bluuebunny/crossref_metadata_2025 huggingface dataset:
Straightforward Synthesis of 2‐ and 2,8‐Substituted Tetracenes
Authors: Woodward Simon , Ackermann Miriam , Ahirwar Saurabh K. , Burroughs Laurence , Garrett Mary Robert , Ritchie John , Shine Jonathan , Tyril Björk , Simpson Kevin , Woodward Peter
Published: April 2017

A simple regiospecific route to otherwise problematic substituted tetracenes is described. The diverse cores (E)‐1,2‐Ar1CH2(HOCH2)C=C(CH2OH)I (Ar1=Ph, 4‐MePh, 4‐MeOPh, 4‐FPh) and (E)‐1,2‐I(HOCH2)C=C(CH2OH)I, accessed from ultra‐low cost HOCH2C≡CCH2OH at multi‐gram scales, allow the synthesis of diol libraries (E)‐1,2‐Ar1CH2(HOCH2)C=C(CH2OH)CH2Ar2 (Ar2=Ph, 4‐MePh, 4‐iPrPh, 4‐MeOPh, 4‐FPh, 4‐BrPh, 4‐biphenyl, 4‐styryl; 14 examples) by efficient Negishi coupling. Copper‐catalysed aerobic oxidation cleanly provides dialdehydes (E)‐1,2‐Ar1CH2(CHO)C=C(CHO)CH2Ar2, which in many cases undergo titanium(IV) chloride‐induced double Bradsher closure, providing a convenient method for the synthesis of regiochemically and analytically pure tetracenes (12 examples). The sequence is typically chromatography‐free, scalable, efficient and technically simple to carry out.
LOCATING OF CONCEALED SKARN IRON ORE DEPOSIT BASED ON MULTIVARIATE INFORMATION CONSTRAINTS: A CASE STUDY OF BEIYA GOLD MINE IN YUNNAN PROVINCE
Authors: Qiao WANG , Xu‐Ben WANG , Jian YANG , Gang MIN , Jing GUO
Published: April 2017

Skarn deposit is one of the main gold‐polymetallic deposits in Beiya, Yunnan, and constrained by its porphyries, structures and stratums, the favorable ore‐prospecting spaces are contact zones between intermediate‐acid rocks and carbonatite. Based on the physical characteristics of rocks, we realized the transition between target geological body and the geophysical field and extracted the useful information. Skarn iron deposits are characterized by low‐medium resistivity in contact zone, low density of porphyries, high susceptibility and high polarizability of the iron ore. Utilizing the geological and geophysical information, we analyzed ore‐controlling factors in different stages, implemented the locating of concealed skarn iron deposits, established a geophysical exploration mode, verified the validity of the study method on the periphery of the ore district and obtained favorable exploration results. We also proposed a locating and predicting method for the concealed skarn iron deposits, which is applicable to Beiya and other similar ore‐forming geological conditions.
A PRELIMINARY STUDY OF SUBMARINE COLD SEEPS BY SEISMIC OCEANOGRAPHY TECHNIQUES
Authors: Jiang‐Xin CHEN , Hai‐Bin SONG , Yong‐Xian GUAN , Sheng‐Xiong YANG , Yang BAI , Ming‐Hui GENG
Published: April 2017

Submarine cold seeps are widely distributed in the continental margin seas around the world. In this study, we apply a conventional multichannel seismic reflection (seismic oceanography) method to image the water column near the seafloor in order to detect cold seeps. In addition to analyzing the fluid escape structures, we also describe and discuss the development positions, seismic reflection characteristics as well as features of the cold seeps. The seismic reflection from the water column is very weak; therefore, the seismic sections above and below the seafloor are processed in two different sequences as follows: (1) geometry definition, direct wave attenuation and amplitude recovery, high‐pass filter, common midpoint sorting, constant velocity (seawater sound velocity) stack, and post‐stack FK filter in some sections; and (2) data quality control, amplitude recovery, 6∼100 Hz bandpass filter, multiple attenuation, deconvolution, velocity analysis, normal move‐out correction, common midpoint stack, post‐stack noise attenuation, 4∼70 Hz bandpass filter, and FX migration. The processed sections are then assembled together along the seafloor after carefully adjusting the color scale. The analysis shows that active cold seeps primarily present plume, broom, and/or irregular shapes that have weak and chaotic seismic reflections in the water column. The seismic reflection amplitude is enhanced at times; this could be attributed to the suspension of mud or particles in the water column. Cold seepage activities are typically associated with fluid escape structures, including mud diapirs, pipes, faults, fractures, gas chimneys, seabed pockmarks, and mud volcanoes. This indicates fluid migration from deep to shallow strata, fluid seepage or escape at the seafloor, as well as the formation of widespread cold seep activities. All the results herein are derived from a comprehensive interpretation of the seismic sections of the water columns and strata; however, further field studies, theoretical simulations, and experiments are required to confirm these conclusions.
The ventromedial hypothalamic nucleus in the zebra finch (Taeniopygia guttata): Afferent and efferent projections in relation to the control of reproductive behavior
Authors: Wild J. Martin
Published: April 2017

Sex‐specific mating behaviors occur in a variety of mammals, with the medial preoptic nucleus (POM) and the ventromedial hypothalamic nucleus (VMH) mediating control of male and female sexual behavior, respectively. In birds, likewise, POM is predominantly involved in the control of male reproductive behavior, but the degree to which VMH is involved in female reproductive behavior is unclear. Here, in male and female zebra finches, a combination of aromatase immunohistochemistry and conventional tract tracing facilitated the definition of two separate but adjacent nuclei in the basal hypothalamus: an oblique band of aromatase‐positive (AR+) neurons, and ventromedial to this, an ovoid, aromatase‐negative (AR–) nucleus. The AR– nucleus, but not the AR+ nucleus, was here shown to receive a projection from rostral parts of the thalamic auditory nucleus ovoidalis and from the nucleus of the tractus ovoidalis. The AR– nucleus also receives an overlapping, major projection from previously uncharted regions of the medial arcopallium and a minor projection from the caudomedial nidopallium. Both the AR– and the AR+ nuclei project to the intercollicular nucleus of the midbrain. No obvious sex differences in either the pattern of AR immunoreactivity or of the afferent projections to the AR– nucleus were observed. The significance of these results in terms of the acoustic control of avian reproductive behavior is discussed, and a comparison with the organization of VMH afferents in lizards suggests a homologous similarity of the caudal telencephalon in sauropsids.
Variation in species‐level plant functional traits over wetland indicator status categories
Authors: McCoy‐Sulentic Miles E. , Kolb Thomas E. , Merritt David M. , Palmquist Emily C. , Ralston Barbara E. , Sarr Daniel A.
Published: April 2017

Wetland indicator status (WIS) describes the habitat affinity of plant species and is used in wetland delineations and resource inventories. Understanding how species‐level functional traits vary across WIS categories may improve designations, elucidate mechanisms of adaptation, and explain habitat optima and niche. We investigated differences in species‐level traits of riparian flora across WIS categories, extending their application to indicate hydrologic habitat. We measured or compiled data on specific leaf area (SLA), stem specific gravity (SSG), seed mass, and mature height of 110 plant species that occur along the Colorado River in Grand Canyon, Arizona. Additionally, we measured leaf δ13C, δ15N, % carbon, % nitrogen, and C/N ratio of 56 species with C3 photosynthesis. We asked the following: (i) How do species‐level traits vary over WIS categories? (ii) Does the pattern differ between herbaceous and woody species? (iii) How well do multivariate traits define WIS categories? (iv) Which traits are correlated? The largest trait differences among WIS categories for herbaceous species occurred for SSG, seed mass, % leaf carbon and height, and for woody species occurred for height, SSG, and δ13C. SSG increased and height decreased with habitat aridity for both woody and herbaceous species. The δ13C and hence water use efficiency of woody species increased with habitat aridity. Water use efficiency of herbaceous species increased with habitat aridity via greater occurrence of C4 grasses. Multivariate trait assemblages differed among WIS categories. Over all species, SLA was correlated with height, δ13C, % leaf N, and C/N; height was correlated with SSG and % leaf C; SSG was correlated with % leaf C. Adaptations of both herbaceous and woody riparian species to wet, frequently inundated habitats include low‐density stem tissue. Adaptations to drier habitats in the riparian zone include short, high‐density cavitation‐resistant stem tissue, and high water use efficiency. The results enhance understanding about using traits to describe plant habitat in riparian systems.
Is bigger really better? Relative and absolute body size influence individual growth rate under competition
Authors: Van Buskirk Josh , Cereghetti Eva , Hess Julia S.
Published: April 2017

Models suggest that the mechanism of competition can influence the growth advantage associated with being large (in absolute body size or relative to other individuals in the population). Large size is advantageous under interference, but disadvantageous under exploitative competition. We addressed this prediction in a laboratory experiment on Rana temporaria tadpoles competing for limited food. There were 166 target individuals spanning a 10‐fold range in body mass reared for 3 days with three other individuals that were either the same size, half as large, or twice as large as the target. Relative growth rate (proportion per day) declined with size, and absolute growth rate (mass per day) reached a peak at intermediate size and declined thereafter. Tadpoles grew slowly if they were large relative to their competitors, although relative body size was less important than absolute size. As a result, size variation declined in groups that were initially composed of individuals of variable size. Thus, bigger was not better under exploitative competition. Our results help connect individual‐level behavior with individual growth and the size distribution of the population.
Arousal Retention Effect of Magnetic Stimulation to Car Drivers Preventing Drowsy Driving without Sleep Rebound
Authors: MOHRI YOSHIYUKI , KAWAGUCHI MASATO , KOJIMA SHIGEYA , YAMADA MUNEO , NAKANO TOMOAKI , MOHRI KANEO
Published: April 2017

We report experimental validation of the existence of so‐called the sleeping rebound phenomenon against each sensory stimulus using a driving simulator and the electroencephalograph for about 105 subjects with evaluation of an arousal index (α + β)/(δ + θ) in the electroencephalogram measurements after each driving operation. We found that methods using the perfume presentation, the alert presentation, the vibration, and chewing gum were resulted in the sleeping rebound phenomenon, while a proposed magnetic stimulation showed an arousal retention effect without the sleeping rebound. Mechanisms of the arousal effect of the magnetic stimulation were discussed with measurements of electric conductivity versus water temperature characteristics of pure water.
Regulation of salt marsh mosquito populations by the 18.6‐yr lunar‐nodal cycle
Authors: Rochlin Ilia , Morris James T.
Published: April 2017

The 18.6‐yr lunar‐nodal cycle drives changes in tidal amplitude globally, affecting coastal habitat formation, species and communities inhabiting rocky shores, and salt marsh vegetation. However, the cycle's influence on salt marsh fauna lacked sufficient long‐term data for testing its effect. We circumvented this problem by using salt marsh mosquito records obtained over a period of over four decades in two estuaries in the northeastern USA. Salt marsh mosquito habitat is near the highest tide level where the impact of the nodal cycle on flood frequency is greatest. Wavelet spectral and cross‐correlation analyses revealed periodicity in salt marsh mosquito abundance that was negatively correlated with tidal amplitude. Tidal amplitude was a significant predictor of salt marsh mosquito abundance with the cycle maxima coinciding with lower mosquito populations, possibly due to access by predatory fish. However, these effects were detected only at the location with extensive salt marsh habitat and astronomical tides and were weakened or lacked significance at the location with small microtidal salt marshes and wind‐driven tides. Mosquitoes can serve as proxy indicators for numerous invertebrate species on the salt marsh. These predictable cycles and their effects need to be taken into consideration when investigating, restoring, or managing intertidal communities that are also facing sea‐level rise.
Ammonia oxidizer populations vary with nitrogen cycling across a tropical montane mean annual temperature gradient
Authors: Pierre S. , Hewson I. , Sparks J. P. , Litton C. M. , Giardina C. , Groffman P. M. , Fahey T. J.
Published: April 2017

Functional gene approaches have been used to better understand the roles of microbes in driving forest soil nitrogen (N) cycling rates and bioavailability. Ammonia oxidation is a rate limiting step in nitrification, and is a key area for understanding environmental constraints on N availability in forests. We studied how increasing temperature affects the role of ammonia oxidizing archaea (AOA) and bacteria (AOB) in soil N cycling and availability by using a highly constrained natural mean annual temperature (MAT) elevation gradient in a tropical montane wet forest. We found that net nitrate (NO3−) bioavailability is positively related to MAT (r2 = 0.79, P = 0.0033), and AOA DNA abundance is positively related to both NO3− availability (r2 = 0.34, P = 0.0071) and MAT (r2 = 0.34, P < 0.001). In contrast, AOB DNA was only detected in some soils across the gradient. We identified three distinct phylotypes within the AOA which differed from one another in abundance and relative gene expression. In addition, one AOA phylotype increased in abundance with MAT, while others did not. We conclude that MAT is the primary driver of ecosystem N availability across this gradient, and AOA population size and structure appear to mediate the relationship between the nitrification and N bioavailability. These findings hold important implications for nutrient limitation in forests and feedbacks to primary production under changing climate.
Catalytic Intramolecular C(sp3)–H Amination of Carbamimidates
Authors: Grelier Gwendal , Rey‐Rodriguez Romain , Darses Benjamin , Retailleau Pascal , Dauban Philippe
Published: April 2017

The RhII‐catalyzed intramolecular C(sp3)–H amination of carbamimidates allowed new nitrogen heterocycles to be isolated in yields up to 99 %. The reaction was best performed in the presence of the Rh2(esp)2 (esp = α,α,α′,α′‐tetramethyl‐1,3‐benzenedipropionic acid) complex by using 2,2,2‐trichloroethoxysulfonyl‐protected compounds. The reaction could be applied to substrates possessing a benzylic, an allylic, a propargylic, or a tertiary C(sp3)–H bond.
Pain thresholds, supra‐threshold pain and lidocaine sensitivity in patients with erythromelalgia, including the I848Tmutation in NaV 1.7
Authors: Helås T. , Sagafos D. , Kleggetveit I.P. , Quiding H. , Jönsson B. , Segerdahl M. , Zhang Z. , Salter H. , Schmelz M. , Jørum E.
Published: April 2017

Objectives

Nociceptive thresholds and supra‐threshold pain ratings as well as their reduction upon local injection with lidocaine were compared between healthy subjects and patients with erythromelalgia (EM).

Methods

Lidocaine (0.25, 0.50, 1.0 or 10 mg/mL) or placebo (saline) was injected intradermally in non‐painful areas of the lower arm, in a randomized, double‐blind manner, to test the effect on dynamic and static mechanical sensitivity, mechanical pain sensitivity, thermal thresholds and supra‐threshold heat pain sensitivity.

Results

Heat pain thresholds and pain ratings to supra‐threshold heat stimulation did not differ between EM‐patients (n = 27) and controls (n = 25), neither did the dose–response curves for lidocaine. Only the subgroup of EM‐patients with mutations in sodium channel subunits NaV1.7, 1.8 or 1.9 (n = 8) had increased lidocaine sensitivity for supra‐threshold heat stimuli, contrasting lower sensitivity to strong mechanical stimuli. This pattern was particularly clear in the two patients carrying the NaV 1.7 I848T mutations in whom lidocaine's hyperalgesic effect on mechanical pain sensitivity contrasted more effective heat analgesia.

Conclusion

Heat pain thresholds are not sensitized in EM patients, even in those with gain‐of‐function mutations in NaV1.7. Differential lidocaine sensitivity was overt only for noxious stimuli in the supra‐threshold range suggesting that sensitized supra‐threshold encoding is important for the clinical pain phenotype in EM in addition to lower activation threshold. Intracutaneous lidocaine dose‐dependently blocked nociceptive sensations, but we did not identify EM patients with particular high lidocaine sensitivity that could have provided valuable therapeutic guidance.

Significance

Acute pain thresholds and supra‐threshold heat pain in controls and patients with erythromelalgia do not differ and have the same lidocaine sensitivity. Acute heat pain thresholds even in EM patients with the NaV 1.7 I848T mutation are normal and only nociceptor sensitivity to intradermal lidocaine is changed. Only in EM patients with mutations in NaV 1.7, 1.8 or 1.9 supra‐threshold heat and mechanical pain shows differential lidocaine sensitivity as compared to controls.
Adult attachment insecurity is positively associated with medically unexplained chronic pain
Authors: McWilliams L.A.
Published: April 2017

Background

Attachment insecurity (i.e. anxiety in relationships and/or discomfort in close relationships) is associated with self‐reports of physical symptoms, medically unexplained symptoms and health conditions involving pain. Medically unexplained chronic pain (MUCP) may represent a particularly severe form of symptom reporting that is also characteristic of individuals with insecure attachment. This study investigated relationships between adult attachment style ratings and past‐year MUCP in a sample of the general U.S. population and the ability of attachment style ratings to account for variance in past‐year MUCP beyond that accounted for by potential confounders.

Method

Data from the National Comorbidity Survey Replication (N = 5645) were used. Attachment was assessed with an interview‐administered version of a commonly used self‐report measure of secure, anxious and avoidant attachment. MUCP was assessed with a brief interview. Depressive and anxiety disorders were included as covariates and were assessed with a fully structured interview based on DSM‐IV criteria.

Results

The past‐year prevalence of MUCP was 2.45% (95% CI = 2.07–2.83). The two insecure attachment styles (i.e. anxious and avoidant) were positively associated with MUCP. These associations remained statistically significant after adjusting for demographic variables and depressive and anxiety disorders. When the two insecure attachment styles were considered together, only avoidant attachment remained significantly associated with MUCP.

Conclusion

Attachment insecurity ratings were positively associated with past‐year MUCP and remained so after statistically adjusting for depressive and anxiety disorders. Further research aimed at understanding the mechanism(s) responsible for the association between attachment insecurity and MUCP is warranted.

Significance

Consistent with earlier research regarding transient physical symptoms, medically unexplained chronic pain was associated with attachment insecurity. Understanding the mechanisms responsible for this association could guide treatment innovations.
Effect of surfactant species and electrophoretic medium composition on the electrophoretic behavior of neutral and water‐insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis
Authors: Fukai Nao , Kitagawa Shinya , Ohtani Hajime
Published: April 2017

We have recently demonstrated the separation of neutral and water‐insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis (NACZE) using a cationic surfactant of cetyltrimethylammonium chloride (CTAC). In this study, eight ionic surfactants were investigated for the separation of four synthetic polymers (polystyrene, polymethylmethacrylates, polybutadiene, and polycarbonate); only three surfactants (CTAC, dimethyldioctadecylammonium bromide, and sodium dodecylsulfate) caused their separation. The order of the interaction between the polymers and the surfactants depended on both the surfactant species and the composition of the electrophoretic medium. Their investigation revealed that the separation is majorly affected by the hydrophobic interactions between the polymers and the ionic surfactants. In addition, the electrophoretic behavior of polycarbonate suggested that electrostatic interaction also affects the selectivity of the polymers.
Add value for graduates with digital credentials
Authors: Hope Joan
Published: April 2017

Proud graduates take photos with their diplomas. Then they sometimes get the credentials framed to hang on the wall, or sometimes they put them in a filing cabinet. But graduates could do more with their diplomas and certificates if they were in digital format.
Variable rate and power M‐QAM for DPS/DPB CoMP with adaptive modulation
Authors: Song Hengguo , Cui Qimei , Zuo Huiling , Zhang Xuefei , Wang Hui
Published: April 2017

Dynamic point selection/dynamic point blanking (DPS/DPB)–based coordinated multipoint (CoMP) has attracted lots of interest because of the significant performance improvement with a particular low complexity. In this paper, we first investigate the average spectral efficiency (ASE) of M‐ary quadrature amplitude modulation (M‐QAM) satisfying instantaneous bit error rate constraint for DPS/DPB CoMP system with 3 different adaptive modulation strategies. Closed‐form expressions of the ASE for continuous‐rate M‐QAM are obtained in which calculus of variations is used to obtain the optimal power allocation policy. We also analyze the ASE for discrete‐rate M‐QAM which is more useful for the practical DPS/DPB CoMP wireless communication systems. Average bit error rate for DPS/DPB CoMP discrete‐rate M‐QAM is also investigated in this paper. Monte Carlo simulations are used to verify the correctness of our analysis. The results reveal that in M‐QAM DPS/DPB CoMP systems, when the channel condition is unfavorable, the transmit power is the crucial parameter to enhance the ASE, otherwise the transmit rate is the key parameter. We can also notice that by using adaptive modulation, DPS/DPB CoMP has an obvious channel capacity improvement compared to the case without coordination among different transmission points.
Clearing the Air on EPA's New Chief
Authors: McGuffey Carroll W. (“Mack”)
Published: April 2017

On November 8, 2016, the citizens of the United States elected not just a new government, but a very different government. With the election of Donald Trump as the 45th president of the United States and the results in the many contested congressional races, the pendulum of politics swung, perhaps harder than it has swung in at least several decades.
Modeling aesthetics to support an ecosystem services approach for natural resource management decision making
Authors: Booth Pieter N , Law Sheryl A , Ma Jane , Buonagurio John , Boyd James , Turnley Jessica
Published: April 2017

This paper reviews literature on aesthetics and describes the development of vista and landscape aesthetics models. Spatially explicit variables were chosen to represent physical characteristics of natural landscapes that are important to aesthetic preferences. A vista aesthetics model evaluates the aesthetics of natural landscapes viewed from distances of more than 1000 m, and a landscape aesthetics model evaluates the aesthetic value of wetlands and forests within 1000 m from the viewer. Each of the model variables is quantified using spatially explicit metrics on a pixel-specific basis within EcoAIM™, a geographic information system (GIS)–based ecosystem services (ES) decision analysis support tool. Pixel values are “binned” into ranked categories, and weights are assigned to select variables to represent stakeholder preferences. The final aesthetic score is the weighted sum of all variables and is assigned ranked values from 1 to 10. Ranked aesthetic values are displayed on maps by patch type and integrated within EcoAIM. The response of the aesthetic scoring in the models was tested by comparing current conditions in a discrete area of the facility with a Development scenario in the same area. The Development scenario consisted of two 6-story buildings and a trail replacing natural areas. The results of the vista aesthetic model indicate that the viewshed area variable had the greatest effect on the aesthetics overall score. Results from the landscape aesthetics model indicate a 10% increase in overall aesthetics value, attributed to the increase in landscape diversity. The models are sensitive to the weights assigned to certain variables by the user, and these weights should be set to reflect regional landscape characteristics as well as stakeholder preferences. This demonstration project shows that natural landscape aesthetics can be evaluated as part of a nonmonetary assessment of ES, and a scenario-building exercise provides end users with a tradeoff analysis in support of natural resource management decisions. Integr Environ Assess Manag 2017;13:926–938. © 2017 SETAC.

Key Points

This paper presents a novel approach to assessing tradeoffs in aesthetic landscape services. The flexibility of the models, such as preference weightings and the ability to create various scenarios, is especially important for settings in which there are numerous ecosystem service beneficiaries, various end users of the tool, and multiple natural resource management objectives.
Density functional theory study of mechanism of epoxy‐carboxylic acid curing reaction
Authors: Ly Uyen Q. , Pham My‐Phuong , Marks Maurice J. , Truong Thanh N.
Published: April 2017

A comprehensive picture on the mechanism of the epoxy‐carboxylic acid curing reactions is presented using the density functional theory B3LYP/6‐31G(d,p) and simplified physical molecular models to examine all possible reaction pathways. Carboxylic acid can act as its own promoter by using the OH group of an additional acid molecule to stabilize the transition states, and thus lower the rate‐limiting barriers by 45 kJ/mol. For comparison, in the uncatalyzed reaction, an epoxy ring is opened by a phenol with an apparent barrier of about 107 kJ/mol. In catalyzed reaction, catalysts facilitate the epoxy ring opening prior to curing that lowers the apparent barriers by 35 kJ/mol. However, this can be competed in highly basic catalysts such as amine‐based catalysts, where catalysts can enhance the nucleophilicity of the acid by forming hydrogen‐bonded complex with it. Our theoretical results predict the activation energy in the range of 71 to 94 kJ/mol, which agrees well with the reported experimental range for catalyzed reactions. © 2017 Wiley Periodicals, Inc.
Comparing the performance of TD‐DFT and SAC‐CI methods in the description of excited states potential energy surfaces: An excited state proton transfer reaction as case study
Authors: Savarese Marika , Raucci Umberto , Fukuda Ryoichi , Adamo Carlo , Ehara Masahiro , Rega Nadia , Ciofini Ilaria
Published: April 2017

The performances, in the description of excited state potential energy surfaces, of several density functional approximations representative of the currently most applied exchange correlation functionals’ families have been tested with respect to post Hartree‐Fock references (here Symmetry Adapted Cluster‐Configuration Interaction results). An experimentally well‐characterized intermolecular proton transfer reaction has been considered as test case. The computed potential energy profiles were analyzed both in the gas phase and in toluene solution, here represented as a polarizable continuum model. The presence of intermolecular (dark) and intramolecular (bright) charge transfer excited states, whose polarity strongly differs along the reaction pathway, makes clear that only subtle compensation between spurious electronic effects—related to the incorrect asymptotic behavior of the functional—and solvent stabilization of polar states leads to the overall correct description of this excited state reaction when using global hybrids with low percentage of Hartree Fock exchange. © 2017 Wiley Periodicals, Inc.
Synthesis and Antimicrobial Evaluation of Novel Dibenzo‐18‐Crown‐6‐Ether Functionalized Pyrimidines
Authors: Jagadale S.D. , Sawant A.D. , Deshmukh M.B.
Published: April 2017

A practical, two‐step synthesis of crown ether functionalized pyrimidines has been developed. The reaction conditions have been optimized, and the protocol is generalized for series of substrates. These newly synthesized compounds exhibited antimicrobial activity against bacterial strains Staphylcoccus aureus (Gram‐positive) and Escherichia coli (Gram‐negative). These compounds were also found to be potent antifungal agents Aspergillus niger and Candida albicans strains, respectively.
Synthesis and Reactions of Pyrido[2,1‐a]isoquinolin‐4‐yl Formimidate Derivatives and Antimicrobial Activities of Isolated Products
Authors: Hassaneen Hamdi M. , Wardakhan Wagnat W. , Mohammed Yasmin Sh.
Published: April 2017

Treatment of arylidene malononitriles 2A–C with 1‐cyanomethylisoquinoline 1 afforded 4‐amino‐2‐arylpyrido[2,1‐a]isoquinoline‐1,3‐dicarbonitrile derivatives 5A–C, which converted to formimidates 6A–C via reaction with triethylorthoformate. Treatment of the latter compounds with hydrazine hydrate gave the corresponding amino–imino compounds 7A–C, which underwent Dimroth rearrangement to afford 13‐aryl‐1‐hydrazinylpyrimido[5′,4′:5,6]pyrido[2,1‐a]isoquinoline‐12‐carbonitrile 8A–C. The latter reacted with aldehyde to give 9a–i. Oxidative cyclization of the latter compounds 9a–i gave [1,2,4]triazolo[4″,3″:1′,6′]‐pyrimido[5′,4′:5,6]pyrido[2,1‐a]isoquinolines 10a,d,g. Such compounds isomerized to the thermodynamically more stable isomers [1,2,4]triazolo[1″,5″:1′,6′]pyrimido[5′,4′:5,6]‐pyrido[2,1‐a]isoquinolines 11a,d,g. Antimicrobial activities for some compounds were studied.
A biomolecular recognition approach for the functionalization of cellulose with gold nanoparticles
Authors: Almeida A. , Rosa A.M.M. , Azevedo A.M. , Prazeres D.M.F.
Published: April 2017

Materials with new and improved functionalities can be obtained by modifying cellulose with gold nanoparticles (AuNPs) via the in situ reduction of a gold precursor or the deposition or covalent immobilization of pre‐synthesized AuNPs. Here, we present an alternative biomolecular recognition approach to functionalize cellulose with biotin‐AuNPs that relies on a complex of 2 recognition elements: a ZZ‐CBM3 fusion that combines a carbohydrate‐binding module (CBM) with the ZZ fragment of the staphylococcal protein A and an anti‐biotin antibody. Paper and cellulose microparticles with AuNPs immobilized via the ZZ‐CBM3:anti‐biotin IgG supramolecular complex displayed an intense red color, whereas essentially no color was detected when AuNPs were deposited over the unmodified materials. Scanning electron microscopy analysis revealed a homogeneous distribution of AuNPs when immobilized via ZZ‐CBM3:anti‐biotin IgG complexes and aggregation of AuNPs when deposited over paper, suggesting that color differences are due to interparticle plasmon coupling effects. The approach could be used to functionalize paper substrates and cellulose nanocrystals with AuNPs. More important, however, is the fact that the occurrence of a biomolecular recognition event between the CBM‐immobilized antibody and its specific, AuNP‐conjugated antigen is signaled by red color. This opens up the way for the development of simple and straightforward paper/cellulose‐based tests where detection of a target analyte can be made by direct use of color signaling.
Some pictures of the history of automotive instrumentation
Authors: Knoll Peter M.
Published: April 2017

The first in vehicle instrument was the speedometer. It was invented by Otto Schulze in 1902. Until then, drivers had to estimate their speed. The speedometer was followed by an alcohol temperature gauge. A few warning lamps surveyed the most important vehicle functions. Later, single gauges like radiator temperature, fuel gauge, and revolution counter were added to the instrumentation. They were superseded by instrument clusters combining several instruments in one housing. Even though the appearance of the instrument cluster did not change significantly from the early days, there was a steady development of the intelligence behind the panel. This huge amount of information could only be handled by graphic displays. When navigation systems came into our cars, a larger graphic display was needed. It found place in the center console. In parallel, the price decline in the computer market and the availability of high‐performing graphic hardware and software made it possible to enhance the classical functions of the instrument board to an interactive multifunctional information panel, with the dashboard being the main interface between car and driver. The windshield was the third zone where information could be placed in a favorable reading position minimizing eyes off the road time. As a consequent evolution step, augmented reality head‐up displays will soon dominate the information center of premium‐class vehicles.
Prospective series of reconstruction of complex composite mandibulectomy defects with double island free fibula flap
Authors: Chang Edward I. , Yu Peirong
Published: April 2017

Background: A double island free fibula (DIFF) flap can be used for reconstruction of through‐and‐through or complex mandibulectomy defects, but prospective studies are lacking.

Methods: Prospective analysis of all double skin paddle fibula flaps performed from 2010 to 2016.

Results: Overall, 16 patients underwent reconstruction with a DIFF flap (average age: 59.1 years). One patient, who underwent a DIFF flap and developed osteoradionecrosis, requiring a second flap. Thirteen patients were males, and 7 had a history of smoking, 13 had prior radiation, and 14 had prior chemotherapy. The most common primary pathology was squamous cell carcinoma (n = 13). Reconstruction using the DIFF was predominantly for mandible reconstruction with one patient undergoing reconstruction following a orbitomaxillectomy. Complications included infection (n = 2), hematoma (n = 1), and donor site complications were limited. Two patients developed venous congestion requiring re‐exploration, and both flaps were successfully salvaged. One patient lost the external skin paddle requiring a pectoralis muscle flap, and there were no total flap losses.

Conclusions: The DIFF flap is a reliable option that can reconstruct complex composite defects often obviating the need for a second free flap, thereby decreasing operating time, added donor site morbidity, and the need for additional recipient vessels.
Does surgery or radiation provide the best overall survival in Ewing's sarcoma? A review of the National Cancer Data Base
Authors: Miller Benjamin J. , Gao Yubo , Duchman Kyle R.
Published: April 2017

Background and Objectives

There is continuing debate regarding the ideal modality for local control of the primary tumor for patients with Ewing's sarcoma. The primary aim of this study is to investigate the impact of the method of local control on overall survival in patients with Ewing's sarcoma.

Methods

The National Cancer Data Base was used to identify patients <40 years of age with high‐grade Ewing's sarcoma of bone. A Kaplan‐Meier survival analysis was performed at 2, 5, and 10 years. Factors with a level of significance of P < 0.1 at the 5‐year time point were included in a multivariate Cox proportional hazards model.

Results

Diminished 5‐year survival was noted for patients with metastatic disease, local control with radiation alone, age ≥18 years, tumor size >8 cm, and male sex while controlling for tumor site. Surgery alone was consistently the method of local control that resulted in the highest overall survival.

Conclusions

Surgery alone resulted in the best overall survival for patients with Ewing's sarcoma of bone. The results of this investigation provide support to the approach of surgical resection with negative margins when possible.
Contribution of translocated greater sage‐grouse to population vital rates
Authors: Duvuvuei Orrin V. , Gruber‐Hadden Natasha W. , Messmer Terry A. , Guttery Michael R. , Maxfield Brian D.
Published: April 2017

Range‐wide declines of greater sage‐grouse (Centrocercus urophasianus; sage‐grouse) populations have been attributed to long‐term habitat alteration and fragmentation. In areas that still exhibit suitable habitats and where population declines have been attributed to other threats (e.g., invasive predators), managers have successfully used translocations to augment declining wildlife populations. However, translocations to augment sage‐grouse populations have had limited success and the relative contribution of translocated sage‐grouse to declining populations is not well understood. From 2009 to 2012 we studied the vital rates of 34 resident (21 yearlings and 13 adults) and 60 translocated radio‐marked female sage‐grouse (30 yearlings and 30 adults) on Anthro Mountain in northeastern Utah, USA to determine the relative contributions of each group to population productivity. We used the encounter histories of the monitored sage‐grouse to construct nest survival models for program MARK to assess the impacts of age and residency status on annual survival and overall reproductive success in the population. Annual survival was not affected by age or residency status and averaged 0.40 (95% CI = 0.31–0.50). The yearling newly translocated females (translocated females during their first yr in the release area) exhibited the lowest nest initiation rates (0.50, 95% CI = 0.30–0.69), whereas adult resident and previously translocated (translocated females that survived ≥1 yr in the release area) females had the highest nest initiation (0.96, 95% CI = 0.88–0.99). Overall nest success (0.43, 95% CI = 0.30–0.55) and brood success (0.55, 95% CI = 0.41–0.69) were not affected by residency status or age. The adult resident and previously translocated females exhibited the highest overall reproductive success (0.22, 95% CI = 0.14–0.31) followed by resident yearling females (0.20, 95% CI = 0.12–0.29), and newly translocated adult females (0.18, 95% CI = 0.10–0.27). Newly translocated yearling females had the lowest overall reproductive success (0.12, 95% CI = 0.05–0.18). Survival of adult females is a major factor influencing sage‐grouse population stability. Although adult and yearling newly translocated females had similar survival rates, adult translocated females were more likely to raise a brood in their first year in the release area. Thus, managers should consider translocating a higher ratio of adult to yearling females in future translocation efforts to see a more immediate effect on population growth in the release area. However, because of the low vitals rates recorded in our study, managers should identify and mitigate the limiting factors affecting the resident population prior to implementing a translocation to augment declining populations. © 2017 The Wildlife Society.
Highly Water‐Soluble Alpha‐Hydroxyalkylphenone Based Photoinitiator for Low‐Migration Applications
Authors: Roth Meinhart , Hennen Daniel , Oesterreicher Andreas , Mostegel Florian , Samusjew Aleksandra , Edler Matthias , Maier Eugen , Griesser Thomas
Published: April 2017

In this study, the bifunctional hydroxyketone based photoinitiator (PI) 1,1′‐{[(2,3‐dihydroxybutane‐1,4‐diyl)bis(oxy)]bis(4,1‐phenylene)}bis(2‐hydroxy‐2‐methylpropan‐1‐one) (Di‐PI) is synthesized with the aim to facilitate a highly photoactive water‐soluble PI which offers high migration stability. Di‐PI provides a five times higher water‐solubility than the state of the art water soluble PI 2‐hydroxy‐1‐[3‐(hydroxymethyl)phenyl]‐2‐methyl‐1‐propanone (I2959). Photo differential scanning calorimetry (Photo‐DSC) measurements reveal that the curing speed and conversion ofN‐acroylmorpholine (NAM) in aqueous solution containing 0.5 mol% of Di‐PI are only slightly lower than formulations containing the reference PI I2959 in a concentration of 1 mol%. Most importantly, Di‐PI offers almost identical activity in dipropylene glycol diacrylate (DPDA) as I2959, although its migration from cured DPDA is significantly reduced by a factor of 7.6 compared to I2959.

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Branching Analysis of Comb‐Shaped Polystyrene with Long Chain Branches
Authors: Lee Sanghoon , Chang Taihyun
Published: April 2017

Model comb‐shaped polystyrene (PS) samples are synthesized by anionic polymerization and the as‐prepared PS heterogeneous combs are further fractionated by temperature gradient interaction chromatography (TGIC) to obtain well‐defined random combs with 1–4 branches at random positions on a backbone. Size exclusion chromatography‐triple detection and TGIC‐triple detection analyses are carried out with the fractionated PS random combs in a good and a theta solvent, respectively. The experimentally observed geometric contraction factor (g), the ratio of the mean square radius of gyration and the hydrodynamic contraction factor (g′), and the ratio of the intrinsic viscosity are compared. It is observed that the two contraction factors follow the relationship of g′ = gε reasonably well and the exponent ε of the PS combs is found as ∼1 in a good solvent and ∼0.66 in a theta solvent. Furthermore, it is found that the theoretical grw is not in good agreement with the experimental results.

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Static and Dynamic Scaling Close to Gelation in Chain‐Polymerization: Effect of Reactor Type
Authors: Das Chinmay , Read Daniel J. , Soulages Johannes M. , Shirodkar Pradeep P.
Published: April 2017

Because of the familiarity of gelation theories in polycondensation reaction of multifunctional groups, often the gel‐point is defined as the point of diverging weight averaged molar mass. The authors present an industrially relevant counter‐example to this common perception. Chain‐growth polymerization in realistic reactors introduces history dependent crosslinking probability. For copolymerization of a two functional monomer (ethylene) with a four functional comonomer (nonconjugated diene), the authors show from a Monte Carlo scheme that standard gelation scaling exponents remain valid for a semibatch reactor. However, for syntheses in a continuous stirred tank reactor (CSTR), all commonly measured molar mass moments (number, weight and “z”‐averaged moment) remain finite at the gel‐point; the first moment to diverge is the fourth moment. Hence, identification of the gel point from experimental observations is difficult, and cannot be achieved through monitoring of the weight averaged molar mass. The authors use a numerical scheme based on the tube model of polymer melts to predict the rheology of the generated molecules. Stress relaxation follows a power‐law decay, but due to dynamic dilution effects the CSTR resins exhibit much slower increase in the zero shear viscosity as the gel point is approached as compared to the semibatch reactor resins.

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Induction of mitochondrial apoptotic pathway in triple negative breast carcinoma cells by methylglyoxal via generation of reactive oxygen species
Authors: Roy Anirban , Ahir Manisha , Bhattacharya Saurav , Parida Pravat Kumar , Adhikary Arghya , Jana Kuladip , Ray Manju
Published: April 2017

Triple negative breast cancer (TNBC) tends to form aggressive tumors associated with high mortality and morbidity which urge the need for development of new therapeutic strategies. Recently, the normal metabolite Methylglyoxal (MG) has been documented for its anti‐proliferative activity against human breast cancer. However, the mode of action of MG against TNBC remains open to question. In our study, we investigated the anticancer activity of MG in MDA MB 231 and 4T1 TNBC cell lines and elucidated the underlying mechanisms. MG dose‐dependently caused cell death, induced apoptosis, and generated ROS in both the TNBC cell lines. Furthermore, such effects were attenuated in presence of ROS scavenger N‐Acetyl cysteine. MG triggered mitochondrial cytochrome c release in the cytosol and up‐regulated Bax while down‐regulated anti‐apoptotic protein Bcl‐2. Additionally, MG treatment down‐regulated phospho‐akt and inhibited the nuclear translocation of the p65 subunit of NF‐κB. MG exhibited a tumor suppressive effect in BALB/c mouse 4T1 breast tumor model as well. The cytotoxic effect was studied using MTT assay. Apoptosis, ROS generation, and mitochondrial dysfunction was evaluated by flow cytometry as well as fluorescence microscopy. Western blot assay was performed to analyze proteins responsible for apoptosis. This study demonstrated MG as a potent anticancer agent against TNBC both in vitro and in vivo. The findings will furnish fresh insights into the treatment of this subgroup of breast cancer.
Non‐digestible carbohydrates supplementation increases miR‐32 expression in the healthy human colorectal epithelium: A randomized controlled trial
Authors: Malcomson Fiona C , Willis Naomi D , McCallum Iain , Xie Long , Lagerwaard Bart , Kelly Seamus , Bradburn D. Michael , Belshaw Nigel J , Johnson Ian T , Mathers John C
Published: April 2017

Colorectal cancer (CRC) risk is modulated by diet and there is convincing evidence of reduced risk with higher non‐digestible carbohydrates (NDCs) consumption. Resistant starch (RS), a NDC, positively modulates the expression of oncogenic microRNAs, suggesting that this could be a mechanism through which NDCs protect against CRC. The present study aimed to investigate the effects of supplementation with two NDCs, RS, and polydextrose (PD), on microRNA expression in the macroscopically‐normal human rectal epithelium using samples from the DISC Study, a randomized, double‐blind, placebo‐controlled dietary intervention. We screened 1008 miRNAs in pooled post‐intervention rectal mucosal samples from participants allocated to the double placebo group and those supplemented with both RS and PD. A total of 111 miRNAs were up‐ or down‐regulated by at least twofold in the RS + PD group compared with the control group. From these, eight were selected for quantification in individual participant samples by qPCR, and fold‐change direction was consistent with the array for seven miRNAs. The inconsistency for miR‐133b and the lower fold‐change values observed for the seven miRNAs is probably because qPCR of individual participant samples is a more robust and sensitive method of quantification than the array. miR‐32 expression was increased by approximately threefold (P = 0.033) in the rectal mucosa of participants supplemented with RS + PD compared with placebo. miR‐32 is involved in the regulation of processes such as cell proliferation that are dysregulated in CRC. Furthermore, miR‐32 may affect non‐canonical NF‐κB signaling via regulation of TRAF3 expression and consequently NIK stabilization.