bluuebunny/crossref_metadata_2025 huggingface dataset:
Establishing Post Spill Environmental Monitoring Processes: Experience from the United Kingdom Premiam Initiative
Authors: Kirby Mark
Published: September 2017

ABSTRACT 2017-258

The Pollution Response in Emergencies: Marine Impact Assessment and Monitoring (Premiam) programme was initiated in 2009. It started life as a 3-year government funded developmental programme and has subsequently developed into a UK wide focus for the improvement of post spill monitoring with wide engagement from both government and industry stakeholders.

In this paper an update of the achievements under the initiative is presented including the development of scientific guidelines, processes for managing and coordinating the mobilisation of monitoring expertise and systems for evaluating preparedness. Inclusion of post-spill monitoring into the UK National Contingency Plan and national response exercises are also discussed.

This paper will also reflect on the most challenging aspects of establishing effective post-spill monitoring including accessing skills and expertise, establishing funding, stakeholder support and consistency of approach across all relevant sectors. Finally, experience from the UK will be used to consider the status of post-spill monitoring in the context of the International Oil Spill Conferences four key areas of Prevent, Prepare, Respond and Restore.

For more information see: www.cefas.co.uk/premiam
ARE OXYGENATED HYDROCARBONS IMPORTANT OIL DEGRADATION PRODUCTS AFTER OIL SPILLS?
Authors: Nabi Deedar , Katz Samuel , Aeppli Christoph
Published: September 2017

ABSTRACT 2017-186

Oxygenated hydrocarbons (OxHC) are major and persistent hydrocarbon degradation products that are formed after oil spills. However, there are still knowledge gaps related to formation, fate and effect of these products. The objective of this study was to find if the OxHCs present in weathered oils are more or less toxic and bioaccumulative than their parent compounds. In this study, we first systematically investigated bioaccumulation potential and toxicity potential of oxygenated oil weathering products, using predictions based on Abraham Solvation Parameters. We then quantified OxHC in select crude and weathered oil samples from the 2010 Deepwater Horizon Oil Spill (DHOS). Seawater-dissolved concentrations were calculated using Raoult’s law, and baseline toxicity of the mixtures towards fathead minnow fish were estimated. We found that while OxHC generally had a lower bioaccumulation potential than corresponding n-alkanes, the baseline toxicity of OxHC was higher than that of their n-alkane precursors due to increased water solubility. After 30 days of weathering, toxicity of the oil residue decreased by a factor of ten. However, following six years of weathering, the calculated residual toxicity only dropped by a further factor of two. In the most weathered sample, toxicity was dominated by OxHC and not polycyclic aromatic hydrocarbons (PAHs). These preliminary data suggest that further research into OxHC toxicity is necessary. In future, additional factors such as reactive toxicity and biotransformation can be implemented to further explore OxHC toxicity and bioaccumulation in long-term environmental impacts of oil spills.
ASSESSING NATURAL RESOURCE DAMAGES FOR COMMERCIALLY AND RECREATIONALLY HARVESTED POPULATIONS
Authors: Wakefield Jeff , Davis Andrew N.
Published: September 2017

Resource Equivalency Analysis (“REA”) is often used to “right-size” (scale) or calibrate compensatory restoration projects implemented as part of Natural Resource Damage Assessments (“NRDAs”) conducted pursuant to the Oil Pollution Act of 1990 (“OPA”). The basic premise underlying REA is that, if a spill results in the loss of individual members of a population, the public can be compensated via a restoration project which creates individuals that otherwise would not exist. This is because the ecological services provided by a population are proportional to the number of individuals in the population. For example, one could compensate the public for spill-related mortality among shrimp by creating wetland terraces which, the literature suggests, would increase the number of shrimp in the population. REA answers the question, “How many wetland terraces need to be created?”

Implicit in the REA construct is the dynamic nature of the population projections. Even with density dependence, population levels fluctuate according to both biological and anthropogenic factors that combine to influence survival, reproductive and growth rates. Thus, if NRDA practitioners are to reliably identify compensatory restoration requirements using REA, it is necessary to: characterize baseline demographic rates; develop a model that uses those baseline demographic rates to project future population levels; and identify the mechanisms that cause post-spill rates to change relative to baseline expectations.

One factor that can cause post-spill demographic rates to vary is a spill-related change in human behavior. For example, if a spill-related fishing closure results in the cancelation of 15,000 recreational shrimping trips, shrimp mortality due to fishing will decrease.

In this paper we use prior OPA NRDA cases to: review the historical treatment of spill-related closures in REA models used by both DOI/USFWS and NOAA; and illustrate that the REA practitioners’ approach to these spill-related changes in human behavior can (and should) change the NRDA liability construct, particularly with respect to species which are commercially and recreationally harvested.
Novel interactors of the Drosophila Survival Motor Neuron (SMN) Complex suggest its full conservation
Authors: Lanfranco Maia , Cacciottolo Rebecca , Borg Rebecca M. , Vassallo Neville , Juge François , Bordonné Rémy , Cauchi Ruben J.
Published: September 2017

The Spinal Muscular Atrophy disease protein Survival Motor Neuron (SMN) operates as part of a multiprotein complex whose components also include Gemins 2‐8 and Unrip. The fruit fly Drosophila melanogaster is thought to have a slightly smaller SMN complex comprised of SMN, Gemin2/3/5 and, possibly, Unrip. Based upon in vivo interaction methods, we have identified novel interacting partners of the Drosophila SMN complex with homologies to Gemin4/6/7/8. The Gemin4 and Gemin8 orthologues are required for neuromuscular function and survival. The Gemin6/7/Unrip module can be recruited via the SMN‐associated Gemin8, hence mirroring the human SMN complex architecture. Our findings lead us to propose that an elaborate SMN complex that is typical in metazoans is also present in Drosophila.
Synergistic interaction of the cannabinoid and death receptor systems – a potential target for future cancer therapies?
Authors: Keresztes Attila , Streicher John M.
Published: September 2017

Cannabinoid receptors have been shown to interact with other receptors, including tumor necrosis factor receptor superfamily (TNFRS) members, to induce cancer cell death. When cannabinoids and death‐inducing ligands (including TNF‐related apoptosis‐inducing ligand) are administered together, they have been shown to synergize and demonstrate enhanced antitumor activity in vitro. Certain cannabinoid ligands have been shown to sensitize cancer cells and synergistically interact with members of the TNFRS, thus suggesting that the combination of cannabinoids with death receptor (DR) ligands induces additive or synergistic tumor cell death. This review summarizes recent findings on the interaction of the cannabinoid and DR systems and suggests possible clinical co‐application of cannabinoids and DR ligands in the treatment of various malignancies.
The Impact of Urbanization on Temporal Changes in Sediment Transport in a Gravel Bed Channel in Southern Ontario, Canada
Authors: Plumb B. D. , Annable W. K. , Thompson P. J. , Hassan M. A.
Published: September 2017

A field investigation has been undertaken to characterize the event‐based bed load transport dynamics of a highly urbanized gravel bed stream. A combination of direct bed load and tracer particle measurements were taken over a 3 year period during which time approximately 30 sediment mobilizing events occurred. Sediment transport measurements were used to calibrate a fractional bed load transport model and combined with hydrometric data which represent four different land use conditions (ranging from rural to highly urbanized) to analyze the differences in discharge magnitude and frequency and its impact on sediment transport. Fractional transport analysis of the bed load measurements indicates that frequent intermediate discharge events can mobilize sand and fine gravel to an approximate equally mobile condition, however, the transport rates at these discharges exhibit greater variability than at discharges above the bankfull discharge. Path lengths of the coarse fraction, measured using tracer clasts, are insensitive to peak discharge, and instead transport at distances less than those reported in other gravel bed channels, which is attributed to the shorter duration discharge events common to urban streams. The magnitude‐frequency analysis reveals that the frequency, time, and volume of competent sediment mobilizing events are increasing with urbanization. Variability in effective discharges suggests that a range of discharges, spanning between frequent, low magnitude events to less frequent, high magnitude events are geomorphically significant. However, trends in the different land use scenarios suggest that urbanization is shifting the geomorphic significance toward more frequent, lower magnitude events.
Increase in Nutrients, Mercury, and Methylmercury as a Consequence of Elevated Sulfate Reduction to Sulfide in Experimental Wetland Mesocosms
Authors: Myrbo A. , Swain E. B. , Johnson N. W. , Engstrom D. R. , Pastor J. , Dewey B. , Monson P. , Brenner J. , Dykhuizen Shore M. , Peters E. B.
Published: September 2017

Microbial sulfate reduction (MSR) in both freshwater and marine ecosystems is a pathway for the decomposition of sedimentary organic matter (OM) after oxygen has been consumed. In experimental freshwater wetland mesocosms, sulfate additions allowed MSR to mineralize OM that would not otherwise have been decomposed. The mineralization of OM by MSR increased surface water concentrations of ecologically important constituents of OM: dissolved inorganic carbon, dissolved organic carbon, phosphorus, nitrogen, total mercury, and methylmercury. Increases in surface water concentrations, except for methylmercury, were in proportion to cumulative sulfate reduction, which was estimated by sulfate loss from the surface water into the sediments. Stoichiometric analysis shows that the increases were less than would be predicted from ratios with carbon in sediment, indicating that there are processes that limit P, N, and Hg mobilization to, or retention in, surface water. The highest sulfate treatment produced high levels of sulfide that retarded the methylation of mercury but simultaneously mobilized sedimentary inorganic mercury into surface water. As a result, the proportion of mercury in the surface water as methylmercury peaked at intermediate pore water sulfide concentrations. The mesocosms have a relatively high ratio of wall and sediment surfaces to the volume of overlying water, perhaps enhancing the removal of nutrients and mercury to periphyton. The presence of wild rice decreased sediment sulfide concentrations by 30%, which was most likely a result of oxygen release from the wild rice roots. An additional consequence of the enhanced MSR was that sulfate additions produced phytotoxic levels of sulfide in sediment pore water.
The Macroseismic Intensity Distribution of the 30 October 2016 Earthquake in Central Italy (Mw 6.6): Seismotectonic Implications
Authors: Galli Paolo , Castenetto Sergio , Peronace Edoardo
Published: September 2017

The central Italy Apennines were rocket in 2016 by the strongest earthquakes of the past 35 years. Two main shocks (Mw 6.2 and Mw 6.6) between the end of August and October caused the death of almost 300 people, and the destruction of 50 villages and small towns scattered along 40 km in the hanging wall of the N165° striking Mount Vettore fault system, that is, the structure responsible for the earthquakes. The 24 August southern earthquake, besides causing all the casualties, razed to the ground the small medieval town of Amatrice and dozens of hamlets around it. The 30 October main shock crushed definitely all the villages of the whole epicentral area (up to 11 intensity degree), extending northward the level of destruction and inducing heavy damage even to the 30 km far Camerino town. The survey of the macroseismic effects started the same day of the first main shock and continued during the whole seismic sequence, even during and after the strong earthquakes at the end of October, allowing the definition of a detailed picture of the damage distribution, day by day. Here we present the results of the final survey in terms of Mercalli‐Cancani‐Sieberg intensity, which account for the cumulative effects of the whole 2016 sequence (465 intensity data points, besides 435 related to the 24 August and 54 to the 26 October events, respectively). The distribution of the highest intensity data points evidenced the lack of any possible overlap between the 2016 earthquakes and the strongest earthquakes of the region, making this sequence a unique case in the seismic history of Italy. In turn, the cross matching with published paleoseismic data provided some interesting insights concerning the seismogenic behavior of the Mount Vettore fault in comparison with other active normal faults of the region.
Minimum Hydraulic Resistance and Least Resistance Path in Heterogeneous Porous Media
Authors: Rizzo Calogero B. , de Barros Felipe P. J.
Published: September 2017

The transport dynamics of a solute plume in porous media are strictly related to the hydrogeological properties. Despite progress in simulation techniques, quantifying transport in strongly heterogeneous geological formations is still a challenge. It is well established that the heterogeneity of the hydraulic conductivity (K) field is one of the main factors controlling solute transport phenomena. Increasing the heterogeneity level of the K‐field will enhance the probability of having preferential paths, that are fundamental in predicting the first time arrivals. In this work, we focus on the relationship between the connectivity structure of the K‐field to transport quantities. We compute connectivity based on the concept of hydraulic resistance and the corresponding least resistance paths. We present a new efficient algorithm based on graph theory that enables us to extract useful information from the K‐field without resorting to the solution of the governing equations for flow and transport. For this reason, an exhaustive and fast analysis can be carried out using a Monte Carlo framework for randomly generated K‐fields which allows the computation of the least resistance path and its uncertainty. We examine the minimum hydraulic resistance for both multi‐Gaussian (MG) and non‐MG
‐fields. The analysis carried out indicates that the expected value of the minimum hydraulic resistance between two points scales exponentially with the standard deviation of the
‐field. Given the strong correlation with plume's first time arrival, our results illustrate how hydraulic resistance and least resistance path can be used as a computationally efficient risk metric.
Weather Typing‐Based Flood Frequency Analysis Verified for Exceptional Historical Events of Past 500 Years Along the Meuse River
Authors: De Niel J. , Demarée G. , Willems P.
Published: September 2017

Governments, policy makers, and water managers are pushed by recent socioeconomic developments such as population growth and increased urbanization inclusive of occupation of floodplains to impose very stringent regulations on the design of hydrological structures. These structures need to withstand storms with return periods typically ranging between 1,250 and 10,000 years. Such quantification involves extrapolations of systematically measured instrumental data, possibly complemented by quantitative and/or qualitative historical data and paleoflood data. The accuracy of the extrapolations is, however, highly unclear in practice. In order to evaluate extreme river peak flow extrapolation and accuracy, we studied historical and instrumental data of the past 500 years along the Meuse River. We moreover propose an alternative method for the estimation of the extreme value distribution of river peak flows, based on weather types derived by sea level pressure reconstructions. This approach results in a more accurate estimation of the tail of the distribution, where current methods are underestimating the design levels related to extreme high return periods. The design flood for a 1,250 year return period is estimated at 4,800 m3 s−1 for the proposed method, compared with 3,450 and 3,900 m3 s−1 for a traditional method and a previous study.
Dosimetric validation of Monaco treatment planning system on an Elekta VersaHD linear accelerator
Authors: Narayanasamy Ganesh , Saenz Daniel L , Defoor Dewayne , Papanikolaou Niko , Stathakis Sotirios
Published: September 2017

The purpose of this study is to perform dosimetric validation of Monaco treatment planning system version 5.1. The Elekta VersaHD linear accelerator with high dose rate flattening filter‐free photon modes and electron energies was used in this study. The dosimetric output of the new Agility head combined with the FFF photon modes warranted this investigation into the dosimetric accuracy prior to clinical usage. A model of the VersaHD linac was created in Monaco TPS by Elekta using commissioned beam data including percent depth dose curves, beam profiles, and output factors. A variety of 3D conformal fields were created in Monaco TPS on a combined Plastic water/Styrofoam phantom and validated against measurements with a calibrated ion chamber. Some of the parameters varied including source to surface distance, field size, wedges, gantry angle, and depth for all photon and electron energies. In addition, a series of step and shoot IMRT, VMAT test plans, and patient plans on various anatomical sites were verified against measurements on a Delta4 diode array. The agreement in point dose measurements was within 2% for all photon and electron energies in the homogeneous phantom and within 3% for photon energies in the heterogeneous phantom. The mean ± SD gamma passing rates of IMRT test fields yielded 93.8 ± 4.7% based on 2% dose difference and 2 mm distance‐to‐agreement criteria. Eight previously treated IMRT patient plans were replanned in Monaco TPS and five measurements on each yielded an average gamma passing rate of 95% with 6.7% confidence limit based on 3%, 3 mm gamma criteria. This investigation on dosimetric validation ensures accuracy of modeling VersaHD linac in Monaco TPS thereby improving patient safety.
Low Hemoglobin and Radiographic Damage Progression in Early Rheumatoid Arthritis: Secondary Analysis From a Phase III Trial
Authors: Möller Burkhard , Everts‐Graber Judith , Florentinus Stefan , Li Yihan , Kupper Hartmut , Finckh Axel
Published: September 2017

Objective

To study low blood hemoglobin concentrations as a predictor of radiographic damage progression in patients with rheumatoid arthritis (RA).

Methods

Post hoc analyses were performed in patients from the PREMIER trial with early RA undergoing 2 years of adalimumab (ADA), methotrexate (MTX), or ADA + MTX combination therapy. Low disease activity was defined as a score <3.2 on the 28‐joint Disease Activity Score using the C‐reactive protein level (DAS28‐CRP), and clinical response by the American College of Rheumatology criteria for 20% improvement at week 24. Baseline or mean hemoglobin concentrations over time, or anemia as defined using sex‐specific World Health Organization criteria, were analyzed in mixed‐effects models for longitudinal data in men and women as predictors of progressive joint damage, as measured by the modified total Sharp/van der Heijde score (ΔSHS). Data were adjusted for treatment and other patient characteristics, including the DAS28‐CRP.

Results

Baseline hemoglobin was inversely associated with ΔSHS in adjusted analyses (P < 0.05 for both sexes). Baseline anemia predicted greater ΔSHS in MTX‐treated patients over 104 weeks, and in ADA‐ and combination‐treated patients over 26 weeks. Lower hemoglobin concentrations over time, as well as time with anemia, were associated with greater damage progression (P < 0.001). The effect of low hemoglobin concentrations on joint damage progression remained significant, even in patients achieving low disease activity.

Conclusion

Low hemoglobin is a DAS28‐CRP‐independent predictor of radiographic joint damage progression in MTX‐treated patients with early RA. This effect decreases over time in ADA‐ and combination‐treated patients, and in clinical responders irrespective of treatment modality.
Nonmineralized and Mineralized Collagen Scaffolds Induce Differential Osteogenic Signaling Pathways in Human Mesenchymal Stem Cells
Authors: Zhou Qi , Ren Xiaoyan , Bischoff David , Weisgerber Daniel W. , Yamaguchi Dean T. , Miller Timothy A. , Harley Brendan A. C. , Lee Justine C.
Published: September 2017

The instructive capabilities of extracellular matrix components in progenitor cell differentiation have recently generated significant interest in the development of bioinspired materials for regenerative applications. Previously, a correlation was described between the osteogenic capabilities of nanoparticulate mineralized collagen glycosaminoglycan scaffolds (MC‐GAG) and an autogenous activation of small mothers against decapentaplegic ( Smad1/5) in the canonical bone morphogenetic protein receptor (BMPR) pathway with a diminished extracellular signal regulated kinase 1/2 (ERK1/2) activation when compared to nonmineralized collagen glycosaminoglycan scaffolds (Col‐GAG). This work utilizes a canonical BMPR inhibitor (dorsomorphin homologue 1, DMH1) and an inhibitor of the mitogen activated protein kinase/ERK kinase (MEK)/(ERK) cascade (PD98059) to characterize the necessity of each pathway for osteogenesis. While DMH1 inhibits runt‐related transcription factor 2 (Runx2) and bone sialoprotein II (BSPII) gene expression of primary human mesenchymal stem cells (hMSCs) on MC‐GAG, PD98059 inhibits BSPII expression on Col‐GAG independent of Runx2 expression. DMH1 inhibits mineralization on both Col‐GAG and MC‐GAG, however, PD98059 only inhibits mineralization on Col‐GAG. DMH1 inhibits both Smad1/5 phosphorylation and Runx2 protein expression, whereas PD98059 inhibits ERK1/2 and c‐Jun amino‐terminal kinase 1/2 (JNK1/2) phosphorylation without affecting Runx2. Thus, activation of the canonical BMPR signaling is necessary for osteogenic differentiation and mineralization of hMSCs on Col‐GAG or MC‐GAG. The MEK/ERK cascade, intimately tied to JNK activation, is necessary for Runx2‐independent osteogenesis on Col‐GAG, while completely dispensable in osteogenesis on MC‐GAG.
Pro‐Regenerative Hydrogel Restores Scarless Skin during Cutaneous Wound Healing
Authors: Sun Guoming
Published: September 2017

The transformation of fibrotic healing process to regenerative one has great potential to fully restore wounded skin. The M2 macrophage phenotype promotes constructive tissue remodeling and instructs tissue repair in a regenerative manner. It is hypothesized that hydrogels that can establish robustness of endogenous cells to regulate M2 phenotype will promote constructive dermal remodeling. Toward this end, a series of dextran‐based bioabsorbable hydrogels are developed and self‐crosslinkable dextran‐isocyanatoethyl methacrylate‐ethylamine (DexIEME) is identified as the potential scaffold. The initial screening study revealed that DexIEME has superior biocompatibility in varying concentrations. Although DexIEME brings about low proinflammatory responses, it promotes M2 macrophage phenotype. Then the optimized hydrogel formulation is tested for acute skin injuries using both murine and porcine models. Preliminary data demonstrated that the innovative DexIEME hydrogel promotes complete skin regeneration with hair regrowth on pre‐existing scars, while untreated scars remain intact. Preclinical studies further demonstrated that the DexIEME hydrogel regenerated perfect skin during deep porcine wound healing. Overall, the approach to investigate immune‐modulated hydrogels yields pro‐regenerative DexIEME hydrogel, which may lead to greater clinical success in treating deep dermal injury and attenuating scar formation.
Elastic Inflatable Actuators for Soft Robotic Applications
Authors: Gorissen Benjamin , Reynaerts Dominiek , Konishi Satoshi , Yoshida Kazuhiro , Kim Joon‐Wan , De Volder Michael
Published: September 2017

The 20th century's robotic systems have been made from stiff materials, and much of the developments have pursued ever more accurate and dynamic robots, which thrive in industrial automation, and will probably continue to do so for decades to come. However, the 21st century's robotic legacy may very well become that of soft robots. This emerging domain is characterized by continuous soft structures that simultaneously fulfill the role of robotic link and actuator, where prime focus is on design and fabrication of robotic hardware instead of software control. These robots are anticipated to take a prominent role in delicate tasks where classic robots fail, such as in minimally invasive surgery, active prosthetics, and automation tasks involving delicate irregular objects. Central to the development of these robots is the fabrication of soft actuators. This article reviews a particularly attractive type of soft actuators that are driven by pressurized fluids. These actuators have recently gained traction on the one hand due to the technology push from better simulation tools and new manufacturing technologies, and on the other hand by a market pull from applications. This paper provides an overview of the different advanced soft actuator configurations, their design, fabrication, and applications.
Large‐Area All‐Textile Pressure Sensors for Monitoring Human Motion and Physiological Signals
Authors: Liu Mengmeng , Pu Xiong , Jiang Chunyan , Liu Ting , Huang Xin , Chen Libo , Du Chunhua , Sun Jiangman , Hu Weiguo , Wang Zhong Lin
Published: September 2017

Wearable pressure sensors, which can perceive and respond to environmental stimuli, are essential components of smart textiles. Here, large‐area all‐textile‐based pressure‐sensor arrays are successfully realized on common fabric substrates. The textile sensor unit achieves high sensitivity (14.4 kPa−1), low detection limit (2 Pa), fast response (≈24 ms), low power consumption (<6 µW), and mechanical stability under harsh deformations. Thanks to these merits, the textile sensor is demonstrated to be able to recognize finger movement, hand gestures, acoustic vibrations, and real‐time pulse wave. Furthermore, large‐area sensor arrays are successfully fabricated on one textile substrate to spatially map tactile stimuli and can be directly incorporated into a fabric garment for stylish designs without sacrifice of comfort, suggesting great potential in smart textiles or wearable electronics.
A Simple and Efficient Method for the Preparation of α‐Halogenated Ketones Using Iron(III) Chloride and Iron(III) Bromide as Halogen Sources with Phenyliodonium Diacetate as Oxidant
Authors: Tang Shi‐Zhong , Zhao Wenshuang , Chen Tao , Liu Yang , Zhang Xiao‐Ming , Zhang Fu‐Min
Published: September 2017

α‐Halogenated ketones are both unique structure moieties existing in biologically natural products and valuable synthetic intermediates for the preparation of functional molecules. An efficient and scalable method for the preparation of α‐halogenated ketone using iron (III) chloride and iron (III) bromide as halogen sources with phenyliodonium diacetate as oxidant has been developed, featuring mild reaction conditions, environmentally friendly reagents, and wide substrate scope. Notably, the three‐step synthesis of drug prasugrel was achieved using this developed method as a key step with 30% yield on gram‐scale. Additionally, the reaction mechanism involving chloride cation was proposed based on some preliminary control experiments.

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Molecularly imprinted polymer membrane for the removal of naphthalene from petrochemical wastewater streams
Authors: Ghasemi Sahar , Nematollahzadeh Ali
Published: September 2017

The aim of this work was the preparation of molecularly imprinted membrane (MiM) using polysulfone (PSf) polymer for targeted removal of polycyclic aromatic hydrocarbons from petrochemical wastewater. Naphthalene was opted as a model pollutant, and the imprinted membrane was fabricated by phase inversion technique. Nonimprinted membrane (NiM) was also prepared in the absence of naphthalene and used as a reference. The polymers (MiM/NiM) were systematically characterized using different characterization techniques. The selectivity property of the membranes was evaluated by their ability in separation of naphthalene through filtration tests. Results showed that in comparison with NiM, the imprinted membrane exhibits higher affinity toward naphthalene molecules. It was found that the selectively of MiM is 2.27‐fold more than that of the corresponding NiM. This finding can be encouraging from industrial applications points of view.
Coexistence of mutations in keratin 10 (KRT10) and the mitochondrial genome in a patient with ichthyosis with confetti and Leber's hereditary optic neuropathy
Authors: Kalinska‐Bienias Agnieszka , Pollak Agnieszka , Kowalewski Cezary , Lechowicz Urszula , Stawinski Piotr , Gergont Aleksandra , Kosinska Joanna , Pronicka Ewa , Kowalski Pawel , Wozniak Katarzyna , Ploski Rafal
Published: September 2017

Ichthyosis with confetti (IWC) is a severe congenital genodermatosis characterized by ichthyosiform erythroderma since birth and confetti‐like spots of normal skin appearing in childhood as a results of revertant mosaicism. This disorder is caused by mutations in KRT10 or KRT1 genes. We report a 16‐year‐old boy who presented ichthyosiform erythroderma with severe desquamation since birth and gradually worsening psycho‐neurological symptoms (mental retardation, ataxia, dystonia, hypoacusis). The patient conspicuously lacked typical confetti‐like spots at the age of 16. The molecular diagnostics by the whole exome sequencing showed a novel de novo (c.1374‐2A>C) mutation in the KRT10 gene responsible for the development of IWC (KRT10 defect was confirmed by immunofluorescent study). Concurrently, the m.14484T>C mutation in mitochondrial MTND6 gene (characteristic for Leber's hereditary optic neuropathy or LHON) was detected in patient, his mother and brother. LHON causes frequent inherited blindness typically appearing during young adult life whose expression can be triggered by additional factors such as smoking or alcohol exposure. We speculate the effects of KRT10 and LHON mutations influence each other—skin inflammatory reaction due to severe ichthyosis might trigger the development of psychoneurological abnormalities whereas the mitochondrial mutation may reduce revertant mosaicism phenomenon resulting in the lack of confetti‐like spots characteristic for IWC. However, based on a single case we should be cautious about attributing phenotypes to digenic mechanisms without functional data.
Mutations in folate transporter genes and risk for human myelomeningocele
Authors: Findley Tina O. , Tenpenny Joy C. , O'Byrne Michelle R. , Morrison Alanna C. , Hixson James E. , Northrup Hope , Au Kit Sing
Published: September 2017

The molecular mechanisms linking folate deficiency and neural tube defect (NTD) risk in offspring remain unclear. Folate transporters (SLC19A1, SLC46A1, SLC25A32, and FOLH1) and folate receptors (FOLR1, FOLR2, and FOLR3) are suggested to play essential roles in transporting folate from maternal intestinal lumen to the developing embryo. Loss of function variants in these genes may affect folate availability and contribute to NTD risk. This study examines whether variants within the folate transporter and receptor genes are associated with an increased risk for myelomeningocele (MM). Exons and their flanking intron sequences of 348 MM subjects were sequenced using the Sanger sequencing method and/or next generation sequencing to identify variants. Frequencies of alleles of single nucleotide polymorphisms (SNPs) in MM subjects were compared to those from ethnically matched reference populations to evaluate alleles’ associated risk for MM. We identified eight novel variants in SLC19A1 and twelve novel variants in FOLR1, FOLR2, and FOLR3. Pathogenic variants include c.1265delG in SLC19A1 resulting in an early stop codon, four large insertion deletion variants in FOLR3, and a stop_gain variant in FOLR3. No new variants were identified in SLC46A1, SLC25A32, or FOLH1. In SLC19A1, c.80A>G (rs1051266) was not associated with our MM cohort; we did observe a variant allele G frequency of 61.7%, higher than previously reported in other NTD populations. In conclusion, we discovered novel loss of function variants in genes involved in folate transport in MM subjects. Our results support the growing evidence of associations between genes involved in folate transport and susceptibility to NTDs.
Biallelic mutations in GPD1 gene in a Chinese boy mainly presented with obesity, insulin resistance, fatty liver, and short stature
Authors: Li Niu , Chang Guoying , Xu Yufei , Ding Yu , Li Guoqiang , Yu Tingting , Yao Ruen , Li Juan , Shen Yiping , Wang Xiumin , Wang Jian
Published: September 2017

Biallelic mutations in the GPD1 gene cause a rare autosomal recessive inherited disease known as transient infantile hypertriglyceridemia (OMIM #614480). To date, only five pathogenic variants have been reported in 15 patients from three studies. The clinical symptoms of the affected individuals present a certain degree of heterogeneity. Here, we describe a chinese adolescent patient who mainly presented with obesity, insulin resistance, fatty liver, and short stature. Targeted next‐generation sequencing revealed a novel compound heterozygous variant in GPD1 gene (c.220‐2A>G and c.820G>A; p.Ala274Thr). In vitro studies demonstrated that the Ala274Thr variant induced a decrease in GPD1 protein expression. Further in vitro investigation of the splicing pattern in a minigene construct in HEK293 cells showed that the c.220‐2A>G variant generated an altered transcript with one cryptic splice site in exon 3, resulting in the loss of 69 bases in exon 3 (c.220_288del, p.74_96del). This is the first report involving an Asian who harbored GPD1 mutations. Our work not only expands the mutant spectrum of the GPD1 gene but also provides new insights on its resulting phenotype.
Noncovalent Functionalization and Charge Transfer in Antimonene
Authors: Abellán Gonzalo , Ares Pablo , Wild Stefan , Nuin Edurne , Neiss Christian , Miguel David Rodriguez‐San , Segovia Pilar , Gibaja Carlos , Michel Enrique G. , Görling Andreas , Hauke Frank , Gómez‐Herrero Julio , Hirsch Andreas , Zamora Félix
Published: September 2017

Antimonene, a novel group 15 two‐dimensional material, is functionalized with a tailormade perylene bisimide through strong van der Waals interactions. The functionalization process leads to a significant quenching of the perylene fluorescence, and surpasses that observed for either graphene or black phosphorus, thus allowing straightforward characterization of the flakes by scanning Raman microscopy. Furthermore, scanning photoelectron microscopy studies and theoretical calculations reveal a remarkable charge‐transfer behavior, being twice that of black phosphorus. Moreover, the excellent stability under environmental conditions of pristine antimonene has been tackled, thus pointing towards the spontaneous formation of a sub‐nanometric oxide passivation layer. DFT calculations revealed that the noncovalent functionalization of antimonene results in a charge‐transfer band gap of 1.1 eV.
Closed Pentaaza[9]helicene and Hexathia[9]/[5]helicene: Oxidative Fusion Reactions of ortho‐Phenylene‐Bridged Cyclic Hexapyrroles and Hexathiophenes
Authors: Chen Fengkun , Tanaka Takayuki , Hong Yong Seok , Mori Tadashi , Kim Dongho , Osuka Atsuhiro
Published: September 2017

Oxidative fusion reactions of ortho‐phenylene‐bridged cyclic hexapyrroles and hexathiophenes furnished novel closed helicenes in a selective manner. X‐Ray diffraction analysis unambiguously revealed the structures to be a closed pentaaza[9]helicene, the longest azahelicene reported so far, and an unexpected double‐helical structure of hexathia[9]/[5]helicene, whose formation was assumed to result from multiple oxidative fusion along with a 1,2‐aryl shift. The pentaaza[9]helicene exhibited well‐defined emission with high fluorescence quantum yield (ΦF=0.31) among the known [9]helicenes. Chiral resolution of the racemic pentaaza[9]helicene and hexathia[9]/[5]helicene were achieved by chiral‐phase HPLC and the enantiomers were characterized by circular dichroism spectra and DFT calculations.
Epitaxial Growth of Hetero‐Ln‐MOF Hierarchical Single Crystals for Domain‐ and Orientation‐Controlled Multicolor Luminescence 3D Coding Capability
Authors: Pan Mei , Zhu Yi‐Xuan , Wu Kai , Chen Ling , Hou Ya‐Jun , Yin Shao‐Yun , Wang Hai‐Ping , Fan Ya‐Nan , Su Cheng‐Yong
Published: September 2017

Core–shell or striped heteroatomic lanthanide metal–organic framework hierarchical single crystals were obtained by liquid‐phase anisotropic epitaxial growth, maintaining identical periodic organization while simultaneously exhibiting spatially segregated structure. Different types of domain and orientation‐controlled multicolor photophysical models are presented, which show either visually distinguishable or visible/near infrared (NIR) emissive colors. This provides a new bottom‐up strategy toward the design of hierarchical molecular systems, offering high‐throughput and multiplexed luminescence color tunability and readability. The unique capability of combining spectroscopic coding with 3D (three‐dimensional) microscale spatial coding is established, providing potential applications in anti‐counterfeiting, color barcoding, and other types of integrated and miniaturized optoelectronic materials and devices.
A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N3O Macrocyclic Ligand
Authors: Monte Pérez Inés , Engelmann Xenia , Lee Yong‐Min , Yoo Mi , Kumaran Elumalai , Farquhar Erik R. , Bill Eckhard , England Jason , Nam Wonwoo , Swart Marcel , Ray Kallol
Published: September 2017

The sluggish oxidants [FeIV(O)(TMC)(CH3CN)]2+ (TMC=1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane) and [FeIV(O)(TMCN‐d12)(OTf)]+ (TMCN‐d12=1,4,7,11‐tetra(methyl‐d3)‐1,4,7,11‐tetraazacyclotetradecane) are transformed into the highly reactive oxidant [FeIV(O)(TMCO)(OTf)]+ (1; TMCO=4,8,12‐trimethyl‐1‐oxa‐4,8,12‐triazacyclotetradecane) upon replacement of an NMe donor in the TMC and TMCN ligands by an O atom. A rate enhancement of five to six orders of magnitude in both H atom and O atom transfer reactions was observed upon oxygen incorporation into the macrocyclic ligand. This finding was explained in terms of the higher electrophilicity of the iron center and the higher availability of the more reactive S=2 state in 1. This rationalizes nature's preference for using O‐rich ligand environments for the hydroxylation of strong C−H bonds in enzymatic reactions.
A Zwitterionic, 10 π Aromatic Hemisphere
Authors: Hafezi Nema , Shewa Wondimagegn T. , Fettinger James C. , Mascal Mark
Published: September 2017

A new concept in anionic 10 π aromaticity is described by the embedding of a compensating charge within an aromatic cyclononatetraenide ring by the symmetric superposition of an alkyl ammonium bridge. This is accomplished by the methylation of azatriquinacene to give a quaternary ammonium salt, followed by oxidation to the tetraene and final deprotonation. The resulting zwitterion is a stable [9]annulene with strong aromaticity as shown by its degree of C−C bond equalization and a nucleus‐independent chemical shift value lower than that of benzene. The solid‐state structure shows an eclipsed stacking motif with the electron‐poor ammonium methyl groups occupying the electron‐rich cavity of the aromatic bowl.
Iron(III) porphyrin catalyzed ionic liquid mediated polymerization of methylmethacrylate
Authors: Singhal Anchal , Ahmad Sohail , Chauhan Shive M.S.
Published: September 2017

A novel application of iron(III)porphyrin catalyst, 5,10,15,20 − tetrakis − (2′,6′‐dichlorophenyl)porphyrinatoiron(III) chloride is reported for the reaction of methyl methacrylate with hydrogen peroxide in imidazolium ionic liquids at ambient temperature. The reaction furnished polymethyl methacrylate in 75–94% yields. The yield of the polymer was optimized upon changing the reaction media, ratio of catalyst, oxidant and substrate, reaction time and quenchers. The polymethyl methacrylate was secured as highly stereoregular with predominantly syndiotactic sequences as analyzed with the aid of NMR (1H and 13C) and infrared spectroscopy. Besides, the number‐average molecular weights (Mn) were attained in the range of 15,000 to 55,000 with narrow polydispersity (~1.1–1.9) as calculated using gel permeable chromatography (GPC).
Green synthesis of silver nanoparticles using water extract of Salvia leriifolia: Antibacterial studies and applications as catalysts in the electrochemical detection of nitrite
Authors: Baghayeri Mehdi , Mahdavi Behnam , Hosseinpor‐Mohsen Abadi Zahra , Farhadi Samaneh
Published: September 2017

Here, a green method is described for the biosynthesis of Ag nanoparticles (Ag NPs) using aqueous extracts of the leaf of Salvia leriifolia as reducing and stabilizing agent. Various techniques such as scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM) and X‐ray diffraction (XRD) were employed for the characterization of the structure and morphology of bio‐synthesized AgNPs. The results reveal that AgNPs synthesized with uniform spherical morphology and average diameters of 27 nm. The AgNPs as a green and efficient heterogeneous catalyst presented superior antibacterial activity. Direct electrochemistry studies of the synthesized AgNPs confirmed that nanoparticles retained their direct electrochemical activity. This is mainly attributed to the proper biosynthesis process, the large specific surface area and the good conductivity of the synthesized nanoparticles. Hence, the present synthesized AgNPs displayed good electrocatalytic activity to the reduction of nitrite ions. The proposed method is highly recommended as a novel platform for the development of electrochemical sensors which can further expand the applications of AgNPs. Antibacterial activity of the synthesized AgNPs was evaluated against nine microorganisms. AgNPs prevented the growth of all selected bacteria. The nanoparticles inhibited the growth of Pseudomonas aeruginosa, Klebsiella pneumonia, Staphylococcus coagulase, Acinetobacter baumannii, and Streptococcus pneumonia more than antibiotic of vancomycin, however, the ability of AgNPs against Echerishia coli and Serratia marcescens was less than the antibiotic. On the other hand AgNPs were active against Citrobacter frurdii, while the antibiotic was inactive.
Effect of Ca2+ induced crosslinking on the mechanical and barrier properties of cast alginate films
Authors: Jost Verena , Reinelt Matthias
Published: September 2017

The use of alginate as a coating material for packaging applications is currently limited due to its difficult processability and high moisture sensitivity. Therefore, this study addresses the crosslinking and scale‐up to a continuous application. Three different crosslinking agents were applied: CaCl2 with ethylene diamine tetraacetic acid and two low soluble salts (CaHPO4 and CaCO3). Those were incorporated by internal setting in an alginate matrix with varying Ca2+ concentration (
) and ratio. With the addition of Ca2+, the tensile strength and elongation at break of the cast alginate films increased. This was optimal for a
of 0.010–0.015 g (g alginate)−1 dependent on the crosslinking agent. The decrease in water vapor and oxygen permeability due to crosslinking was independent of the crosslinking agent. However, the optimal
aiming to decrease permeability was different for the crosslinking agents: CaHPO4 showed best results at a
of 0.010 g (g alginate)−1, CaCl2 at 0.012 g (g alginate)−1, and CaCO3 at 0.027 g (g alginate)−1. Upon all analyzed properties CaHPO4 was the most promising crosslinking agent for alginate. Moreover, selected alginate formulations were successfully processed in a continuous lacquering plant. The produced two‐layer systems have very low oxygen permeabilities which can be further reduced by crosslinking. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45754.
Preparation and property of starch nanoparticles reinforced aldehyde–hydrazide covalently crosslinked PNIPAM hydrogels
Authors: Li Shanshan , Xia Yuzheng , Qiu Yang , Chen Xiaonong , Shi Shuxian
Published: September 2017

Injectable, de‐crosslinkable, and thermosensitive hydrogels are obtained by hydrazide‐functionalized poly(N‐isopropylacrylamide) and aldehyde‐functionalized dextrin through in situ crosslinked method. Natural based and degradable starch nanoparticles (SNPs) are used as fillers in order to improve mechanical property of hydrogels. Internal morphology, dynamic modulus, thermosensitivity property, de‐crosslinking performance, drug release, and in vitro cytotoxicity of hydrogels are investigated. Results show that SNPs disperse well throughout hydrogel and have no significant influence on gelation time and de‐crosslinking performance. Elasticity property of composite hydrogel prepared from 9.0 wt % precursors with 1.5 wt % fillers is improved significantly by SNPs and maximum storage modulus reaches 399.2 kPa, but 89.6 kPa of unreinforced hydrogels. Hydrogels exhibit good thermosensitive performance at alternating cyclic temperature of 25 and 37 °C. Doxorubicin hydrochloride‐loaded hydrogels can release more than 25 days. No significant cytotoxicity to L929 fibroblast cells is observed through a CCK‐8 assay for hydrogels, precursors, and SNPs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45761.
Tailoring terpenoid plasma polymer properties by controlling the substrate temperature during PECVD
Authors: Kumar Avishek , Grant Daniel S. , Bazaka Kateryna , Jacob Mohan V.
Published: September 2017

Polymers derived from natural, minimally‐processed materials have recently emerged as a more sustainable alternative to synthetic polymers, with promising applications in biocompatible and biodegradable devices. Plasma‐enhanced deposition is well‐suited to one‐step, fast, and efficient synthesis of highly crosslinked inert polymers directly from natural resources, however, fabrication of biologically active polymers remains a challenge. Plasma processing parameters influence the properties such as surface energy, roughness, morphology, and chemical composition of deposited polymers and thus their final applications. This article reports on the important role of substrate temperature (TS) in the chemical composition, wettability, refractive index, and crosslinking density of plasma polymers derived from terpenoids. Experiments are conducted as a function of deposition power Pd, and substrate temperature, TS. TS varied from 40 to 280 °C and is externally controlled. Atomic force microscopy analysis reveals the change in deposition mechanism attributed to shadowing effect at higher TS and Pd. Increase in band gap (Eg) with high Ts deposition for terpenoid based plasma polymers is observed. Swelling behavior analyzed by in situ ellipsometry affirms the enhanced crosslink density with increasing deposition rate. Fourier transform infrared analysis exhibits the formation of additional chemical moieties with increasing TS. Increase in deposition rate with increasing TS at higher Pd supports the theory of direct incorporation of depositing particles as dominant mechanism of plasma polymerization in this study. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45771.