bluuebunny/crossref_metadata_2025 huggingface dataset:
Condensation nuclei measurements in the midlatitude (1982–2012) and Antarctic (1986–2010) stratosphere between 20 and 35 km
Authors: Campbell Patrick , Deshler Terry
Published: December 2013

Balloon‐borne stratospheric condensation nuclei (CN) measurements have been made from McMurdo Station, Antarctica (78°S), 1986–2010, and from Laramie, Wyoming (41°N), 1982 to the present. In the Antarctic region, the measurements show the formation of a layer of enhanced concentrations of stratospheric CN, between 21 and 27 km, around mid August, reaching its maximum extent between September and early October. CN concentrations increase from backgrounds of 10–20 cm−3 to over 100 cm−3 in the layer. In the northern midlatitudes, the measurements show a quasi‐annual and smaller layer of enhanced CN concentrations between 25 and 31 km in late winter and early spring. In the quasi‐annual layers, CN concentrations increase from backgrounds of 1–10 cm−3 to over 20 cm−3. Volcanic eruptions appear to enhance the CN layers observed over Laramie and McMurdo. The Arctic Oscillation generally correlates with the magnitude of the Laramie CN layer, suggesting the importance of meridional transport. Volatility measurements and nucleation modeling support a sulfuric acid and water composition and binary homogeneous nucleation as the likely CN formation mechanism in both locations. Bimonthly measurements above Laramie support coagulation as the main reason for the dissipation of the CN layer. Air parcel trajectory modeling confirms that the CN layer forms locally to McMurdo and that it is related to solar exposure, while above Laramie trajectory analysis indicates that Arctic conditions and ambient temperature changes during northerly transport impact the magnitude of the CN layer above Laramie.
Hygroscopic properties of particles nebulized from water extracts of aerosols collected at Chichijima Island in the western North Pacific: An outflow region of Asian dust
Authors: Boreddy S. K. R. , Kawamura Kimitaka , Jung Jinsang
Published: December 2013

We present 2 year measurements of hygroscopic properties of water‐soluble matter (WSM) extracted from marine aerosols from remote Chichijima Island in the western North Pacific during 2001–2002. Hygroscopic growth factors (g) of WSM were measured by a hygroscopicity tandem differential mobility analyzer with initial dry particle diameter of 100 nm. The observed g at 90% relative humidity (RH), g(90%), ranged from 1.42 to 1.89 with an average of 1.79 ± 0.11. The g values are significantly lower than that of seawater (2.1) and slightly lower than those previously reported for marine aerosols (>1.8), probably due to the atmospheric processing associated with chlorine depletion; mean Cl−/Na+ molar ratio (1.10 ± 0.23) was smaller than seawater (1.18), and organometal interaction (e.g., formation of water‐insoluble calcium oxalate, g(90%) < 1). Inorganic salts accounted for 87–98% of WSM. Na+ and Cl− are two major species, contributing 63% of total inorganic ion mass. The calculated aerosol water content (Vw/Vdry) at 85% RH during hydration experiment ranged from 1 to 3.66 (mean of 2.75 ± 0.81). Vw/Vdry is negatively correlated with organic mass fraction, indicating that organics may suppress the hygroscopicity of the marine aerosol particles. The declined g(90%) and Cl−/Na+ molar ratio and increased abundance of water‐soluble organics in spring demonstrated that the atmospheric mixing of anthropogenic pollutants (e.g., NO3, SOx) and water‐soluble organics can decrease the growth factor of marine aerosols. The two case studies of spring aerosols demonstrated that Asian dusts were internally mixed with hygroscopic species in different ways, depending on their transport pathway.
Dynamic variability of the Asian monsoon anticyclone observed in potential vorticity and correlations with tracer distributions
Authors: Garny H. , Randel W. J.
Published: December 2013

The Asian summer monsoon is associated with strong upward transport of tropospheric source gases and isolation of air within the upper tropospheric anticyclone, with a high degree of dynamical variability. Here we study the anticyclone in terms of potential vorticity (PV) as derived from reanalysis data. The strength of the anticyclone, as measured by low PV area, varies on subseasonal time scales (periods of  30–40 days), driven by variability in convection. The convective forcing of low PV areas is associated with heating in the middle troposphere and divergent motion in the upper troposphere, and we find that upper level divergence is a good predictor of the anticyclone strength. Low PV air is often observed to propagate from the forcing region to the west, and occasionally to the east. Carbon monoxide (CO) measured by the Aura Microwave Limb Sounder is used to study the covariability of chemical tracers with the anticyclone strength and location. Concentrations of CO maximize within the upper tropospheric anticyclone, and enhanced CO is well correlated with the spatial distribution of low PV. Time variations of CO concentrations in the upper troposphere (around 360 K) are not strongly correlated with anticyclone strength, probably because CO transport also involves coupling with surface CO sources (unlike PV). Temporal correlations with PV are stronger for CO at higher levels (380–400 K), suggesting that advective upward transport is important for tracer evolution at these levels.
Hybrid Material for Protein Sensing Based on Electrosynthesized MIP on a Mannose Terminated Self‐Assembled Monolayer
Authors: Dechtrirat Decha , Gajovic‐Eichelmann Nenad , Bier Frank F. , Scheller Frieder W.
Published: December 2013

A novel strategy to prepare a surface confined molecularly imprinted polymer (MIP) film directly on a transducer surface for protein sensing is achieved by combining interaction with a natural binding receptor and binding to a fully synthetic MIP. A thiolated oligoethyleneglycol (OEG)/mannose conjugate is first self‐assembled on the transducer surface. Then the carbohydrate binding protein, concanavalin A (ConA), is “vectorially” immobilized as a submonolayer on the underlying mannose modified surface. Afterwards, an ultrathin polyscopoletin film with the thickness comparable to that of the protein is electrodeposited on the top. This architecture ensures that the target is confined to the film surface. The resulting functional material shows an approximately 20‐fold higher affinity than that obtained from the mannose self‐assembled monolayer. This result shows a synergism between multivalent binding of the natural sugar ligand and the non‐covalent interactions of the target within the MIP cavities. Recognition capability of the film is characterized by a real‐time measurement using quartz crystal microbalance. In comparison to the non‐imprinted film, the imprinted film reveals 8.6 times higher binding capacity towards ConA. High discrimination towards the target protein's homologues shows size and shape specificity of the imprint.
A d10 Ni–(H2) Adduct as an Intermediate in HH Oxidative Addition across a NiB Bond
Authors: Harman W. Hill , Lin Tzu‐Pin , Peters Jonas C.
Published: December 2013

Bifunctional EH activation offers a promising approach for the design of two‐electron‐reduction catalysts with late first‐row metals, such as Ni. To this end, we have been pursuing H2 activation reactions at late‐metal boratranes and herein describe a diphosphine–borane‐supported Ni—(H2) complex, [(PhDPBiPr)Ni(H2)], which has been characterized in solution. 1H NMR spectroscopy confirms the presence of an intact H2 ligand. A range of data, including electronic‐structure calculations, suggests a d10 configuration for [(PhDPBiPr)Ni(H2)] as most appropriate. Such a configuration is highly unusual among transition‐metal H2 adducts. The nonclassical H2 adduct is an intermediate in the complete activation of H2 across the NiB interaction. Reaction‐coordinate analysis suggests synergistic activation of the H2 ligand by both the Ni and B centers of the nickel boratrane subunit, thus highlighting an important role of the borane ligand both in stabilizing the d10 Ni—(H2) interaction and in the H—H cleavage step.
Preparation and characterization of epoxy nanocomposites containing surface‐modified graphene oxide
Authors: Liu Tianxi , Zhao Zishuai , Tjiu Weng Weei , Lv Jian , Wei Chun
Published: December 2013

A three‐step grafting procedure has been used to graft the epoxy monomers (DER332) and the curing agents (diamino diphenyl methane (DDM), onto graphene oxide (GO) surface. The surface modification of GO has been performed by grafting of Jeffamine D‐2000, followed with subsequent grafting of DER332 and DDM, respectively. Fourier transform spectroscopy and thermogravimetric analysis indicate successful surface modification. The resulting modified GO, that is, (DED)‐GO, can be well dispersed in the epoxy monomers. The epoxy nanocomposites containing different GO contents can then be prepared through curing processes. The dispersion of GO in the nanocomposites is characterized by transmission electron microscopy. It is found that the tensile strength and elongation at break of epoxy nanocomposite with only 0.2 wt % DED‐GO are increased by 30 and 16% as compared with the neat epoxy resin, respectively. Dynamic mechanical analysis results show that 62% increase in storage modulus and 26°C enhancement in the glass transition temperature of the nanocomposite have been achieved with the incorporation of only 0.2 wt % of DED‐GO into the epoxy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40236.
Goal achieving probabilities of cone‐constrained mean‐variance portfolios
Authors: Labbé Chantal , Watier François
Published: December 2013

In this paper, we establish closed‐form formulas for key probabilistic properties of the cone‐constrained optimal mean‐variance strategy, in a continuous market model driven by a multidimensional Brownian motion and deterministic coefficients. In particular, we compute the probability to obtain to a point, during the investment horizon, where the accumulated wealth is large enough to be fully reinvested in the money market, and safely grow there to meet the investor's financial goal at terminal time. We conclude that the result of Li and Zhou [Ann. Appl. Prob., v.16, pp.1751–1763, (2006)] in the unconstrained case carries over when conic constraints are present: the former probability is lower bounded by 80% no matter the market coefficients, trading constraints, and investment goal. We also compute the expected terminal wealth given that the investor's goal is underachieved, for both the mean‐variance strategy and the aforementioned hybrid strategy where transfer to the money market occurs if it allows to safely achieve the goal. The former probabilities and expectations are also provided in the case where all risky assets held are liquidated if financial distress is encountered. These results provide investors with novel practical tools to support portfolio decision‐making and analysis. Copyright © 2013 John Wiley & Sons, Ltd.
Assessment of a Nonsteroidal Aromatase Inhibitor, Letrozole, in Juvenile Rats
Authors: Pouliot Louise , Schneider Marilynn , DeCristofaro Marc , Samadfam Rana , Smith Susan Y. , Beckman David A.
Published: December 2013

BACKGROUND

The timing and duration of letrozole administration was designed to encompass the majority of postnatal development in the rat with the intent of evaluating the potential for a broad range of effects but with emphasis on expected effects on skeletal maturation.

METHODS

Sprague‐Dawley rats were administered letrozole via oral gavage at doses of 0.003, 0.03, and 0.3 mg/kg/day beginning on postpartum day (PPD) 7 through 91 followed by a 6‐week recovery period. Clinical signs, body weight, food consumption, developmental endpoints, bone, ophthalmology, behavioral assessments, clinical/anatomic pathology, toxicokinetics, and reproductive assessments were conducted.

RESULTS

Growth (body weight gain and crown‐to‐rump length) and food consumption were increased in females at ≥0.03 mg/kg/day and decreased in males at ≥0.003 mg/kg/day. Delayed sexual maturation in both sexes and adverse effects on reproductive function occurred at all doses. Effects on bone growth and maturation were noted in both sexes at all doses. Evidence of recovery was noted for males at 0.003 mg/kg/day and females at 0.003 and 0.03 mg/kg/day upon withdrawal of treatment. Histopathological changes in the pituitary–adrenal–gonadal axis correlated with effects on reproductive function.

CONCLUSIONS

The observed effects in juvenile rats were considered predictable and primarily related to the mechanism of action of letrozole upon estrogen synthesis.
Scaling of dorsal‐ventral patterning in the Xenopus laevis embryo
Authors: Ben‐Zvi Danny , Fainsod Abraham , Shilo Ben‐Zion , Barkai Naama
Published: December 2013

Scaling of pattern with size has been described and studied for over a century, yet its molecular basis is understood in only a few cases. In a recent, elegant study, Inomata and colleagues proposed a new model explaining how bone morphogenic protein (BMP) activity gradient scales with embryo size in the early Xenopus laevis embryo. We discuss their results in conjunction with an alternative model we proposed previously. The expansion‐repression mechanism (ExR) provides a conceptual framework unifying both mechanisms. Results of Inomata and colleagues implicate the chordin‐stabilizing protein sizzled as the expander molecule enabling scaling, while we attributed this role to the BMP ligand Admp. The two expanders may work in concert, as suggested by the mathematical model of Inomata et al. We discuss approaches for differentiating the contribution of sizzled and Admp to pattern scaling.
The insanity sentence: Oregon's psychiatric security review board
Authors: Rogers Jeffrey L. , Bloom Joseph D.
Published: December 2013

In response to the dilemma of management of mentally ill persons who commit crimes, Oregon has created the Psychiatric Security Review Board (PSRB) to administrate the supervision and treatment of insanity acquittees. This paper presents an overview of the PSRB structure and examines the quasi‐criminal justice features of Oregon's Insanity Sentence. The primary goal of the PSRB is the protection of societý. The maximum sentence, had the individual been found guilty, becomes the PSRB's jurisdictional period for that former defendant. A review of the administrative rules for conditional release and revocation of release that the PSRB is now in the process of adopting are described. The authors conclude that the PSRB is a promising approach which offers better community protection and better treatment for mentally ill offenders (NGRIs) than does the present prison parole system.
Pathological gambling as an insanity defense
Authors: Cunnien Alan J.
Published: December 2013

Recognition of pathological gambling as a diagnostic and clinical entity has been paralleled by its use as an insanity defense by gamblers engaged in criminal behavior. The societal ramifications of exculpation for crimes committed by volitionally impaired defendants require a critical analysis of the relationship between mental illness and criminal acts. Following a summary of current knowledge about pathological gambling as a clinical disorder, case law relevant to its use as an insanity defense is reviewed. It is argued that pathological gambling is not a serious mental illness for the purposes of the criminal law and that it bears no causal relationship to criminal activity. Legal and societal interests dictate that pathological gambling be excluded as a potential insanity defense.
Comparing patients treated in special security civil state hospital units with patients in forensic programs
Authors: Way Bruce B.
Published: December 2013

Psychiatric inpatients in special units designed for the treatment/management of violence (secure care) are compared with inpatients in three forensic programs. Although program designers anticipated that secure care and forensic patients would be similar, they were not. Principally, secure care patients were lower functioning in the psychiatric areas and were more likely to have engaged in a physical assault in the last 30 days.
The naming of the cranial nerves: A historical review
Authors: Davis Matthew C. , Griessenauer Christoph J. , Bosmia Anand N. , Tubbs R. Shane , Shoja Mohammadali M.
Published: December 2013

The giants of medicine and anatomy have each left their mark on the history of the cranial nerves, and much of the history of anatomic study can be viewed through the lens of how the cranial nerves were identified and named. A comprehensive literature review on the classification of the cranial names was performed. The identification of the cranial nerves began with Galen in the 2nd century AD and evolved up through the mid‐20th century. In 1778, Samuel Sömmerring, a German anatomist, classified the 12 cranial nerves as we recognize them today. This review expands on the excellent investigations of Flamm, Shaw, and Simon et al., with discussion of the historical identification as well as the process of naming the human cranial nerves. Clin. Anat. 27:14–19, 2014. © 2013 Wiley Periodicals, Inc.
Inhibitory and multisynaptic spines, and hemispherical synaptic specialization in the posterodorsal medial amygdala of male and female rats
Authors: Brusco Janaina , Merlo Suélen , Ikeda Érika T. , Petralia Ronald S. , Kachar Bechara , Rasia‐Filho Alberto A. , Moreira Jorge E.
Published: December 2013

The density of dendritic spines is sexually dimorphic and variable throughout the female estrous cycle in the rat posterodorsal medial amygdala (MePD), a relevant area for the modulation of reproductive behavior in rats. The local synaptic activity differs between hemispheres in prepubertal animals. Here we used serial section transmission electron microscopy to produce 3D reconstructions of dendritic shafts and spines to characterize synaptic contacts on MePD neurons of both hemispheres in adult males and in females along the estrous cycle. Pleomorphic spines and nonsynaptic filopodia occur in the MePD. On average, 8.6% of dendritic spines received inputs from symmetric gamma‐aminobutyric acid (GABA)‐immunoreactive terminals, whereas 3.6% received two synaptic contacts on the spine head, neck, or base. Presynaptic terminals in female right MePD had a higher density of synaptic vesicles and docked vesicles than the left MePD, suggesting a higher rate of synaptic vesicle release in the right MePD of female rats. In contrast, males did not show laterality in any of those parameters. The proportion of putative inhibitory synapses on dendritic shafts in the right MePD of females in proestrus was higher than in the left MePD, and higher than in the right MePD in males, or in females in diestrus or estrus. This work shows synaptic laterality depending on sex and estrous cycle phase in mature MePD neurons. Most likely, sexual hormone effects are lateralized in this brain region, leading to higher synaptic activity in the right than in the left hemisphere of females, mediating timely neuroendocrine and social/reproductive behavior. J. Comp. Neurol. 522:2075–2088, 2014. © 2013 Wiley Periodicals, Inc.
White lighting: A provisional model for predicting perceived tint in “white” illumination
Authors: Rea M. S. , Freyssinier J. P.
Published: December 2013

Recently, a line of minimum tint in chromaticity space for sources of illumination of different correlated color temperatures (CCTs) from 2700 K to 6500 K has been reported. This line of minimum tint did not correspond to the line of blackbody radiation implicitly associated with sources of white illumination used in architectural applications. It was noted that chromaticities along the line of minimum tint were not metamers but, rather, should represent, for a given CCT, chromaticities where the neural signals from the two spectral opponent channels were minimized. Earlier work provided a theoretical framework for representing the four unique hues where the neural signals from one spectral opponent channel are minimized. This framework was used here to quantitatively represent the line of minimum tint and then to empirically test whether this representation could predict the amount of tint perceived in six different sources of “white” Illumination.” Based on these results, a provisional model is proposed for describing the tint and the amount of tint perceived in “white” Illumination used in architectural applications. © 2013 Wiley Periodicals, Inc. Col Res Appl, 39, 466–479, 2014
Influence of lighting conditions on the appearance of typical interior materials
Authors: Lasauskaite Schüpbach Ruta , Reisinger Markus , Schrader Björn
Published: December 2013

Two studies investigated how lighting influences perception of various materials. Experiment 1 focused on preferences of cold or warm light. Participants' task was to indicate preference for either coolish or warmish light for 20 different materials. The selection included materials typically used for wall or floor of interior spaces. Different hues and surface characteristics were present. Specifically two materials of blue color (cold hue) were preferred in a cold light while red carpet (warm hue) and synthetic turf materials were preferred in warm light. This latter choice was explained by automatic reference of synthetic turf to the appearance of natural grass. There were no clear light source preferences for other materials. Experiment 2 explored how the same 20 materials are evaluated under LED lighting in comparison to three other lighting situations (halogen lamp, high‐intensity discharge lamp, and compact fluorescent lamp). The results of this explorative study were not conclusive. The materials chosen for this experiment differed greatly in their structure and optical properties. In conclusion, light influence on the evaluation of materials needs systematic investigation in future research. © 2013 Wiley Periodicals, Inc. Col Res Appl, 40, 50–61, 2015
The arcane roots of colour psychology, chromotherapy, and colour forecasting
Authors: Whitfield T. W. Allan , Whelton Jianne
Published: December 2013

This article explores the genesis of the apparently disparate fields of colour psychology, chromotherapy, and colour forecasting. They came to the fore during the 20th century, and while ostensibly unrelated, their common ancestry lies in the late 18th and 19th centuries. This period witnessed the discovery of such strange forces as magnetism, electricity, X‐rays, and radio waves—in addition to odic forces and the colour aura. These were all invisible, mysterious, and to the public and many prominent scientists, equally plausible. This article traces a major influence back to spiritualism and Theosophy: both privileged colour and attributed powerful influences to it. This legacy remains, though not in the scientific domain. © 2013 Wiley Periodicals, Inc. Col Res Appl, 40, 99–106, 2015
Efficient and Robust Reforming Catalyst in Severe Reaction Conditions by Nanoprecursor Reduction in Confined Space
Authors: Dacquin Jean‐Philippe , Sellam Djamila , Batiot‐Dupeyrat Catherine , Tougerti Asma , Duprez Daniel , Royer Sébastien
Published: December 2013

The in situ autocombustion synthesis route is shown to be an easy and efficient way to produce nanoscaled nickel oxide containing lanthanum‐doped mesoporous silica composite. Through this approach, ∼3 nm NiO particles homogeneously dispersed in the pores of silica are obtained, while lanthanum is observed to cover the surface of the silica pore wall. Subsequent reduction of such composite precursors under hydrogen generates Ni0 nanoparticles of a comparable size. Control over the size and size distribution of metallic nanoparticles clearly improved catalytic activity in the methane dry reforming reaction. In addition, these composite materials exhibit excellent stability under severe reaction conditions. This was achieved through the presence of LaOx species, which reduced active‐site carbon poisoning, and the confinement effect of the mesoporous support, which reduced metallic particle sintering.
Nachhaltigkeit bei Außenwandkonstruktionen mit WDVS
Authors: Vogdt Frank U. , Schäfers Martin
Published: December 2013

Auf der Grundlage des Bewertungssystems Nachhaltiges Bauen BNB werden Mauerwerkskonstruktionen mit Wärmedämm‐Verbundsystem (WDVS) im Hinblick auf ihren Einfluss auf die Nachhaltigkeit von Gebäuden betrachtet. Dabei erweisen sich Außenwandkonstruktionen mit WDVS in besonderem Maße als nachhaltig. Neben den ökonomischen und ökologischen Aspekten der Nachhaltigkeit ergeben sich insbesondere auch im funktional‐technischen Bereich – wie zum Beispiel dem Schallschutz – deutliche Vorteile. Des weiteren sind die positiven Effekte im Hinblick auf die Behaglichkeit zu nennen.

Sustainability of exterior walls with ETICS. On the basis of the rating system “sustainable building BNB”, masonry constructions with ETICS are evaluated in respect of their influence on sustainability of Buildings. Thereby, exterior walls with ETICS prove to be notably sustainable. In Addition to economical and ecological aspects of sustainability, in particular technological criteria – for example noise protection – provide clear benefits. Furthermore, positive effects concerning comfortableness can be mentioned.
Punktförmige Wärmebrücken bei Verblendmauerwerk
Authors: Vogdt Frank U. , Keßlau Hendrik , Bredemeyer Jan
Published: December 2013

Die mit dem steigenden Wärmeschutzniveau von Außenbauteilen einhergehenden hohen Dämmstoffdicken von bis zu 20 cm machen bei Außenwandkonstruktionen mit Verblendmauerwerk auch eine Weiterentwicklung der erforderlichen Konstruktionselemente wie Verblenderkonsolen und Luftschichtanker notwendig. Hierbei rücken neben einem sicheren Lastabtrag im Zusammenhang mit Kraglängen von bis zu ca. 30 cm zunehmend auch wärmeschutztechnische Aspekte ins Blickfeld, da Verblenderkonsolen und Luftschichtanker die Dämmschicht durchdringen und insofern Wärmebrücken darstellen. Der Einfluss dieser Wärmebrücken auf den Wärmedurchgang steigt mit zunehmendem Wärmedurchlasswiderstand von Außenwandkonstruktionen. Bei Kenntnis der relevanten Einflussfaktoren lassen sich diese Wärmebrücken durch wärmeschutztechnische Innovationen insbesondere im Bereich von Verblenderkonsolen signifikant reduzieren. Entsprechende Bemessungskonzepte ermöglichen zudem eine zuverlässige Quantifizierung der zusätzlichen Wärmeverluste über punktbezogene Wärmedurchgangskoeffizienten c im Zusammenhang mit energieoptimierten Bauweisen und insoweit die planerische Festlegung wirtschaftlicher Dämmstoffdicken.

Punctual thermal bridges in faced brickwork – influences, consequences and energetic optimization. The rising heat insulation level of external structural components that entails a high insulation thickness of up to 20 cm means that for exterior wall structures with faced brickwork the necessary construction elements such as brickwork support brackets and cavity wall ties also need to be developed. Here the focus of attention, in addition to secure load transfer in the context of protruding lengths of up to approx. 30 cm, is also increasingly on heat insulation aspects, because brickwork support brackets and cavity wall ties penetrate the insulating layer and thus constitute a thermal bridge. The influence of these thermal bridges on thermal transfer increases as the planar thermal resistance of exterior wall constructions increases. If the relevant influencing factors are known, these thermal bridges can be significantly reduced through innovation in heat insulation especially in the area of brickwork support brackets. The appropriate design concepts allow accurate quantification of the additional heat loss through punctual thermal transmittance coefficients χ in the context of energy‐optimised construction and thus the planning of economical insulation thicknesses.
Base‐Induced 1,3‐Sigmatropic Rearrangement of Mesitylphosphonium Salts
Authors: Solomon Sophia A. , Allen Lucy K. , Dane Sarah B. J. , Wright Dominic S.
Published: December 2013

Attempted synthesis of the ylide dianion [2,4,6‐Me3C6H2P(CHR)3]2– (2,4,6‐Me3C6H2 = mesityl, R = H or Me) by the reaction of mesitylphosphonium iodides [2,4,6‐Me3C6H2PR3]+I– (R = Me, 1; R = Et, 2) with tBuLi at reflux does not result in the anticipated deprotonation of the phosphorus‐bonded R groups. Instead, quantitative 1,3‐sigmatropic rearrangement occurs to give new benzylic phosphonium salts [(3,5‐Me2C6H3)CH2PR3]+I– (R = Me, 6; R = Et, 7), in which the phosphonium centre, the R3P group, is transferred to an ortho‐CH3 group. In situ 31P NMR spectroscopic studies show that the reaction is base‐activated and stoichiometric with respect to tBuLi. DFT calculations support the conclusion that the rearrangement is thermodynamically favourable in the gas phase and in THF and show that the rearrangement is enthalpically driven.
Hydrodechlorination of Et3NBCl3 Catalyzed by Amorphous Nickel Boride – A Mechanistic Approach
Authors: Reller Christian , Mertens Florian O. R. L.
Published: December 2013

The catalytic hydrodechlorination of BCl3 with molecular hydrogen in the presence of tertiary amines is a viable strategy for the energy‐efficient generation of valuable B–H bonds. A mechanistic study based on experiments with isolated intermediates and deuterium labeling experiments is presented. The occurrence of the rate‐limiting reverse reaction from the insoluble Et3NHCl adduct was identified as a major cause of low Et3NBH3 yields. In addition, amines with NCH2 units, which also serve in the corresponding cases as solvents, have a strong influence on the reaction kinetics; they are directly involved in the hydrogen transfer at elevated temperatures and assume the role of a cocatalyst. A catalytic cycle for the reaction on a nickel boride catalyst is proposed.
Platinum(IV) Complexes Featuring One or Two Axial Ferrocene Bearing Ligands – Synthesis, Characterization, and Cytotoxicity
Authors: Banfić Jelena , Legin Anton A. , Jakupec Michael A. , Galanski Mathea Sophia , Keppler Bernhard K.
Published: December 2013

Ferrocenyl compounds show interesting antiproliferative properties. Consequently, ferrocene bearing moieties were prepared and coupled for the first time to anticancer platinum(IV) complexes. The compounds, featuring either one or two axially coordinated ferrocene‐containing ligands, were fully characterized by ESI‐MS and multinuclear (1H, 13C, 15N, and 195Pt) one‐ and two‐dimensional NMR spectroscopy. Their cytotoxicity was investigated in three human cancer cell lines deriving from ovarian carcinoma (CH1), colon carcinoma (SW480), and non‐small‐cell lung carcinoma (A549) by means of the colorimetric MTT assay. Promising IC50 values in the low micromolar range in CH1 and SW480 human cancer cells were found.
1,6‐Enyne Cyclizations Catalyzed by N‐Heterocyclic Carbene Supported Gold Complexes: Deconvoluting Sterics and Electronics
Authors: Arumugam Kuppuswamy , Varghese Bibin , Brantley Johnathan N. , Konda Sai S. M. , Lynch Vincent M. , Bielawski Christopher W.
Published: December 2013

A series of N‐heterocyclic carbene (NHC) supported gold(I) complexes were synthesized, characterized in solution as well as in the solid state, and examined as precatalysts for 1,6‐enyne cycloisomerization reactions. The product mixtures obtained for a variety of 1,6‐enyne isomerizations were governed primarily by the electronic properties of the aforementioned precatalysts. In particular, precatalysts containing electronic‐rich NHC ligands showed increased selectivity for bicyclic products, whereas analogous precatalysts supported by electron‐deficient NHCs preferentially afforded olefinic products.
Epigenetic regulation: The interface between prenatal and early‐life exposure and asthma susceptibility
Authors: de Planell‐Saguer Mariàngels , Lovinsky‐Desir Stephanie , Miller Rachel L.
Published: December 2013

Asthma is a complex disease with genetic and environmental influences and emerging evidence suggests that epigenetic regulation is also a major contributor. Here, we focus on the developing paradigm that epigenetic dysregulation in asthma and allergy may start as early as in utero following several environmental exposures. We summarize the pathways important to the allergic immune response that are epigenetically regulated, the key environmental exposures associated with epigenetic changes in asthma genes, and newly identified epigenetic biomarkers that have been linked to clinical asthma. We conclude with a brief discussion about the potential to apply newly developing technologies in epigenetics to the diagnosis and treatment of asthma and allergy. The inherent plasticity of epigenetic regulation following environmental exposures offers opportunities for prevention using environmental remediation, measuring novel biomarkers for early identification of those at risk, and applying advances in pharmaco‐epigenetics to tailor medical therapies that maximize efficacy of treatment. ‘Precision Medicine’ in asthma and allergy is arriving. As the field advances this may involve an individually tailored approach to the prevention, early detection, and treatment of disease based on the knowledge of an individual's epigenetic profile. Environ. Mol. Mutagen. 55:231–243, 2014. © 2013 Wiley Periodicals, Inc.
Treatment of rheumatoid arthritis: current and future
Authors: Foot Oliver , Malaviya Anshuman
Published: December 2013

Rheumatoid arthritis (RA) is a chronic systemic inflammatory condition characterised by an erosive arthropathy and other extraarticular manifestations. It affects approximately 1 per cent of the population1 and the incidence is three times higher in women than men, peaking between the ages of 40 and 70 years. The disease has a significant impact on the quality of life of patients as well as on society at large and effective treatments are highly sought after. Although biologic therapies have transformed the management of RA, there is still scope for newer therapies and treatment strategies continue to evolve. This review will focus on the presently available treatments, the current unmet need and the future therapeutic strategy with a focus on some of newer molecules that show promise.
Radiocarbon Dating of Interdune Paleo‐Wetland Deposits to Constrain the Age of Mid‐to‐Late Holocene Microlithic Artifacts from the Zhongba site, Southwestern Qinghai‐Tibet Plateau
Authors: Hudson Adam M. , Olsen John W. , Quade Jay
Published: December 2013

Microlithic artifacts, some found in situ, are abundant in the Zhongba archaeological site in southwestern Tibet. The site environment consists of extant wetlands and paleo‐wetland deposits found in depressions between sand dunes derived from the Yarlung Tsangpo floodplain. Constraining 14C dates from wetland vegetation and shell from one site fall between ca. 6600–2600 cal. yr B.P., while a second site is dated 3400–1200 cal. yr B.P. A significant and variable 14C reservoir effect—up to 1400 14C yr—limits these ranges to terminus post quem constraints. The in situ artifacts are supplemented by surface collections fully characterizing raw material and typological variability for each site. Raw material found at Zhongba is chert and chalcedony likely sourced from Cretaceous bedrock near the site. Typologically, microblades are nongeometric and are derived from conical and wedge‐shaped cores similar to those identified in the Qinghai Lake Basin and the Chang Tang Nature Reserve of similar or greater age. The later occupation period at Zhongba is broadly contemporaneous with sites on the Qinghai‐Tibet Plateau containing bronze and iron artifacts, indicating microlithic technology remained an important tool‐making strategy in western Tibet late into the protohistoric period.
Strengthening and Deepening Education for Personal and Social Responsibility
Authors: Glass Chris R.
Published: December 2013

The chapter examines the effectiveness and long‐term viability of reform efforts designed to advance education for personal and social responsibility.
Internalizing behaviours in school‐age children born very preterm are predicted by neonatal pain and morphine exposure
Authors: Ranger M. , Synnes A.R. , Vinall J. , Grunau R.E.
Published: December 2013

Background

Greater neonatal pain is associated with higher internalizing behaviours in very preterm infants at 18 months corrected age, but it is unknown whether this relationship persists to school age. Moreover, it is unclear whether morphine ameliorates or exacerbates the potential influence of neonatal pain/stress on internalizing behaviours. We examined whether neonatal pain‐related stress is associated with internalizing behaviours at age 7 years in children born very preterm, and whether morphine affects this relationship.

Methods

One hundred one children born very preterm (≤32 weeks gestation) were seen at mean age 7.7 years. A parent completed the Parenting Stress Index and Child Behavior Checklist questionnaires. Neonatal pain‐related stress (the number of skin‐breaking procedures adjusted for clinical factors associated with prematurity) was examined in relation to internalizing behaviour, separately in subjects mechanically ventilated and exposed to both pain and morphine (n = 57) and those never mechanically ventilated, exposed to pain but not morphine (n = 44).

Results

In the non‐ventilated group, higher skin‐breaking procedures (p = 0.037) and parenting stress (p = 0.004) were related to greater internalizing behaviours. In the ventilated group, greater morphine exposure (p = 0.004) was associated with higher child internalizing scores.

Conclusions

In very preterm children who undergo mechanical ventilation, judicious use of morphine is important, since morphine may mitigate the negative effects of neonatal pain on nociception but adversely affect internalizing behaviours at school age. Management of procedural pain needs to be addressed in very preterm infants in the neonatal intensive care unit, to prevent long‐term effects on child behaviour.
Wellness of Minority Female Counselor Educators
Authors: Shillingford M. Ann , Trice‐Black Shannon , Butler S. Kent
Published: December 2013

Minority female counselor educators are faced with numerous challenges. This qualitative study revealed that for female minority counselor educators, these challenges continue to negatively affect their professional and personal experiences. It is through operational wellness practices and optimal balance and functioning that minority female counselor educators have often prevailed. Implications for minority female counselor educators, university administrators, and counselor educators from the majority population are provided.
Career counselor training and supervision: role of the supervisory working alliance
Authors: Parcover Jason A. , Swanson Jane L.
Published: December 2013

The importance of career counseling within our educational and professional systems is clearly recognized, yet little attention has been directed toward explicating the career counseling supervision process. Research on personal–emotional counseling supervision has stressed the critical importance of the supervisory relationship. The purpose of this study was to better understand the nature and effect of the supervisory working alliance in the supervision of career counselors, using case study methodology. Results point to the importance of explicitly addressing the working alliance early in the work, exploration of affect in supervision, and cognizance of the power differential inherent in a training relationship.
MATERNAL ENGAGEMENT IN A HOME VISITING INTERVENTION: WHAT LIES BENEATH PSYCHOLOGICAL RESOURCES?
Authors: Booth Ailbhe , Munsell Eylin Palamaro , Doyle Orla
Published: December 2013

This study examined the factors influencing participant engagement in a home visiting program. Specifically, it explored the relationship between dosage and the constituent components of psychological resources: mental health, mastery, and cognitive resources. Multiple linear regression analyses were conducted utilising implementation data from a sample (n = 95) of participants in an Irish home visiting program. Psychological resources significantly predicted dosage, yet an investigation of each component found that only cognitive resources remained significant. Furthermore, when considering types of cognitive resources, verbal ability was found to significantly predict the number of home visits but not the average duration of visits. Conversely, perceptual reasoning was found to predict the average duration of home visits but not the number of home visits. These results suggest that cognitive resources may be the driving component behind previous findings that link psychological resources and level of dosage in home visiting programs. Practice and policy implications are explored.
Polycyclic N‐Heterocyclic Compounds. Part 80: Synthesis and Evaluation of Effects on In Vitro Pentosidine Formation of 5,6‐Dihydro[1]benzothieno[3′,2′:2,3]thiepino[4,5‐d]pyrimidine and Related Compounds
Authors: Okuda Kensuke , Itsuji Yutaka , Hirota Takashi , Sasaki Kenji
Published: December 2013

Reaction of 3‐(3‐cyanopropylthio)[1]benzothiophene‐2‐carbonitrile with tert‐BuONa gave 5‐amino‐1,2‐dihydro[1]benzothieno[3,2‐d]thieno[2,3‐b]pyridine and 5‐amino‐2,3‐dihydro[1]benzothieno[3,2‐b]thiepin‐4‐carbonitrile. The latter compound served as a convenient scaffold for the synthesis of the new heterocycles, [1]benzothieno[3′,2′:2,3]thiepino[4,5‐d]pyrimidines. All of our new tetracyclic products were evaluated for in vitro inhibitory activity on the formation of pentosidine, which is one of representative advanced glycation end products.
Diastereoselective Synthesis of (Z)‐6‐(2‐Oxo‐1,2‐dihydro‐3H‐indol‐3‐ylidene)‐3,3a,9,9a‐tetrahydroimidazo[4,5‐e]thiazolo[3,2‐b]‐1,2,4‐triazin‐2,7(1H,6H)‐diones
Authors: Gazieva Galina A. , Shishkova Ekaterina A. , Kulikova Ludmila B. , Kolotyrkina Natal'ya G. , Sigay Natal'ya V. , Kravchenko Angelina N.
Published: December 2013

Two efficient and diastereoselective procedures for the synthesis of (Z)‐6‐(2‐oxo‐1,2‐dihydro‐3H‐indol‐3‐ylidene)‐3,3a,9,9a‐tetrahydroimidazo[4,5‐e]thiazolo[3,2‐b]‐1,2,4‐triazin‐2,7(1H,6H)‐diones by aldol‐crotonic condensation of 1,3‐dimethyl‐3a,9a‐diphenyl‐3,3a,9,9a‐tetrahydroimidazo[4,5‐e]thiazolo[3,2‐b]‐1,2,4‐triazin‐2,7(1H,6H)‐dione with isatins under acidic or basic catalysis are reported. Isomerization in (Z)‐7‐(1‐allyl‐2‐oxo‐1,2‐dihydro‐3H‐indol‐3‐ylidene)‐1,3‐dimethyl‐3a,9a‐diphenyl‐1,3a,4,9a‐tetrahydroimidazo[4,5‐e]thiazolo[2,3‐c]‐1,2,4‐triazin‐2,8(3H,7H)‐dione was observed under basic conditions.
Mechanism and Kinetics of Dithiobenzoate‐Mediated RAFT Polymerization – Status of the Dilemma
Authors: Moad Graeme
Published: December 2013

Dithiobenzoates are among the most popular agents for reversible addition‐fragmentation chain transfer (RAFT) polymerization. This is attributed to the better control over molecular weight and end‐group fidelity found in RAFT polymerization of methacrylates and methacrylamides. However, in polymerization of styrenes, acrylates, and acrylamides, their use has diminished, mainly in favour of trithiocarbonates, because of issues with retardation, as well as hydrolytic and thermal instability. This paper critically assesses developments in understanding the mechanism and kinetics of dithiobenzoate‐mediated RAFT polymerization from 2006 to 2013, with specific reference to the choice of reagents, polymerization conditions, side reactions, and factors leading to retardation.

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Topology‐Dependent Swichability of Peptide Secondary Structures in Bioconjugates with Complex Architectures
Authors: Börner Hans G. , Sütterlin Romina I. , Theato Patrick , Wiss Kerstin T.
Published: December 2013

Peptide sequences, which exhibit a reversible pH‐responsive coil to α‐helix secondary structure transition, are conjugated to polymer precursors to yield linear AB and graft ABA peptide–poly(ethylene oxide) conjugates. While the PEO B‐block is comparable, the conjugates differ in topologies of the peptide bearing A‐blocks. The influences of topology on the structure transitions in the peptide segments are investigated, comparing linear AB‐bioconjugates with graft ABA‐bioconjugates having multiple peptide segments combined in star or pom‐pom topologies.

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A Stimuli‐Responsive Nanogel‐Based Sensitive and Selective Fluorescent Sensor for Cr3+ with Thermo‐Induced Tunable Detection Sensitivity
Authors: Wan Xuejuan , Liu Haiyang , Yao Shen , Liu Tianqi , Yao Youwei
Published: December 2013

Stimuli‐responsive poly(N‐isopropylacrylamide) nanogel with covalently labeled rhodamine B urea derivatives (P(NIPAM‐co‐RhBUA)) is utilized as a sensitive fluorescent probe for Cr3+ in aqueous solution, and its thermo‐induced tunable detection capacity is investigated. At 20 °C, non‐fluorescent nanogel can selectively bind with Cr3+ over some other metal ions, leading to prominent fluorescence OFF–ON switching due to the recognition of RhBUA with Cr3+. Upon heating above the phase transition temperature, enhanced fluorescence intensity is observed (≈61‐fold increase at 45 °C) for the nanogel in the presence of Cr3+, accompanied with an improved detection sensitivity, which suggest that hydrophobic microenvironment generated in the collapsed nanogel plays an active role for their detection performance.

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Randomized trial of safinamide add‐on to levodopa in Parkinson's disease with motor fluctuations
Authors: Borgohain Rupam , Szasz J. , Stanzione P. , Meshram C. , Bhatt M. , Chirilineau D. , Stocchi F. , Lucini V. , Giuliani R. , Forrest E. , Rice P. , Anand R. ,   Study 016 Investigators
Published: December 2013

Levodopa is effective for the motor symptoms of Parkinson's disease (PD), but is associated with motor fluctuations and dyskinesia. Many patients require add‐on therapy to improve motor fluctuations without exacerbating dyskinesia. The objective of this Phase III, multicenter, double‐blind, placebo‐controlled, parallel‐group study was to evaluate the efficacy and safety of safinamide, an α‐aminoamide with dopaminergic and nondopaminergic mechanisms, as add‐on to l‐dopa in the treatment of patients with PD and motor fluctuations. Patients were randomized to oral safinamide 100 mg/day (n = 224), 50 mg/day (n = 223), or placebo (n = 222) for 24 weeks. The primary endpoint was total on time with no or nontroublesome dyskinesia (assessed using the Hauser patient diaries). Secondary endpoints included off time, Unified Parkinson's Disease Rating Scale (UPDRS) Part III (motor) scores, and Clinical Global Impression‐Change (CGI‐C). At week 24, mean ± SD increases in total on time with no or nontroublesome dyskinesia were 1.36 ± 2.625 hours for safinamide 100 mg/day, 1.37 ± 2.745 hours for safinamide 50 mg/day, and 0.97 ± 2.375 hours for placebo. Least squares means differences in both safinamide groups were significantly higher versus placebo. Improvements in off time, UPDRS Part III, and CGI‐C were significantly greater in both safinamide groups versus placebo. There were no significant between‐group differences for incidences of treatment‐emergent adverse events (TEAEs) or TEAEs leading to discontinuation. The addition of safinamide 50 mg/day or 100 mg/day to l‐dopa in patients with PD and motor fluctuations significantly increased total on time with no or nontroublesome dyskinesia, decreased off time, and improved parkinsonism, indicating that safinamide improves motor symptoms and parkinsonism without worsening dyskinesia. © 2013 International Parkinson and Movement Disorder Society