bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydrothermal activity recorded in post Noachian‐aged impact craters on Mars
Authors: Turner Stuart M. R. , Bridges John C. , Grebby Stephen , Ehlmann Bethany L.
Published: March 2016

Hydrothermal systems have previously been reported in ancient Noachian and Hesperian‐aged craters on Mars using CRISM but not in Amazonian‐aged impact craters. However, the nakhlite meteorites do provide evidence of Amazonian hydrothermal activity. This study uses CRISM data of 144 impact craters of ≥7 km diameter and 14 smaller craters (3–7 km diameter) within terrain mapped as Amazonian to search for minerals that may have formed as a result of impact‐induced hydrothermal alteration or show excavation of ancient altered crust. No evidence indicating the presence of hydrated minerals was found in the 3–7 km impact craters. Hydrated minerals were identified in three complex impact craters, located at 52.42°N, 39.86°E in the Ismenius Lacus quadrangle, at 8.93°N, 141.28°E in Elysium, and within the previously studied Stokes crater. These three craters have diameters 20 km, 62 km, and 51 km. The locations of the hydrated mineral outcrops and their associated morphology indicate that two of these three impact craters—the unnamed Ismenius Lacus Crater and Stokes Crater—possibly hosted impact‐induced hydrothermal systems, as they contain alteration assemblages on their central uplifts that are not apparent in their ejecta. Chlorite and Fe serpentine are identified within alluvial fans in the central uplift and rim of the Ismenius Lacus crater, whereas Stokes crater contains a host of Fe/Mg/Al phyllosilicates. However, excavation origin cannot be precluded. Our work suggests that impact‐induced hydrothermalism was rare in the Amazonian and/or that impact‐induced hydrothermal alteration was not sufficiently pervasive or spatially widespread for detection by CRISM.
Overland flow resistances on varying slope gradients and partitioning on grassed slopes under simulated rainfall
Authors: Pan Chengzhong , Ma Lan , Wainwright John , Shangguan Zhouping
Published: March 2016

It is still unclear how slope steepness (S) and revegetation affect resistance (f) to overland flow. A series of experiments on runoff hydraulics was conducted on granular surfaces (bare soil and sandpaper) and grassed surfaces, including grass plots (GP), GP with litter (GL), and GP without leaves (GS) under simulated rainfall and inflow (30<Re<1400) with varying slopes ranging from 2.6% to 50%. The results show that the observed f based on a small‐size runoff plot under rainfall conditions tends to be overestimated due to the increase in flow rate, or Re (Reynolds number), with downward cross sections and a good f‐Re relation (f = KRe−1). There exists a good f‐Re relation for granular surfaces and a good f‐Fr relation (Fr, Froude number) for grass plots. A greater f occurred at the gentle and steep slopes for the granular surfaces, while f decreased with increasing slopes for the grass treatments. The different f‐S relations suggest that f is not a simple function of S. When Re≈1000, the sowing rye grass with level lines increased f by approximately 100 times and decreased bed shear stress to approximately 5%. The contribution of grass leaves, stems, litter, and grain surface to total resistance in the grass plots were averagely 52%, 32%, 16%, and 1%. The greater resistance from leaves may result from the leaves lying at the plot surface impacted by raindrop impact. These results are beneficial to understand the dynamics of runoff and erosion on hillslopes impacted by vegetation restoration.
Subsidence along the Atlantic Coast of North America: Insights from GPS and late Holocene relative sea level data
Authors: Karegar Makan A. , Dixon Timothy H. , Engelhart Simon E.
Published: March 2016

The Atlantic Coast of North America is increasingly affected by flooding associated with tropical and extratropical storms, exacerbated by the combined effects of accelerated sea‐level rise and land subsidence. The region includes the collapsing forebulge of the Laurentide Ice Sheet. High‐quality records of late Holocene relative sea‐level (RSL) rise are now available, allowing separation of long‐term glacial isostatic adjustment‐induced displacement from modern vertical displacement measured by GPS. We compare geological records of late Holocene RSL to present‐day vertical rates from GPS. For many coastal areas there is no significant difference between these independent data. Exceptions occur in areas of recent excessive groundwater extraction, between Virginia (38°N) and South Carolina (32.5°N). The present‐day subsidence rates in these areas are approximately double the long‐term geologic rates, which has important implications for flood mitigation. Tide gauge records, therefore, should be used with caution for studying sea‐level rise in this region.
Predictability of the recent slowdown and subsequent recovery of large‐scale surface warming using statistical methods
Authors: Mann Michael E. , Steinman Byron A. , Miller Sonya K. , Frankcombe Leela M. , England Matthew H. , Cheung Anson H.
Published: March 2016

The temporary slowdown in large‐scale surface warming during the early 2000s has been attributed to both external and internal sources of climate variability. Using semiempirical estimates of the internal low‐frequency variability component in Northern Hemisphere, Atlantic, and Pacific surface temperatures in concert with statistical hindcast experiments, we investigate whether the slowdown and its recent recovery were predictable. We conclude that the internal variability of the North Pacific, which played a critical role in the slowdown, does not appear to have been predictable using statistical forecast methods. An additional minor contribution from the North Atlantic, by contrast, appears to exhibit some predictability. While our analyses focus on combining semiempirical estimates of internal climatic variability with statistical hindcast experiments, possible implications for initialized model predictions are also discussed.
Lithospheric thickness controlled compositional variations in potassic basalts of Northeast China by melt‐rock interactions
Authors: Liu Jian‐Qiang , Chen Li‐Hui , Zeng Gang , Wang Xiao‐Jun , Zhong Yuan , Yu Xun
Published: March 2016

Melt‐rock interaction is a common mantle process; however, it remains unclear how this process affects the composition of potassic basalt. Here we present a case study to highlight the link between compositional variations in the potassic basalts and melt‐rock interaction in cold lithosphere. Cenozoic potassic basalts in Northeast China are strongly enriched in incompatible elements and show EM1‐type Sr–Nd–Pb isotopes, suggesting an enriched mantle source. These rocks show good correlations between 87Sr/86Sr and K2O/Na2O and Rb/Nb. Notably, these ratios decrease with increasing lithospheric thickness, which may reflect melt‐lithosphere interaction. Phlogopite precipitated when potassic melts passed through the lithospheric mantle, and K and Rb contents of the residual melts decreased over time. The thicker the lithosphere, the greater the loss of K and Rb from the magma. Therefore, the compositions of potassic basalts were controlled by both their enriched sources and reactions with lithospheric mantle.
Impact of increasing heat waves on U.S. ozone episodes in the 2050s: Results from a multimodel analysis using extreme value theory
Authors: Shen L. , Mickley L. J. , Gilleland E.
Published: March 2016

We develop a statistical model using extreme value theory to estimate the 2000–2050 changes in ozone episodes across the United States. We model the relationships between daily maximum temperature (Tmax) and maximum daily 8 h average (MDA8) ozone in May–September over 2003–2012 using a Point Process (PP) model. At ~20% of the sites, a marked decrease in the ozone‐temperature slope occurs at high temperatures, defined as ozone suppression. The PP model sometimes fails to capture ozone‐Tmax relationships, so we refit the ozone‐Tmax slope using logistic regression and a generalized Pareto distribution model. We then apply the resulting hybrid‐extreme value theory model to projections of Tmax from an ensemble of downscaled climate models. Assuming constant anthropogenic emissions at the present level, we find an average increase of 2.3 d a−1 in ozone episodes (>75 ppbv) across the United States by the 2050s, with a change of +3–9 d a−1 at many sites.
Mechanisms of step‐like tilt changes and very long period seismic signals during the 2000 Miyakejima eruption: Insights from kinematic GPS
Authors: Munekane Hiroshi , Oikawa Jun , Kobayashi Tomokazu
Published: March 2016

During the 2000 eruption of the Miyakejima volcano in Japan, step‐like tilt changes (TC) generally accompanied by very long period (VLP) seismic signals with a pulse‐like shape and widths of ∼50 s were repeatedly observed (TC/VLP events). Kinematic GPS time series for Miyakejima were investigated in order to detect displacements associated with these events. We found that the kinematic GPS time series could be interpreted as the superposition of the following features: (1) displacement associated with the TC/VLP events, the source of which possibly corresponded to a shallow magma chamber represented by an almost vertical ellipsoidal cavity elongated NE–SW at a depth of 2–3 km; (2) displacement following TC/VLP events that may have been caused by exponential‐type volume decreases of the same magma chamber with a decay constant of approximately half a day; and (3) displacements that may be caused by continuous volume decreases of the same magma chamber. These features broadly support the piston model of VLP seismic signals, in which a vertical piston of solid conduit material intermittently sinks into a magma chamber located a few kilometer beneath the edifice following deflation caused by continuous outflux of magma. The volume increase of the magma chamber associated with the TC/VLP events was found to be much smaller than that of the collapsed caldera, suggesting that most of the mass in the conduit sank into the magma chamber without generating VLP seismic waves or step‐like TC.
Activities of wild‐type and variant tissue‐type plasminogen activators retained on vascular endothelial cells
Authors: Suzuki Yuko , Sano Hideto , Tomczyk Martyna , Brzoska Tomasz , Urano Tetsumei
Published: March 2016

We reported that tissue‐type plasminogen activator (tPA) secreted from vascular endothelial cells (VECs) is retained on the cell surface and effectively evokes both plasminogen activation and fibrin clot dissolution (fibrinolysis) on VECs. Here, to evaluate possibly different behaviors of variants of tPA, we quantitatively assessed these two events separately using green fluorescent protein (GFP)‐conjugated tPA in cultured human VECs. The amount of secreted wild‐type tPA‐GFP correlated well with both the activities of plasminogen activation (r = 0.66) and fibrinolysis (r = −0.93). A variant of tPA‐GFP, with a lower affinity to the surface of VECs but higher affinity to fibrin, showed higher fibrinolysis and lower plasminogen activation activity compared to the wild‐type.
Pathways to romantic relational aggression through adolescent peer aggression and heavy episodic drinking
Authors: Woodin Erica M. , Sukhawathanakul Paweena , Caldeira Valerie , Homel Jacqueline , Leadbeater Bonnie
Published: March 2016

Adolescent peer aggression is a well‐established correlate of romantic relational aggression; however, the mechanisms underlying this association are unclear. Heavy episodic drinking (or “binge” alcohol use) was examined as both a prior and concurrent mediator of this link in a sample of 282 12–18 year old interviewed four times over 6 years. Path analyses indicated that early peer relational and physical aggression each uniquely predicted later romantic relational aggression. Concurrent heavy episodic drinking fully mediated this effect for peer physical aggression only. These findings highlight two important mechanisms by which peer aggression may increase the risk of later romantic relational aggression: a direct pathway from peer relational aggression to romantic relational aggression and an indirect pathway through peer physical aggression and concurrent heavy episodic drinking. Prevention programs targeting romantic relational aggression in adolescence and young adulthood may benefit from interventions that target multiple domains of risky behavior, including the heavy concurrent use of alcohol. Aggr. Behav. 42:563–576, 2016. © 2016 Wiley Periodicals, Inc.
A Roadmap for Controlled and Efficient n‐Type Doping of Self‐Assisted GaAs Nanowires Grown by Molecular Beam Epitaxy
Authors: Orrù Marta , Repiso Eva , Carapezzi Stefania , Henning Alex , Roddaro Stefano , Franciosi Alfonso , Rosenwaks Yossi , Cavallini Anna , Martelli Faustino , Rubini Silvia
Published: March 2016

N‐type doping of GaAs nanowires has proven to be difficult because the amphoteric character of silicon impurities is enhanced by the nanowire growth mechanism and growth conditions. The controllable growth of n‐type GaAs nanowires with carrier density as high as 1020 electron cm−3 by self‐assisted molecular beam epitaxy using Te donors is demonstrated here. Carrier density and electron mobility of highly doped nanowires are extracted through a combination of transport measurement and Kelvin probe force microscopy analysis in single‐wire field‐effect devices. Low‐temperature photoluminescence is used to characterize the Te‐doped nanowires over several orders of magnitude of the impurity concentration. The combined use of those techniques allows the precise definition of the growth conditions required for effective Te incorporation.
Current Enhancement in Organic Films through Gap Compression by Cold and Hot Isostatic Pressing
Authors: Esaki Yu , Matsushima Toshinori , Adachi Chihaya
Published: March 2016

The spatial gaps in organic films are compressed using cold and hot isostatic pressing (CIP and HIP, respectively) with the aim of enhancing their electrical characteristics. The microscopic gaps formed in amorphous organic films by inefficient molecular packing are difficult to compress using CIP and HIP; however, the macroscopic gaps formed between grains and other grains or substrates in polycrystalline organic films can be compressed using CIP and HIP. The gap compression by CIP and HIP in polycrystalline films enhances their electrical characteristics. Conversely, the electrical characteristics of amorphous films remain unchanged after CIP and HIP. HIP gives almost the same results as CIP in terms of gap compression and current enhancement, probably because the expected activation of molecular motion at high temperature is suppressed under high applied pressure. CIP markedly improves the performance of organic light‐emitting diodes, organic solar cells, and organic field‐effect transistors containing polycrystalline films. These findings are important for understanding the carrier injection and transport mechanisms of organic films containing gaps as well as enhancing the performance of future organic devices, especially those with polycrystalline films.
A Biodesigned Nanocomposite Biomaterial for Auricular Cartilage Reconstruction
Authors: Nayyer Leila , Jell Gavin , Esmaeili Ali , Birchall Martin , Seifalian Alexander M.
Published: March 2016

Current biomaterials for auricular replacement are associated with high rates of infection and extrusion. The development of new auricular biomaterials that mimic the mechanical properties of native tissue and promote desirable cellular interactions may prevent implant failure. A porous 3D nanocomposite scaffold (NS) based on POSS‐PCU (polyhedral oligomeric silsesquioxane nanocage into polycarbonate based urea‐urethane) is developed with an elastic modulus similar to native ear. In vitro biological interactions on this NS reveal greater protein adsorption, increased fibroblast adhesion, proliferation, and collagen production compared with Medpor (the current synthetic auricular implant). In vivo, the POSS‐PCU with larger pores (NS2; 150–250 μm) have greater tissue ingrowth (≈5.8× and ≈1.4 × increase) than the POSS‐PCU with smaller pores (NS1; 100–50 μm) and when compared to Medpor (>100 μm). The NS2 with the larger pores demonstrates a reduced fibrotic encapsulation compared with NS1 and Medpor (≈4.1× and ≈1.6×, respectively; P < 0.05). Porosity also influences the amount of neovascularization within the implants, with no blood vessel observed in NS1 (12 weeks postimplantation). The lack of chronic inflammatory response for all materials may indicate that the elastic modulus and pore size of the implant scaffold could be important design considerations for influencing fibrotic responses to auricular and other soft tissue implants.
From Filter Paper to Functional Actuator by Poly(Ionic Liquid)‐Modified Graphene Oxide
Authors: Song Haojie , Lin Huijuan , Antonietti Markus , Yuan Jiayin
Published: March 2016

A commercially available membrane filter paper composed of mixed cellulose esters bearing typically an interconnected pore structure is transformed into a stimuli‐responsive bilayer actuator by depositing a thin film of poly(ionic liquid)‐modified graphene oxide sheets (GO‐PIL) onto the filter paper. In acetone vapor, the as‐synthesized bilayer actuator bends readily into multiple loops at a fast speed with the GO‐PIL top film inward. Upon pulling back into air, the actuator recovers its original shape. The asymmetric swelling of the top GO‐PIL film and the bottom porous filter paper toward organic vapor offers a favorably synergetic function to drive the actuation. The PIL polymer chains in the hybrid film are proven crucial to enhance the adhesion strength between the GO sheets and the adjacent filter paper to avoid interfacial delamination and thus improve force transfer. The overall construction allows a prolonged lifetime of the bilayer actuator under constant operation, especially when compared to that of the GO/filter paper bilayer actuator without PIL.
A Mild TEMPO‐Catalyzed Aerobic Oxidative Conversion of Aldehydes into Nitriles
Authors: Fang Chaojie , Li Meichao , Hu Xinquan , Mo Weimin , Hu Baoxiang , Sun Nan , Jin Liqun , Shen Zhenlu
Published: March 2016

An efficient method to prepare nitriles from aldehydes using hexamethyldisilazane (HMDS) as the nitrogen source has been developed. The reactions were performed with 2,2,6,6‐tetramethylpiperidine l‐oxyl (TEMPO) as the catalyst, NaNO2 or TBN as the co‐catalyst, and molecular oxygen as the terminal oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.

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Four‐Electron Electrocyclic Ring‐Opening/Intermolecular [4+2] Cycloadditions of α‐Hydroxycyclobutenones: Stereoselective Synthesis of Multiple Substituted δ‐Lactams
Authors: Song Peidong , Li Qing , Wang Congcong , Wu Wenfa , Mao Xu , Wang Jiajia , Hu Xiangdong
Published: March 2016

A four‐electron electrocyclic ring‐opening/intermolecular [4+2] cycloaddition of α‐hydroxycyclobutenones is reported. The reaction represents the first example for the intermolecular cycloaddition of the extensively studied enol‐ketene intermediate, and provides a new synthetic route to multiply substituted δ‐lactams in high stereoselectivity.

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Y chromosome diversity in a linguistic isolate (Mirandese, NE Portugal)
Authors: Marques Sofia L. , Gusmão Leonor , Amorim Antonio , Prata Maria João , Alvarez Luis
Published: March 2016

Objectives

The purpose of this study was to genetically characterize the male lineages of people who speak Mirandese, an interesting case of a linguistic relict that can still be found in the municipality of Miranda do Douro, NE Portugal. This region lies within the area of the Leonese dialects, which are remnants of the Romance dialects spoken in the Kingdom of Leon currently grouped in the Astur–Leonese linguistic continuum. We intended to disclose affinities with surrounding populations, namely from Spain where the Astur–Leonese is also spoken.

Methods

Eighty‐eight unrelated males (58 from Miranda and 30 from Bragança, the broad Portuguese region where Miranda is located) were genotyped with the combined use of 17 Y chromosome short tandem repeats (Y‐STRs) and a high resolution Y chromosome single nucleotide polymorphism (Y‐SNPs) strategy. Moreover, 236 males from Miranda and neighboring regions, previously classified as R‐M269, were also genotyped.

Results

R‐P312 was the most frequent haplogroup in the Mirandese, followed by J‐12f2.1 and T‐M70. The male lineages J‐12f2.1 and T‐M70 were also well represented, and both were shared with descendants of Sephardic Jews. No signs of diversity reduction were detected.

Conclusions

Mirandese speakers display a Y chromosome gene pool that shows a subtle differentiation from neighboring populations, mainly attributable to the assimilation of lineages ascribed to be of Jewish ancestry. Although not revealing signs of geographic/linguistic isolation, no clear affinities with other Astur–Leonese populations were detected. The results suggest that in Miranda language sharing is not accompanied by significant gene flow between populations from both sides of the political border. Am. J. Hum. Biol. 28:671–680, 2016. © 2016 Wiley Periodicals, Inc.
The International Frontal Sinus Anatomy Classification (IFAC) and Classification of the Extent of Endoscopic Frontal Sinus Surgery (EFSS)
Authors: Wormald Peter‐John , Hoseman Werner , Callejas Claudio , Weber Rainer K. , Kennedy David W. , Citardi Martin J. , Senior Brent A. , Smith Timothy L. , Hwang Peter H. , Orlandi Richard R. , Kaschke Oliver , Siow Jin Keat , Szczygielski Kornel , Goessler Ulrich , Khan Martin , Bernal‐Sprekelsen Manuel , Kuehnel Thomas , Psaltis Alkis
Published: March 2016

The frontal recess and frontal sinus anatomy can vary from simple to complex. The variations in the anatomy of the frontal recess and frontal sinus are considerable but almost all variations can be classified if the various cell patterns are analyzed. This consensus document was developed to improve the ability of the surgeon to understand these possible variations, plan the surgery, and communicate these complexities when teaching or reporting outcomes. Once the surgeon understands the anatomical pattern of the frontal sinus and recess cells, the extent of surgery can be planned. This document presents a classification of the extent of surgery based on the anatomical classification.
Interleukin‐9 and interleukin‐17C in chronic rhinosinusitis
Authors: Olcott Clara M. , Han Joseph K. , Cunningham Tina D. , Franzese Christine B.
Published: March 2016

Background

Interleukin (IL)‐9 and IL‐17C have been known to play a role in allergic inflammation, yet, their roles in chronic rhinosinusitis (CRS) are not well defined. IL‐9 induces changes in epithelial cell gene expression leading to goblet cell metaplasia, whereas IL‐17C is functionally distinct in that its expression can be induced by bacterial challenge and inflammatory stimuli. This study aimed to compare levels of IL‐9 and IL‐17C in CRS with nasal polyps (CRSwNP) and without nasal polyps (CRSsNP) as well as atopy.

Methods

Nasal polyp or sinus mucosal specimens from CRSwNP (n = 36), CRSsNP (n = 9), and control (n = 9) groups were collected and processed. Patient atopy status was determined by history of skin‐prick test and pulmonary function test. Immunohistochemistry was carried out using anti‐human IL‐9 and IL‐17C antibodies. Positively‐stained cells were enumerated under high‐power (×400) magnification in 5 consecutive fields.

Results

The level of expression of IL‐9 was higher in CRSwNP than CRSsNP and control. Similar findings were demonstrated in IL‐17C with higher expression in CRSwNP than CRSsNP and control. Both the averages of positively‐stained cells expressing IL‐9 and IL‐17C were higher in CRS with asthma and allergy compared to control. This suggested that IL‐9 and IL‐17C were both involved in the pathogenesis of CRS, allergy, and asthma.

Conclusion

Inflammatory cell expression of IL‐9 and IL‐17C were increased in CRS, particularly with allergy and asthma. These interleukins may contribute to the pathogenesis of CRSwNP as well as atopy and may serve as therapeutic targets for disease management.
Human rhinovirus in experimental infection after peroral Lactobacillus rhamnosus GG consumption, a pilot study
Authors: Tapiovaara Laura , Kumpu Minna , Mäkivuokko Harri , Waris Matti , Korpela Riitta , Pitkäranta Anne , Winther Birgit
Published: March 2016

Background

Data has emerged on possible beneficial effects of probiotics in respiratory tract viral infections, but it is unclear if the promising positive effects evidenced are due to a reduced viral load during infections. The aims of this work were to investigate the effect of peroral probiotic Lactobacillus rhamnosus GG (American Type Culture Collection [ATCC], Accession No. 53103) consumption on human rhinovirus (HRV) load in nasopharyngeal lavage samples in experimental HRV infection, and to correlate viral load to clinical symptoms.

Methods

Intranasal HRV A39 inoculation was performed on 59 adults, who had consumed juice enriched with live or heat‐inactivated L. rhamnosus GG or control juice for 3 weeks prior to inoculation in a randomized, controlled, pilot trial setting. Nasopharyngeal lavage samples and symptom data were analyzed on day 0 before inoculation, and on days 2 and 5. Samples were subjected to quantitative HRV detection by polymerase chain reaction (PCR).

Results

Before inoculation 9 of 59 (15%) samples presented with another HRV strain than the studied A39. There was a tendency toward the lowest HRV loads in the L. rhamnosus GG groups and the highest in placebo group (log10 copies/mL, 95% confidence interval [CI], 6.20 [5.18 to 7.40] in live, 6.30 [4.91 to 7.08] in inactivated L. rhamnosus GG, and 7.25 [5.81 to 7.52] in placebo group, p = 0.57 in day 2) in the wild‐type excluded population. The HRV load positively correlated with the symptom scores on days 2 and 5 (correlation coefficient 0.61 [p < 0.001] and 0.28 [p = 0.034], respectively).

Conclusion

Results did not show statistical differences in viral loads in subjects using L. rhamnosus GG when compared to placebo. HRV load positively correlated with the total symptom scores.
Radiological–pathological correlation of diffusion tensor and magnetization transfer imaging in a closed head traumatic brain injury model
Authors: Tu Tsang‐Wei , Williams Rashida A. , Lescher Jacob D. , Jikaria Neekita , Turtzo L. Christine , Frank Joseph A.
Published: March 2016

Objective

Metrics of diffusion tensor imaging (DTI) and magnetization transfer imaging (MTI) can detect diffuse axonal injury in traumatic brain injury (TBI). The relationship between the changes in these imaging measures and the underlying pathologies is still relatively unknown. This study investigated the radiological–pathological correlation between these imaging techniques and immunohistochemistry using a closed head rat model of TBI.

Methods

TBI was performed on female rats followed longitudinally by magnetic resonance imaging (MRI) out to 30 days postinjury, with a subset of animals selected for histopathological analyses. A MRI‐based finite element analysis was generated to characterize the pattern of the mechanical insult and estimate the extent of brain injury to direct the pathological correlation with imaging findings.

Results

DTI axial diffusivity and fractional anisotropy (FA) were sensitive to axonal integrity, whereas radial diffusivity showed significant correlation to the myelin compactness. FA was correlated with astrogliosis in the gray matter, whereas mean diffusivity was correlated with increased cellularity. Secondary inflammatory responses also partly affected the changes of these DTI metrics. The magnetization transfer ratio (MTR) at 3.5ppm demonstrated a strong correlation with both axon and myelin integrity. Decrease in MTR at 20ppm correlated with the extent of astrogliosis in both gray and white matter.

Interpretation

Although conventional T2‐weighted MRI did not detect abnormalities following TBI, DTI and MTI afforded complementary insight into the underlying pathologies reflecting varying injury states over time, and thus may substitute for histology to reveal diffusive axonal injury pathologies in vivo. This correlation of MRI and histology furthers understanding of the microscopic pathology underlying DTI and MTI changes in TBI. Ann Neurol 2016;79:907–920
Observation of Fano resonance and classical analog of electromagnetically induced transparency in toroidal metamaterials
Authors: Han Song , Cong Lonqing , Gao Fei , Singh Ranjan , Yang Helin
Published: March 2016

Toroidal multipoles have recently been explored in various scientific communities, ranging from atomic and molecular physics, electrodynamics, and solid‐state physics to biology. Here we experimentally and numerically demonstrate a three‐dimensionsal toroidal metamaterial where two different toroidal dipoles along orthogonal directions have been observed. The chosen toroidal metamaterial also simultaneously supports Fano resonance and the classical analog of electromagnetically induced transparency (EIT) phenomena in the transmission spectra that originate from the electric–toroidal dipole and electric–magnetic dipole destructive interference. The intriguing properties of the toroidal resonances may open up avenues for applications in toroidal moments generator, sensing and slow‐light devices.
The Sudbury Neutrino Observatory: Observation of flavor change for solar neutrinos
Authors: McDonald Arthur B.
Published: March 2016

The Sudbury Neutrino Observatory (SNO) experiment was constructed by an international scientific collaboration primarily to provide a clear determination of whether solar neutrinos change their flavor in transit from the core of the sun to the earth. The detector used 1000 tonnes of heavy water (>99.92% D2O) in an ultra‐clean location 2 km underground in INCO's Creighton mine near Sudbury, Canada to observe two separate reactions of neutrinos on deuterium. The first reaction was sensitive only to electron flavor neutrinos and the second reaction was equally sensitive to all neutrino flavors. The measurements by SNO showed clearly that the hypothesis of no neutrino flavor change was ruled out by more than 5.3 standard deviations. The observation of flavor change for neutrinos implies that they have a non‐zero mass. The measured total flux of active neutrinos from 8B decay in the sun was found to be in excellent agreement with the predictions of solar model calculations. This paper describes the history and scientific measurements of the SNO experiment.
Mit Peptiden dekorierte Dendrimere und ihre biotechnologische Nutzung
Authors: Wan Jingjing , Alewood Paul F.
Published: March 2016

Peptid‐dekorierte Dendrimere (PDDs) bilden eine Klasse kugelförmiger, regulärer, verzweigter Polymere, die an ihren Oberflächen kovalent durch Peptide modifiziert sind. PDDs sind als Proteinmimetika, neuartige Biomaterialien sowie für ein breites Spektrum biomedizinischer Anwendungen zum Einsatz gekommen. Seit ihrer Konzeption und Entwicklung in den späten 1980er Jahren ist Poly‐l‐lysin die bevorzugte Kernstruktur für PDDs. Jüngst haben zahlreiche Innovationen in der Polymer‐ und Ligationschemie das Feld neu belebt. Dies hat dazu geführt, dass heute wohldefinierte Dendrimere mit vielfältigeren Strukturen und Funktionen vorliegen. Dieser Kurzaufsatz beleuchtet die Entwicklung von PDDs als Produkte einer signifikant verbesserten Ligationschemie unter Einbeziehung strukturell wohldefinierter Peptide sowie erste Anwendungen von PDDs in den Bereichen Bildgebung und Wirkstoffentwicklung.
Synthesis of Octafluoroporphyrin
Authors: Kashi Chiranjeevulu , Wu Chu‐Chun , Mai Chi‐Lun , Yeh Chen‐Yu , Chang Chi K.
Published: March 2016

Despite the long list of known fluoroporphyrinoids, the most fundamental 2,3,7,8,12,13,17,18‐octafluoroporphyrin (OFP) has not been synthesized until now. It is achieved by condensation of two molecules of tetrafluoro‐dipyrrylmethane‐2‐carboxaldehyde in the presence of magnesium(II) salts. The fluorinated dipyrrylmethane also gives 5,15‐bis(pentafluorophenyl)‐OFP (F18P) with a reasonable yield. Both Mg/OFP and Zn/F18P in the solid‐state reveal an essentially flat structure. The fluoro groups impart as much as a 0.5 V anodic shift for porphyrin ring oxidation/reduction, as well as hypsochromic shifts in the Uv‐vis spectra.
Nickel‐Catalyzed Carboxylation of Benzylic C−N Bonds with CO2
Authors: Moragas Toni , Gaydou Morgane , Martin Ruben
Published: March 2016

A user‐friendly Ni‐catalyzed reductive carboxylation of benzylic C−N bonds with CO2 is described. This procedure outperforms state‐of‐the‐art techniques for the carboxylation of benzyl electrophiles by avoiding commonly observed parasitic pathways, such as homodimerization or β‐hydride elimination, thus leading to new knowledge in cross‐electrophile reactions.
A Mixed‐Ligand Chiral Rhodium(II) Catalyst Enables the Enantioselective Total Synthesis of Piperarborenine B
Authors: Panish Robert A. , Chintala Srinivasa R. , Fox Joseph M.
Published: March 2016

A novel, mixed‐ligand chiral rhodium(II) catalyst, Rh2(S‐NTTL)3(dCPA), has enabled the first enantioselective total synthesis of the natural product piperarborenine B. A crystal structure of Rh2(S‐NTTL)3(dCPA) reveals a “chiral crown” conformation with a bulky dicyclohexylphenyl acetate ligand and three N‐naphthalimido groups oriented on the same face of the catalyst. The natural product was prepared on large scale using rhodium‐catalyzed bicyclobutanation/ copper‐catalyzed homoconjugate addition chemistry in the key step. The route proceeds in ten steps with an 8 % overall yield and 92 % ee.
Halogenase‐inspirierte oxidative Chlorierung mittels Flavin‐ Photokatalyse
Authors: Hering Thea , Mühldorf Bernd , Wolf Robert , König Burkhard
Published: March 2016

Chlorierte Arene sind Bestandteil vieler Pharmazeutika, Agrochemikalien und Polymere sowie wichtige Startmaterialien für übergangsmetallkatalysierte Kreuzkupplungen. Für ihre Herstellung nutzen Chemiker meist Chlorgas oder elektropositive Chlorierungsreagentien. Die Natur hingegen chloriert ausgehend von Chloridionen mithilfe von FAD‐abhängigen Halogenasen und O2 als Oxidationsmittel. Wir beschreiben hier eine diesem enzymatischen Prozess nachempfundene photokatalytische oxidative Chlorierung unter Verwendung des organischen Farbstoffes Riboflavintetraacetat. Dieses chemische Verfahren ermöglicht die Umsetzung von Arenen innerhalb eines definierten Redoxbereichs und hat eine größere Substratbreite als die Aktivierung durch eine substratspezifische Enzymbindungstasche.
Construction of an Artificial Ferrimagnetic Lattice by Lithium Ion Insertion into a Neutral Donor/Acceptor Metal–Organic Framework
Authors: Taniguchi Kouji , Narushima Keisuke , Mahin Julien , Kosaka Wataru , Miyasaka Hitoshi
Published: March 2016

Construction of a molecular system in which the magnetic lattice exhibits long‐range order is one of the fundamental goals in materials science. In this study, we demonstrate the artificial construction of a ferrimagnetic lattice by doping electrons into acceptor sites of a neutral donor/acceptor metal–organic framework (D/A‐MOF). This doping was achieved by the insertion of Li‐ions into the D/A‐MOF, which was used as the cathode of a Li‐ion battery cell. The neutral D/A‐MOF is a layered system composed of a carboxylate‐bridged paddlewheel‐type diruthenium(II,II) complex as the donor and a TCNQ derivative as the acceptor. The ground state of the neutral form was a magnetically disordered paramagnetic state. Upon discharge of the cell, spontaneous magnetization was induced; the transition temperature was variable. The stability of the magnetically ordered lattice depended on the equilibrium electric potential of the D/A‐MOF cathode, which reflected the electron‐filling level.
Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand
Authors: Tatematsu Ryo , Inomata Tomohiko , Ozawa Tomohiro , Masuda Hideki
Published: March 2016

A novel nickel(II) complex [Ni(L)2Cl]Cl with a bidentate phosphinopyridyl ligand 6‐((diphenylphosphino)methyl)pyridin‐2‐amine (L) was synthesized as a metal‐complex catalyst for hydrogen production from protons. The ligand can stabilize a low Ni oxidation state and has an amine base as a proton transfer site. The X‐ray structure analysis revealed a distorted square‐pyramidal NiII complex with two bidentate L ligands in a trans arrangement in the equatorial plane and a chloride anion at the apex. Electrochemical measurements with the NiII complex in MeCN indicate a higher rate of hydrogen production under weak acid conditions using acetic acid as the proton source. The catalytic current increases with the stepwise addition of protons, and the turnover frequency is 8400 s−1 in 0.1 m [NBu4][ClO4]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV.
Transparent Aluminium Oxide Coatings of Polymer Brushes
Authors: Micciulla Samantha , Duan XiaoFei , Strebe Julia , Löhmann Oliver , Lamb Robert N. , von Klitzing Regine
Published: March 2016

A novel method for the preparation of transparent Al2O3 coatings of polymers is presented. An environmental‐friendly sol–gel method is employed, which implies mild conditions and low costs. A thermoresponsive brush is chosen as a model surface. X‐ray photoelectron spectroscopy is used to characterize the samples during the conversion of the precursor Al(OH)3 into oxide and to prove the mildness of the protocol. The study evidences a relation between lateral homogeneity of alumina and the wettability of the polymer surface by the precursor solution, while morphology and elasticity are dominated by the polymer properties. The study of the swelling behavior of the underneath brush reveals the absence of water uptake, proving the impermeability of the alumina layer. The broad chemical and structural variety of polymers, combined with the robustness of transparent alumina films, makes these composites promising as biomedical implants, protective sheets and components for electric and optical devices.
Block Copolymerization of Lactide and an Epoxide Facilitated by a Redox Switchable Iron‐Based Catalyst
Authors: Biernesser Ashley B. , Delle Chiaie Kayla R. , Curley Julia B. , Byers Jeffery A.
Published: March 2016

A cationic iron(III) complex was active for the polymerization of various epoxides, whereas the analogous neutral iron(II) complex was inactive. Cyclohexene oxide polymerization could be “switched off” upon in situ reduction of the iron(III) catalyst and “switched on” upon in situ oxidation, which is orthogonal to what was observed previously for lactide polymerization. Conducting copolymerization reactions in the presence of both monomers resulted in block copolymers whose identity can be controlled by the oxidation state of the catalyst: selective lactide polymerization was observed in the iron(II) oxidation state and selective epoxide polymerization was observed in the iron(III) oxidation state. Evidence for the formation of block copolymers was obtained from solubility differences, GPC, and DOSY‐NMR studies.
Direct Time‐Domain Observation of Conformational Relaxation in Gas‐Phase Cold Collisions
Authors: Drayna Garrett K. , Hallas Christian , Wang Kenneth , Domingos Sergio R. , Eibenberger Sandra , Doyle John M. , Patterson David
Published: March 2016

Cooling molecules in the gas phase is important for precision spectroscopy, cold molecule physics, and physical chemistry. Measurements of conformational relaxation cross sections shed important light on potential energy surfaces and energy flow within a molecule. However, gas‐phase conformational cooling has not been previously observed directly. In this work, we directly observe conformational dynamics of 1,2‐propanediol in cold (6 K) collisions with atomic helium using microwave spectroscopy and buffer‐gas cooling. Precise knowledge and control of the collisional environment in the buffer‐gas allows us to measure the absolute collision cross‐section for conformational relaxation. Several conformers of 1,2‐propanediol are investigated and found to have relaxation cross‐sections with He ranging from σ=4.7(3.0)×10−18 cm2 to σ>5×10−16 cm2. Our method is applicable to a broad class of molecules and could be used to provide information about the potential energy surfaces of previously uninvestigated molecules.
Multicompartmental Microcapsules with Orthogonal Programmable Two‐Way Sequencing of Hydrophobic and Hydrophilic Cargo Release
Authors: Xu Weinan , Ledin Petr A. , Iatridi Zacharoula , Tsitsilianis Constantinos , Tsukruk Vladimir V.
Published: March 2016

Multicompartmental responsive microstructures with the capability for the pre‐programmed sequential release of multiple target molecules of opposite solubility (hydrophobic and hydrophilic) in a controlled manner have been fabricated. Star block copolymers with dual‐responsive blocks (temperature for poly(N‐isopropylacrylamide) chains and pH for poly(acrylic acid) and poly(2‐vinylpyridine) arms) and unimolecular micellar structures serve as nanocarriers for hydrophobic molecules in the microcapsule shell. The interior of the microcapsule can be loaded with water‐soluble hydrophilic macromolecules. For these dual‐loaded microcapsules, a programmable and sequential release of hydrophobic and hydrophilic molecules from the shell and core, respectively, can be triggered independently by temperature and pH variations. These stimuli affect the hydrophobicity and chain conformation of the star block copolymers to initiate out‐of‐shell release (elevated temperature), or change the overall star conformation and interlayer interactions to trigger increased permeability of the shell and out‐of‐core release (pH). Reversing stimulus order completely alters the release process.
Compact, Polyvalent Mannose Quantum Dots as Sensitive, Ratiometric FRET Probes for Multivalent Protein–Ligand Interactions
Authors: Guo Yuan , Sakonsinsiri Chadamas , Nehlmeier Inga , Fascione Martin A. , Zhang Haiyan , Wang Weili , Pöhlmann Stefan , Turnbull W. Bruce , Zhou Dejian
Published: March 2016

A highly efficient cap‐exchange approach for preparing compact, dense polyvalent mannose‐capped quantum dots (QDs) has been developed. The resulting QDs have been successfully used to probe multivalent interactions of HIV/Ebola receptors DC‐SIGN and DC‐SIGNR (collectively termed as DC‐SIGN/R) using a sensitive, ratiometric Förster resonance energy transfer (FRET) assay. The QD probes specifically bind DC‐SIGN, but not its closely related receptor DC‐SIGNR, which is further confirmed by its specific blocking of DC‐SIGN engagement with the Ebola virus glycoprotein. Tuning the QD surface mannose valency reveals that DC‐SIGN binds more efficiently to densely packed mannosides. A FRET‐based thermodynamic study reveals that the binding is enthalpy‐driven. This work establishes QD FRET as a rapid, sensitive technique for probing structure and thermodynamics of multivalent protein–ligand interactions.
Crafting Core/Graded Shell–Shell Quantum Dots with Suppressed Re‐absorption and Tunable Stokes Shift as High Optical Gain Materials
Authors: Jung Jaehan , Lin Chun Hao , Yoon Young Jun , Malak Sidney T. , Zhai Yaxin , Thomas Edwin L. , Vardeny Valy , Tsukruk Vladimir V. , Lin Zhiqun
Published: March 2016

The key to utilizing quantum dots (QDs) as lasing media is to effectively reduce non‐radiative processes, such as Auger recombination and surface trapping. A robust strategy to craft a set of CdSe/Cd1−xZnxSe1−ySy/ZnS core/graded shell–shell QDs with suppressed re‐absorption, reduced Auger recombination rate, and tunable Stokes shift is presented. In sharp contrast to conventional CdSe/ZnS QDs, which have a large energy level mismatch between CdSe and ZnS and thus show strong re‐absorption and a constrained Stokes shift, the as‐synthesized CdSe/Cd1−xZnxSe1−ySy/ZnS QDs exhibited the suppressed re‐absorption of CdSe core and tunable Stokes shift as a direct consequence of the delocalization of the electron wavefunction over the entire QD. Such Stokes shift‐engineered QDs with suppressed re‐absorption may represent an important class of building blocks for use in lasers, light emitting diodes, solar concentrators, and parity‐time symmetry materials and devices.
Generation and Reaction of Carbamoyl Anions in Flow: Applications in the Three‐Component Synthesis of Functionalized α‐Ketoamides
Authors: Nagaki Aiichiro , Takahashi Yusuke , Yoshida Jun‐ichi
Published: March 2016

Using a flow microreactor system, carbamoyllithium compounds were successfully generated and used for reactions with electrophiles to give various amides, including α‐ketoamides. The present method could be applied to the three‐component synthesis of functionalized α‐ketoamides using a carbamoyllithium compound, methyl chloroformate, and a functionalized organolithium reagent.
Surface modification and immobilization in poly(acrylic acid) of Ag/ZnO for photocatalytic degradation of endocrine‐disrupting compounds
Authors: Jasso‐Salcedo Alma Berenice , Meimaroglou Dimitrios , Hoppe Sandrine , Pla Fernand , Escobar‐Barrios Vladimir A.
Published: March 2016

Silver‐modified ZnO particles (Ag/ZnO) are effective catalysts for the photodegradation of water pollutants such as bisphenol‐A. However, until now, their use in continuous processes was back‐drawn because of difficulties associated with their recovery. To overcome this problem, the present work aimed at immobilizing Ag/ZnO in cross‐linked poly(acrylic acid) ‐PAA‐. Ag/ZnO was first silanized using (3‐glycidyloxypropyl)trimethoxysilane and thoroughly dispersed in a water‐acrylic acid solution. The suspension was then submitted to radical polymerization in presence of a cross‐linker (N,N′‐Methylenebisacrylamide). The resulting composites were characterized in terms of chemical structure, morphology, crystallinity, thermal properties, and photostability. Their analyses showed that the silanized particles were chemically anchored to PAA and homogeneously distributed in the matrix. UV‐assisted photocatalysis of bisphenol‐A aqueous solutions showed that immobilized Ag/ZnO can achieve photodegradation performances comparable to pure Ag/ZnO and allows its use in successive cycles and, consequently, in continuous processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43528.
Preparation and hemocompatibility of electrospun O‐carboxymethyl chitosan/PVA nanofibers
Authors: Zeng Qinghuan , Qin Jinmin , Yin Xueqiong , Liu Haifang , Zhu Li , Dong Wenyuan , Zhang Song
Published: March 2016

Chitosan was deacetylated and carboxymethylated to prepare O‐carboxymethyl chitosan (CMC) for further electrospinning. CMC was characterized using FTIR, NMR, and chemical titration, indicating a degree of carboxymethylation of 51.4%. CMC was electrospun together with poly(vinyl alcohol) (PVA) to prepare membranes composed of nanofibers. The electrospinning conditions were optimized. The CMC/PVA membrane obtained at the conditions of 15.2 g/mL CMC 50 mL, 8 g/mL PVA 5 mL, 25 kV, and a distance of 23 cm, had nanofibers without beads, with diameters of 70–200 nm. The mats were crosslinked by glutaraldehyde before platelet adhesion measurement. The nanofibrous structure remained after crosslinking while the wettability decreased. CMC/PVA mats with higher CMC amount and fewer beads, had fewer adherent platelets and less platelets aggregation showing better hemocompatibility. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43565.