bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient Vanadium‐Catalyzed Aerobic C−C Bond Oxidative Cleavage of Vicinal Diols
Authors: Amadio Emanuele , González‐Fabra Joan , Carraro Davide , Denis William , Gjoka Blerina , Zonta Cristiano , Bartik Kristin , Cavani Fabrizio , Solmi Stefania , Bo Carles , Licini Giulia
Published: May 2018

The aerobic oxidative C−C bond cleavage of vicinal diols catalyzed by vanadium amino triphenolates is described. Our results show that C−C bond cleavage can be performed in different solvents, under an air or oxygen atmosphere, with a large variety of glycols (cyclic or linear, with aromatic or aliphatic substituents) affording the corresponding carbonyl derivatives with high chemoselectivity. Reactions can be performed with as little as 10 ppm of catalyst reaching TON up to 81,000 and TOFs of up to 4150 h−1. A reaction mechanism, rationalized by density functional theory calculations, is also proposed.

magnified image
HPLC‐MS detection of pyrrolizidine alkaloids and their N‐oxides in herbarium specimens dating back to the 1850s
Authors: Tasca Julia A. , Smith Chelsea R. , Burzynski Elizabeth A. , Sundberg Brynn N. , Lagalante Anthony F. , Livshultz Tatyana , Minbiole Kevin P. C.
Published: May 2018

Premise of the Study

Understanding the phylogenetic distribution of defensive plant secondary metabolites is essential to the macroevolutionary study of chemically mediated plant–animal interactions. The chemical ecology of pyrrolizidine alkaloids (PAs) has been extensively studied in a number of plant–herbivore systems, including Apocynaceae (the milkweed and dogbane family) and Danainae (the milkweed and clearwing butterflies). A systematic survey is necessary to establish a detailed understanding of their occurrence across Apocynaceae. A survey of this species‐rich, mainly tropical and subtropical family will rely heavily on small tissue samples removed from herbarium specimens, some of which will be very old and/or preserved with alcohols or mercuric chloride.

Methods

We optimized PA extraction methods from small leaf fragments of recently collected silica‐dried leaves of the PA‐positive Echites umbellatus, varying crushing and extraction time. We then applied our optimized method to leaf fragments from 70–167‐year‐old herbarium specimens of E. umbellatus. To simulate the effect of alcohol treatment on PA detectability in herbarium specimens, we incubated freshly collected leaves of the PA‐positive Parsonsia alboflavescens in three different alcohols before drying and compared PA recovery to freshly dried controls. PAs were quantified using high‐performance liquid chromatography–mass spectrometry analysis. X‐ray fluorescence was used to identify mercury‐containing specimens.

Results

Fifteen seconds of leaf crushing followed by 24 h of extraction were optimal for PA free‐base and N‐oxide recovery. This method yielded ~50‐fold greater PA recovery than prior methods. Half of the herbarium specimens (13 of 23), including the oldest, tested positive for PAs; leaf age did not correlate with success in PA extraction. Treatment of fresh leaves with alcohol before drying did not diminish PA recovery; mercury was observed in both PA‐positive and PA‐negative specimens.

Conclusions

PAs can be reliably detected in small tissue samples from herbarium specimens up to 167 years old, including specimens that had been treated with alcohol or mercury salts. The variability of PA presence among herbarium specimens of E. umbellatus indicates that multiple specimens will need to be tested before a particular species is determined to lack PAs.
Palladium‐Catalyzed Mizoroki–Heck‐Type Alkenylation of Monoaryldialkylsulfoniums
Authors: Uno Daisuke , Minami Hiroko , Otsuka Shinya , Nogi Keisuke , Yorimitsu Hideki
Published: May 2018

Mizoroki–Heck‐type alkenylation of monoaryldialkylsulfoniums has been accomplished by means of palladium catalysts. Various combinations of monoarylsulfoniums and alkenes were adapted to the present reaction. Because monoaryldimethylsulfoniums were readily prepared from the corresponding aryl methyl sulfides and methyl triflate, one‐pot alkenylation of aryl methyl sulfide could also be executed.
Ruthenium‐Mediated Distal C−H Activation
Authors: Khan Farheen Fatima , Sinha Soumya Kumar , Lahiri Goutam Kumar , Maiti Debabrata
Published: May 2018

Addressing remote C−H functionalization is a prominent challenge in the field of homogeneous catalysis. The past two decades have accounted for major developments in this domain, proclaiming efficient selectivity at the meta and para positions. Recognizing such transformations remains significant, owing to their importance in the biological and chemical industries. This focus review aims to summarize the relatively new concept of σ‐C−H activation enabled by a ruthenium metal center.
Analysis of retinol, α‐tocopherol, 25‐hydroxyvitamin D2 and 25‐hydroxyvitamin D3 in plasma of patients with cardiovascular disease by HPLC–MS/MS method
Authors: Karaźniewicz‐Łada Marta , Główka Anna , Komosa Anna , Kruszyna Łukasz , Graczyk‐Szuster Agnieszka , Lesiak Maciej , Sowińska Dagmara , Przysławski Juliusz
Published: May 2018

Fat‐soluble vitamins play a pivotal role in the progression of atherosclerosis and the development of cardiovascular disease. Therefore, plasma monitoring of their concentrations may be useful in the diagnosis of these disorders as well as in the process of treatment. The study aimed to develop and validate an HPLC–MS/MS method for determination of retinol, α‐tocopherol, 25‐hydroxyvitamin D2 and 25‐hydroxyvitamin D3 in plasma of patients with cardiovascular disease. The analytes were separated on an HPLC Kinetex F5 column via gradient elution with water and methanol, both containing 0.1% (v/v) formic acid. Detection of the analytes was performed on a triple‐quadrupole MS with multiple reaction monitoring via electrospray ionization. The analytes were isolated from plasma samples with liquid–liquid extraction using hexane. Linearity of the analyte calibration curves was confirmed in the ranges 0.02–2 μg/mL for retinol, 0.5–20 μg/mL for α‐tocopherol, 5–100 ng/mL for 25‐hydroxyvitamin D2 and 2–100 ng/mL for 25‐hydroxyvitamin D3. Intra‐ and inter‐assay precision and accuracy of the method were satisfactory. Short‐ and long‐term stabilities of the analytes were determined. The HPLC‐MS/MS method was applied for the determination of the above fat‐soluble vitamin concentrations in patient plasma as potential markers of the cardiovascular disease progression.
Elucidating the Importance of Hydrochloric Acid as a Cocatalyst for Resorcinarene‐Capsule‐Catalyzed Reactions
Authors: Köster Jesper M. , Tiefenbacher Konrad
Published: May 2018

This survey of resorcinarene‐capsule‐catalyzed reactions demonstrates that HCl functions as a crucial cocatalyst by increasing the capsule's inherent Brønsted acidity to enable or accelerate cationic reactions. The presence of HCl appears to be without consequences for other reactions.
Effects of agriculture and topography on tropical amphibian species and communities
Authors: Ribeiro José Wagner , Siqueira Tadeu , Brejão Gabriel Lourenço , Zipkin Elise F.
Published: May 2018

Habitat loss is the greatest threat to the persistence of forest‐dependent amphibians, but it is not the only factor influencing species occurrences. The composition of the surrounding matrix, structure of stream networks, and topography are also important landscape characteristics influencing amphibian distributions. Tropical forests have high diversity and endemism of amphibians, but little is known about the specific responses of many of these species to landscape features. In this paper, we quantify the response of amphibian species and communities to landscape‐scale characteristics in streams within the fragmented Brazilian Atlantic Forest. We surveyed amphibian communities during a rainy season in 50 independent stream segments using Standardized Acoustic and Visual Transect Sampling (active) and Automated Acoustic Recorders (passive) methods. We developed a hierarchical multi‐species occupancy model to quantify the influence of landscape‐scale characteristics (forest cover, agriculture, catchment area, stream density, and slope) on amphibian occurrence probabilities while accounting for imperfect detection of species using the two survey methods. At the community level, we estimated an overall mean positive relationship between amphibian occurrence probabilities and forest cover, and a negative relationship with agriculture. Catchment area and slope were negatively related with amphibian community structure (95% credible interval [CI] did not overlap zero). The species‐level relationships with landscape covariates were highly variable but showed similar patterns to those at the community level. Species detection probabilities varied widely and were influenced by the sampling method. For most species, the active method resulted in higher detection probabilities than the passive approach. Our findings suggest that small streams and flat topography lead to higher amphibian occurrence probabilities for many species in Brazil's Atlantic Forest. Our results combined with land use and topographic maps can be used to make predictions of amphibian occurrences and distributions beyond our study area. Such projections can be useful to determine where to conduct future research and prioritize conservation efforts in human‐modified landscapes.
Invoking adaptation to decipher the genetic legacy of past climate change
Authors: de Lafontaine Guillaume , Napier Joseph D. , Petit Rémy J. , Hu Feng Sheng
Published: May 2018

Persistence of natural populations during periods of climate change is likely to depend on migration (range shifts) or adaptation. These responses were traditionally considered discrete processes and conceptually divided into the realms of ecology and evolution. In a milestone paper, Davis and Shaw (2001)Science292:673 argued that the interplay of adaptation and migration was central to biotic responses to Quaternary climate, but since then there has been no synthesis of efforts made to set up this research program. Here we review some of the salient findings from molecular genetic studies assessing ecological and evolutionary responses to Quaternary climate change. These studies have revolutionized our understanding of population processes associated with past species migration. However, knowledge remains limited about the role of natural selection for local adaptation of populations to Quaternary environmental fluctuations and associated range shifts, and for the footprints this might have left on extant populations. Next‐generation sequencing technologies, high‐resolution paleoclimate analyses, and advances in population genetic theory offer an unprecedented opportunity to test hypotheses about adaptation through time. Recent population genomics studies have greatly improved our understanding of the role of contemporary adaptation to local environments in shaping spatial patterns of genetic diversity across modern‐day landscapes. Advances in this burgeoning field provide important conceptual and methodological bases to decipher the historical role of natural selection and assess adaptation to past environmental variation. We suggest that a process called “temporal conditional neutrality” has taken place: some alleles favored in glacial environments become selectively neutral in modern‐day conditions, whereas some alleles that had been neutral during glacial periods become under selection in modern environments. Building on this view, we present a new integrative framework for addressing the interplay of demographic and adaptive evolutionary responses to Quaternary climate dynamics, the research agenda initially envisioned by Davis and Shaw (2001)Science292:673.
Chronic impacts of invasive herbivores on a foundational forest species: a whole‐tree perspective
Authors: Wilson Claire M. , Schaeffer Robert N. , Hickin Mauri L. , Rigsby Chad M. , Sommi Amanda F. , Thornber Carol S. , Orians Colin M. , Preisser Evan L.
Published: May 2018

Forests make up a large portion of terrestrial plant biomass, and the long‐lived woody plants that dominate them possess an array of traits that deter consumption by forest pests. Although often extremely effective against native consumers, invasive species that avoid or overcome these defenses can wreak havoc on trees and surrounding ecosystems. This is especially true when multiple invasive species co‐occur, since interactions between invasive herbivores may yield non‐additive effects on the host. While the threat posed by invasive forest pests is well known, long‐term field experiments are necessary to explore these consumer‐host interactions at appropriate spatial and temporal scales. Moreover, it is important to measure multiple variables to get a “whole‐plant” picture of their combined impact. We report the results of a 4‐yr field experiment addressing the individual and combined impacts of two invasive herbivores, the hemlock woolly adelgid (Adelges tsugae) and elongate hemlock scale (Fiorinia externa), on native eastern hemlock (Tsuga canadensis) in southern New England. In 2011, we planted 200 hemlock saplings into a temperate forest understory and experimentally manipulated the presence/absence of both herbivore species; in 2015, we harvested the 88 remaining saplings and assessed plant physiology, growth, and resource allocation. Adelgids strongly affected hemlock growth: infested saplings had lower above/belowground biomass ratios, more needle loss, and produced fewer new needles than control saplings. Hemlock scale did not alter plant biomass allocation or growth, and its co‐occurrence did not alter the impact of adelgid. While both adelgid and scale impacted the concentrations of primary metabolites, adelgid effects were more pronounced. Adelgid feeding simultaneously increased free amino acids local to feeding sites and a ~30% reduction in starch. The cumulative impact of adelgid‐induced needle loss, manipulation of nitrogen pools, and the loss of stored resources likely accelerates host decline through disruption of homeostatic source‐sink dynamics occurring at the whole‐plant level. Our research stresses the importance of considering long‐term impacts to predict how plants will cope with contemporary pressures experienced in disturbed forests.
Tick‐borne disease risk in a forest food web
Authors: Ostfeld Richard S. , Levi Taal , Keesing Felicia , Oggenfuss Kelly , Canham Charles D.
Published: May 2018

Changes to the community ecology of hosts for zoonotic pathogens, particularly rodents, are likely to influence the emergence and prevalence of zoonotic diseases worldwide. However, the complex interactions between abiotic factors, pathogens, vectors, hosts, and both food resources and predators of hosts are difficult to disentangle. Here we (1) use 19 yr of data from six large field plots in southeastern New York to compare the effects of hypothesized drivers of interannual variation in Lyme disease risk, including the abundance of acorns, rodents, and deer, as well as a series of climate variables; and (2) employ landscape epidemiology to explore how variation in predator community structure and forest cover influences spatial variation in the infection prevalence of ticks for the Lyme disease bacterium, Borrelia burgdorferi, and two other important tick‐borne pathogens, Anaplasma phagocytophilum and Babesia microti. Acorn‐driven increases in the abundance of mice were correlated with a lagged increase in the abundance of questing nymph‐stage Ixodes scapularis ticks infected with Lyme disease bacteria. Abundance of white‐tailed deer 2 yr prior also correlated with increased density of infected nymphal ticks, although the effect was weak. Density of rodents in the current year was a strong negative predictor of nymph density, apparently because high current abundance of these hosts can remove nymphs from the host‐seeking population. Warm, dry spring or winter weather was associated with reduced density of infected nymphs. At the landscape scale, the presence of functionally diverse predator communities or of bobcats, the only obligate carnivore, was associated with reduced infection prevalence of I. scapularis nymphs with all three zoonotic pathogens. In the case of Lyme disease, infection prevalence increased where coyotes were present but smaller predators were displaced or otherwise absent. For all pathogens, infection prevalence was lowest when forest cover within a 1 km radius was high. Taken together, our results suggest that a food web perspective including bottom‐up and top‐down forcing is needed to understand drivers of tick‐borne disease risk, a result that may also apply to other rodent‐borne zoonoses. Prevention of exposure based on ecological indicators of heightened risk should help protect public health.
Pyrolysis and carbon dioxide gasification kinetics of hydrochar produced from cow manure
Authors: Saha Pretom , McGaughy Kyle , Hasan Md. Rifat , Reza M. Toufiq
Published: May 2018

This study focuses on determining the kinetic parameters of pyrolysis and gasification of manure‐derived hydrochar. Hydrochar was first pyrolyzed in Thermogravimetric analyzer at heating rates of 5, 10, and 20°C min−1 with N2 and gasified afterwards with CO2 at 800, 900, and 1000°C for 30, 60, and 90 min. Morphology of the pyrolysis and gasified chars were analyzed with FT‐IR and scanning electron microscope (SEM). Kissinger's method was used to evaluate kinetic parameters for pyrolysis, while Arrhenius method was implemented to evaluate gasification kinetic parameters. Activation energy for pyrolysis and gasification were 211.5 ± 7.7 kJ mol−1 and 270 ± 20 kJ mol−1, respectively. FT‐IR analysis revealed that ‐OH and aliphatic C‐H groups were significantly reduced compare to raw hydrochar during gasification. A decrease of particle size and an increase of amorphous region were observed in SEM analysis, while energy‐dispersive x‐ray spectroscopy analysis revealed an increase in oxygen and carbon contents in gasified char. © 2018 American Institute of Chemical Engineers Environ Prog, 38: 154–162, 2019
Graphene quantum dots coated on quartz sand as efficient and low‐cost adsorbent for removal of Hg2+ and Pb2+ from aqueous solutions
Authors: Mohammad‐Rezaei Rahim , Jaymand Mehdi
Published: May 2018

Herein, a novel, efficient and inexpensive adsorbent based on graphene quantum dots (GQDs) coated on quartz sand (GQDs|QS) for removal of Hg2+ and Pb2+ from aqueous solutions was reported. The GQDs|QS was characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy, and X‐ray powder diffraction techniques. To optimize operation parameters and study removal efficiency of the prepared adsorbent, a batch removal system followed by anodic stripping voltammetry technique was used during the experiments. The maximum adsorption capacity of GQDs|QS for Hg2+ and Pb2+ were calculated 24.65 and 24.92 mg g−1, respectively, which reveal more improved adsorption capacitance of the GQDs|QS in comparison with nontreated QS. According to experimental results, adsorption of Hg2+ and Pb2+ on the developed adsorbent follows pseudo‐second order kinetic model. In addition, equilibrium experimental data appropriately fit with the Langmuir isotherm (R2 > 0.99). It was found that the stability and removal performance of the GQDs|QS strongly depend to the particle size of GQDs. Due to low cost, stability and effectiveness of the GQDs|QS, it could be used as a suitable choice for water treatment in industrial scale. © 2018 American Institute of Chemical Engineers Environ Prog, 38: S24–S31, 2019
Removal of cobalt ion from aqueous solution using magnetic graphene oxide/chitosan composite
Authors: Zhuang Shuting , Wang Jianlong
Published: May 2018

The magnetic graphene oxide (GO)/chitosan composite was prepared, characterized, and applied for the removal of cobalt ions from aqueous solutions. One‐step coprecipitation method was used to synthesize magnetic GO/chitosan beads, which were characterized by VMS, FTIR, SEM, and EDX. The composites show a good porous structure and magnetic separation ability. The adsorption process is endothermic (ΔH0 = 12.08 kJ mol−1) and pH in the range of 5–9 has a slight effect on Co2+ adsorption. The adsorption kinetic data could be fitted with the pseudo‐second‐order model (R2 = 0.995) best, followed by the intraparticle diffusion (R2 = 0.950) and pseudo‐first‐order (R2 = 0.943) models. In addition, the Langmuir model (R2 = 0.995) was better at fitting the adsorption equilibrium data than that of the Freundlich (R2 = 0.814) and the Temkin (R2 = 0.806) models. The maximum adsorption capacity (qm) was calculated to be 15.24 mg·g−1 based on the weight of chitosan and GO by the Langmuir model. The magnetic GO/chitosan composite beads can be used for the removal of cobalt ions from aqueous solutions. © 2018 American Institute of Chemical Engineers Environ Prog, 38: S32–S41, 2019
Study on the effects Nano‐SiO2 and spent catalyst ratios on characteristics of metakaolin‐based geopolymers
Authors: Cheng Ta‐Wui , Lo Kang‐Wei , Lin Kae‐Long , Lan Ju‐Ying
Published: May 2018

This study focused on nano‐SiO2 (NS) addition levels (0.5%–2%) and spent catalyst replacement levels (0%–20%) in the geopolymerization reaction and subsequent network formation of metakaolin‐based geopolymers (MKGP), which affect the mechanical properties and microstructure of the geopolymers. The geopolymers had high flexural strength (72.9 MPa), high bulk density (1.37 g/cm3), and low porosity (41.4%) when 0.5% NS was constantly added and the spent catalyst replacement level was 5%. The geopolymer weight loss was due to the structural water evaporation occurring at temperatures ranging from 350°C to 550°C. Therefore, weight loss was slightly higher than 0.5% NS MKGP without spent catalyst (1.25%) at the spent catalyst replacement level of 5% (1.44%). Regarding the chemical shifts in 29Si MAS NMR spectra, when the geopolymer contained 0.5% NS, the peak center of Q4 (2Al, −97 ppm) shifted to an even higher magnetic of Q4 (3Al, −90 ppm). The NS surface, which was in an active and high free‐energy state, reacted with the geopolymerization system, forming chemical interfacial bonding with the binder phase. The MKGP with 0.5% NS content and 5% spent catalyst replacement yielded more favorable mechanical characteristics and microstructure, according to the flexural strength, TG/DTA, and NMR analyses. © 2018 American Institute of Chemical Engineers Environ Prog, 38: 220–227, 2019
Different parameters affecting the condensation rate on an active solar still—A review
Authors: Manokar A. Muthu , Vimala M. , Winston D. Prince , Ramesh R. , Sathyamurthy Ravishankar , Nagarajan P. K. , Bharathwaaj R.
Published: May 2018

Passive solar stills are used for solar distillation. But the yield of passive still is very low, and often fails to meet the demand. Water is one of the fundamental sources for the survival of mankind on the globe. As world having just a little measure of water assets for utilization purpose, individuals living in undeveloped countries and urban zones are getting affected by consuming dirty water that prompts water‐borne illness. Despite the fact that groundwater is accessible in little amount, it must be suitably treated before its utilization for domestic use. Salty water contains dissolved and undissolved substance, and henceforth, it is not advisable for family drinking purpose. To enhance the productivity of fresh water, several techniques were employed. Furthermore, increase in yield of fresh water depends on various environmental parameters and rate of condensation. In this article, a complete review of various methods employed to enhance the condensation rate on an active solar still has been presented. Solar still incorporated with the evacuated tube collectors (ETC) and thermo electric modules (TEM) increased the still effectiveness up to 68%. © 2018 American Institute of Chemical Engineers Environ Prog, 38: 286–296, 2019
Petroleum hydrocarbon mixture toxicity and a trait-based approach to soil invertebrate species for site-specific risk assessments
Authors: Gainer Amy , Cousins Mark , Hogan Natacha , Siciliano Steven D.
Published: May 2018

Although petroleum hydrocarbons released to the environment typically occur as mixtures, petroleum hydrocarbon remediation guidelines often reflect individual substance toxicity. It is well documented that groups of aliphatic petroleum hydrocarbons act via the same mechanism of action (nonpolar narcosis) and, theoretically, concentration addition mixture toxicity principles apply. To assess this theory, 10 standardized acute and chronic soil invertebrate toxicity tests on a range of organisms (Eisenia fetida, Lumbricus terrestris, Enchytraeus crypticus, Folsomia candida, Oppia nitens, and Hypoaspis aculeifer) were conducted with a refined petroleum hydrocarbon binary mixture. Reference models for concentration addition and independent action were applied to the mixture toxicity data with consideration of synergism, antagonism, and dose level toxicity. Both concentration addition and independent action, without further interactions, provided the best fit with observed response to the mixture. Individual fraction effective concentration values were predicted from optimized, fitted reference models. Concentration addition provided a better estimate than independent action of individual fraction effective concentrations based on comparison with available literature and species trends observed in toxic responses to the mixture. Interspecies differences in standardized laboratory soil invertebrate species responses to petroleum hydrocarbon–contaminated soil was reflected in unique traits. Diets that included soil, large body size, permeable cuticle, low lipid content, lack of ability to molt, and no maternal transfer were traits linked to a sensitive survival response to petroleum hydrocarbon–contaminated soil in laboratory tests. Traits linked to sensitive reproduction response in organisms tested were long life span and small clutch size. By deriving single-fraction toxicity endpoints considerate of mixtures, we can reduce the resources and time required to conduct site-specific risk assessments for the protection of a soil organism's exposure pathway. Environ Toxicol Chem 2018;37:2222–2234. © 2018 SETAC
The sensitivity of a deep-sea fish species (Anoplopoma fimbria) to oil-associated aromatic compounds, dispersant, and Alaskan North Slope crude oil
Authors: McConville Megan M. , Roberts John P. , Boulais Myrina , Woodall Benjamin , Butler Joshua D. , Redman Aaron D. , Parkerton Thomas F. , Arnold W. Ray , Guyomarch Julian , LeFloch Stéphane , Bytingsvik Jenny , Camus Lionel , Volety Aswani , Brander Susanne M.
Published: May 2018

A predominant concern following oil spills is toxicity to aquatic organisms. However, few data are available on effects in deep-sea cold water fishes. The present study had 3 major objectives. The first was to investigate the relative sensitivity of the deep-sea species Anoplopoma fimbria (sablefish) to acute effects of 3 aromatic compounds (toluene, 2-methylnaphthalene, and phenanthrene), dispersant alone, and chemically enhanced water accommodated fractions (CEWAFs) of Alaskan North Slope crude oil. The second was to determine the critical target lipid body burden (CTLBB) for sablefish by fitting aromatic hydrocarbon toxicity data to the target lipid model (TLM), which then allowed expression of CEWAF exposures in terms of dissolved oil toxic units. The final aim was to apply a passive sampling method that targets bioavailable, dissolved hydrocarbons as an alternative analytical technique for improved CEWAF exposure assessment. The results indicate that sablefish exhibit sensitivity to Corexit 9500 (96-h median lethal concentration [LC50] = 72.2 mg/L) within the range reported for other fish species. However, the acute CTLBB of 39.4 ± 2.1 μmol/goctanol lies at the lower end of the sensitivity range established for aquatic species. The utility of both toxic units and passive sampling measurements for describing observed toxicity of dispersed oil is discussed. The present study is novel in that a new test species is investigated to address the uncertainty regarding the sensitivity of deep-sea fishes, while also employing modeling and measurements to improve exposure characterization in oil toxicity tests. Environ Toxicol Chem 2018;37:2210–2221. © 2018 SETAC
Caspase Recruitment Domain Protein 6 Protects Against Hepatic Steatosis and Insulin Resistance by Suppressing Apoptosis Signal–Regulating Kinase 1
Authors: Sun Peng , Zeng Qiang , Cheng Daqing , Zhang Kuo , Zheng Jilin , Liu Yupeng , Yuan Yu‐Feng , Tang Yi‐Da
Published: May 2018

The rapidly increasing prevalence of metabolic disorders associated with nonalcoholic fatty liver disease (NAFLD) warrants further study of the underlying mechanisms to identify key regulators as targets for the development of therapeutic interventions. Caspase recruitment domain protein 6 (Card6), as a member of the CARD family that regulates cell death and immunity, may potentially control this process. Indeed, Card6 down‐regulation was found to be closely associated with the fatty livers observed in NAFLD patients, obese mice, and a palmitate‐treated hepatocyte model. Gain‐of‐function and loss‐of‐function Card6 mouse models demonstrated that Card6 protected mice from insulin resistance, hepatic steatosis, and inflammatory responses upon high‐fat diet administration. Mechanistically, Card6 interacted with and inhibited apoptosis signal–regulating kinase 1 (Ask1) and its subsequent downstream c‐Jun N‐terminal kinase/p38 signaling. Furthermore, Ask1 was sufficient to mediate Card6 function, and the interaction between Ask1 and Card6 was absolutely required for Card6 function in vivo. Adenovirus‐mediated Card6 overexpression in the liver effectively ameliorated insulin resistance and hepatic steatosis in ob/ob mice. Therefore, we identified Card6 as an important negative regulator in NAFLD. Conclusion: Targeting Ask1 by Card6 may be a good strategy to develop a therapeutic method against NAFLD.
Variability in Nontarget Terrestrial Plant Studies Should Inform Endpoint Selection
Authors: Staveley Jane P , Green John W , Nusz Josie , Edwards Dan , Henry Kevin , Kern Matt , Deines Andrew M , Brain Richard , Glenn Brad , Ehresman Nathan , Kung Tiffany , Ralston-Hooper Kimberly , Kee Faith , McMaster Steve
Published: May 2018

Inherent variability in nontarget terrestrial plant (NTTP) testing of pesticides creates challenges for using and interpreting these data for risk assessment. Standardized NTTP testing protocols were initially designed to calculate the application rate causing a 25% effect (ER25, used in the United States) or a 50% effect (ER50, used in Europe) for various measures based on the observed dose–response. More recently, the requirement to generate a no-observed-effect rate (NOER), or, in the absence of an NOER, the rate causing a 5% effect (ER05), has raised questions about the inherent variability in, and statistical detectability of, these tests. Statistically significant differences observed between test and control groups may be a product of this inherent variability and may not represent biological relevance. Attempting to derive an ER05 and the associated risk-assessment conclusions drawn from these values can overestimate risk. To address these concerns, we evaluated historical data from approximately 100 seedling emergence and vegetative vigor guideline studies on pesticides to assess the variability of control results across studies for each plant species, examined potential causes for the variation in control results, and defined the minimum percent effect that can be reliably detected. The results indicate that with current test design and implementation, the ER05 cannot be reliably estimated. Integr Environ Assess Manag 2018;14:639–648. © 2018 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC)

Key Points

Inherent variability in nontarget terrestrial plant (NTTP) testing of pesticides creates challenges for risk assessment. An evaluation of approximately 100 seedling emergence and vegetative vigor guideline studies was performed to assess the variability in control results and define the minimum percent effect that can be reliably detected. With current NTTP test design and implementation, it will often be impossible to reliably estimate an ER05, and it will rarely be possible to reliably estimate an ER10.
Chitinase‐3‐like protein 1 ameliorates atherosclerotic responses via PPARδ‐mediated suppression of inflammation and ER stress
Authors: Jung Tae Woo , Park Hyung Sub , Choi Geum Hee , Kim Daehwan , Jeong Ji Hoon , Lee Taeseung
Published: May 2018

Chitinase 3‐like protein 1 (CHI3L1) is a novel biomarker of systemic inflammation. However, the effects of CHI3L1 on the progression of atherosclerosis remain to be explored. In the current study, we found that CHI3L1 induces peroxisome proliferator‐activated receptor delta (PPARδ) expression, leading to a dose‐dependent increase in oxygen‐regulated protein 150 (ORP150) expression. We demonstrated that CHI3L1 suppresses atherosclerotic reactions caused by LPS treatment via a PPARδ‐dependent pathway. Treatment of HUVECs and THP‐1 cells with CHI3L1 suppressed LPS‐induced phosphorylation of nuclear factor kappa B (NFκB) and secretion of proinflammatory cytokines such as TNFα and MCP‐1. In HUVECs, expression of adhesion molecules and LPS‐stimulated adhesion of THP‐1 cells to the endothelium were significantly reduced after CHI3L1 treatment. Furthermore, LPS‐induced endoplasmic reticulum (ER) stress and cell apoptosis were significantly ameliorated after treatment of HUVECs with CHI3L1. Particularly, all of the pro‐atherosclerotic effects were significantly mitigated by treatment with small interfering (si) RNA for PPARδ. In conclusion, CHI3L1 ameliorates LPS‐induced atherosclerotic reactions via PPARδ‐mediated suppression of inflammation and ER stress.
Flexible quantum dot light‐emitting devices for targeted photomedical applications
Authors: Chen Hao , Yeh Tzu‐Hung , He Juan , Zhang Caicai , Abbel Robert , Hamblin Michael R. , Huang Yingying , Lanzafame Raymond J. , Stadler Istvan , Celli Jonathan , Liu Shun‐Wei , Wu Shin‐Tson , Dong Yajie
Published: May 2018

Quantum dot light‐emitting devices (QLEDs), originally developed for displays, were recently demonstrated to be promising light sources for various photomedical applications, including photodynamic therapy cancer cell treatment and photobimodulation cell metabolism enhancement. With exceptional emission wavelength tunability and potential flexibility, QLEDs could enable wearable, targeted photomedicine with maximized absorption of different medical photosensitizers. In this paper, we report, for the first time, the in vitro study to demonstrate that QLEDs‐based photodynamic therapy can effectively kill Methicillin‐resistant Staphylococcus aureus, an antibiotic‐resistant bacterium. We then present successful synthesis of highly efficient quantum dots with narrow spectra and specific peak wavelengths to match the absorption peaks of different photosensitizers for targeted photomedicine. Flexible QLEDs with a peak external quantum efficiency of 8.2% and a luminance of over 20,000 cd/m2 at a low driving voltage of 6 V were achieved. The tunable, flexible QLEDs could be employed for oral cancer treatment or diabetic wound repairs in the near future. These results represent one fresh stride toward realizing QLEDs' long‐term goal to enable the wide clinical adoption of photomedicine.
Novel directional projection screen using divergent corner cube retroreflector with a three‐sided curved surface (D‐CCR)
Authors: Ohtera Ryosuke , Wako Kazuhiro , Ishitaka Yumiko , Kano Mitsuru , Käläntär K. , Uchida Tatsuo
Published: May 2018

We devised and developed a novel directive projection screen for applications such as personal use, small group meeting, automotive pillar, and near‐eye. This screen reflects diffused light at an angle Δθview around a direction deviated by θview from the direction of the projector. By applying this screen to automobiles, for example, by installing a projector at a position slightly shifted from the driver, it is possible to reflect the projected light with high efficiency to a certain range around the face of driver. To realize such a characteristic, a hollow corner cube retroreflector (CCR) was modified as follows. The bottom surface of the CCR was tilted by θview/2 to change the direction of the reflected light by θview from the retroreflection direction. In addition, three sides' surfaces of the CCR were curved, so that the light to be diffused within a designed angle (θview ± Δθview/2). The novel retroreflector CCR (D‐CCR) has a single divergent surface with a three‐sided curved surface. We fabricated a prototype with θview = 10° and Δθview = 16° (i.e., the viewing angle for a single D‐CCR, 10° ± 8°), simulated, and measured its optical properties. We closely confirmed the desired characteristics in which an optical gain of 16 was obtained.
A novel low‐power gate driver architecture for large 8 K 120 Hz liquid crystal display employing IGZO technology
Authors: Iwase Yasuaki , Tagawa Akira , Takeuchi Yohei , Watanabe Takuya , Horiuchi Satoshi , Asai Yoshihiro , Yamamoto Kaoru , Daitoh Tohru , Matsuo Takuya
Published: May 2018

A novel low‐power gate driver architecture was developed for large 8 K 120 Hz liquid crystal display panel. For this application, not only high‐speed driving but also low power consumption is required. We employed a high mobility In‐Ga‐Zn‐O, dual VGL level driving method, and gate driver circuit driven by DC supply. The simulation results show that our proposals meet 8 K 120 Hz driving requirements. Also, we have fabricated a prototype panel and confirmed both high‐speed driving and low power consumption.
A novel approach to columellar reconstruction in a child
Authors: Scott Andrew R. , Boahene Kofi D.
Published: May 2018

We present a novel method for columellar reconstruction using a hidden donor site and review the challenges and limitations of columellar reconstruction in children with Fitzpatrick VI skin type. A staged reconstruction was conceived in which a full‐thickness skin graft was transferred to the superior gingivolabial sulcus in the area of the maxillary frenulum. Six months later, the prelaminated soft tissue flap was delivered through a horizontal incision at the subnasale, and the donor site closed primarily. We report satisfactory results following a novel approach to composite soft tissue reconstruction of the columellar subunit in a 9‐year‐old child.

Level of Evidence

4Laryngoscope, 128:2718–2720, 2018
One‐Step Fabrication of Uniform Biodegradable Microbeads with Unimodal and Bimodal Porous Structures Using Spontaneous Microphase Separation
Authors: Baek Seung Woon , Moon Seung‐Kwan , Kang Rae Hyung , Ah Youngchang , Kim Hyuk , Choi Sung‐Wook
Published: May 2018

Uniform poly(l‐lactic acid) (PLLA) microbeads with unimodal or bimodal porous structures are fabricated using a simple fluidic device based on a single oil‐in‐water emulsion method, where an alkane (octane, undecane, tridecane, and pentadecane) serves as the porogen. During the solvent evaporation, the alkanes spontaneously undergo a microphase separation, resulting in a highly porous structure. The size and size distribution of the pores in the PLLA microbeads can be easily controlled by changing the alkane type and concentration. When the undecane, tridecane, and pentadecane are used as the porogen at 6 wt%, the PLLA microbeads have the bimodal porous structure with a large hollow pore in the center and many small pores. In vitro and in vivo studies reveal that those PLLA microbeads with the bimodal porous structure readily facilitate the penetration and proliferation of cells and host tissues compared with the other PLLA microbeads. These results indicate that the superior properties of PLLA porous microbeads with a bimodal porous structure are suitable for diverse biomedical applications such as tissue engineering, cell delivery, and plastic surgery.
Understanding purchase determinants of luxury vintage products
Authors: Amatulli Cesare , Pino Giovanni , De Angelis Matteo , Cascio Robert
Published: May 2018

Despite increasing interest toward luxury vintage products, companies often struggle to understand why consumers buy those products. This article is aimed to advance knowledge about luxury vintage product consumption by identifying the latent determinants of Italian consumersʼ purchasing of these products. The article utilizes the means‐end chain (MEC) approach and the laddering interview technique to achieve this goal. Results show that consumers buy luxury vintage products mainly to satisfy their individual identity, improve their self‐confidence, and achieve a sense of fulfillment. The hierarchical value mapping resulting from the MEC analysis demonstrates that luxury vintage product consumption is undeniably aimed to improve consumersʼ perception of their desired and ideal individual self‐image. The article discusses the managerial implications of the study, along with its limitations and directions for future research.
Lower‐limb reconstruction with chimeric flaps: The quad flap*
Authors: Azouz Solomon M. , Castel Nikki A. , Vijayasekaran Aparna , Rebecca Alanna M. , Lettieri Salvatore C.
Published: May 2018

Early soft‐tissue coverage is critical for treating traumatic open lower‐extremity wounds. As free‐flap reconstruction evolves, injuries once thought to be nonreconstructable are being salvaged. Free‐tissue transfer is imperative when there is extensive dead space or exposure of vital structures such as bone, tendon, nerves, or blood vessels. We describe 2 cases of lower‐extremity crush injuries salvaged with the quad flap. This novel flap consists of parascapular, scapular, serratus, and latissimus dorsi free flaps in combination on one pedicle. This flap provides the large amount of soft‐tissue coverage necessary to cover substantial defects from skin degloving, tibia and fibula fractures, and soft‐tissue loss. In case 1, a 51‐year‐old woman was struck by an automobile and sustained bilateral tibia and fibula fractures, a crush degloving injury of the left leg, and a right forefoot traumatic amputation. She underwent reconstruction with a contralateral quad free flap. In case 2, a 53‐year‐old man sustained a right tibia plateau fracture with large soft‐tissue defects from a motorcycle accident. He had a crush degloving injury of the entire anterolateral compartment over the distal and lower third of the right leg. The large soft‐tissue defect was reconstructed with a contralateral quad flap. In both cases, the donor site was closed primarily and without early flap failures. There was one surgical complication, an abscess in case 2; the patient was taken back to the operating room for débridement of necrotic tissue. There have been no long‐term complications in either case. Both patients achieved adequate soft‐tissue coverage, avoided amputation, and had satisfactory aesthetic and functional outcomes. With appropriate surgical technique and patient selection, the quad‐flap technique is promising for reconstructing the lower extremity.
Reassessment of stopping power ratio uncertainties caused by mean excitation energies using a water‐based formalism
Authors: De Smet Valérie , Labarbe Rudi , Vander Stappen François , Macq Benoît , Sterpin Edmond
Published: May 2018

Purpose

In proton therapy planning, the accuracy of the Stopping Power Ratios (SPR) calculated in the stoichiometric CT calibration is affected by, among others, uncertainties on the mean excitation energies (I‐values) of human tissues and water. Traditionally, the contribution of these uncertainties on the SPR has been conservatively estimated of the order of 1% or more for a reference tissue of known composition. This study provides a methodology that enables a finer estimation of this uncertainty, eventually showing that the traditional estimates of the uncertainty are too conservative.

Methods

Since human tissues contain water, a correlation exists between the I‐values of tissues and water. As the SPR is the ratio of the tissue stopping power to that of water, this correlation decreases the uncertainty of the SPR. Our formalism considers this by expressing the I‐value of the tissue as a function of the water weight fraction and the I‐value of water, while applying Bragg's additivity rule only to the nonaqueous mixture of the tissue. For 22 reference tissue compositions, the SPR uncertainty was estimated by randomly sampling Gaussian distributions, based on ICRU data, for the I‐values of water and the nonaqueous mixture, as well as for the water weight fraction.

Results

The relative standard deviation of the SPR, estimated at 150 MeV, is in the range of 0.1%–0.3% for soft tissues with an average water weight percentage of at least 60%. For tissues with a low water content (e.g., adipose and bones), this uncertainty is in the range of 0.5%–0.7%.

Conclusion

Uncertainties on the I‐values of human tissues and water appear to have a significantly lower impact on the SPR uncertainty than traditionally expected. In the future, this may provide a rationale for using smaller distal and proximal margins on the target volume, provided that all other range uncertainty components are correctly estimated too.
Noncanonical interactions between serpin and β‐amylase in barley grain improve β‐amylase activity in vitro
Authors: Cohen Maja , Fluhr Robert
Published: May 2018

Serpin protease inhibitors and β‐amylase starch hydrolases are very abundant seed proteins in the endosperm of grasses. β‐amylase is a crucial enzyme in the beer industry providing maltose for fermenting yeast. In animals and plants, inhibitory serpins form covalent linkages that inactivate their cognate proteases. Additionally, in animals, noninhibitory functions for serpins are observed such as metabolite carriers and chaperones. The function of serpins in seeds has yet to be unveiled. In developing endosperm, serpin Z4 and β‐amylase showed similar in vivo spatio‐temporal accumulation properties and colocalize in the cytosol of transformed tobacco leaves. A molecular interaction between recombinant proteins of serpin Z4 and β‐amylase was revealed by surface plasmon resonance and microscale thermophoresis yielding a dissociation constant of 10−7 M. Importantly, the addition of serpin Z4 significantly changes β‐amylase enzymatic properties by increasing its maximal catalytic velocity. The presence of serpin Z4 stabilizes β‐amylase activity during heat treatment without affecting its critical denaturing temperature. Oxidative stress, simulated by the addition of CuCl2, leads to the formation of high molecular weight polymers of β‐amylase similar to those detected in vivo. The polymers were cross‐linked through disulfide bonds, the formation of which was repressed when serpin Z4 was present. The results suggest an unprecedented function for a plant seed serpin as a β‐amylase‐specific chaperone‐like partner that could optimize β‐amylase activity upon germination. This report is the first to describe a noninhibitory function for a serpin in plants.