bluuebunny/crossref_metadata_2025 huggingface dataset:
Changes in seismicity and stress loading on subduction faults in the Kanto region, Japan, 2011–2014
Authors: Gardonio Blandine , Marsan David , Lengliné Olivier , Enescu Bogdan , Bouchon Michel , Got Jean‐Luc
Published: March 2015

Seismic activity has increased in the Kanto region, Japan, following the 2011 M9.0 Tohoku earthquake. We here reassess this increase up to June 2014, to show that normal, Omori‐like relaxation characterizes the activity on crustal faults as well as on the Philippine Sea plate, but not on the deeper Pacific plate. There repeating earthquakes display a twofold rate of occurrence (still ongoing in June 2014) as compared to the pre‐Tohoku rate, suggesting enhanced creep. We compute the Coulomb stress changes on the upper locked portion of the Philippine Sea plate, which last ruptured in 1923. We find that this fault was little affected by either the coseismic, the postseismic, the accelerated creep, or the 2011 Boso silent slip event.
Tropical rainforest response to marine sky brightening climate engineering
Authors: Muri Helene , Niemeier Ulrike , Kristjánsson Jón Egill
Published: March 2015

Tropical forests represent a major atmospheric carbon dioxide sink. Here the gross primary productivity (GPP) response of tropical rainforests to climate engineering via marine sky brightening under a future scenario is investigated in three Earth system models. The model response is diverse, and in two of the three models, the tropical GPP shows a decrease from the marine sky brightening climate engineering. Partial correlation analysis indicates precipitation to be important in one of those models, while precipitation and temperature are limiting factors in the other. One model experiences a reversal of its Amazon dieback under marine sky brightening. There, the strongest partial correlation of GPP is to temperature and incoming solar radiation at the surface. Carbon fertilization provides a higher future tropical rainforest GPP overall, both with and without climate engineering. Salt damage to plants and soils could be an important aspect of marine sky brightening.
Nonlinear interactions of waves and tides in a subterranean estuary
Authors: Xin Pei , Wang Shen S. J. , Lu Chunhui , Robinson Clare , Li Ling
Published: March 2015

Previous studies have revealed hysteretic behavior in subterranean estuaries in response to intensified wave conditions caused by offshore storm events, showing dependence of submarine groundwater discharge (SGD) and subsurface salt distribution on historic wave conditions. Although most shorelines worldwide are also exposed to tidal fluctuations, it is unclear how tides moderate wave‐induced SGD and salinity distribution in subterranean estuaries. This study presents numerical simulations that explore the combined influence of intensified wave conditions and tides on groundwater flow and salt transport in a subterranean estuary. The results show that tides weaken the hysteretic wave effect on SGD, suggesting that a tidally influenced subterranean estuary is less sensitive to intensified wave conditions with respect to the water fluxes across the aquifer‐sea interface. However, due to enhancement of salt‐freshwater mixing, tides strengthen the hysteretic wave effect on the salt fluxes across the aquifer‐sea interface, prolonging the recovery of salt distribution in the subterranean estuary to the prestorm state. These findings reveal the nonlinear, coupling nature of processes driven by oceanic oscillations at different time scales in subterranean estuaries.
Disappearance of plasmaspheric hiss following interplanetary shock
Authors: Su Zhenpeng , Zhu Hui , Xiao Fuliang , Zheng Huinan , Wang Yuming , Shen Chao , Zhang Min , Wang Shui , Kletzing C. A. , Kurth W. S. , Hospodarsky G. B. , Spence H. E. , Reeves G. D. , Funsten H. O. , Blake J. B. , Baker D. N. , Wygant J. R.
Published: March 2015

Plasmaspheric hiss is one of the important plasma waves controlling radiation belt dynamics. Its spatiotemporal distribution and generation mechanism are presently the object of active research. We here give the first report on the shock‐induced disappearance of plasmaspheric hiss observed by the Van Allen Probes on 8 October 2013. This special event exhibits the dramatic variability of plasmaspheric hiss and provides a good opportunity to test its generation mechanisms. The origination of plasmaspheric hiss from plasmatrough chorus is suggested to be an appropriate prerequisite to explain this event. The shock increased the suprathermal electron fluxes, and then the enhanced Landau damping promptly prevented chorus waves from entering the plasmasphere. Subsequently, the shrinking magnetopause removed the source electrons for chorus, contributing significantly to the several‐hours‐long disappearance of plasmaspheric hiss.
TEM Study of Schottky Junctions in Reconfigurable Silicon Nanowire Devices
Authors: Banerjee Sayanti , Löffler Markus , Muehle Uwe , Berent Katarzyna , Heinzig André , Trommer Jens , Weber Walter , Zschech Ehrenfried
Published: March 2015

The physical and electrical properties of a silicon nanowire reconfigurable field effect transistor (RFETs) are determined by the Schottky junction between the participating phases. TEM studies on such junctions require a careful FIB‐based target preparation of thin lamellae with minimal ion‐beam induced damage. In the current study, the nickel silicide phase forming the Schottky junction with silicon is identified using EDX in the TEM, considering a calibration based on the Fourier transforms of the HRTEM micrographs of known diffraction patterns of the nickel silicide phases. The TEM lamellae are prepared using the so‐called lift‐out technique and low voltage Ga+ ion polishing to minimize the near‐surface amorphization. The structural and compositional data of the nickel silicide phase are needed for engineering the Schottky junction and corresponding theoretical modeling.
Anisotropic Wettability of Biomimetic Micro/Nano Dual‐Scale Inclined Cones Fabricated by Ferrofluid‐Molding Method
Authors: Huang Chen‐Yu , Lai Mei‐Feng , Liu Wen‐Lin , Wei Zung‐Hang
Published: March 2015

Learning from nature, a series of cone‐shaped structures resembling trichomes of plants are fabricated by ferrofluid molding to understand the influence of geometry on wettability. Experimentally, ferrofluid microdroplets are generated under an external magnetic field, and their shape can be changed from right cones into oblique cones by tilting the external magnetic field. Followed by hard molds made with UV‐curable tri(propylene glycol) diacrylate, polydimethylsiloxane microcones with different inclination angle (θ) are subsequently generated. Nickel thin film is deposited onto the microcones to form micro/nano dual‐scale structures. The largest contact angle (CA) is obtained in nickel‐deposited right cones (CA = 163.1° ± 2.5°). Anisotropic wettability is exhibited in oblique cones and the retention forces in the pin and release directions differ up to 12 μN (cones θ = 50°). As explained by a model as a function of the inclination angle of the cone structures, the contact and retention forces of droplet move in pin and release directions exhibit considerable differences. Results suggest the inclination of the trichomes assist the balance between repellency and retention of water in a direction‐selective manner.
Ruthenium Complex‐Catalyzed Domino Addition/exo‐ Cycloisomerization of Propargylic Alcohols and Tosyl Isocyanate to Form Oxazolidinones
Authors: Li Deng Yuan , Chen Hao Jie , Liu Pei Nian
Published: March 2015

A ruthenium complex with a tetradentate nitrogen–phosphorus mixed ligand is shown to be an efficient catalyst for domino addition/exo‐cycloisomerization of propargylic alcohols and tosyl isocyanate. In the presence of 2–5 mol% ruthenium complex, a range of terminal propargylic alcohols were reacted with tosyl isocyanate to furnish the corresponding oxazolidinone product exclusively in moderate to excellent yields. Mechanistic studies suggest that propargylic alcohol and tosyl isocyanate undergo addition firstly to generate propargylic carbamate, which is then activated by the ruthenium complex to form an η2‐alkyne complex, rather than the ruthenium vinylidene intermediate, to afford the final oxazolidinone product.

magnified image
Palladium on Carbon‐Catalyzed Aqueous Transformation of Primary Alcohols to Carboxylic Acids Based on Dehydrogenation under Mildly Reduced Pressure
Authors: Sawama Yoshinari , Morita Kosuke , Asai Shota , Kozawa Masami , Tadokoro Shinsuke , Nakajima Junichi , Monguchi Yasunari , Sajiki Hironao
Published: March 2015

The catalytic dehydrogenation of alcohols to carbonyl products is a green sustainable oxidation with no production of waste except for hydrogen, which can be an energy source. Additionally, a reusable heterogeneous catalyst is valuable from the viewpoint of process chemistry and water is a green solvent. We have accomplished the palladium on carbon (Pd/C)‐catalyzed dehydrogenation of primary alcohols to carboxylic acids in water under a mildly reduced pressure (800 hPa). The reduced pressure can be easily controlled by the vacuum controller of the rotary evaporator to remove the excess of generated hydrogen, which causes the reduction (reverse reaction) of aldehydes to alcohols (starting materials) and other undesirable side reactions. The present method is applicable to the reaction of various aliphatic and benzylic alcohols to the corresponding carboxylic acids, and the Pd/C could be reused at least 5 times.

magnified image
Very Important Publication: Iridium‐Catalyzed Intramolecular Enantioselective CH Alkylation at the C‐2 Position of N‐Alkenylindoles
Authors: Shibata Takanori , Ryu Naoto , Takano Hideaki
Published: March 2015

Intramolecular enantioselective alkylation of N‐alkenylindoles proceeded via CH bond cleavage at the C‐2 position in the presence of a cationic iridium catalyst with a diphosphine ligand. Aroyl groups at the C‐3 position of the indoles operated as effective directing groups, and chiral 1‐substituted‐2,3‐dihydro‐1H‐pyrrolo[1,2‐a]indoles were obtained in high yield with excellent ee.

magnified image
Being born after your brother is not a disadvantage: Reproductive success does not depend on the sex of the preceding sibling
Authors: Puskarczyk Karolina , Galbarczyk Andrzej , Klimek Magdalena , Nenko Ilona , Odrzywołek Ludwik , Jasienska Grazyna
Published: March 2015

Objectives

The aim of the present study is to examine whether being born after a brother versus after a sister differentially impacts reproductive outcomes in a contemporary population. The sex of the preceding sibling may influence an individual's fitness, and, in fact, individuals born after a brother have been shown to have lower reproductive success in historical populations. Males, as the more expensive sex, constitute a drain on maternal resources and elicit an immune response during pregnancy, which may have negative consequences on subsequent siblings.

Methods

A questionnaire was used to collect data on reproductive health and family history from 951 women and 380 men between 20 and 92 years of age in villages throughout the Mogielica Human Ecology Study Site in southern Poland. Number of children, number of sons and daughters, age at menarche, age at marriage, age at menopause, and age at first and last reproduction were tested as components of reproductive success.

Results

The sex of one's preceding sibling had no statistically significant impact on any of the reproductive characteristics tested.

Conclusions

Our results suggest that potential immunological and nutritional disadvantages experienced during prenatal life by individuals born after male siblings do not have long‐lasting effects in modern, well‐nourished populations. Am. J. Hum. Biol. 27:731–733, 2015. © 2015 Wiley Periodicals, Inc.
Theory and Practice: Bulk Synthesis of C3B and its H2‐ and Li‐Storage Capacity
Authors: King Timothy C. , Matthews Peter D. , Glass Hugh , Cormack Jonathan A. , Holgado Juan Pedro , Leskes Michal , Griffin John M. , Scherman Oren A. , Barker Paul D. , Grey Clare P. , Dutton Siân E. , Lambert Richard M. , Tustin Gary , Alavi Ali , Wright Dominic S.
Published: March 2015

Previous theoretical studies of C3B have suggested that boron‐doped graphite is a promising H2‐ and Li‐storage material, with large maximum capacities. These characteristics could lead to exciting applications as a lightweight H2‐storage material for automotive engines and as an anode in a new generation of batteries. However, for these applications to be realized a synthetic route to bulk C3B must be developed. Here we show the thermolysis of a single‐source precursor (1,3‐(BBr2)2C6H4) to produce graphitic C3B, thus allowing the characteristics of this elusive material to be tested for the first time. C3B was found to be compositionally uniform but turbostratically disordered. Contrary to theoretical expectations, the H2‐ and Li‐storage capacities are lower than anticipated, results that can partially be explained by the disordered nature of the material. This work suggests that to model the properties of graphitic materials more realistically, the possibility of disorder must be considered.
Multifunctional Reagents for Quantitative Proteome‐Wide Analysis of Protein Modification in Human Cells and Dynamic Profiling of Protein Lipidation During Vertebrate Development
Authors: Broncel Malgorzata , Serwa Remigiusz A. , Ciepla Paulina , Krause Eberhard , Dallman Margaret J. , Magee Anthony I. , Tate Edward W.
Published: March 2015

Novel multifunctional reagents were applied in combination with a lipid probe for affinity enrichment of myristoylated proteins and direct detection of lipid‐modified tryptic peptides by mass spectrometry. This method enables high‐confidence identification of the myristoylated proteome on an unprecedented scale in cell culture, and allowed the first quantitative analysis of dynamic changes in protein lipidation during vertebrate embryonic development.
1D NMR Homodecoupled 1H Spectra with Scalar Coupling Constants from 2D NemoZS‐DIAG Experiments
Authors: Cotte Axelle , Jeannerat Damien
Published: March 2015

A two‐dimensional liquid‐state NMR experiment cleanly separating chemical shifts and scalar couplings information is introduced. This DIAG experiment takes advantage of a drastic reduction of the spectral window in the indirect dimension to be quickly recorded and of a new non‐equidistant modulation of the selective pulse to improve the sensitivity of the broadband homodecoupling Zangger–Sterk sequence element by one order of magnitude. A simple automatic analysis results in 1D spectra displaying singlets and lists of the scalar couplings for first‐order multiplets. This facilitates the analysis of 1D spectra by resolving multiplets based on their differences in chemical shifts and coupling structures.
Organocatalytic Enantioselective Oxidative CH Alkenylation and Arylation of N‐Carbamoyl Tetrahydropyridines and Tetrahydro‐β‐carbolines
Authors: Liu Xigong , Meng Zhilin , Li Chengkun , Lou Hongxiang , Liu Lei
Published: March 2015

The first organocatalytic enantioselective CH alkenylation and arylation reactions of N‐carbamoyl tetrahydropyridines and tetrahydro‐β‐carbolines (THCs) are described. The metal‐free processes represent an efficient and straightforward approach to a variety of structurally and electronically diverse α‐substituted tetrahydropyridines and THCs in good yields with excellent regio‐ and enantioselectivities. Preliminary control experiments provide important insights into the reaction mechanism.
Formation of BN Isosteres of Azo Dyes by Ring Expansion of Boroles with Azides
Authors: Braunschweig Holger , Celik Mehmet Ali , Hupp Florian , Krummenacher Ivo , Mailänder Lisa
Published: March 2015

Herein, we present the results of our investigations on the effect of ortho substitution of aryl azides on the ring‐expansion reaction of boroles, five‐membered unsaturated boron heterocycles. These studies led to the isolation of the first 1,2‐azaborinine‐substituted azo dyes, which are bright yellow solids. One of the derivatives, (E)‐2‐mesityl‐1‐(mesityldiazenyl)‐3,4,5,6‐tetraphenyl‐1,2‐azaborinine, was found to be unstable in solution and to transform through a Jacobsen‐like reaction into an indazole and 1‐hydro‐1,2‐azaborinine. DFT calculations were performed to shed light on possible mechanisms to rationalize the unexpected azo‐azaborinine formation and to draw conclusions about the role played by the ortho substituents in the reaction.
A mixed complementarity model for the US biofuel market with federal policy interventions
Authors: Christensen Adam , Siddiqui Sauleh
Published: March 2015

Policymakers in the USA have provided various mechanisms to grow the domestic biofuel industry. One of the most significant policies in the USA is the volume mandate specified within the Renewable Fuel Standard (RFS). There are a number of other overlapping factors that impact the use of biofuels, namely the so‐called blend wall, or the 10% blend limit of ethanol in gasoline, along with a complex system of tax credits. All of these policies directly affect the value of a Renewable Identification Number (RIN), the tradable compliance certificate created as part of the RFS. Regulators track RIN prices carefully because they are a measure of the cost of compliance. In this work a mixed complementarity problem (MCP) is presented to combine these market dynamics into one model. This tool was specifically designed for policymakers to compare scenarios and study the effects on key market variables including RIN, gasoline, and diesel prices, along with production quantities for a number of different finished blended fuels. Our results suggest that RIN prices will increase with an increase in the volume of biofuel mandated by the Environmental Protection Agency (EPA); however the behavior of the different RIN prices depends on how the biofuel volumes are assigned among all the subcategories. Under scenarios investigated in this study, it is likely that a primary compliance strategy is to blend more biodiesel into diesel fuel. This behavior would increase the price of the D4 RIN but the premium could be mitigated by reinstating the biodiesel production tax credit. © 2015 Society of Chemical Industry and John Wiley & Sons, Ltd
Simultaneous determination of three banned psychiatric drugs in pig feed and tissue using solid‐phase reactor on‐line oxidizing and HPLC‐fluorescence detection
Authors: Qi Liang , Duan Li‐Min , Sun Xiao‐Huan , Zhang Jing , Zhang Zhi‐Qi
Published: March 2015

The banned addition of psychiatric drugs such as phenothiazines to animal feed and foodstuffs increases the risk of human organ lesion. Phenothiazines usually exhibit weak native fluorescence and can be oxidized to strongly fluorescent compounds. In this study, a novel, sensitive and convenient method of HPLC‐fluorescence detection based on post‐column on‐line oxidizing with lead dioxide solid‐phase reactor has been developed for simultaneous determination of three banned psychotropic drugs, promethazine, chlorpromazine and thioridazine. Three compounds were successfully separated on an Agilent TC‐C18 column with mobile phase of acetonitrile (A) and water (B), both containing 0.5% (v/v) formic acid. A gradient elution was programmed and fluorimetric detection was performed at λex/λem of 332/373 nm for promethazine, 340/380 nm for chlorpromazine and 352/432 nm for thioridazine. The calibration graphs gave good linearity over the concentration ranges of 30.0–4976.4 µg/L for promethazine, 2.0–2153.2 µg/L for chlorpromazine, and 15.0–3088.0 µg/L for thioridazine, and correlation coefficients (r) were ≥0.995. The method was applied to the determination of phenothiazines in pig feed and pig tissue, and the average spiked recoveries were in the range 69.1–115.4%. Copyright © 2015 John Wiley & Sons, Ltd.
Characteristics of women in a prison mental health assessment unit in England and Wales (2008–2010)
Authors: Hales Heidi , Somers Nadia , Reeves Chrissy , Bartlett Annie
Published: March 2015

Background

The high prevalence of mental disorders among women in prison is recognised worldwide. In England and Wales, successive governments and independent reports have argued that the equivalent of community care in prisons is acceptable but that some mental health assessment units (MHAUs), staffed by professional clinicians, should remain. These have not been researched.

Aims

This paper aimed to explore patterns of use of a MHAU in a women's prison in England and to test the hypothesis that it was being used only, as intended – to hold women pending transfer to a health service hospital or in a bona fide crisis.

Methods

Anonymised data on all women transferred to one MHAU between 1 January 2008 and 31 August 2010 were obtained from the prison files and subjected to descriptive analysis.

Results

Less than a third of these women were transferred to an outside hospital; this group stayed longest in the unit. An overlapping group of 52% of the women was under a special assessment, care in custody and teamwork protocol because of suicide or serious self‐harm risk. Thus, 188 (68%) admissions fulfilled national protocol criteria for MHAU admissions. Two in five women admitted were released or returned to ordinary prison locations. Nevertheless, over 80% of the women were known to external mental health services, and 64 (30%) were so unwell on arrival in prison that they were transferred directly to the MHAU. Over a third of admissions were of women admitted more than once during the 32 months of study, and this was significantly more likely after release from prison directly to the community.

Conclusions

Our hypothesis was not sustained, and it seems unlikely that this prison MHAU is unique in being used outside its strict remit. A shift from studying the epidemiology of mental disorder in prisons to the epidemiology of mental health needs could benefit this vulnerable group and the wider community alike. Copyright © 2015 John Wiley & Sons, Ltd.
Influence of Metal Particle Size on Oxidative CO2 Reforming of Methane over Supported Nickel Catalysts: Effects of Second‐Metal Addition
Authors: Bhavani Annabathini Geetha , Kim Won Young , Lee Jin Woo , Lee Jae Sung
Published: March 2015

Oxidative CO2 reforming of methane is studied over Ni/AlCeZrOx catalyst with addition of a second metal element (Mg, Co, La, Mn, or Fe) aiming to improve the performance of the catalyst and increase their resistance to coking. Addition of Mg produces the best catalyst showing high CH4 and CO2 conversions as well as high selectivities to synthesis gas with no severe coke deposition. Addition of Co, La, and Mn also exhibits significant improvement, whereas Fe brings only a moderate improvement. The high activity is accompanied by high stability and low amount of deposited coke. The high activity and stability are attributed mainly to nanosized metallic particles, which accompany high amounts of available surface oxygen, and high basicity of the surface. The basicity of the catalyst promotes adsorption and dissociation of CO2, and surface oxygen can oxidize surface carbon intermediates to regenerate active metal sites before they turn to coke to sustain catalytic cycle.
Facile Synthesis of Crystalline Polymeric Carbon Nitrides with an Enhanced Photocatalytic Performance under Visible Light
Authors: Liang Qinghua , Huang Zheng‐Hong , Kang Feiyu , Yang Quan‐Hong
Published: March 2015

Poly(triazine imides) intercalated with Li+ and X− (PTI/X, X=Cl or Br), which are described widely as crystalline polymeric carbon nitrides, were synthesized in a facile manner by heating a mixture of melamine and LiX. This method has the advantages of low cost, scalable production, and high efficiency. Importantly, both PTI/Cl and PTI/Br exhibit an enhanced photocatalytic performance compared to conventional graphitic polymeric carbon nitride in the degradation of rhodamine B under visible‐light irradiation because of their higher visible‐light‐harvesting ability and charge carrier separation efficiency.
Highly Efficient Chirality Transfer from Diamines Encapsulated within a Self‐Assembled Calixarene–Salen Host
Authors: Martínez‐Rodríguez Luis , Bandeira Nuno A. G. , Bo Carles , Kleij Arjan W.
Published: March 2015

A calix[4]arene host equipped with two bis‐[Zn(salphen)] complexes self‐assembles into a capsular complex in the presence of a chiral diamine guest with an unexpected 2:1 ratio between the host and the guest. Effective chirality transfer from the diamine to the calix–salen hybrid host is observed by circular dichroism (CD) spectroscopy, and a high stability constant K2,1 of 1.59×1011 M−2 for the assembled host–guest ensemble has been determined with a substantial cooperativity factor α of 6.4. Density functional calculations are used to investigate the origin of the stability of the host–guest system and the experimental CD spectrum compared with those calculated for both possible diastereoisomers showing that the M,M isomer is the one that is preferentially formed. The current system holds promise for the chirality determination of diamines, as evidenced by the investigated substrate scope and the linear relationship between the ee of the diamine and the amplitude of the observed Cotton effects.
Ln0.5A0.5MnO3 (Ln=Lanthanide, A= Ca, Sr) Perovskites Exhibiting Remarkable Performance in the Thermochemical Generation of CO and H2 from CO2 and H2O
Authors: Dey Sunita , Naidu B. S. , Rao C. N. R.
Published: March 2015

Perovskite oxides of the Ln0.5A0.5MnO3 (Ln=lanthanide, A=Sr, Ca) family have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO respectively. The amounts of O2 and CO produced strongly depend on the size of the rare earth ions and alkaline earth ions. The manganite with the smallest rare earth possessing the highest distortion and size disorder as well as the smallest tolerance factor, gives out the maximum amount of O2, and, hence, the maximum amount of CO. Thus, the best results are found with Y0.5Sr0.5MnO3, which possesses the highest distortion and size disorder. Y0.5Sr0.5MnO3 shows remarkable fuel production activity even at the reduction and oxidation temperatures as low as 1200 °C and 900 °C, respectively.
Palladium‐Catalyzed Aminocarbonylation of N‐Chloroamines with Boronic Acids
Authors: Li Wanfang , Wu Xiao‐Feng
Published: March 2015

Aryl (pseudo)halide‐based (CX) carbonylation reactions have been extensively studied during the past few decades. From both academic and synthetic points of view, the carbonylative transformation of NX bonds represents an interesting and attractive area of investigation. In light of this, the first carbonylative cross‐coupling between N‐chloroamines and organoboronic acids has been developed. This new type of aminocarbonylation proceeds at mild temperatures (45–55 °C) with 2 mol % Pd/C (10 wt %) as the ligand‐free catalyst. Not only arylboronic acids, but also alkenyl‐ and alkylboronic acids can be applied as the substrates and bromide and iodide substituents in the substrates are well tolerated. Initial mechanistic investigations have also been performed.
MLT1 links cytoskeletal asymmetry to organelle placement in chlamydomonas
Authors: Mittelmeier Telsa M. , Thompson Mark D. , Lamb Mary Rose , Lin Huawen , Dieckmann Carol L.
Published: March 2015

Asymmetric placement of the photosensory eyespot organelle in Chlamydomonas is patterned by mother‐daughter differences between the two basal bodies, which template the anterior flagella. Each basal body is associated with two bundled microtubule rootlets, one with two microtubules and one with four, forming a cruciate pattern. In wild‐type cells, the single eyespot is positioned at the equator in close proximity to the plus end of the daughter rootlet comprising four microtubules, the D4. Here we identify mutations in two linked loci,MLT1andMLT2, which cause multiple eyespots. Antiserum raised against MLT1 localized the protein along the D4 rootlet microtubules, from the basal bodies to the eyespot. MLT1 associates immediately with the new D4 as it extends during cell division, before microtubule acetylation. MLT1 is a low‐complexity protein of over 300,000 Daltons. The expression or stability of MLT1 is dependent onMLT2, predicted to encode a second large, low‐complexity protein. MLT1 was not restricted to the D4 rootlet in cells with thevfl2‐220mutation in the gene encoding the basal body‐associated protein centrin. The cumulative data highlight the role of mother‐daughter basal body differences in establishing asymmetry in associated rootlets, and suggest that eyespot components are directed to the correct location by MLT1 on the D4 microtubules. © 2015 Wiley Periodicals, Inc.
Benzo[b]tryptanthrin Inhibits MDR1, Topoisomerase Activity, and Reverses Adriamycin Resistance in Breast Cancer Cells
Authors: Jun Kyu‐Yeon , Park So‐Eun , Liang Jing Lu , Jahng Yurngdong , Kwon Youngjoo
Published: March 2015

Tryptanthrin is an indoloquinazoline alkaloid isolated from indigo. Tryptanthrin and its benzo‐annulated derivative, benzo[b]tryptanthrin, inhibit both topoisomerases I (topo I) and II (topo II) and cause cytotoxicity in several human cancer cell lines. From diverse assessment methods, including cleavage complex stabilization, comet, DNA unwinding/intercalation, topo II ATPase inhibition, ATP competition for topo II, and wound‐healing assays, we determined that the mode of action of benzo[b]tryptanthrin is as a DNA non‐intercalative and ATP‐competitive topo I and II dual catalytic inhibitor. Benzo[b]tryptanthrin induced apoptosis through the cleavage of caspase‐3 and PARP in HCT15 colon cancer cells. Additionally, benzo[b]tryptanthrin reversed adriamycin resistance by down‐regulation of multidrug resistance protein 1 (MDR1) in adriamycin‐resistant MCF7 breast cancer cells (MCF7adr) with more potent inhibitory activity than tryptanthrin. Taken together, derivatization by benzo‐annulation of tryptanthrin ameliorated the MDR‐reversing effect of tryptanthrin and may pave the way to the discovery of a novel potent adjuvant agent for chemotherapy.
Localization and Dynamics of Long‐Lived Excitations in Colloidal Semiconductor Nanocrystals with Dual Quantum Confinement
Authors: Liu Su , Borys Nicholas J. , Sapra Sameer , Eychmüller Alexander , Lupton John M.
Published: March 2015

Semiconductor nanocrystals consisting of a quantum dot (QD) core and a quantum well (QW) shell, where the QD and QW are separated by a tunneling barrier, offer a unique opportunity to engineer the photophysical properties of individual nanostructures. Using the thicknesses of the corresponding layers, the excitons of the first and second excited states can be separated spatially, localizing one state to the QD and the other to the QW. Thus the wave function overlap of the two states can be minimized, suppressing non‐radiative thermalization between the two wells, which in turn leads to radiative relaxation from both states. The molecular analogy to such dual emission would be the inhibition of internal conversion, a special case that violates Kasha′s rule. Using nanosecond time‐resolved spectroscopy of QDQW CdSe/ZnS onion‐like nanocrystals, an intermediate regime of exciton separation and suppressed thermalization is identified where the non‐radiative relaxation of the higher‐energy state is slowed, but not completely inhibited. In this intermediate thermalization regime, the temporal evolution of the delayed emission spectra resulting from trapped carriers mimic the dynamics of such states in nanocrystals that consist of only a QD core. In stark contrast, when a higher‐energy metastable state exists in the QW shell due to strongly suppressed interwell thermalization, the spectral dynamics of the long‐lived excitations in the QD and QW, which are spectrally distinct, are amplified and differ from each other as well as from those in the core‐only nanocrystals. This difference in spectral dynamics demonstrates the utility of exploiting well‐defined exciton localization to study the nature and spatial dependence of the intriguing photophysics of colloidal semiconductor nanocrystals, and illustrates the power of nanosecond gated luminescence spectroscopy in illuminating complex relaxation dynamics which are entirely masked in steady‐state or ultrafast spectroscopy.
Comparison of the Stability of Functionalized GaN and GaP
Authors: Wilkins Stewart J. , Paskova Tania , Reynolds C. Lewis , Ivanisevic Albena
Published: March 2015

Surface functionalization via 1 H,1 H,2 H,2H‐perfluoro octanephosphonic acid was done in the presence of phosphoric acid to provide a simplified surface passivation technique for gallium nitride (GaN) and gallium phosphide (GaP). In an effort to identify the leading causes of surface instabilities, hydrogen peroxide was utilized as an additional chemical modification to cap unsatisfied bonds. The stability of the surfaces was studied in an aqueous environment and subsequently characterized. A physical characterization was carried out to evaluate the surface roughness and water hydrophobicity pre and post stability testing via atomic force microscopy and water goniometry. Surface‐chemistry changes and solution leaching were quantified by X‐ray photoelectron spectroscopy and inductively coupled plasma mass spectrometry. The results indicate a sensitivity to hydroxyl terminated species for both GaN and GaP under aqueous environments, as the increase of the degree of leaching was more significant for hydrogen peroxide treated samples. The results support the notion that hydroxyl species act as precursors to gallium oxide formation and lead to subsequent instability in aqueous solutions.
Ultrafast Charge‐Transfer Reactions of Indoline Dyes with Anchoring Alkyl Chains of Varying Length in Mesoporous ZnO Solar Cells
Authors: Rohwer Egmont , Minda Iulia , Tauscher Gabriele , Richter Christoph , Miura Hidetoshi , Schlettwein Derck , Schwoerer Heinrich
Published: March 2015

The front cover artwork is provided by H. Schwoerer and I. Minda (Stellenbosch University). The image shows one of our cells in the African sun light with an indoline dye attached and accompanied by a femtosecond transient absorption landscape. Read the full text of the article at 10.1002/cphc.201402784.
The Signature Program: Bringing the Protocol to the Patient
Authors: Kang BP , Slosberg E , Snodgrass S , Lebedinsky C , Berry DA , Corless CL , Stein S , Salvado A
Published: March 2015

Early‐phase clinical development in oncology has evolved dramatically with the deciphering of the human genome in 2004. Genomic analysis and the tools identifying genetically disrupted pathways within a patient's tumor have been a driving force for personalized medicine and for the development of highly targeted novel therapies. Tumors are often genetically heterogeneous, with multiple concurrent genetic abnormalities. On the other hand, tumors arising from different tissues may share identical molecular drivers.
Pharmacokinetics, Pharmacodynamics, and Safety of Lisinopril in Pediatric Kidney Transplant Patients: Implications for Starting Dose Selection
Authors: Trachtman H , Frymoyer A , Lewandowski A , Greenbaum LA , Feig DI , Gipson DS , Warady BA , Goebel JW , Schwartz GJ , Lewis K , Anand R , Patel UD ,   on behalf of the Best Pharmaceuticals for Children Act–Pediatric Trials Network Administrative Core Committee
Published: March 2015

Hypertension in pediatric kidney transplant recipients contributes to long‐term graft loss, yet treatment options—including angiotensin‐converting enzyme inhibitors—are poorly characterized in this vulnerable population. We conducted a multicenter, open‐label pharmacokinetic (PK) study of daily oral lisinopril in 22 children (ages 7–17 years) with stable kidney transplant function. Standard noncompartmental PK analyses were performed at steady state. Effects on blood pressure were examined in lisinopril‐naïve patients (n = 13). Oral clearance declined in proportion to underlying kidney function; however, in patients with low estimated glomerular filtration rate (30–59 ml/min per 1.73m2), exposure (standardized to 0.1 mg/kg/day dose) was within the range reported previously in children without a kidney transplant. In lisinopril‐naïve patients, 85% and 77% had a ≥ 6 mmHg reduction in systolic and diastolic blood pressure, respectively. Lisinopril was well tolerated. Our study provides initial insight on lisinopril use in children with a kidney transplant, including starting dose considerations.
Monoclinic Copper(I) Selenide Nanocrystals and Copper(I) Selenide/Palladium Heterostructures: Synthesis, Characterization, and Surface‐Enhanced Raman Scattering Performance
Authors: Zhang Long , Zhao Shulin , Li Yafei , Lan Yaqian , Han Min , Dai Zhihui , Bao Jianchun
Published: March 2015

We have developed a simple and facile approach to the fabrication of monoclinic Cu2Se nanocrystals and Cu2Se/Pd heterostructures. [(C2H5)4N]2[CuCl4] was chosen as the copper source and SeO2/terpineol was used as the Se–II precursor for the generation of hexagonal CuSe and cubic Cu2–xSe through the “hot‐injection” and “one‐pot” methods, respectively. Both CuSe and Cu2–xSe could be further transformed into monoclinic Cu2Se through heat treatment with trioctylphosphine (TOP) at 220 °C. Cu2Se/Pd as well as CuSe/Pd and Cu2–xSe/Pd were readily obtained by simply mixing copper selenides and Pd(NO3)2 in a 2‐propanol solution. The Pd nanoparticles were distributed on the surface of the copper selenides. The effect of certain reaction parameters on the formation of copper selenides was studied. The amount of terpineol used played an important role in the phase‐selective synthesis of CuSe and Cu2–xSe. The surface‐enhanced Raman scattering (SERS) performance of the heterostructures was investigated with 4‐mercaptopyridine (4‐Mpy) as a probe molecule. Owing to the strong synergistic effects between Cu2Se and Pd, Cu2Se/Pd showed greater SERS performance than pure Pd or Cu2Se. Moreover, compared to those of CuSe/Pd and Cu2–xSe/Pd, Cu2Se/Pd exhibited the highest SERS sensitivity to 4‐Mpy with a detection limit as low as 1.0 × 10–9 M, which revealed its phase‐ and composition‐dependent characteristics. This Cu2Se/Pd heterostructure exhibits potential applications in the chemical and biological sensing fields.
Fluorescence and Label Free Impedimetric DNA Detection on SnO2 Nanopillars
Authors: Le Minh Hai , Fradetal Louis , Delabouglise Didier , Mai Anh Tuan , Stambouli Valerie
Published: March 2015

SnO2 is a n‐type semiconductive oxide with attractive characteristics mainly based on easy elaboration and functionalization routes in addition to chemical robustness. We have fabricated SnO2 nanopillars based DNA sensor to perform the label free (without any redox compound) impedimetric DNA detection. The non faradaic electrochemical impedance spectroscopic (EIS) behavior and more particularly the evolution of the polarization resistance the SnO2 nanopillars has been thoroughly investigated upon the different steps of their functionalization process up to DNA hybridization. Similarly to our previous study on planar 2D SnO2 surfaces, the DNA hybridization induces a systematic increase of the polarization resistance, the magnitude of which decreases with the target DNA concentration. This DNA concentration dependence matches the one obtained from epifluorescence intensity measurements. A common value of DNA detection limit, i.e. 2 nM, is found from both measurement techniques. Interestingly the 3D view intensity obtained by confocal scanning laser fluorescence microscopy confirms that the DNA molecules are mainly grafted along the SnO2 nanopillars. Finally both impedance and fluorescence measurements obtained in the case of 1‐ and 2‐base mismatch hybridizations demonstrate the selectivity of the SnO2 nanopillars based DNA sensor. These preliminary results open the way to further investigations on the influence of both the shape ratio and electrical properties of the SnO2 nanopillars on the impedance variations related to DNA hybridization, notably in view of improving the sensor performances.
Faradic Peaks Enhanced by Carbon Nanotubes in Microsomal Cytochrome P450 Electrodes
Authors: Baj‐Rossi C. , Müller C. , von Mandach U. , De Micheli G. , Carrara S.
Published: March 2015

In this work we present an investigation on the behavior of microsomes containing human cytochrome P450 in cyclic voltammetry for drug detection. The microsomes are adsorbed on the surface of multi‐walled carbon nanotubes by drop‐casting. We demonstrate that the hydrophobic and highly electroactive surface of multi‐walled carbon nanotubes enables to distinguish more clearly the contributions in reduction peak current attributed to the enzymatic components of microsomes. Voltammetric measurements were performed under several experimental conditions with two cytochrome P450‐isoforms, 1A2 and 3A4. We show that the reduction current for the component of cytochrome P450‐microsome linearly increases in the presence of a substrate.
Sequential Determination of 13 Elements in Complex Matrices by Stripping Voltammetry with Mixed Complexing Electrolytes
Authors: Muratt Diana T. , M. de Carvalho Leandro , Viana Carine , C. do Nascimento Paulo , Reis Gabriel , R. Dal Molin Thaís , Grassmann Carla , Smidt Geerd , Koschinsky Andrea
Published: March 2015

This paper presents the determination of 13 elements in a simultaneous and sequential analysis using solochrome violet (SVRS), chloranilic acid (CA), diethylenetriaminepentaacetic acid (DTPA), dimethylglyoxime (DMG), and oxine as complexing electrolytes. The Methods were applied to determine Al3+, Fe3+, Mo6+, Zn2+, Cd2+, Pb2+, Cu2+, Ni2+, Co2+, Tl+, U6+, V5+, and Cr6+ in fertilizers, plant materials, and foodstuffs. The Method was found to be selective and accurate (82.13–119.03 %) for elemental analysis in complex matrices that were previously submitted to a total oxidative digestion step (calcination and wet digestion). Mutual interferences of the elements were systematically investigated. The Sequential Method could be useful for the routine quality control of foodstuffs and fertilizer formulations regarding mineral nutrients or contaminants.
In‐capillary self‐assembly study of quantum dots and protein using fluorescence coupled capillary electrophoresis
Authors: Wang Jianhao , Li Jingyan , Li Jinchen , Qin Yuqin , Wang Cheli , Qiu Lin , Jiang Pengju
Published: March 2015

As a vast number of novel materials in particular inorganic nanoparticles have been invented and introduced to all aspects of life, public concerns about how they might affect our ecosystem and human life continue to arise. Such incertitude roots at a fundamental question of how inorganic nanoparticles self‐assemble with biomolecules in solution. Various techniques have been developed to probe the interaction between particles and biomolecules, but very few if any can provide advantages of both rapid and convenient. Herein, we report a systematic investigation on quantum dots (QDs) and protein self‐assembly inside a capillary. QDs and protein were injected to a capillary one after another. They were mixed inside the capillary when a high voltage was applied. Online separation and detection were then achieved. This new method can also be used to study the self‐assembly kinetics of QDs and protein using the Hill equation, the KD value for the self‐assembly of QDs and protein was calculated to be 8.8 μM. The obtained results were compared with the previous out of‐capillary method and confirmed the effectiveness of the present method.
Modeling and interpreting biological effects of mixtures in the environment: Introduction to the metal mixture modeling evaluation project
Authors: Van Genderen Eric , Adams William , Dwyer Robert , Garman Emily , Gorsuch Joseph
Published: March 2015

The fate and biological effects of chemical mixtures in the environment are receiving increased attention from the scientific and regulatory communities. Understanding the behavior and toxicity of metal mixtures poses unique challenges for incorporating metal-specific concepts and approaches, such as bioavailability and metal speciation, in multiple-metal exposures. To avoid the use of oversimplified approaches to assess the toxicity of metal mixtures, a collaborative 2-yr research project and multistakeholder group workshop were conducted to examine and evaluate available higher-tiered chemical speciation-based metal mixtures modeling approaches. The Metal Mixture Modeling Evaluation project and workshop achieved 3 important objectives related to modeling and interpretation of biological effects of metal mixtures: 1) bioavailability models calibrated for single-metal exposures can be integrated to assess mixture scenarios; 2) the available modeling approaches perform consistently well for various metal combinations, organisms, and endpoints; and 3) several technical advancements have been identified that should be incorporated into speciation models and environmental risk assessments for metals. Environ Toxicol Chem 2015;34:721–725. © 2015 SETAC
Toward ecosystem-based sediment quality guidelines for polychlorinated biphenyls (PCBs)
Authors: Arblaster Jennifer , Ikonomou Michael G , Gobas Frank APC
Published: March 2015

To investigate whether Sediment Quality Guidelines (SQGs) for polychlorinated biphenyls (PCBs) in Canada and British Columbia achieve their objective of protecting ecosystems, we measured and compiled concentrations of PCB congeners in sediments, bivalves, crustaceans, fish, and marine mammals from 3 areas off the Pacific coast of British Columbia, Canada. The concentration data showed that whereas PCB concentrations in sediments were predominantly below the SQG of 20 µg/kg dry weight, large fractions of the PCB concentrations in fish and shellfish species exceeded the tissue residue guideline for the consumption of fish and shellfish by wildlife (i.e., 50 µg/kg wet weight [ww]) but were below the tissue residue guideline for the consumption of fish and shellfish by human populations (i.e., 2000 µg/kg ww). Also, PCB concentrations in marine mammals exceeded toxicity reference concentrations. The concentration data were used to develop species- and location-specific Biota-Sediment Accumulation Factors (BSAF = Cbiota/Csediment), that were used to estimate PCB concentrations in wildlife species that may exist if the PCB concentration in sediments are equal to the SQGs. The results show that if the PCB concentration is equal to the SQGs, then PCB concentrations in most wildlife species can be expected to exceed the tissue residue guideline for the consumption of fish and shellfish by wildlife species and by humans, as well as toxicity reference concentrations for marine mammals. A methodology for developing SQGs for PCBs that are protective of the health of different wildlife species and human consumers of fish and shellfish from general Canadian and coastal First Nations populations was developed and applied. The proposed guidelines may provide useful guidance to establish SQGs for PCBs that can account for the ecological diversity in coastal environments and that better achieve the intent of the guidelines to protect ecosystems. The proposed methodology for guideline development may also be useful in the development of SQGs for other bioaccumulative substances. Integr Environ Assess Manag 2015;X:000–000. ©2015 SETAC

Key Points

A food-web based field bioaccumulation study on the Pacific Coast shows that current sediment quality guidelines for bioaccumulative substances such as PCBs do not protect most ecological receptors (other than benthic invertebrates). A new methodology for the derivation of sediment quality guidelines is presented that aims to develop sediment quality guidelines for bioaccumulative substances that consider a range of ecological receptors and human health risk endpoints. Sediment quality guidelines to achieve various environmental and human health goals are presented for PCBs.