bluuebunny/crossref_metadata_2025 huggingface dataset:
Late Tertiary reorganizations of deformation in northeastern Tibet constrained by stratigraphy and provenance data from eastern Longzhong Basin
Authors: Liu Shanpin , Li Jijun , Stockli Daniel F. , Song Chunhui , Nie Junsheng , Peng Tingjiang , Wang Xiuxi , He Kuang , Hui Zhengchuang , Zhang Jun
Published: June 2015

The deformation of the Tibetan Plateau is central to unraveling the process and mechanism of continental tectonics. Although most agree that crust shortening and plateau growth were protracted throughout the Cenozoic Indo‐Asian collision, particular deformation histories relating to tectonic kinematics and dynamics are still incomplete due to sparseness of diagnostic geological information from plateau margin. Here we present combined investigation of stratigraphy, magnetostratigraphy, and provenance for the eastern margin of Longzhong Basin to show two reorganizations of basin formation and tectonic regime during the late Tertiary. First, the depocenter migrated from the dispersed Paleogene sequences to the Wushan‐Tianshui foreland sequence during the earliest Miocene (circa 22 Ma), accompanied by shift of sedimentary provenance from double sources including the eastern Qilian block and eastern West Qinling terrain to single source within the West Qinling. It suggests reorganization of deformation from NW‐SE extension to NE‐SW contraction and initial uplift of the eastern West Qinling. Second, massive coarse‐grained fluvial beds were revived in the Wushan Basin during the late Miocene (circa 10 Ma), associated by eastward depositional expansion and another shift of sedimentary provenance toward northeast. It reflects thrusting up of the northern edge of the West Qinling and Liupan Shan Mountains linked with relocation of crust shortening from NE‐SW direction to ENE‐WSW direction and accelerated deformation of northeastern Tibet. These transitions of deformation regimes imply variation of geodynamic mechanisms during the process of plateau growth.
Magnetic mineral diagenesis in the river‐dominated inner shelf of the East China Sea, China
Authors: Ge Can , Zhang Weiguo , Dong Chenyin , Dong Yan , Bai Xuexin , Liu Jinyan , Hien Nguyen Thi Thu , Feng Huan , Yu Lizhong
Published: June 2015

The inner shelf of the East China Sea is a river‐dominated margin characterized by fine‐grained mud deposits and a rapid sedimentation rate. Three short sediment cores (~2.7 m in length) were examined to characterize spatial variations in magnetic mineral diagenesis. The sediment cores were analyzed for sedimentation rates, magnetic properties, particle size distribution, organic carbon, and total sulfur content. The two more proximal cores with higher sedimentation rates (~2.2 cm/yr and ~0.96 cm/yr) do not exhibit obvious effects of reductive dissolution of magnetite with increasing depth, which is consistent with their lower total sulfur content. The offshore core, A12‐4, which has a lower sedimentation rate, contains clear evidence of magnetite dissolution and increasing total sulfur content with depth. The three cores have a similar sediment source and organic matter input; therefore, we suggest that a higher sedimentation rate will lead to less reductive diagenesis of magnetite, assuming that other factors are constant. The iron‐ to sulfate‐reduction boundary, i.e., revealed by the onset of a rapid decline of magnetic susceptibility, is located 1.0 m below seafloor in core A12‐4. This is much deeper than is reported in many other coastal marine environments and can be explained by the higher sedimentation rate, the presence of refractory terrestrial organic matter, and an abundant input of detrital iron oxides. This study demonstrates that analyses of the magnetic mineral zonation provide a straightforward approach to assess diagenetic organic carbon decomposition pathways in marine environments.
Striping noise mitigation in ATMS brightness temperatures and its impact on cloud LWP retrievals
Authors: Ma Yuan , Zou Xiaolei
Published: June 2015

Advanced Technology Microwave Sounder (ATMS) on board Suomi National Polar‐orbiting Partnership (NPP) satellite provides global distributions of microwave brightness temperature measurements at 22 temperature and humidity sounding channels twice daily. However, the differences between observations and brightness temperature simulations exhibit a systematic along‐track striping noise for all channels. In this study, a set of 22 “optimal” filters is designed to remove the striping noise in different channels. It is shown that the original method for ATMS striping noise mitigation developed by Qin et al. () can be simplified and made suitable for use in an operational context. Impacts of striping noise mitigation on small‐scale weather features are investigated by comparing ATMS cloud liquid water path (LWP) retrieved before and after striping noise mitigation. It is shown that the optimal filters do not affect small‐scale cloud features while smoothing out striping noise in brightness temperatures. It is also shown that the striping noise is present in the LWP retrievals if the striping noise in brightness temperatures of ATMS channels 1 and 2 is not removed. The amplitude of the striping noise in LWP is linearly related to the magnitude of striping noise in ATMS brightness temperature observations.
Characteristics of submicron particulate matter at the urban roadside in downtown Hong Kong—Overview of 4 months of continuous high‐resolution aerosol mass spectrometer measurements
Authors: Lee Berto P. , Li Yong Jie , Yu Jian Zhen , Louie Peter K. K. , Chan Chak K.
Published: June 2015

Hong Kong, one of the world's most densely populated cities and an international financial center, has been suffering from traffic‐related air pollution. This study presents the first real‐time high‐resolution aerosol mass spectrometry measurements of submicron nonrefractory particulate matter (NR‐PM1) at the urban roadside in Hong Kong from March to July 2013 with the aim to identify major sources, to assess local and nonlocal emissions, and to characterize trends at different time scales. Organics were dominant, with fresh primary organic aerosol representing two thirds of the total measured organics. Cooking contributions in organic aerosol were assessed directly for the first time in Hong Kong and exceeded those related to vehicles although traffic was still the major PM1 source when elemental carbon was included. These findings were supported by additional measurements including traffic data, elemental/organic carbon, and VOC data. Springtime concentrations were about double of those in summer, due to a strong seasonal transition which affected meteorological conditions and street‐level circulation. Local formation of secondary species was not clearly discernible in either season. The elemental composition of organic aerosol remained stable with similar elemental ratios across the covered seasons: OM/OC: 1.49 ± 0.13, O/C: 0.25 ± 0.10, H/C: 1.68 ± 0.08 for spring and OM/OC: 1.43 ± 0.14, O/C: 0.21 ± 0.11, H/C: 1.69 ± 0.08 for summer. Diurnal changes in H/C and O/C as a result of mixing of primary organic aerosol and secondary organic aerosol were evident in the van Krevelen plot.
On the significance of the interannual relationship between the Asian‐Pacific Oscillation and the North Atlantic Oscillation
Authors: Zhou Botao , Wang Zunya
Published: June 2015

Using monthly data from the European Centre for Medium‐Range Weather Forecasts 40 year Re‐Analysis, this study investigated the interannual relationship between the Asian‐Pacific Oscillation (APO) and the North Atlantic Oscillation (NAO) for the period of May to August. The NAO is represented by the leading Empirical Orthogonal Function of sea level pressure anomalies over the Atlantic sector. The difference of upper tropospheric eddy air temperature (T′) between Asia and the North Pacific is used to measure the APO. Results clearly show that the APO and the NAO correlated very well on the interannual time scale, with the positive (negative) phase of the APO corresponding to the strong (weak) NAO. Such a relationship is well supported by the atmospheric dynamic process. When the APO is in the positive phase (characterized by the positive T′ anomaly over Asia and the negative T′ anomaly over the North Pacific in the upper troposphere), the upper tropospheric geopotential height increases over Asia and decreases over the North Pacific. Accordingly, anticyclonic circulation and cyclonic circulation anomalies are introduced, respectively, over Asia and south of the North Pacific, and a zonal teleconnection wave train is excited from Asia to the North Atlantic. As a consequence, an anomalous anticyclonic circulation prevails in the low level of the North Atlantic and an anomalous cyclonic circulation appears to its north, which corresponds to the atmospheric pattern of strong NAO. Further study proposes that the quasi‐stationary wave pattern emanating from the western North Pacific region may serve as a bridge for this linkage.
Light‐absorbing properties of ambient black carbon and brown carbon from fossil fuel and biomass burning sources
Authors: Healy R. M. , Wang J. M. , Jeong C.‐H. , Lee A. K. Y. , Willis M. D. , Jaroudi E. , Zimmerman N. , Hilker N. , Murphy M. , Eckhardt S. , Stohl A. , Abbatt J. P. D. , Wenger J. C. , Evans G. J.
Published: June 2015

The optical properties of ambient black carbon‐containing particles and the composition of their associated coatings were investigated at a downtown site in Toronto, Canada, for 2 weeks in June 2013. The objective was to assess the relationship between black carbon (BC) coating composition/thickness and absorption. The site was influenced by emissions from local vehicular traffic, wildfires in Quebec, and transboundary fossil fuel combustion emissions in the United States. Mass concentrations of BC and associated nonrefractory coatings were measured using a soot particle–aerosol mass spectrometer (SP‐AMS), while aerosol absorption and scattering were measured using a photoacoustic soot spectrometer (PASS). Absorption enhancement was investigated both by comparing ambient and thermally denuded PASS absorption data and by relating absorption data to BC mass concentrations measured using the SP‐AMS. Minimal absorption enhancement attributable to lensing at 781 nm was observed for BC using both approaches. However, brown carbon was detected when the site was influenced by wildfire emissions originating in Quebec. BC coating to core mass ratios were highest during this period (~7), and while direct absorption by brown carbon resulted in an absorption enhancement at 405 nm (>2.0), no enhancement attributable to lensing at 781 nm was observed. The efficiency of BC coating removal in the denuder decreased substantially when wildfire‐related organics were present and may represent an obstacle for future similar studies. These findings indicate that BC absorption enhancement due to lensing is minimal for downtown Toronto, and potentially other urban locations, even when impacted by long‐range transport events.
Relationships between climate variability, soil moisture, and Australian heatwaves
Authors: Perkins Sarah E. , Argüeso Daniel , White Christopher J.
Published: June 2015

While it is established that low‐frequency climate variability modes have a dominant role on Australia's climate, limited work to date has focused on relationships between climate variability and Australian heatwaves. Moreover, heatwaves are a distinctive type of extreme weather that can be classified by multiple characteristics, such as intensity, frequency, duration, and timing. This study identifies the relationships between known modes of climate variability that influence Australian climate, and discrete seasonal characteristics of the intensity, frequency, duration, and timing of heatwaves. The large‐scale seasonal modes of the El Niño/Southern Oscillation (ENSO), the Indian Ocean Dipole (IOD), and the Southern Annular Mode (SAM) are investigated for extended Austral summers commencing between the years 1911 and 2012. While ENSO is found to have the strongest relationship with Australian heatwave characteristics, this study finds that ENSO's influence differs between heatwave frequency, duration, intensity, and timing. Regions dominated by ENSO experience more, longer lasting and hotter heatwaves combined with an earlier commencement of the heatwave season during El Niño phases. The exception to this is southeast Australia, where SAM is generally more dominant. In contrast, the IOD provides little indication of seasonal heatwave characteristics due to its relative inactivity during the Austral summer months. Lastly, we show that antecedent soil moisture has varying strengths of relationships with Australian heatwave characteristics, exhibiting relationships with heatwave intensity and timing over some regions where none are detected between large‐scale modes. However, while significant relationships between dry antecedent soil moisture and extreme heatwaves do exist over Australia, these appear to be slightly weaker than similar relationships over Europe reported in other studies.
Heterogeneity in Karakoram glacier surges
Authors: Quincey Duncan J. , Glasser Neil F. , Cook Simon J. , Luckman Adrian
Published: June 2015

Many Karakoram glaciers periodically undergo surges during which large volumes of ice and debris are rapidly transported downglacier, usually at a rate of 1–2 orders of magnitude greater than during quiescence. Here we identify eight recent surges in the region and map their surface velocities using cross‐correlation feature tracking on optical satellite imagery. In total, we present 44 surface velocity data sets, which show that Karakoram surges are generally short‐lived, lasting between 3 and 5 years in most cases, and have rapid buildup and relaxation phases, often lasting less than a year. Peak velocities of up to 2 km a−1 are reached during summer months, and the surges tend to diminish during winter months. Otherwise, they do not follow a clearly identifiable pattern. In two of the surges, the peak velocity travels down‐ice through time as a wave, which we interpret as a surge front. Three other surges are characterized by high velocities that occur simultaneously across the entire glacier surface, and acceleration and deceleration are close to monotonic. There is also no consistent seasonal control on surge initiation or termination. We suggest that the differing styles of surge can be partly accounted for by individual glacier configurations and that while some characteristics of Karakoram surges are akin to thermally controlled surges elsewhere (e.g., Svalbard), the dominant surge mechanism remains unclear. We thus propose that these surges represent a spectrum of flow instabilities and the processes controlling their evolution may vary on a glacier by glacier basis.
Global Nomads: A Resource Hidden in Plain Sight
Authors: Appel–Schumacher Maggie
Published: June 2015

Maggie Appel–Schumacher shares her experiences as a “global nomad” and claims these often overlooked members of the student population should be integrated into the international focus of many colleges and universities.
Hybrid Filtration Membranes incorporating Nanoporous Silica within a Nanoscale Alumina Fibre Scaffold
Authors: Su Veronica Mei Tiing , Clyne Trevor William
Published: June 2015

Membranes were produced from fine (∼10 nm) alumina fibres, by dispersing them in liquid and using controlled sedimentation to produce two types of membrane – one a duplex structure (layers of well‐dispersed fibres and micro‐bundles) and the other entirely micro‐bundles. Incorporation of silica, via a sol‐gel route, produced “hybrid” forms. Filtration and separation efficiencies were assessed using two ionic dyes of similar molecular weight, but opposite charge. Successful separation of these is attributed to surface electrical effects within nano‐pores. Hybrid duplex membranes give an excellent combination of fine scale filtration efficiency and high permeability.
Microscopic Complexity in Phase‐Change Materials and its Role for Applications
Authors: Deringer Volker L. , Dronskowski Richard , Wuttig Matthias
Published: June 2015

Phase‐change materials (PCMs) are widely used for data storage and in other functional devices. Despite their seemingly simple compositions, these materials exhibit intriguing microscopic complexity and a portfolio of interesting properties. In this Feature Article, it is shown that structural and electronic peculiarities on the atomic scale are key determinants for the technological success of PCMs. Particular emphasis is put on the interplay of different experimental and theoretical methods, on the bonding nature of crystalline and amorphous PCMs, and on the role of surfaces and nanostructures. Then, unconventional transport properties of the crystalline phases are highlighted, both with regard to electrical and heat conduction. Finally, perspectives and future directions are drawn: for finding new PCMs based on microscopic understanding, and also for new applications of these materials in emerging fields.
Layered, Nanonetwork Composite Cathodes for Flexible, High‐Efficiency, Organic Light Emitting Devices
Authors: Xu Junwei , Smith Gregory M. , Dun Chaochao , Cui Yue , Liu Jiwen , Huang Huihui , Huang Wenxiao , Carroll David L.
Published: June 2015

In this work, the application of an aluminum (Al)/multiwall carbon nanotube (MWCNT)/Al, multilayered electrode to flexible, high‐efficiency, alternating current driven organic electroluminescent devices (AC‐OEL), is reported. The electrode is fabricated by sandwiching a spray‐cast nanonetwork film of MWCNTs between two evaporated layers of Al. The resulting composite film facilitates a uniform charge distribution across a robust crack‐free electrode under various bending angles. It is demonstrated that these composite electrodes stabilize the power efficiency of flexible devices for bending angles up to 120°, with AC‐OEL device power efficiencies of ≈22 lm W−1 at luminances of ≈4000 cd m−2 (using no output coupling). Microscopic examination of the Al/MWCNTs/Al electrode after bending of up to 1300 cycles suggests that the nanotubes significantly enhance the mechanical properties of the thin Al layers while providing a moderate modification to the work function of the metal. While the realization of robust, high‐brightness, and high‐efficiency AC‐OEL devices is potentially important in their future lighting applications, it is anticipated that this to also have significant impact in standard organic light emitting diodes lighting applications.
Leaf‐Like Graphene‐Oxide‐Wrapped Sulfur for High‐Performance Lithium–Sulfur Battery
Authors: Yuan Shouyi , Guo Ziyang , Wang Lina , Hu Shuang , Wang Yonggang , Xia Yongyao
Published: June 2015

Carbon/sulfur composites are attracting extensive attention because of their improved performances for Li–S batteries. However, the achievements are generally based on the low S‐content in the composites and the low S‐loading on the electrode. Herein, a leaf‐like graphene oxide (GO), which includes an inherent carbon nanotube midrib in the GO plane, is synthesized for preparing GO/S composites. Owing to the inherent high conductivity of carbon nanotube midribs and the abundant surface groups of GO for S‐immobilization, the composite with an S‐content of 60 wt% exhibits ultralong cycling stability over 1000 times with a low capacity decay of 0.033% per cycle and a high rate up to 4C. When the S‐content is increased to 75 wt%, the composite still shows a perfect cycling performance over 1000 cycles. Even with the high S‐loading of 2.7 mg cm−2 on the electrode and the high S‐content of 85 wt%, it still shows a promising cycling performance over 600 cycles.
Face the Edges: Catalytic Active Sites of Nanomaterials
Authors: Ni Bing , Wang Xun
Published: June 2015

Edges are special sites in nanomaterials. The atoms residing on the edges have different environments compared to those in other parts of a nanomaterial and, therefore, they may have different properties. Here, recent progress in nanomaterial fields is summarized from the viewpoint of the edges. Typically, edge sites in MoS2 or metals, other than surface atoms, can perform as active centers for catalytic reactions, so the method to enhance performance lies in the optimization of the edge structures. The edges of multicomponent interfaces present even more possibilities to enhance the activities of nanomaterials. Nanoframes and ultrathin nanowires have similarities to conventional edges of nanoparticles, the application of which as catalysts can help to reduce the use of costly materials. Looking beyond this, the edge structures of graphene are also essential for their properties. In short, the edge structure can influence many properties of materials.
XANES Investigation of Dynamic Phase Transition in Olivine Cathode for Li‐Ion Batteries
Authors: Pongha Sarawut , Seekoaon Boonyarit , Limphirat Wanwisa , Kidkhunthod Pinit , Srilomsak Sutham , Chiang Yet‐Ming , Meethong Nonglak
Published: June 2015

Dynamic phase transformation in olivine LiFePO4 involving formation of one or more intermediate or metastable phases is revealed by an in situ time‐resolved X‐ray absorption near edge structure (XANES) technique. The XANES spectra measured during relaxation immediately after the application of relatively high overpotentials, where metastable phases are expected, show a continuous shift of the Fe K‐edge toward higher energy. Surprisingly, the Fe K‐edge relaxes to higher energies after current interrupt regardless of whether the cell is being charged or discharged. This relaxation phenomenon is superimposed upon larger shifts in K‐edge due to changes in Fe2+/Fe3+ ratio due to charging and discharging, and implies an intermediate phase of larger FeO bond length than any of the known crystalline phases. No intermediate crystalline phases are observed by X‐ray diffraction (XRD). A metastable amorphous phase formed during dynamic cycling and which structurally relaxes to the equilibrium crystalline phases over a time scale of about 10 min after cessation of charging/discharging current is consistent with the experimental observations.
Erythrocyte pyruvate kinase deficiency: 2015 status report
Authors: Grace Rachael F. , Zanella Alberto , Neufeld Ellis J. , Morton D. Holmes , Eber Stefan , Yaish Hassan , Glader Bertil
Published: June 2015

Over the last several decades, our understanding of the genetic variation, pathophysiology, and complications of the hemolytic anemia associated with red cell pyruvate kinase deficiency (PKD) has expanded. Nonetheless, there remain significant gaps in our knowledge with regard to clinical care and monitoring. Treatment remains supportive with phototherapy and/or exchange transfusion in the newborn period, regular or intermittent red cell transfusions in children and adults, and splenectomy to decrease transfusion requirements and/or anemia related symptoms. In this article, we review the clinical diversity of PKD, the current standard of treatment and for supportive care, the complications observed, and future treatment directions.Am. J. Hematol. 90:825–830, 2015. © 2015 Wiley Periodicals, Inc.
Developmental trajectories of aggressive behavior in children from ages 8 to 10: The role of sex and hormones
Authors: Azurmendi Aitziber , Pascual‐Sagastizabal Eider , Vergara Ana I. , Muñoz Jose M. , Braza Paloma , Carreras Rosario , Braza Francisco , Sánchez‐Martín José R.
Published: June 2015

Objectives

This study explored the developmental trajectory of aggressive behavior from age 8 to age 10 in school‐aged children, taking into account possible sex differences, as well as the involvement of certain hormones.

Methods

Participants were 90 children (49 boys and 41 girls) from four schools. At the beginning of the study, the children were 8‐year old and were in 3rd grade of primary school. The second data collection phase was carried out two years later (at age 10) when the children were in 5th grade (primary). Their aggressive behavior was measured by the Direct and Indirect Aggression Scale, an instrument which uses peer rating. Hormone levels, testosterone, cortisol and estradiol were analyzed using an enzymoimmunoassay technique in saliva samples.

Results

The results revealed a difference in aggressive behavior between the ages of 8 and 10, in boys only, who were found to be more aggressive at age 10. A regression analysis revealed that cortisol and estradiol contributed to explaining the changes observed in aggressive behavior in boys. Boys whose cortisol levels rose most between the ages of 8 and 10 were also those whose aggressive behavior increased most during the same timeframe. Moreover, boys whose estradiol levels rose most between the ages of 8 and 10 were also those whose aggressive behavior decreased most during the same timeframe.

Conclusions

Our results highlight the importance of studying aggressive behavior from a longitudinal perspective, taking into account sex differences and biological measures. Am. J. Hum. Biol. 28:90–97, 2016. © 2015 Wiley Periodicals, Inc.
Prevalence of occupational exposure to carcinogens among workers of Arabic, Chinese and Vietnamese ancestry in Australia
Authors: Boyle Terry , Carey Renee N. , Glass Deborah C. , Peters Susan , Fritschi Lin , Reid Alison
Published: June 2015

Background

Although job‐related diseases result in more deaths per year than job‐related injuries, most research concerning ethnic minority workers has concerned accidents and injuries rather than disease‐causing exposures such as carcinogens.

Methods

We conducted a telephone‐based cross‐sectional survey to estimate the prevalence of occupational exposure to carcinogens among a sample of ethnic minority workers in Australia, and compared their exposure prevalence to that of a sample of the general Australian‐born working population (‘Australian workers’).

Results

One‐third of the ethnic minority workers were exposed to at least one carcinogen at work. The likelihood of exposure to carcinogens was not significantly different from that of Australian workers, although the likelihood of exposure to individual carcinogens varied by ethnicity.

Conclusion

Knowing the prevalence of exposure to carcinogens in the workplace in different ethnic groups will allow better targeted and informed occupational health and safety measures to be implemented where necessary. Am. J. Ind. Med. 58:923–932, 2015. © 2015 Wiley Periodicals, Inc.
Maternal and fetal capillary malformation–arteriovenous malformation (CM–AVM) due to a novel RASA1 mutation presenting with prenatal non‐immune hydrops fetalis
Authors: Overcash Rachael T. , Gibu Christopher K. , Jones Marilyn C. , Ramos Gladys A. , Andreasen Tara S.
Published: June 2015

RASA1 mutations have been shown to cause capillary malformation–arteriovenous malformation (CM–AVM). We describe a patient with CM–AVM and a fetus who presented with non‐immune hydrops fetalis during the pregnancy. Sequencing revealed a novel RASA1 mutation in the RASGAP domain that results in a loss of function of p120‐RasGap. This report expands our current genetic and clinical understanding of CM–AVM in pregnancy. © 2015 Wiley Periodicals, Inc.
Multi‐system involvement in a severe variant of fibrodysplasia ossificans progressiva (ACVR1c.772G>A; R258G): A report of two patients
Authors: Kaplan Frederick S. , Kobori Joyce A. , Orellana Carmen , Calvo Inmaculada , Rosello Monica , Martinez Francisco , Lopez Berta , Xu Meiqi , Pignolo Robert J. , Shore Eileen M. , Groppe Jay C.
Published: June 2015

Severe variants of fibrodysplasia ossificans progressiva (FOP) affect <2% of all FOP patients worldwide, but provide an unprecedented opportunity to probe the phenotype–genotype relationships that propel the pathology of this disabling disease. We evaluated two unrelated children who had severe reduction deficits of the hands and feet with absence of nails, progressive heterotopic ossification, hypoplasia of the brain stem, motor and cognitive developmental delays, facial dysmorphology, small malformed teeth, and abnormal hair development. One child had sensorineural hearing loss, microcytic anemia, and a tethered spinal cord and the other had a patent ductus arteriosus and gonadal dysgenesis with sex reversal (karyotype 46, XY female). Both children had an identical mutation inACVR1c.772A>G; p.Arg258Gly (R258G), not previously described in FOP. Although many, if not most, FOP mutations directly perturb the structure of the GS regulatory subdomain and presumably the adjacent αC helix, substitution with glycine at R258 may directly alter the position of the helix in the kinase domain, eliminating a key aspect of the autoinhibitory mechanism intrinsic to the wild‐type ACVR1 kinase. The high fidelity phenotype–genotype relationship in these unrelated children with the most severe FOP phenotype reported to date suggests that the shared features are due to the dysregulated activity of the mutant kinase during development and postnatally, and provides vital insight into the structural biology and function of ACVR1 as well as the design of small molecule inhibitors. © 2015 Wiley Periodicals, Inc.
Efficient Palladium‐Catalyzed Direct C−H Phenylselenylation of (Hetero)Arenes in Water
Authors: Jin Weiwei , Zheng Poonnapa , Wong Wing‐Tak , Law Ga‐Lai
Published: June 2015

An efficient, palladium‐catalyzed, direct phenylselenylation of arenes and heteroarenes in water by using N‐(phenylseleno)phthalimide (N‐PSP) as the coupling partner is reported. A variety of diaryl selenides with high functional group tolerance have been obtained in good to excellent yields and regioselectivity.
Precise Macroscopic Supramolecular Assembly by Combining Spontaneous Locomotion Driven by the Marangoni Effect and Molecular Recognition
Authors: Xiao Meng , Xian Yiming , Shi Feng
Published: June 2015

Macroscopic supramolecular assembly bridges fundamental research on molecular recognition and the potential applications as bulk supramolecular materials. However, challenges remain to realize stable precise assembly, which is significant for further functions. To handle this issue, the Marangoni effect is applied to achieve spontaneous locomotion of macroscopic building blocks to reach interactive distance, thus contributing to formation of ordered structures. By increasing the density of the building blocks, the driving force for assembly transforms from a hydrophobic–hydrophobic interaction to hydrophilic–hydrophilic interaction, which is favorable for introducing hydrophilic coatings with supramolecular interactive groups on matched surfaces, consequently realizing the fabrication of stable precise macroscopic supramolecular assemblies.
Facile Access to Fluoromethylated Arenes by Nickel‐Catalyzed Cross‐Coupling between Arylboronic Acids and Fluoromethyl Bromide
Authors: An Lun , Xiao Yu‐Lan , Min Qiao‐Qiao , Zhang Xingang
Published: June 2015

The nickel‐catalyzed fluoromethylation of arylboronic acids was achieved with the industrial raw material fluoromethyl bromide (CH2FBr) as the coupling partner. The reaction proceeded under mild reaction conditions with high efficiency; it features the use of a low‐cost nickel catalyst, synthetic simplicity, and excellent functional‐group compatibility, and provides facile access to fluoromethylated biologically relevant molecules. Preliminary mechanistic studies showed that a single‐electron‐transfer (SET) pathway is involved in the catalytic cycle.
Metal‐Free Dehydrogenative Diels–Alder Reactions of 2‐Methyl‐3‐Alkylindoles with Dienophiles: Rapid Access to Tetrahydrocarbazoles, Carbazoles, and Heteroacenes
Authors: Zhou Liejin , Xu Bing , Zhang Junliang
Published: June 2015

An unprecedented strategy for in situ generation of indole‐based ortho‐quinodimethanes (oQDMs) from 2‐methyl‐3‐alkylmethylindoles by either a metal‐free DDQ‐ or BQ‐mediated dehydrogenative process was developed. These oQDMs were trapped by electron‐deficient dienophiles to provide a facile approach to synthetically valuable tetrahydrocarbazoles, carbazoles, and hetereoacenes. The salient features of this transformation include direct C(sp3)H bond functionalizations, readily available starting materials, metal‐free conditions, high efficiency, operational simplicity, and ease of scale‐up.
Precise Molecular Fission and Fusion: Quantitative Self‐Assembly and Chemistry of a Metallo‐Cuboctahedron
Authors: Xie Ting‐Zheng , Guo Kai , Guo Zaihong , Gao Wen‐Yang , Wojtas Lukasz , Ning Guo‐Hong , Huang Mingjun , Lu Xiaocun , Li Jing‐Yi , Liao Sheng‐Yun , Chen Yu‐Sheng , Moorefield Charles N. , Saunders Mary Jane , Cheng Stephen Z. D. , Wesdemiotis Chrys , Newkome George R.
Published: June 2015

Inspiration for molecular design and construction can be derived from mathematically based structures. In the quest for new materials, the adaptation of new building blocks can lead to unexpected results. Towards these ends, the quantitative single‐step self‐assembly of a shape‐persistent, Archimedean‐based building block, which generates the largest molecular sphere (a cuboctahedron) that has been unequivocally characterized by synchrotron X‐ray analysis, is described. The unique properties of this new construct give rise to a dilution‐based transformation into two identical spheres (octahedra) each possessing one half of the molecular weight of the parent structure; concentration of this octahedron reconstitutes the original cuboctahedron. These chemical phenomena are reminiscent of biological fission and fusion processes. The large 6 nm cage structure was further analyzed by 1D and 2D NMR spectroscopy, mass spectrometry, and collision cross‐section analysis. New routes to molecular encapsulation can be envisioned.
Rhodium‐Catalyzed ortho‐Selective CF Bond Borylation of Polyfluoroarenes with BpinBpin
Authors: Guo Wen‐Hao , Min Qiao‐Qiao , Gu Ji‐Wei , Zhang Xingang
Published: June 2015

An ortho‐selective CF bond borylation between N‐heterocycle‐substituted polyfluoroarenes and Bpin‐Bpin with simple and commercially available [Rh(cod)2]BF4 as a catalyst is now reported. The reaction proceeds under mild reaction conditions with high efficiency and broad substrate scope, even toward monofluoroarene, thus providing a facile access to a wide range of borylated fluoroarenes that are useful for photoelectronic materials. Preliminary mechanistic studies reveal that a RhIII/V catalytic cycle via a key intermediate rhodium(III) hydride complex [(H)RhIIILn(Bpin)] may be involved in the reaction.
Acetone‐Linked Peptides: A Convergent Approach for Peptide Macrocyclization and Labeling
Authors: Assem Naila , Ferreira David J. , Wolan Dennis W. , Dawson Philip E.
Published: June 2015

Macrocyclization is a broadly applied approach for overcoming the intrinsically disordered nature of linear peptides. Herein, it is shown that dichloroacetone (DCA) enhances helical secondary structures when introduced between peptide nucleophiles, such as thiols, to yield an acetone‐linked bridge (ACE). Aside from stabilizing helical structures, the ketone moiety embedded in the linker can be modified with diverse molecular tags by oxime ligation. Insights into the structure of the tether were obtained through co‐crystallization of a constrained S‐peptide in complex with RNAse S. The scope of the acetone‐linked peptides was further explored through the generation of N‐terminus to side chain macrocycles and a new approach for generating fused macrocycles (bicycles). Together, these studies suggest that acetone linking is generally applicable to peptide macrocycles with a specific utility in the synthesis of stabilized helices that incorporate functional tags.
Structural Elucidation of the Bispecificity of A Domains as a Basis for Activating Non‐natural Amino Acids
Authors: Kaljunen Heidi , Schiefelbein Stephan H. H. , Stummer Daniela , Kozak Sandra , Meijers Rob , Christiansen Guntram , Rentmeister Andrea
Published: June 2015

Many biologically active peptide secondary metabolites of bacteria are produced by modular enzyme complexes, the non‐ribosomal peptide synthetases. Substrate selection occurs through an adenylation (A) domain, which activates the cognate amino acid with high fidelity. The recently discovered A domain of an Anabaenopeptin synthetase from Planktothrix agardhii (ApnA A1) is capable of activating two chemically distinct amino acids (Arg and Tyr). Crystal structures of the A domain reveal how both substrates fit into to binding pocket of the enzyme. Analysis of the binding pocket led to the identification of three residues that are critical for substrate recognition. Systematic mutagenesis of these residues created A domains that were monospecific, or changed the substrate specificity to tryptophan. The non‐natural amino acid 4‐azidophenylalanine is also efficiently activated by a mutant A domain, thus enabling the production of diversified non‐ribosomal peptides for bioorthogonal labeling.
A novel hydrogen peroxide sensor based on Ag nanoparticles decorated polyaniline/graphene composites
Authors: Li Shan , Xiong Jianxin , Shen Jingsong , Qin Yong , Li Juan , Chu Fuqiang , Kong Yong , Deng Linhong
Published: June 2015

A novel electrochemical sensor based on Ag nanoparticles (AgNPs) decorated polyaniline/graphene composites (PANI/G) is developed, which can be used for sensitive determination of H2O2. For the construction of the H2O2 sensor, polyaniline (PANI) is first electrodeposited on the surface of graphene (G) to form PANI/G, and then horseradish peroxidase (HRP) loaded on AgNPs (HRP/AgNPs) is immobilized on to the PANI/G. H2O2 can be catalyzed by HRP to generate current response which can be significantly enhanced by AgNPs, and thus the PANI/G based sensor can be utilized for the detection of H2O2. Under the optimized conditions, the proposed H2O2 sensor exhibits wide linear response to H2O2 concentration ranging from 0.25 to 2.25 mM with a detection limit of 0.03 mM (signal‐to‐noise ratio of 3), and it also shows high selectivity and reproducibility. The method is simple and cost‐effective, and can be a promising candidate as the sensitive sensing platform for H2O2. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42409.
Antibacterial poly(lactic acid) (PLA) films grafted with electrospun PLA/allyl isothiocyanate fibers for food packaging
Authors: Kara Hasan H. , Xiao Fugang , Sarker Majher , Jin Tony Z. , Sousa Ana M. M. , Liu Cheng‐Kung , Tomasula Peggy M. , Liu LinShu
Published: June 2015

Poly(lactic acid) (PLA) fibers of submicron sizes encapsulating allyl isothiocyanate (AITC) (PfA) were made and electrospun onto the surfaces of PLA films. SEM examination confirmed the fusion of the two phases to form a bilayered fiber‐grafted film after the film underwent air blowing and water washing to remove the nongrafted fibers. The fiber‐grafted PLA films (PfA‐g‐film) retain the mechanical properties of PLA. The release of AITC from the fibers was temperature dependent. At temperatures lower than 4°C, the incorporated AITC remained within the fibers without losing activity; at room temperature, AITC released in a sustained manner over weeks. The release of AITC was also dependent on its initial concentration in the PLA electrospinning solution; samples with more AITC incorporated showed a higher release rate. PfA‐g‐films significantly inhibited the growth of Listeria innocua and Escherichia coli k12 when tested on package foods. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42475.
Solubility factors as screening tools of biodegradable toughening agents of polylactide
Authors: Ruellan Alexandre , Guinault Alain , Sollogoub Cyrille , Ducruet Violette , Domenek Sandra
Published: June 2015

Changes in the thermomechanical properties of polylactide (PLA) plasticized by two biodegradable and biobased molecules, Polysorb ID37 (PID37) and squalene, were compared to formulations with petroleum‐based plasticizers, namely, acetyl tributyl citrate, poly(ethylene glycol) 400, and dioctyl adipate (DOA). The solubility parameters of the additives were calculated and were related to the plasticization behaviors. PID37 proved to be miscible with PLA because of its polar functions and short alkyl groups. It decreased the PLA glass‐transition temperature (Tg) and increased in ductility when Tg approached room temperature. Squalene had a low miscibility because of the absence of polar groups. Tg was not depressed. Ductility improvements were nevertheless reached because the immiscible inclusions efficiently induced crazing by the distribution of stress concentration points all over the material; this delayed failure. The maximum elongations at break were 60% for squalene, 400% for DOA, and 500% for PID37. The solubility factors were, thus, an efficient prediction tool for the plasticizing behavior. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42476.
Production of bacterial nanobiocomposites of polyhydroxyalkanoates derived from waste and bacterial nanocellulose by the electrospinning enabling melt compounding method
Authors: Martínez‐Sanz Marta , Lopez‐Rubio Amparo , Villano Marianna , Oliveira Catarina S. S. , Majone Mauro , Reis Maria , Lagarón Jose M.
Published: June 2015

This work reports on the characterization of nanocomposites fully synthesized by bacteria, consisting of polyhydroxybutyrate‐co‐hydroxyvalerate (PHBV) matrices reinforced with bacterial cellulose nanowhiskers (BCNW). Two PHBV grades, with 9% HV (PHBV9) and 16% HV (PHBV16), were synthesized using food industry waste feedstocks and compared with a 3% HV commercial grade (PHBV3). Whereas PHBV3 presented a high barrier performance but excessive brittleness, PHBV9 and PHBV16 showed a more ductile behavior and reduced barrier properties. Subsequently, BCNW were incorporated into the PHBVs by a high‐throughput electrospinning technique to produce master‐batch formulations with relatively high nanofiller concentrations. The hybrid ultrathin fibers showed homogeneous morphologies and greater thermal stability than the pure PHBV fibers. Nanocomposites were then produced by melt mixing PHBVs with the hybrid fibers. Despite the low compatibility between the extremely hydrophilic BCNW and the hydrophobic PHBVs, the nanofiller was highly dispersed and provided a reduction in oxygen permeability of the PHBV3 matrix without relevant modifications in mechanical performance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42486.
Heritability of the Human Craniofacial Complex
Authors: Šešelj Maja , Duren Dana L. , Sherwood Richard J.
Published: June 2015

Quantifying normal variation and the genetic underpinnings of anatomical structures is one of the main goals of modern morphological studies. However, the extent of genetic contributions to normal variation in craniofacial morphology in humans is still unclear. The current study addresses this gap by investigating the genetic underpinnings of normal craniofacial morphology. The sample under investigation consists of 75 linear and angular measurements spanning the entire craniofacial complex, recorded from lateral cephalographs of 1,379 participants in the Fels Longitudinal Study. Heritabilities for each trait were estimated using SOLAR, a maximum‐likelihood variance components approach utilizing all pedigree information for parameter estimation. Trait means and mean effects of the covariates age, sex, age2, sex × age, and sex × age2 were simultaneously estimated in the analytic models. All traits of the craniofacial complex were significantly heritable. Heritability estimates ranged from 0.10 to 0.60, with the majority being moderate. It is important to note that we found similar ranges of heritability occurring across the different functional/developmental components of the craniofacial complex, the splanchnocranium, the basicranium, and the neurocranium. This suggests that traits from different regions of the craniofacial complex are of comparable utility for the purposes of population history and phylogeny reconstruction. At the same time, this genetic influence on craniofacial morphology signals a caution to researchers of nongenetic studies to consider the implications of this finding when selecting samples for study given their project design and goals. Anat Rec, 298:1535–1547, 2015. © 2015 Wiley Periodicals, Inc.
VENOM FROM THE ECTOPARASITIC WASP Habrobracon hebetor ACTIVATES CALCIUM‐DEPENDENT DEGRADATION OF Galleria mellonella LARVAL HEMOCYTES
Authors: Kryukova Natalia A. , Chertkova Ekaterina A. , Semenova Alexandra D , Glazachev Yuri I. , Slepneva Irina A. , Glupov Victor V.
Published: June 2015

Ectoparasitoids inject venom into hemolymph during oviposition. We determined the influence of envenomation by the parasitoid, Habrobracon hebetor, on the hemocytes of its larval host, Galleria mellonella. An increase in both intracellular Са2+ content and phospholipase C activity of the host hemocytes was recorded during 2 days following envenomation by the parasitoid. The decreased hemocyte viability was detected 1, 2, and 24 h after the envenomation. Injecting of the crude venom (final protein concentration 3 μg/ml) into the G. mellonella larvae led to the reduced hemocyte adhesion. The larval envenomation caused a decrease in transmembrane potential of the hemocytes. These findings document the suppression of hemocytic immune effectors in the parasitized host larvae.
A Solution‐Processable Molecule using Thieno[3,2‐b]thiophene as Building Block for Efficient Organic Solar Cells
Authors: Wei Huan , Chen Weichao , Han Liangliang , Wang Ting , Bao Xichang , Li Xiaoyun , Liu Jie , Zhou Yuanhang , Yang Renqiang
Published: June 2015

A solution‐processed acceptor‐π‐donor‐π‐acceptor (A‐π‐D‐π‐A) type small molecule, namely DCATT, has been designed and synthesized for the application as donor material in organic solar cells. The fused aromatic unit thieno[3,2‐b]thiophene (TT) flanked with thiophene is applied as π bridge, while 4,8‐bisthienyl substituted benzodithiophene (BDT) and 2‐ethylhexyl cyanoacetate are chosen as the central building block and end group, respectively. Introduction of fused ring to the small molecule enhances the conjugation length of the main chain, and gives a strong tendency to form π–π stacking with a large overlapping area which favors to high charge carrier transport. Small‐molecule organic solar cells based on blends of DCATT and fullerene acceptor exhibit power conversion efficiencies as high as 5.20 % under the illumination of AM 1.5G, 100 mW cm−2.
Finely Resolved Threshold for the Sharp M12L24/M24L48 Structural Switch in Multi‐Component MnL2n Polyhedral Assemblies: X‐ray, MS, NMR, and Ultracentrifugation Analyses
Authors: Yokoyama Hiroyuki , Ueda Yoshihiro , Fujita Daishi , Sato Sota , Fujita Makoto
Published: June 2015

In the self‐assembly of MnL2n polyhedra, the bend angle (θ) of the divalent ligand components determines the final structure. The threshold for the sharp structural switch between M12L24 and M24L48 was finely resolved to within just 4° by demonstrating the exclusive formation of M12L24 cuboctahedra or M24L48 rhombicuboctahedra from two similar ligands with θ values of 130° and 134°. This sharp structural switch was fully confirmed by X‐ray crystallography, mass spectrometry, NMR spectroscopy, and ultracentrifugation analyses.
Nano PdAu Bimetallic Alloy as an Effective Catalyst for the Buchwald–Hartwig Reaction
Authors: Chen Zheng , Wang Shuo , Lian Chao , Liu Yuxi , Wang Dingsheng , Chen Chen , Peng Qing , Li Yadong
Published: June 2015

It is highly challenging but desirable to develop efficient heterogeneous catalysts for C−Cl bond activation in coupling reactions. Here, we succeeded in synthesizing bimetallic Pd‐Au nanoparticles through a convenient one‐pot wet chemical route. The composition and alloyed structure of the as‐prepared nanoparticles were fully characterized. We have evaluated the catalytic activity of these Pd‐Au alloy catalysts in Buchwald–Hartwig reactions of aryl chlorides. The excellent catalytic activity of the as‐obtained Pd‐Au nanoparticles indicates that exploiting the catalytic power of nano‐alloy catalysts could enable effective C−Cl bond activation suitable for cross‐coupling reactions.