erupting column. Smaller particles always exit the choking point faster than big particles, as expected. Even though particle‐particle interaction is neglected, the particle distributions influence each other by momentum exchange through the gas. Therefore, the structure of the dispersion relation as well as the eruption or choking velocities and subsequent column height and particle deposition bear information on how eruption dynamics are controlled by size distribution and relative volume fractions of small and big particles. We suggest that unimodal distributions, with one dominant small particle size, favor development of vertical plinian eruptions, while bimodal distributions, with a comparable mean size, lead to pyroclastic lateral flows.
Nodal variations and long‐term changes in the main tides on the coasts of China
Authors: Feng Xiangbo , Tsimplis Michael N. , Woodworth Philip L.
Published: February 2015

The long‐term changes in the main tidal constituents (O1, K1, M2, N2, and S2) along the coasts of China and in adjacent seas are investigated based on 17 tide‐gauge records covering the period 1954–2012. The observed 18.61 year nodal modulations of the diurnal constituents O1 and K1 are in agreement with the equilibrium tidal theory, except in the South China Sea. The observed modulations of the M2 and N2 amplitudes are smaller than theoretically predicted at the northern stations and larger at the southern stations. The discrepancies between the theoretically predicted nodal variations and the observations are discussed. The 8.85 year perigean cycle is identifiable in the N2 parameters at most stations, except those in the South China Sea. The radiational component of S2 contributes on average 16% of the observed S2 except in the Gulf of Tonkin, on the south coast, where it accounts for up to 65%. We confirmed the existence of nodal modulation in S2, which is stronger on the north coast. The semidiurnal tidal parameters show significant secular trends in the Bohai and Yellow Seas, on the north coast, and in the Taiwan Strait. The largest increase is found for M2 for which the amplitude increases by 4–7 mm/yr in the Yellow Sea. The potential causes for the linear trends in tidal constants are discussed.
Using single‐scattering albedo spectral curvature to characterize East Asian aerosol mixtures
Authors: Li Jing , Carlson Barbara E. , Lacis Andrew A.
Published: February 2015

Spectral dependence of aerosol single‐scattering albedo (SSA) has been used to infer aerosol composition. In particular, aerosol mixtures dominated by dust absorption will have monotonically increasing SSA with wavelength while that dominated by black carbon absorption has monotonically decreasing SSA spectra. However, by analyzing SSA measured at four wavelengths, 440, 675, 870, and 1020 nm from the Aerosol Robotic Network data set, we find that the SSA spectra over East Asia are frequently peaked at 675 nm. In these cases, we suggest that SSA spectral curvature, defined as the negative of the second derivative of SSA as a function of wavelength, can provide additional information on the composition of these aerosol mixtures. Aerosol SSA spectral curvatures for East Asia during fall and winter are considerably larger than those found in places primarily dominated by biomass burning or dust aerosols. SSA curvature is found to increase as the SSA magnitude decreases. The curvature increases with coarse mode fraction (CMF) to a CMF value of about 0.4, then slightly decreases or remains constant at larger CMF. Mie calculations further verify that the strongest SSA curvature occurs at ~40% dust fraction, with 10% scattering aerosol fraction. The nonmonotonic SSA spectral dependence is likely associated with enhanced absorption in the shortwave by dust, absorption by black carbon at longer wavelengths, and also the flattened absorption optical depth spectral dependence due to the increased particle size.
Advanced Micro‐Lattice Materials
Authors: Xiong Jian , Mines Robert , Ghosh Ranajay , Vaziri Ashkan , Ma Li , Ohrndorf Arne , Christ Hans‐Jürgen , Wu Linzhi
Published: February 2015

Topological management of materials at a Micro‐scale is one of the fundamental building principles of nature. This combination of material and structural properties results in marked changes in the properties of solids. Nowadays physicists, chemists, materials scientists and engineers explore those effects by synthesizing, characterizing, and modeling Micro‐lattice materials from all material classes. Applications have been identified in the fields of ultra‐lightweight structures, thermal equipment, electrochemical devices, high absorption capacity and bio‐repair materials. This article aims to review recent progress in the development of such advanced Micro‐lattice materials.
Ambient Layer‐by‐Layer ZnO Assembly for Highly Efficient Polymer Bulk Heterojunction Solar Cells
Authors: Eita Mohamed , Labban Abdulrahman El , Cruciani Federico , Usman Anwar , Beaujuge Pierre M. , Mohammed Omar F.
Published: February 2015

The use of metal oxide interlayers in polymer solar cells has great potential because metal oxides are abundant, thermally stable, and can be used in flexible devices. Here, a layer‐by‐layer (LbL) protocol is reported as a facile, room‐temperature, solution‐processed method to prepare electron transport layers from commercial ZnO nanoparticles and polyacrylic acid (PAA) with a controlled and tunable porous structure, which provides large interfacial contacts with the active layer. Applying the LbL approach to bulk heterojunction polymer solar cells with an optimized ZnO layer thickness of ≈25 nm yields solar cell power‐conversion efficiencies (PCEs) of ≈6%, exceeding the efficiency of amorphous ZnO interlayers formed by conventional sputtering methods. Interestingly, annealing the ZnO/PAA interlayers in nitrogen and air environments in the range of 60–300 °C reduces the device PCEs by almost 20% to 50%, indicating the importance of conformational changes inherent to the PAA polymer in the LbL‐deposited films to solar cell performance. This protocol suggests a new fabrication method for solution‐processed polymer solar cell devices that does not require postprocessing thermal annealing treatments and that is applicable to flexible devices printed on plastic substrates.
Building Biomedical Materials using Photochemical Bond Cleavage
Authors: Bao Chunyan , Zhu Linyong , Lin Qiuning , Tian He
Published: February 2015

Light can be used as an external trigger to precisely determine where and when a process is initiated as well as how much of the process is being consumed. Phototriggers are a type of photoresponsive functional group that undergo an irreversible photolysis reaction by selectively breaking a chemical bond, enabling three fundamental functions: the photoactivation of fluorescent and bioactive molecules; the photocleavable degradation of macromolecular materials; and the photorelease of drugs, active groups, or surface charges from carriers and interfaces. With the expanded applications of light‐controlled technology, particularly in living systems, new challenges and improvements of phototriggers are required to fulfill the demands for better sensitivity, faster kinetics, and more‐demanding biomedical applications. Here, improvements to several conventional phototriggers are highlighted, and their notable, representative biomedical applications and their challenges are discussed.
Electrochemical Approach to Copper‐Catalyzed Reversed Atom Transfer Radical Cyclization
Authors: Isse Abdirisak A. , Visonà Giulia , Ghelfi Franco , Roncaglia Fabrizio , Gennaro Armando
Published: February 2015

Electrochemically mediated atom transfer radical cyclization (eATRC) has been developed as an easy and clean method allowing the synthesis of halogenated cyclic compounds. This method has been successfully applied to the copper‐catalyzed atom transfer radical cyclization of some N‐allyl‐α,α‐dichloroamides in acetonitrile (CH3CN) using a copper complex with tris(2‐pyridylmethyl)amine (TPMA) with a metal loading of 1%. The catalyst is introduced as [Cu(II)TPMA]2+ and is activated and continuously regenerated to its active copper(I) form by reduction at a platinum (Pt) electrode. During the ATRC process a new copper(II) complex, namely, [ClCu(II)TPMA]+, whose reduction potential is ca. 0.350 V more negative than that of the starting [Cu(II)TPMA]2+, is formed. Therefore, the choice of the applied potential is critical and should be done taking care that all copper(II) species are reduced to copper(I). The compounds undergo very high conversions (79–100%) in a few hours of electrolysis, producing a cyclic γ‐lactam (yield 60–98%) as a mixture of two isomers, with a good cis‐diastereoselectivity [dr (cis/trans)=59/41–83/17]. [Cu(II)PMDETA]2+ (PMDETA=N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine), which is much cheaper, albeit less reactive than [Cu(II)TPMA]2+, was also investigated but the results were not satisfactory.

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Gold‐Catalyzed Carbenoid Transfer Reactions of Diynes – Pinacol Rearrangement versus Retro‐Buchner Reaction
Authors: Lauterbach Tobias , Higuchi Takafumi , Hussong Matthias W. , Rudolph Matthias , Rominger Frank , Mashima Kazushi , Hashmi A. Stephen K.
Published: February 2015

Aromatic diyne systems bearing one terminal propargylic acetate moiety and one tertiary propargylic alcohol subunit were converted in the presence of a gold catalyst. After an initial 1,2‐migration of the acetoxy group at the terminal alkyne, a gold carbenoid is formed which is then transferred onto the internal alkyne of the propargylic alcohol. This combination enables the use of propargylic acetates as precursors for a gold‐catalyzed pinacol‐type rearrangement. In the final pinacol‐like step the shift of an alkyl or aryl moiety onto an electrophilic gold carbenoid/cation terminates the reaction and 1‐naphthyl ketones are obtained as products. If electron‐rich aromatic backbones are used, a mechanistically interesting alternative pathway including a retro‐Buchner reaction is opened.

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The addition of dexamethasone to bortezomib for patients with relapsed multiple myeloma improves outcome but ongoing maintenance therapy has minimal benefit
Authors: Harrison Simon J. , Quach Hang , Link Emma , Feng Huaibao , Dean Joanne , Copeman Michael , Van De Velde Helgi , Schwarer Anthony , Baker Bartrum , Spencer Andrew , Catalano John , Campbell Philip , Augustson Bradley , Romeril Ken , Prince Henry Miles
Published: February 2015

Despite the common practice of combining dexamethasone (Dex) with bortezomib (Bz) in patients with multiple myeloma (MM), until now there has been few prospective trials undertaken. We undertook a trial that recapitulated the original APEX study except that dexamethasone was incorporated from cycle 1. We also incorporated an exploratory maintenance component to the study. Twenty sites enrolled 100 relapsed/or refractory MM patients utilizing eight 21 day cycles of IV Bz [1.3 mg/m2; Day (D) 1, 4, 8, 11] and three 35 day cycles; Bz (1.3 mg/m2; Day (D) 1, 8, 15, 22). Our study was registered at www.clinicaltrials.gov (NCT00335348). Patients with stable disease or better received maintenance Bz (1.3 mg/m2) every 14 days until progression. Dexamethasone (20 mg) was given for 2 days with each Bz dose. A prospectively defined matched‐analysis of primary (overall response rate; ORR) and secondary endpoints [Complete Response (CR) and time to progression (TTP)] compared our cohort to those on the Bz arm of the APEX trial. The addition of Dex improved ORR by 20% (56% vs. 36%) [odds ratio 0.44 (0.24–0.80)]. The median TTP was also significantly longer (10.1 vs. 5.1 months) (hazard ratio 0.50, 95% CI: 0.35‐0.72, P = 0.0002) and our landmark analysis demonstrated that this was largely due to the early use of dexamethasone, as we were unable to demonstrate any benefit of bortezomib/dexamethasone maintenance therapy. Am. J. Hematol. 90:E86–E91, 2015. © 2015 Wiley Periodicals, Inc.
Der elektronische Faktor in der Alkanoxidationskatalyse
Authors: Eichelbaum Maik , Hävecker Michael , Heine Christian , Wernbacher Anna Maria , Rosowski Frank , Trunschke Annette , Schlögl Robert
Published: February 2015

Die vorliegende Arbeit beschäftigt sich mit der fundamentalen Frage, inwieweit halbleiterphysikalische Konzepte nützlich sind, um die Arbeitsweise heterogener Oxidationskatalysatoren zu beschreiben und ob es mithilfe dieser Konzepte sogar möglich ist, zwischen selektiven und unselektiven Reaktionspfaden zu differenzieren. Mit In‐situ‐Röntgenphotoelektronenspektroskopie konnte am Beispiel der Oxidation von n‐Butan zu Maleinsäureanhydrid über dem hochselektiven Katalysator Vanadylpyrophosphat und der mäßig selektiven MoVTeNbOx‐M1‐Phase anhand der Gasphasenabhängigkeit der Austrittsarbeit, der Elektronenaffinität und der Oberflächenpotentialbarriere gezeigt werden, dass sich diese Katalysatoren wie halbleitende Gassensoren mit einem dynamischen Ladungstransfer zwischen Volumen und Oberfläche verhalten. Demgegenüber hat die Gasphase nur einen geringen Einfluss auf die Halbleitereigenschaften des Verbrennungskatalysators V2O5, und es wurde in diesem Fall keine dynamische Oberflächenpotentialbarriere beobachtet. Das Oberflächenpotential wird demnach als Deskriptor für selektive Katalysatoren vorgeschlagen.
Design of Photocaged Puromycin for Nascent Polypeptide Release and Spatiotemporal Monitoring of Translation
Authors: Buhr Florian , Kohl‐Landgraf Jörg , tom Dieck Susanne , Hanus Cyril , Chatterjee Deep , Hegelein Andreas , Schuman Erin M. , Wachtveitl Josef , Schwalbe Harald
Published: February 2015

The antibiotic puromycin, which inhibits protein translation, is used in a broad range of biochemical applications. The synthesis, characterization, and biological applications of NVOC‐puromycin, a photocaged derivative that is activated by UV illumination, are presented. The caged compound had no effect either on prokaryotic or eukaryotic translation or on the viability of HEK 293 cells. Furthermore, no significant release of ribosome‐bound polypeptide chains was detected in vitro. Upon illumination, cytotoxic activity, in vitro translation inhibition, and polypeptide release triggered by the uncaging of NVOC‐puromycin were equivalent to those of the commercial compound. The quantum yield of photolysis was determined to be 1.1±0.2 % and the NVOC‐puromycin was applied to the detection of newly translated proteins with remarkable spatiotemporal resolution by using two‐photon laser excitation, puromycin immunohistochemistry, and imaging in rat hippocampal neurons.
Chamäleon‐artige Bindungsmodi in der Leitstrukturoptimierung: wechselnde Bindungsgeometrien bei Aspartylprotease‐Inhibitoren
Authors: Kuhnert Maren , Köster Helene , Bartholomäus Ruben , Park Ah Young , Shahim Amir , Heine Andreas , Steuber Holger , Klebe Gerhard , Diederich Wibke E.
Published: February 2015

Eine erfolgreiche strukturbasierte Leitstrukturoptimierung beruht auf der korrekten Interpretation der zugrundeliegenden Struktur‐Wirkungs‐Beziehungen, auf deren Grundlage üblicherweise die nächsten zu synthetisierenden Moleküle vorgeschlagen werden. Folglich stellt sich die Frage, wie oft ein experimentell bestimmter Bindungsmodus während der Optimierung überprüft werden muss, um sicherzustellen, dass man nicht aufgrund falscher Annahmen im weiteren Optimierungsprozess in die Irre geführt wird. Wie hier gezeigt wird, können bereits kleine, in der medizinischen Chemie jedoch überaus übliche Variationen eines Liganden zu einer drastischen Änderung der Bindungsgeometrien führen: Überraschenderweise wurden innerhalb einer Serie von acht Liganden vier verschiedene Bindungsmodi im Komplex mit der Aspartylprotease Endothiapepsin, die als Modellenzym für Renin und β‐Sekretase dient, röntgenkristallographisch gefunden. Wir schlagen eine Methode vor, mit der ein erster Anhaltspunkt darüber gewonnen werden kann, wann eine experimentelle Überprüfung des ursprünglich gefundenen Bindungsmodus sinnvoll ist.
σ‐Aromaticity in an Unsaturated Ring: Osmapentalene Derivatives Containing a Metallacyclopropene Unit
Authors: Zhu Congqing , Zhou Xiaoxi , Xing Hongjie , An Ke , Zhu Jun , Xia Haiping
Published: February 2015

In general, aromaticity can be clarified as π‐ and σ‐aromaticity according to the type of electrons with major contributions. The traditional π‐aromaticity generally describes the π‐conjugation in fully unsaturated rings whereas σ‐aromaticity may stabilize fully saturated rings with delocalization caused by σ‐electron conjugation. Reported herein is an example of σ‐aromaticity in an unsaturated three‐membered ring (3 MR), which is supported by experimental observations and theoretical calculations. Specifically, when the 3 MR in cyclopropaosmapentalene is cleaved by ethane through two isodesmic reactions, both of them are highly endothermic (+29.7 and +35.0 kcal mol−1). These positive values are in sharp contrast to the expected exothermicity, thus indicating aromaticity in the 3 MR. Further nucleus‐independent chemical shift and anisotropy of the current‐induced density calculations reveal the nature of σ‐aromaticity in the unsaturated 3 MR.
Rutile TiO2 Submicroboxes with Superior Lithium Storage Properties
Authors: Yu Xin‐Yao , Wu Hao Bin , Yu Le , Ma Fei‐Xiang , Lou Xiong Wen (David)
Published: February 2015

Hollow structures of rutile TiO2, and especially with non‐spherical shape, have rarely been reported. Herein, high‐quality rutile TiO2 submicroboxes have been synthesized by a facile templating method using Fe2O3 submicrocubes as removable templates. Compared to other rutile TiO2 nanomaterials, the as‐prepared rutile TiO2 submicroboxes manifest superior lithium storage properties in terms of high specific capacity, long‐term cycling stability, and excellent rate capability.
Rapid Formation of a Supramolecular Polypeptide–DNA Hydrogel for In Situ Three‐Dimensional Multilayer Bioprinting
Authors: Li Chuang , Faulkner‐Jones Alan , Dun Alison R. , Jin Juan , Chen Ping , Xing Yongzheng , Yang Zhongqiang , Li Zhibo , Shu Wenmiao , Liu Dongsheng , Duncan Rory R.
Published: February 2015

A rapidly formed supramolecular polypeptide–DNA hydrogel was prepared and used for in situ multilayer three‐dimensional bioprinting for the first time. By alternative deposition of two complementary bio‐inks, designed structures can be printed. Based on their healing properties and high mechanical strengths, the printed structures are geometrically uniform without boundaries and can keep their shapes up to the millimeter scale without collapse. 3D cell printing was demonstrated to fabricate live‐cell‐containing structures with normal cellular functions. Together with the unique properties of biocompatibility, permeability, and biodegradability, the hydrogel becomes an ideal biomaterial for 3D bioprinting to produce designable 3D constructs for applications in tissue engineering.
Efficient Synthesis of Sterically Hindered Arenes Bearing Acyclic Secondary Alkyl Groups by Suzuki–Miyaura Cross‐Couplings
Authors: Li Chengxi , Chen Tianyu , Li Bowen , Xiao Guolan , Tang Wenjun
Published: February 2015

Bulky P,PO ligands were designed to inhibit isomerization and reduction side reactions during the cross coupling between sterically hindered aryl halides and alkylboronic acids. Suzuki–Miyaura cross‐couplings between di‐ortho‐substituted aryl bromides and acyclic secondary alkylboronic acids have been achieved with high yields. The method has also enabled the preparation of ortho‐alkoxy di‐ortho‐substituted arenes bearing isopropyl groups in excellent yields. The utility of the synthetic method has been demonstrated in a late‐stage modification of estrone and in the application to a new synthetic route toward gossypol.
L‐Lysine: Exploiting Powder X‐ray Diffraction to Complete the Set of Crystal Structures of the 20 Directly Encoded Proteinogenic Amino Acids
Authors: Williams P. Andrew , Hughes Colan E. , Harris Kenneth D. M.
Published: February 2015

During the last 75 years, crystal structures have been reported for 19 of the 20 directly encoded proteinogenic amino acids in their natural (enantiomerically pure) form. The crystal structure is now reported for the final member of this set: L‐lysine. As crystalline L‐lysine has a strong propensity to incorporate water under ambient atmospheric conditions to form a hydrate phase, the pure (non‐hydrate) crystalline phase can be obtained only by dehydration under rigorously anhydrous conditions, resulting in a microcrystalline powder sample. For this reason, modern powder X‐ray diffraction methods have been exploited to determine the crystal structure in this final, elusive case.
One‐Pot Synthesis of Pt–Co Alloy Nanowire Assemblies with Tunable Composition and Enhanced Electrocatalytic Properties
Authors: Xia Bao Yu , Wu Hao Bin , Li Nan , Yan Ya , Lou Xiong Wen (David) , Wang Xin
Published: February 2015

Three‐dimensional (3D) Pt‐based alloy nanostructures composed of one‐dimensional (1D) nanowires/nanorods have recently attracted significant interest as electrocatalysts. In this work, we report an effective solvothermal method for the direct preparation of 3D Pt–Co nanowire assemblies (NWAs) with tunable composition. The composition‐ and structure‐dependent electrocatalytic performance is thoroughly investigated. Because of the bimetallic synergetic effect and unique structural advantage, the as‐prepared 3D Pt3Co NWA outperforms commercial Pt/carbon and Pt black catalysts and even 3D Pt NWA. The electrochemical results demonstrate that the 3D Pt3Co NWA is indeed a promising electrocatalyst with enhanced catalytic activity and improved durability for practical electrocatalytic applications.
Enhanced Luminescent Properties of an Open‐Shell (3,5‐Dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl Radical by Coordination to Gold
Authors: Hattori Yohei , Kusamoto Tetsuro , Nishihara Hiroshi
Published: February 2015

A gold(I) complex containing an open‐shell luminescent (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl (PyBTM) radical was prepared. The complex showed fluorescence centered mainly on the coordinated PyBTM ligand. The photophysical and photochemical properties were positively modulated upon coordination to AuI; the photoluminescence quantum yield, fluorescence wavelength, and the stability in the photoexcited state all increased.
trans‐Hydrogenation: Application to a Concise and Scalable Synthesis of Brefeldin A
Authors: Fuchs Michael , Fürstner Alois
Published: February 2015

The important biochemical probe molecule brefeldin A (1) has served as an inspirational target in the past, but none of the many routes has actually delivered more than just a few milligrams of product, where documented. The approach described herein is clearly more efficient; it hinges upon the first implementation of ruthenium‐catalyzed trans‐hydrogenation in natural products total synthesis. Because this unorthodox reaction is selective for the triple bond and does not touch the transannular alkene or the lactone site of the cycloalkyne, it outperforms the classical Birch‐type reduction that could not be applied at such a late stage. Other key steps en route to 1 comprise an iron‐catalyzed reductive formation of a non‐terminal alkyne, an asymmetric propiolate carbonyl addition mediated by a bulky amino alcohol, and a macrocyclization by ring‐closing alkyne metathesis catalyzed by a molybdenum alkylidyne.
Carboxylic Acids as Traceless Directing Groups for the Rhodium(III)‐Catalyzed Decarboxylative CH Arylation of Thiophenes
Authors: Zhang Yuanfei , Zhao Huaiqing , Zhang Min , Su Weiping
Published: February 2015

A rhodium(III)‐catalyzed carboxylic acid directed decarboxylative CH/CH cross‐coupling of carboxylic acids with thiophenes has been developed. With a slight adjustment of the reaction conditions based on the nature of the substrates, aryl carboxylic acids with a variety of substituents could serve as suitable coupling partners, and a broad variety of functional groups were tolerated. This method provides straightforward access to biaryl scaffolds with diverse substitution patterns, many of which have conventionally been synthesized through lengthy synthetic sequences. An illustrative example is the one‐step gram‐scale synthesis of a biologically active 3,5‐substituted 2‐arylthiophene by way of the current method.
Easy Access to Modified Cyclodextrins by an Intramolecular Radical Approach
Authors: Alvarez‐Dorta Dimitri , León Elisa I. , Kennedy Alan R. , Martín Angeles , Pérez‐Martín Inés , Suárez Ernesto
Published: February 2015

A simple method to modify the primary face of cyclodextrins (CDs) is described. The 6I‐O‐yl radical of α‐, β‐, and γ‐CDs regioselectively abstracts the H5II, located in the adjacent D‐glucose unit, by an intramolecular 1,8‐hydrogen‐atom‐transfer reaction through a geometrically restricted nine‐membered transition state to give a stable 1,3,5‐trioxocane ring. The reaction has been extended to the 1,4‐diols of α‐ and β‐CD to give the corresponding bis(trioxocane)s. The C2‐symmetric bis(trioxocane) corresponding to the α‐CD is a stable crystalline solid whose structure was confirmed by X‐ray diffraction analysis. The calculated geometric parameters confirm that the primary face is severely distorted toward a narrower elliptical shape for this rim.
A Möbius Aromatic [28]Hexaphyrin Bearing a Diethylamine Group: A Rigid but Smooth Conjugation Circuit
Authors: Higashino Tomohiro , Soya Takanori , Kim Woojae , Kim Dongho , Osuka Atsuhiro
Published: February 2015

The reaction of [26]hexaphyrin with triethylamine in the presence of BF3⋅OEt2 and O2 furnished a diastereomeric mixture of a diethylamine‐bearing [28]hexaphyrin as a rare example of a Möbius aromatic metal‐free expanded porphyrin. The Möbius aromaticity of these molecules is large, as indicated by their large diatropic ring currents, which are even preserved at 100 °C, owing to their internally multiply bridged robust structure with a smooth conjugation network. These molecules were reduced with NaBH4 to give an antiaromatic [28]hexaphyrin, and were oxidized with MnO2 to give aromatic [26]hexaphyrins, both through a Möbius‐to‐Hückel topology switch induced by a CN bond cleavage.
A Scalable Biomimetic Synthesis of Resveratrol Dimers and Systematic Evaluation of their Antioxidant Activities
Authors: Matsuura Bryan S. , Keylor Mitchell H. , Li Bo , Lin YuXuan , Allison Shelby , Pratt Derek A. , Stephenson Corey R. J.
Published: February 2015

An efficient synthetic route to the resveratrol oligomers quadrangularin A and pallidol is reported. It features a scalable biomimetic oxidative dimerization that proceeds in excellent yield and with complete regioselectivity. A systematic evaluation of the natural products and their synthetic precursors as radical‐trapping antioxidants has revealed that, contrary to popular belief, this mode of action is unlikely to account for their observed biological activity.
Phosphine‐Initiated Cation Exchange for Precisely Tailoring Composition and Properties of Semiconductor Nanostructures: Old Concept, New Applications
Authors: Gui Jing , Ji Muwei , Liu Jiajia , Xu Meng , Zhang Jiatao , Zhu Hesun
Published: February 2015

Phosphine‐initiated cation exchange is a well‐known inorganic chemistry reaction. In this work, different phosphines have been used to modulate the thermodynamic and kinetic parameters of the cation exchange reaction to synthesize complex semiconductor nanostructures. Besides preserving the original shape and size, phosphine‐initiated cation exchange reactions show potential to precisely tune the crystallinity and composition of metal/semiconductor core–shell and doped nanocrystals. Furthermore, systematic studies on different phosphines and on the elementary reaction mechanisms have been performed.
An Efficient Approach to Chiral Allyloxyamines by Stereospecific Allylation of Nitrosoarenes with Chiral Allylboronates
Authors: Li Yuanming , Chakrabarty Shyamal , Studer Armido
Published: February 2015

A novel and efficient approach to allyloxyamines by the allylation of nitrosoarenes with α‐chiral allylboronates is described. CO bond formation occurs with high stereospecificity and the product allyloxyamines are easily transformed into valuable chiral building blocks such as isoxazolidines and allylic alcohols. The reaction features complete regioselectivity (O‐selectivity), high E/Z selectivity, and excellent chirality transfer.
A New Way to Silicone‐Based Peptide Polymers
Authors: Jebors Said , Ciccione Jeremie , Al‐Halifa Soultan , Nottelet Benjamin , Enjalbal Christine , M'Kadmi Céline , Amblard Muriel , Mehdi Ahmad , Martinez Jean , Subra Gilles
Published: February 2015

We describe a new class of silicone‐containing peptide polymers obtained by a straightforward polymerization in water using tailored chlorodimethylsilyl peptide blocks as monomeric units. This general strategy is applicable to any type of peptide sequences, yielding linear or branched polymer chains composed of well‐defined peptide sequences.