bluuebunny/crossref_metadata_2025 huggingface dataset:
Disentangling the impacts of heat wave magnitude, duration and timing on the structure and diversity of sessile marine assemblages
Authors: Smale Dan A. , Yunnie Anna L.E. , Vance Thomas , Widdicombe Stephen
Published: June 2016

Extreme climatic events, including heat waves (HWs) and severe storms, influence the structure of marine and terrestrial ecosystems. Despite growing consensus that anthropogenic climate change will increase the frequency, duration and magnitude of extreme events, current understanding of their impact on communities and ecosystems is limited. Here, we used sessile invertebrates on settlement panels as model assemblages to examine the influence of HW magnitude, duration and timing on marine biodiversity patterns. Settlement panels were deployed in a marina in southwest UK for ≥5 weeks, to allow sufficient time for colonisation and development of sessile fauna, before being subjected to simulated HWs in a mesocosm facility. Replicate panel assemblages were held at ambient sea temperature (∼17 °C), or +3 °C or +5 °C for a period of 1 or 2 weeks, before being returned to the marina for a recovery phase of 2–3 weeks. The 10-week experiment was repeated 3 times, staggered throughout summer, to examine the influence of HW timing on community impacts. Contrary to our expectations, the warming events had no clear, consistent impacts on the abundance of species or the structure of sessile assemblages. With the exception of 1 high-magnitude long-duration HW event, warming did not alter not assemblage structure, favour non-native species, nor lead to changes in richness, abundance or biomass of sessile faunal assemblages. The observed lack of effect may have been caused by a combination of (1) the use of relatively low magnitude, realistic heat wave treatments compared to previous studies (2), the greater resilience of mature adult sessile fauna compared to recruits and juveniles, and (3) the high thermal tolerance of the model organisms (i.e., temperate fouling species, principally bryozoans and ascidians). Our study demonstrates the importance of using realistic treatments when manipulating climate change variables, and also suggests that biogeographical context may influence community-level responses to short-term warming events, which are predicted to increase in severity in the future.
Microstructural and geochemical constraints on the evolution of deep arc lithosphere
Authors: Chin Emily J. , Soustelle Vincent , Hirth Greg , Saal Alberto E. , Kruckenberg Seth C. , Eiler John M.
Published: June 2016

Mantle xenoliths from the Sierra Nevada, California, USA, sampled a vertical column (60–120 km) of lithosphere that formed during Mesozoic continental arc magmatism. This lithosphere experienced an anticlockwise P‐T‐t path resulting in rapid cooling that effectively “quenched in” features inherited from earlier high‐temperature conditions. Here we combine new mineral chemistry data (water, trace element, and major element concentrations) with mineral crystallographic preferred orientations (CPOs) to investigate the relationship between melt infiltration and deformation. The peridotites record a refertilization trend with increasing depth, starting from shallow, coarse‐protogranular, less‐melt‐infiltrated spinel peridotite with strong, orthorhombic olivine CPO to deep, fine‐porphyroclastic, highly melt‐infiltrated garnet peridotite with weak, axial‐[010] olivine CPO. In contrast to the observed axial‐[010] CPOs, subgrain boundary orientations and misorientation axes suggest the dominant activation of the (001)[100] slip system, suggesting deformation under moderately hydrous conditions. After accounting for effects of subsolidus cooling, we see coherent trends between mineral trace element abundance and water content, indicating that melt infiltration led to an increase in water content of the peridotites. However, measured olivine and pyroxene water contents in all peridotites (5–10 and 30–500 wt ppm, respectively) are lower than that required to promote dominant (001)[100] slip system observed in both natural and experimental samples. These results suggest that deformation occurred earlier along the P‐T path, probably during or shortly after hydrous melt infiltration. Subsequent rapid cooling at 90 Ma led to water loss from olivine (owing to decreased solubility at low temperature), leaving behind a deep arc lithosphere that remained viscously coupled to the Farallon slab until the opening of the slab window in the late Cenozoic.
Time series of temperature in Fram Strait determined from the 2008–2009 DAMOCLES acoustic tomography measurements and an ocean model
Authors: Sagen Hanne , Dushaw Brian D. , Skarsoulis Emmanuel K. , Dumont Dany , Dzieciuch Matthew A. , Beszczynska‐Möller Agnieszka
Published: June 2016

A pilot acoustic tomography program in Fram Strait during 2008–2009 measured a year‐long record of acoustic travel times along a 130 km range acoustic path crossing the West Spitsbergen Current. Individual ray arrivals were not observed. Rather, the arrival patterns consisted of a single, stable, broad arrival pulse of about 100 ms duration. Travel time variations of ±0.15 s recorded the vigorous mesoscale environment of the region and the seasonal cycle. To estimate ocean temperature from the tomography data an inverse scheme employed a high‐resolution ocean model for Fram Strait as the reference ocean. The information from the tomographic measurements is primarily average temperature. Estimated temperatures, averaged over 0–1000 m depth and over range, had a mean of 1.11°C and variations of ±0.33°C; the uncertainty of the tomography estimates was about 60m°C. Agreement with an alternate inverse approach based on EOFs and a Markov Chain Monte Carlo inversion scheme relying on a matched‐peak approach was excellent, indicating a robust estimate for ocean temperature. The inverse estimates for average temperature agreed with the equivalent estimates from hydrographic sections obtained along the acoustic path at the start and end of the program. Among other deficiencies, the ocean model greatly underestimated the intensity of the mesoscale fluctuations and exhibited a warm bias of about 0.38°C in section‐averaged temperature. Tomographic measurements in Fram Strait offer unique large‐scale temperature constraints for ocean models through data assimilation. It is anticipated that these constraints will lead to more accurate estimates of the circulation and transports in Fram Strait.
No significant increase in long‐term CH4 emissions on North Slope of Alaska despite significant increase in air temperature
Authors: Sweeney Colm , Dlugokencky Edward , Miller Charles E. , Wofsy Steven , Karion Anna , Dinardo Steve , Chang Rachel Y.‐W. , Miller John B. , Bruhwiler Lori , Crotwell Andrew M. , Newberger Tim , McKain Kathryn , Stone Robert S. , Wolter Sonja E. , Lang Patricia E. , Tans Pieter
Published: June 2016

Continuous measurements of atmospheric methane (CH4) mole fractions measured by NOAA's Global Greenhouse Gas Reference Network in Barrow, AK (BRW), show strong enhancements above background values when winds come from the land sector from July to December from 1986 to 2015, indicating that emissions from arctic tundra continue through autumn and into early winter. Twenty‐nine years of measurements show little change in seasonal mean land sector CH4 enhancements, despite an increase in annual mean temperatures of 1.2 ± 0.8°C/decade (2σ). The record does reveal small increases in CH4 enhancements in November and December after 2010 due to increased late‐season emissions. The lack of significant long‐term trends suggests that more complex biogeochemical processes are counteracting the observed short‐term (monthly) temperature sensitivity of 5.0 ± 3.6 ppb CH4/°C. Our results suggest that even the observed short‐term temperature sensitivity from the Arctic will have little impact on the global atmospheric CH4 budget in the long term if future trajectories evolve with the same temperature sensitivity.
Evidence of underground electric current generation during the 2009 L'Aquila earthquake: Real or instrumental?
Authors: Masci F. , Thomas J. N.
Published: June 2016

We investigate magnetic effects in correspondence of the Mw6.1 L'Aquila earthquake. Magnetic and seismic records are analyzed. Rapid and distinct changes and an offset can be seen in magnetic field components after the main shock. We show that these effects result from electromagnetic induction due to the movement of the sensors through the Earth's magnetic field and from a permanent displacement of the sensors from their original position caused by the passing seismic waves. A transient signal in total field data from an overhauser magnetometer apparently occurs in correspondence with the earthquake. Our analysis shows that the transient was not observed by other sensors that were operating in close proximity to the overhauser. Thus, the transient signal in the total magnetic field data, and the offset in the magnetic field components, cannot be associated with a hypothetical underground electric current generated by the earthquake, as suggested by Nenovski (2015).
Crustal structure beneath the Blue Mountains terranes and cratonic North America, eastern Oregon, and Idaho, from teleseismic receiver functions
Authors: Christian Stanciu A. , Russo Raymond M. , Mocanu Victor I. , Bremner Paul M. , Hongsresawat Sutatcha , Torpey Megan E. , VanDecar John C. , Foster David A. , Hole John A.
Published: June 2016

We present new images of lithospheric structure obtained from P‐to‐S conversions defined by receiver functions at the 85 broadband seismic stations of the EarthScope IDaho‐ORegon experiment. We resolve the crustal thickness beneath the Blue Mountains province and the former western margin of cratonic North America, the geometry of the western Idaho shear zone (WISZ), and the boundary between the Grouse Creek and Farmington provinces. We calculated P‐to‐S receiver functions using the iterative time domain deconvolution method, and we used the H‐k grid search method and common conversion point stacking to image the lithospheric structure. Moho depths beneath the Blue Mountains terranes range from 24 to 34 km, whereas the crust is 32–40 km thick beneath the Idaho batholith and the regions of extended crust of east‐central Idaho. The Blue Mountains group Olds Ferry terrane is characterized by the thinnest crust in the study area, ~24 km thick. There is a clear break in the continuity of the Moho across the WISZ, with depths increasing from 28 km west of the shear zone to 36 km just east of its surface expression. The presence of a strong midcrustal converting interface at ~18 km depth beneath the Idaho batholith extending ~20 km east of the WISZ indicates tectonic wedging in this region. A north striking ~7 km offset in Moho depth, thinning to the east, is present beneath the Lost River Range and Pahsimeroi Valley; we identify this sharp offset as the boundary that juxtaposes the Archean Grouse Creek block with the Paleoproterozoic Farmington zone.
Changes in anthropogenic carbon storage in the Northeast Pacific in the last decade
Authors: Chu Sophie N. , Wang Zhaohui Aleck , Doney Scott C. , Lawson Gareth L. , Hoering Katherine A.
Published: June 2016

In order to understand the ocean's role as a sink for anthropogenic carbon dioxide (CO2), it is important to quantify changes in the amount of anthropogenic CO2 stored in the ocean interior over time. From August to September 2012, an ocean acidification cruise was conducted along a portion of the P17N transect (50°N 150°W to 33.5°N 135°W) in the Northeast Pacific. These measurements are compared with data from the previous occupation of this transect in 2001 to estimate the change in the anthropogenic CO2 inventory in the Northeast Pacific using an extended multiple linear regression (eMLR) approach. Maximum increases in the surface waters were 11 µmol kg−1 over 11 years near 50°N. Here, the penetration depth of anthropogenic CO2 only reached ∼300 m depth, whereas at 33.5°N, penetration depth reached ∼600 m. The average increase of the depth‐integrated anthropogenic carbon inventory was 0.41 ± 0.12 mol m−2 yr−1 across the transect. Lower values down to 0.20 mol m−2 yr−1 were observed in the northern part of the transect near 50°N and increased up to 0.55 mol m−2 yr−1 toward 33.5°N. This increase in anthropogenic carbon in the upper ocean resulted in an average pH decrease of 0.002 ± 0.0003 pH units yr−1 and a 1.8 ± 0.4 m yr−1 shoaling rate of the aragonite saturation horizon. An average increase in apparent oxygen utilization of 13.4 ± 15.5 µmol kg−1 centered on isopycnal surface 26.6 kg m−3 from 2001 to 2012 was also observed.
Sea spray aerosol in the Great Barrier Reef and the presence of nonvolatile organics
Authors: Mallet Marc , Cravigan Luke , Miljevic Branka , Vaattovaara Petri , Deschaseaux Elisabeth , Swan Hilton , Jones Graham , Ristovski Zoran
Published: June 2016

Sea spray aerosol (SSA) particles produced from the ocean surface in regions of biological activity can vary greatly in size, number and composition, and in their influence on cloud formation. Algal species such as phytoplankton can alter the SSA composition. Numerous studies have investigated nascent SSA properties, but all of these have focused on aerosol particles produced by seawater from noncoral related phytoplankton and in coastal regions. Bubble chamber experiments were performed with seawater samples taken from the reef flat around Heron Island in the Great Barrier Reef during winter 2011. Here we show that the SSA from these samples was composed of an internal mixture of varying fractions of sea salt, semivolatile organics, as well as nonvolatile (below 550°C) organics. A relatively constant volume fraction of semivolatile organics of 10%–13% was observed, while nonvolatile organic volume fractions varied from 29% to 49% for 60 nm SSA. SSA organic fractions were estimated to reduce the activation ratios of SSA to cloud condensation nuclei by up to 14% when compared with artificial sea salt. Additionally, a sea‐salt calibration was applied so that a compact time‐of‐flight aerosol mass spectrometer could be used to quantify the contribution of sea salt to submicron SSA, which yielded organic volume fractions of 3%–6%. Overall, these results indicate a high fraction of organics associated with wintertime Aitken mode SSA generated from Great Barrier Reef seawater. Further work is required to fully distinguish any differences coral reefs have on SSA composition when compared to open oceans.
The Role of Temporal and Spatial Information Cues in Locating Missing Persons
Authors: Moore Kara N. , Lampinen James M. , Provenzano Andrew C.
Published: June 2016

Prospective person memory refers to the search for a missing or wanted person. Performance on prospective person memory tasks has been found to be poor in field‐based experiments. Prior research suggests that the size of the search space may influence success on prospective person memory tasks. In the present research, we gave participants randomly assigned temporal and spatial cues about a mock missing person's whereabouts. Participants were offered a monetary reward for accurately reporting seeing the missing person. Participants who were told the missing person would appear in the building, where they were, had higher expectations of encountering the missing person and made more sightings than participants told the missing person would appear on the university campus. Expectations of encounter predicted participants' intent to look for the missing person, which predicted actual looking behavior, which ultimately predicted accurate sightings.Copyright © 2016 John Wiley & Sons, Ltd.
“Nano‐Fishnet” Structure Making Silk Fibers Tougher
Authors: Liu Ruchuan , Deng Qinqiu , Yang Zhen , Yang Daiwen , Han Ming‐Yong , Liu Xiang Yang
Published: June 2016

Based on the combined technologies of atomic force microscopy, X‐ray diffraction/scattering, Fourier transform infrared spectra analysis, etc., it is demonstrated that the nano‐fishnet‐like networks, one of the most flexible but toughest structures, turn out to be the basic structure of silk filaments. The force patterns of pulling individual fibrils allow the identification of the pathways of unfolding protein segments in stacking β‐crystallites, which reveal the fishnet‐like topology. The calculation shows that the β‐crystallites in silk nanofibrils are the cross‐linking points of the nano‐fishnets, which may enhance the toughness of silk filaments up to 1000 times, compared with amyloid‐like and unlinked string structures. It follows that the strong β‐sheet–β‐sheet interaction, a high degree of ordering, and a high density of β‐crystallites in silk fibers toughen the fishnet structure, then strengthen silk filaments, in consistency with the experiments for both spider and silkworm silks. The knowledge on the fishnet structure of silk fibers sheds light on the design and synthesis of either protein or synthetic fibers of ultraperformance in a more generic way.
The Effect of Gradations in Mineral Content, Matrix Alignment, and Applied Strain on Human Mesenchymal Stem Cell Morphology within Collagen Biomaterials
Authors: Mozdzen Laura C. , Thorpe Stephen D. , Screen Hazel R. C. , Harley Brendan A. C.
Published: June 2016

The tendon‐bone junction is a unique, mechanically dynamic, structurally graded anatomical zone, which transmits tensile loads between tendon and bone. Current surgical repair techniques rely on mechanical fixation and can result in high re‐failure rates. A new class of collagen biomaterial that contains discrete mineralized and structurally aligned regions linked by a continuous interface to mimic the graded osteotendinous insertion has been recently described. Here the combined influence of graded biomaterial environment and increasing levels of applied strain (0%–20%) on mesenchymal stem cell (MSC) orientation and alignment have been reported. Inosteotendinousscaffolds, which contain opposing gradients of mineral content and structural alignment characteristic of the native osteotendinous interface, MSC nuclear, and actin alignment is initially dictated by the local pore architecture, while applied tensile strain enhances cell alignment in the direction of strain. Comparatively, inlayeredscaffolds that do not contain any structural alignment cues, MSCs are randomly oriented in the unstrained condition, then become oriented in a direction perpendicular to applied strain. These findings provide an initial understanding of how scaffold architecture can provide significant, potentially competitive, feedback influencing MSC orientation under applied strain, and form the basis for future tissue engineering efforts to regenerate the osteotendinous enthesis.
Hierarchical Targeting Strategy for Enhanced Tumor Tissue Accumulation/Retention and Cellular Internalization
Authors: Wang Sheng , Huang Peng , Chen Xiaoyuan
Published: June 2016

Targeted delivery of therapeutic agents is an important way to improve the therapeutic index and reduce side effects. To design nanoparticles for targeted delivery, both enhanced tumor tissue accumulation/retention and enhanced cellular internalization should be considered simultaneously. So far, there have been very few nanoparticles with immutable structures that can achieve this goal efficiently. Hierarchical targeting, a novel targeting strategy based on stimuli responsiveness, shows good potential to enhance both tumor tissue accumulation/retention and cellular internalization. Here, the recent design and development of hierarchical targeting nanoplatforms, based on changeable particle sizes, switchable surface charges and activatable surface ligands, will be introduced. In general, the targeting moieties in these nanoplatforms are not activated during blood circulation for efficient tumor tissue accumulation, but re‐activated by certain internal or external stimuli in the tumor microenvironment for enhanced cellular internalization.
Nonrecirculating flow of a yield stress fluid around a circular cylinder in a poiseuille flow
Authors: Ozogul Hamdullah , Jay Pascal , Magnin Albert
Published: June 2016

Although yield stress fluids are very present today in everyday life and in industry, their flow behavior is still poorly understood and the databases are incomplete at this time. The present experimental and numerical study focuses on laminar nonrecirculating flows of an elastoviscoplastic model fluid in a rectangular duct. An original experimental set‐up has been developed. The Particle Image Velocimetry method is used for analyzing the kinematical fields. Results provided concern the morphology of the flow and the evolution of the velocity field around a cylindrical obstacle. Information is provided on the size of the rigid zones where the fluid behaves as a solid. The experimental data are compared with numerical results involving a regularized Herschel–Bulkley viscoplastic model. © 2016 American Institute of Chemical EngineersAIChE J, 62: 4554–4563, 2016
Kriging meta‐model assisted calibration of computational fluid dynamics models
Authors: Kajero Olumayowa T. , Thorpe Rex B. , Chen Tao , Wang Bo , Yao Yuan
Published: June 2016

Computational fluid dynamics (CFD) is a simulation technique widely used in chemical and process engineering applications. However, computation has become a bottleneck when calibration of CFD models with experimental data (also known as model parameter estimation) is needed. In this research, the kriging meta‐modeling approach (also termed Gaussian process) was coupled with expected improvement (EI) to address this challenge. A new EI measure was developed for the sum of squared errors (SSE) which conforms to a generalized chi‐square distribution and hence existing normal distribution‐based EI measures are not applicable. The new EI measure is to suggest the CFD model parameter to simulate with, hence minimizing SSE and improving match between simulation and experiments. The usefulness of the developed method was demonstrated through a case study of a single‐phase flow in both a straight‐type and a convergent‐divergent‐type annular jet pump, where a single model parameter was calibrated with experimental data. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4308–4320, 2016
The application of dynamic modeling for thermal risks analysis of the acid‐catalyzed hydrolysis of glycidol
Authors: Ojeda Toro Juan Carlos , Dobrosz‐Gómez Izabela , Gómez García Miguel Ángel
Published: June 2016

The aim of this work was to determine the limits of safe operation of continuous flow stirred‐tank reactor (CSTR) for the acid‐catalyzed hydrolysis of glycidol. The stability analysis was performed by dynamic modelling. The obtained results were compared with the experimental data reported in the open literature. For this purpose, dimensionless variables and parameters were introduced and unstable material and energy balances were defined. The system equations were solved using Matcont (Matlab® software). Thus, bifurcation diagrams (in one and two dimensions) were mapped. All different dynamic states were identified and studied (thermal stability and instability, with unique and multiple solutions; Hopf bifurcations; turning points and envelope of periodic solutions). Finally, the intrinsic thermal unstable and cycle behavior of the acid‐catalyzed hydration of glycidol to produce glycerol was identified. The appropriate conditions to guarantee safe operation of CSTR were found. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4418–4426, 2016
A new family with an SLC9A6 mutation expanding the phenotypic spectrum of Christianson syndrome
Authors: Masurel‐Paulet Alice , Piton Amélie , Chancenotte Sophie , Redin Claire , Thauvin‐Robinet Christel , Henrenger Yvan , Minot Delphine , Creppy Audrey , Ruffier‐Bourdet Marie , Thevenon Julien , Kuentz Paul , Lehalle Daphné , Curie Aurore , Blanchard Gaelle , Ghosn Ezzat , Bonnet Marlene , Archimbaud‐Devilliers Mélanie , Huet Frédéric , Perret Odile , Philip Nicole , Mandel Jean‐Louis , Faivre Laurence
Published: June 2016

Using targeted next generation sequencing, we have identified a splicing mutation (c.526‐9_526‐5del) in the SLC9A6 gene in a 9‐year‐old boy with mild intellectual disability (ID), microcephaly, and social interaction disabilities. This intronic microdeletion leads to the skipping of exon 3 and to an in‐frame deletion of 26 amino acids in the TM4 domain. It segregates with cognitive impairment or learning difficulties in other members of the family. Mutations in SLC9A6 have been reported in X‐linked Christianson syndrome associating severe to profound intellectual deficiency and an Angelman‐like phenotype with microcephaly, absent speech, ataxia with progressive cerebellar atrophy, ophthalmoplegia, epilepsy, and neurological regression. The proband and his maternal uncle both have an attenuated phenotype with mild ID, attention deficit disorder, speech difficulties, and mild asymptomatic cerebellar atrophy. The proband also have microcephaly. The mutation cosegregated with learning disabilities and speech difficulties in the female carriers (mother and three sisters of the proband). Detailed neuropsychological, speech, and occupational therapy investigations in the female carriers revealed impaired oral and written language acquisition, with dissociation between verbal and performance IQ. An abnormal phenotype, ranging from learning disability with predominant speech difficulties to mild intellectual deficiency, has been described previously in a large proportion of female carriers. Besides broadening the clinical spectrum of SLC9A6 gene mutations, we present an example of a monogenic origin of mild learning disability. © 2016 Wiley Periodicals, Inc.
Determinants of sleep disturbances in Rett syndrome: Novel findings in relation to genotype
Authors: Boban Sharolin , Wong Kingsley , Epstein Amy , Anderson Barbara , Murphy Nada , Downs Jenny , Leonard Helen
Published: June 2016

Rett syndrome is a rare but severe neurological disorder associated with a mutation in the methyl CpG binding protein 2 (MECP2) gene. Sleep problems and epilepsy are two of many comorbidities associated with this disorder. This study investigated the prevalence and determinants of sleep problems in Rett syndrome using an international sample. Families with a child with a confirmed Rett syndrome diagnosis and a MECP2 mutation registered in the International Rett Syndrome Phenotype Database (InterRett) were invited to participate. Questionnaires were returned by 364/461 (78.9%) either in web‐based or paper format. Families completed the Sleep Disturbance Scale for Children and provided information on the presence, nature, and frequency of their child's sleep problems. Multivariate multinomial regression was used to investigate the relationships between selected sleep problems, age group, and genotype and linear regression for the relationships between sleep disturbance scales and a range of covariates. Night waking was the most prevalent sleep problem affecting over 80% with nearly half (48.3%) currently waking often at night. Initiating and maintaining sleep was most disturbed for younger children and those with a p.Arg294* mutation. Severe seizure activity was associated with poor sleep after adjusting for age group, mutation type, and mobility. We were surprised to find associations between the p.Arg294* mutation and some sleep disturbances given that other aspects of its phenotype are milder. These findings highlight the complexities of aberrant MECP2 function in Rett syndrome and explain some of the variation in manifestation of sleep disturbances. © 2016 Wiley Periodicals, Inc.
Interstitial 1q23.3q24.1 deletion in a patient with renal malformation, congenital heart disease, and mild intellectual disability
Authors: Mackenroth Luisa , Hackmann Karl , Klink Barbara , Weber Julia Sara , Mayer Brigitte , Schröck Evelin , Tzschach Andreas
Published: June 2016

Interstitial deletions including chromosome region 1q23.3q24.1 are rare. Only eight patients with molecularly characterized deletions have been reported to date. Their phenotype included intellectual disability/developmental delay, growth retardation, microcephaly, congenital heart disease, and renal malformations. We report on a female patient with mild developmental delay, congenital heart disease, and bilateral renal hypoplasia in whom an interstitial de novo deletion of approximately 2.7 Mb in 1q23.3q24.1 was detected by array CGH. This is the smallest deletion described in this region so far. Genotype–phenotype comparison with previously published patients allowed us to propose LMX1A and RXRG as potential candidate genes for intellectual disability, PBX1 as a probable candidate gene for renal malformation, and enabled us to narrow down a chromosome region associated with microcephaly. © 2016 Wiley Periodicals, Inc.
Iminiumkatalyse in einer selbstorganisierten supramolekularen Kapsel: Modulation des Enantiomerenüberschusses
Authors: Bräuer Thomas M. , Zhang Qi , Tiefenbacher Konrad
Published: June 2016

Die nichtkovalente Kombination eines supramolekularen Wirts mit Iminium‐Organokatalyse wird beschrieben. Aufgrund von Kation‐π‐Wechselwirkungen wird die reaktive Iminiumspezies im Wirt eingeschlossen und reagiert in dieser begrenzten Umgebung. Die gebildeten Produkte unterscheiden sich um bis zu 92 % ee von den Kontrollversuchen ohne zugegebenen Wirt. Ein Modell, das die beobachteten Unterschiede erklärt, wird vorgestellt.
N‐Substituted Dicyanomethylphenyl Radicals: Dynamic Covalent Properties and Formation of Stimuli‐Responsive Cyclophanes by Self‐Assembly
Authors: Kobashi Toshiyuki , Sakamaki Daisuke , Seki Shu
Published: June 2016

Dynamic covalent bonds and their chemistry have been of particular interest both from a fundamental and materials science aspect. Demonstrated herein is that triphenylamine (TPA) and carbazole (Cz), substituted with a dicyanomethyl radical, are useful motifs for dynamic covalent chemistry as they have the appropriate bond strength between monomer units as well as high stability and synthetic simplicity. TPA and Cz units substituted by two dicyanomethyl radicals formed macrocyclic oligomers classified as novel types of azacyclophanes, and in particular, the TPA‐based diradical gave a cyclic dimer in almost quantitative yield. The cyclic oligomers exhibited thermo‐ and mechanochromic behavior resulting from the generation of radical species by intermonomer C−C bond cleavage.
Iminium Catalysis inside a Self‐Assembled Supramolecular Capsule: Modulation of Enantiomeric Excess
Authors: Bräuer Thomas M. , Zhang Qi , Tiefenbacher Konrad
Published: June 2016

The noncovalent combination of a supramolecular host with iminium organocatalysis is described. Due to cation–π interactions the reactive iminium species is held inside the host and reacts in this confined environment. The products formed differ up to 92 % ee from the control experiments without added host. A model rationalizing the observed difference is presented.
Cyclic Guanidine Compounds from Toxic Newts Support the Hypothesis that Tetrodotoxin is Derived from a Monoterpene
Authors: Kudo Yuta , Yasumoto Takeshi , Mebs Dietrich , Cho Yuko , Konoki Keiichi , Yotsu‐Yamashita Mari
Published: June 2016

The biosynthesis of tetrodotoxin (TTX), a potent neurotoxin consisting of a 2,4‐dioxaadamantane skeleton and a guanidine moiety, is an unsolved problem in natural product chemistry. Recently, the first C5–C10 directly bonded TTX analogue, 4,9‐anhydro‐10‐hemiketal‐5‐deoxyTTX, was obtained from toxic newts and its carbon skeleton suggested a possible monoterpene origin. On the basis of this hypothesis, screening of predicted biosynthetic intermediates of TTX was performed using two MS‐guided methods. Herein, five novel cyclic guanidine compounds from toxic newts are reported which commonly contain a cis‐fused bicyclic structure including a six‐membered cyclic guanidine. These structures could be biosynthetically derived from geranyl guanidine through oxidation, cyclization, and/or isomerization steps. LC–MS analysis confirmed the widespread distribution of the five novel compounds in toxic newt species. These results support the hypothesis that TTX is derived from a monoterpene.
Fabrication and characterization of maleic anhydride grafted polypropylene membranes with high antifouling properties
Authors: Jahanbakhshi Nader , Mousavi Seyyed Abbas , Farhadi Fathollah
Published: June 2016

In this study, maleic anhydride grafted polypropylene microporous flat‐sheet membranes were prepared via a thermally induced phase separation method with a mixture of dibutyl phthalate and dioctyl phthalate as a diluent. The effects of the polymer composition and coagulation bath temperature on the morphology and performance of the fabricated membranes were investigated. The hydrophilicity results of the membranes demonstrated that membrane modification reduced the water contact angle by about 45°, whereas the pure water flux was enhanced about four times. The antifouling behavior of the fabricated membranes was also investigated in a membrane bioreactor. The results show that the pure water flux, membrane pore size, and porosity decreased, whereas the antifouling performance was improved with increasing polymer concentration and decreasing bath temperature. Finally, the results reveal that the removal efficiency of contaminates was independent on the membrane characterization and was done exclusively through biological removal. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43857.
Covalent EGFR Inhibitors: Binding Mechanisms, Synthetic Approaches, and Clinical Profiles
Authors: Hossam Monia , Lasheen Deena S. , Abouzid Khaled A. M.
Published: June 2016

Being overexpressed in several types of cancer, the epidermal growth factor receptor (EGFR) is considered one of the key therapeutic targets in oncology. Although many first‐generation EGFR inhibitors had been FDA approved for the treatment of certain types of cancer, patients soon developed resistance to these reversible ATP competitive inhibitors via mutations in the kinase domain of EGFR. A new trend was adopted to design covalent irreversible inhibitors, that is, second‐ and third‐generation inhibitors. Second‐generation inhibitors can inhibit the mutant forms but, unfortunately, they had dose limiting side effects due to wild‐type EGFR inhibition. Third‐generation inhibitors emerged shortly, which were capable of inhibiting the mutant forms exclusively while sparing the wild type. Many other strategies have also been developed to reduce the risk of covalent interactions with off‐targets, thus improving the pharmacokinetic and/or pharmacodynamic profile of the antiproliferative agents. In this review, we focused mainly on second‐ and third‐generation EGFR inhibitors, their binding mechanisms (either docking studies or co‐crystallized structures), their synthetic approaches, clinical profiles, and limitations.
Augmented Lagrangian Pattern Search Based Multi‐Agent Model Predictive Control of Rhine‐Meuse Delta
Authors: Sharafi Narjes , Safavi Ali Akbar
Published: June 2016

In Large Scale Systems the concept of centrality fails due to the lack of centralized computing capability. The control of such systems has to be performed using multiple control agents. In this case, the matter of interactions among neighboring subsystems needs to be considered. In this paper, a water control system in the Netherlands is studied as a real large scale system. A multi‐agent scheme is applied to control the flow through the system which is decomposed into two interconnected subsystems. Each agent employs a model‐based predictive control (MPC) technique. The model of this large scale system is nonlinear and nonconvex. Therefore, an augmented Lagrangian pattern search optimization algorithm is used to implement multi‐agent MPC for this system. This proposed algorithm is applied by each control agent to solve its own interconnected optimization problem, at each subsystem of whole the water system. Simulation results show the effectiveness of the proposed approach.
Conditional Release of Forensic Psychiatric Patients Consistent with or Contrary to Behavioral Experts' Recommendations in the Netherlands: Prevalence Rates, Patient Characteristics and Recidivism After Discharge from Conditional Release
Authors: Nagtegaal Maria H , Boonmann Cyril
Published: June 2016

The present study examined a group of 447 Dutch forensic psychiatric patients on conditional release (CR). After a brief overview of the Dutch CR system for forensic psychiatric patients is presented, two sets of factors were studied: factors associated with behavioral experts' recommendations on CR readiness (prevalence rates of recommendations in contrast to or consistent with the judge's decision on CR, written vs. oral recommendations and consensus among parties); and characteristics of forensic psychiatric patients on CR imposed consistent with or contrary to behavioral experts' recommendations (i.e., demographic variables, psychopathology, judicial background and outcomes of violent behavior). Patients on CR consistent with or contrary to the behavioral experts' recommendations did not differ in demographic background variables and psychopathology. Patients on CR contrary to the behavioral experts' recommendations, however, had more prior convictions, and their index offense more often included a sex offense and a property offense (with or without violence) as compared to patients on CR consistent with the behavioral experts' recommendations. In addition, decisions contrary to the behavioral experts' recommendations were more often reached after a 3‐month continuation adjournment and after an appeal. Also, patients on CR contrary to the behavioral experts' recommendations were less often found to have been on trial leave before their CR. Finally, recidivism rates were found to be much higher for those on CR contrary to, as compared with those on CR consistent with the behavioral experts' recommendations. However, when corrected for other well‐known static predictors of recidivism, this significant difference was no longer prevalent. The implications for evaluators' CR readiness reports and lessons that may be learned from the Dutch forensic psychiatric CR system are discussed. Copyright © 2016 John Wiley & Sons, Ltd.
Thrombocytopenia‐associated multiorgan failure occurring in an infant at the onset of type 1 diabetes successfully treated with fresh frozen plasma
Authors: Kumar Revati , McSharry Brent , Bradbeer Peter , Wiltshire Esko , Jefferies Craig
Published: June 2016

Key Clinical Message

TAMOF is a devastating microangiopathy that can occur in association with the new onset of T1DM, and should be considered with the onset of thrombocytopenia, renal failure, and raised LDH. Treatment with fresh frozen plasma should be considered as a first‐line option in such cases prior to plasma exchange.
Spontaneous bilateral patellar tendon rupture: case report and review of fluoroquinolone‐induced tendinopathy
Authors: Rosa Bárbara , Campos Pedro , Barros André , Karmali Samir , Gonçalves Ricardo
Published: June 2016

Key Clinical Message

The present case emphasizes the importance of adhering to strict indications when prescribing fluoroquinolones. Although rare, drug‐induced tendinopathy is not confined to fluoroquinolones. The patient's and physician's awareness should be increased to reduce fluoroquinolones‐associated morbidity, particularly in patients with previously described risk factors.
Self‐Compassion: A Mentorship Framework for Counselor Educator Mothers
Authors: Solomon Coralis , Barden Sejal Mehta
Published: June 2016

Counselor educators experience high levels of stress. Mothers in academia face an additional set of emotional stressors. The authors offer a self‐compassion framework for mentors to increase emotional resilience of mothers in counselor education.
Model‐Based Optimization of a Photocatalytic Reactor with Light‐Emitting Diodes
Authors: Khodadadian Fatemeh , Poursaeidesfahani Ali , Li Zonghan , van Ommen J. Ruud , Stankiewicz Andrzej I. , Lakerveld Richard
Published: June 2016

The complicated interplay between mass and photon transfer within a photocatalytic reactor calls for an integrated design approach. A model‐based optimization approach for LED‐based photocatalytic reactors is presented. First, a model that describes the distribution of reactants and photons within a photocatalytic reactor is developed. Then, several design variables related to the reactor dimensions and light sources are optimized simultaneously using the photocatalytic degradation of toluene as a model system. The results demonstrate how different formulations of the problem can be used to either minimize the reactor cost or to obtain a specified concentration profile within the reactor.
Mixed Boron(III) and Phosphorous(V) Complexes of meso‐Triaryl 25‐Oxasmaragdyrins
Authors: Ganapathi Emandi , Kalita Hemanta , Theophall Gregory G. , Lakshmi K. V. , Ravikanth Mangalampalli
Published: June 2016

Two unprecedented mixed BIII/PV complexes of meso‐triaryl 25‐oxasmaragdyrins were synthesized in appreciable yields under mild reaction conditions. These unusual 25‐oxasmaragdyrin complexes containing one or two seven‐membered heterocyclic rings comprised of five different atoms (B, C, N, O, and P) were prepared by reacting B(OH)(Ph)‐smaragdyrin and B(OH)2‐smaragdyrin complexes, respectively, with POCl3 in toluene at reflux temperature. The products were characterized by HRMS and 1D‐ and 2D‐NMR spectroscopy. X‐ray crystallography of one of the mixed BIII/PV smaragdyrin complexes indicated that the macrocycle is significantly distorted and contains a stable seven‐membered heterocyclic ring within the macrocycle. The bands in the absorption and emission spectra were bathochromically shifted with reduced quantum yields and singlet‐state lifetimes relative to the free base, meso‐triaryl 25‐oxasmaragdyrin. The mixed BIII/PV complexes were difficult to oxidize but easier to reduce than the free base. The DFT‐optimized structure of the 25‐oxasmaragdyrin complex with two seven‐membered heterocycles indicated that it was a bicyclic spiro compound with two half‐chair‐like conformers. This was in contrast to the chair‐like conformation of the complex with a single seven‐membered heterocyclic ring. Moreover, incorporation of a second phosphate group in the former case stabilized the bonding geometry and resulted in higher stability, which was reflected in the bathochromic shift of the absorption spectra, more‐positive oxidation potential, and less‐negative reduction potential.
Exploring the Effect of Ligand Structural Isomerism in Langmuir–Blodgett Films of Chiral Luminescent EuIII Self‐Assemblies
Authors: Galanti Agostino , Kotova Oxana , Blasco Salvador , Johnson Chloe J. , Peacock Robert D. , Mills Shaun , Boland John J. , Albrecht Martin , Gunnlaugsson Thorfinnur
Published: June 2016

Here we have investigated the influence of the antenna group position on both the formation of chiral amphiphilic EuIII‐based self‐assemblies in CH3CN solution and, on the ability to form monolayers on the surface of quartz substrates using the Langmuir–Blodgett technique, by changing from the 1‐naphthyl (2(R), 2(S)) to the 2‐naphthyl (1(R), 1(S)) position. The evaluation of binding constants of the self‐ assemblies in CH3CN solution was achieved using conventional techniques such as UV/Visible and luminescence spectroscopies along with more specific circular dichroism (CD) spectroscopy. The binding constants obtained for EuL, EuL2 and EuL3 species in the case of 2‐naphthyl derivatives were comparable to those obtained for 1‐naphthyl derivatives. The analysis of the changes in the CD spectra of 1(R) and 1(S) upon addition of EuIII not only allowed us to evaluate the values of the binding constants but the resulting recalculated spectra may also be used as fingerprints for assignment of the chiral self‐assembly species formed in solution. The obtained monolayers were predominantly formed from EuL3 (≈85 %) with the minor species present in ≈15 % EuL2.
A New Ir‐NHC Catalyst for Signal Amplification by Reversible Exchange in D2O
Authors: Spannring Peter , Reile Indrek , Emondts Meike , Schleker Philipp P. M. , Hermkens Niels K. J. , van der Zwaluw Nick G. J. , van Weerdenburg Bram J. A. , Tinnemans Paul , Tessari Marco , Blümich Bernhard , Rutjes Floris P. J. T. , Feiters Martin C.
Published: June 2016

NMR signal amplification by reversible exchange (SABRE) has been observed for pyridine, methyl nicotinate, N‐methylnicotinamide, and nicotinamide in D2O with the new catalyst [Ir(Cl)(IDEG)(COD)] (IDEG=1,3‐bis(3,4,5‐tris(diethyleneglycol)benzyl)imidazole‐2‐ylidene). During the activation and hyperpolarization steps, exclusively D2O was used, resulting in the first fully biocompatible SABRE system. Hyperpolarized 1H substrate signals were observed at 42.5 MHz upon pressurizing the solution with parahydrogen at close to the Earth's magnetic field, at concentrations yielding barely detectable thermal signals. Moreover, 42‐, 26‐, 22‐, and 9‐fold enhancements were observed for nicotinamide, pyridine, methyl nicotinate, and N‐methylnicotinamide, respectively, in conventional 300 MHz studies. This research opens up new opportunities in a field in which SABRE has hitherto primarily been conducted in CD3OD. This system uses simple hardware, leaves the substrate unaltered, and shows that SABRE is potentially suitable for clinical purposes.
Biodegradable Oxamide‐Phenylene‐Based Mesoporous Organosilica Nanoparticles with Unprecedented Drug Payloads for Delivery in Cells
Authors: Croissant Jonas G. , Fatieiev Yevhen , Julfakyan Khachatur , Lu Jie , Emwas Abdul‐Hamid , Anjum Dalaver H. , Omar Haneen , Tamanoi Fuyuhiko , Zink Jeffrey I. , Khashab Niveen M.
Published: June 2016

We describe biodegradable mesoporous hybrid nanoparticles (NPs) in the presence of proteins and their applications for drug delivery. We synthesized oxamide phenylene‐based mesoporous organosilica nanoparticles (MON) in the absence of a silica source which had remarkably high organic content and high surface areas. Oxamide functions provided biodegradability in the presence of trypsin model proteins. MON displayed exceptionally high payloads of hydrophilic and hydrophobic drugs (up to 84 wt %), and a unique zero premature leakage without the pore capping, unlike mesoporous silica. MON were biocompatible and internalized into cancer cells for drug delivery.
Antifungal Imidazole‐Decorated Cationic Amphiphiles with Markedly Low Hemolytic Activity
Authors: Benhamou Raphael I. , Steinbuch Kfir B. , Fridman Micha
Published: June 2016

Herein we report that an imidazole‐decorated cationic amphiphile derived from the pseudo‐disaccharide nebramine has potent antifungal activity against strains of Candida glabrata pathogens. In combination with the natural bis‐benzylisoquinoline alkaloid tetrandrine the reported antifungal cationic amphiphile demonstrated synergistic antifungal activity against Candida albicans pathogens. This unique membrane disruptor caused no detectible mammalian red blood cell hemolysis at concentrations up to more than two orders of magnitude greater than its minimal inhibitory concentrations against the tested C. glabrata strains. We provide evidence that potency against C. glabrata may be associated with differences between the drug efflux pumps of C. albicans and C. glabrata. Imidazole decorated‐cationic amphiphiles show promise for the development of less toxic membrane‐disrupting antifungal drugs and drug combinations.
Rh‐Catalyzed Direct Amination of Unactivated C(sp3)−H bond with Anthranils Under Mild Conditions
Authors: Tang Conghui , Zou Miancheng , Liu Jianzhong , Wen Xiaojin , Sun Xiang , Zhang Yiqun , Jiao Ning
Published: June 2016

C−N Bond formation is of great significance due to the ubiquity of nitrogen‐containing compounds. Here, a mild and efficient RhIII‐catalyzed C(sp3)−H aryl amination reaction is reported. Anthranil is employed as the nitrogen source with 100 % atom efficiency. This C−H amination reaction exhibits broad substrate scope without using any external oxidants. Mechanistic studies including rhodacycle intermediates, H–D exchange, kinetic isotope effect (KIE) experiments, and in situ IR are presented.