bluuebunny/crossref_metadata_2025 huggingface dataset:
Satellite‐detected fluorescence: Decoupling nonphotochemical quenching from iron stress signals in the South Atlantic and Southern Ocean
Authors: Browning T. J. , Bouman H. A. , Moore C. M.
Published: May 2014

Satellite‐detected sunlight‐induced chlorophyll fluorescence could offer valuable information about the physiological status of phytoplankton on a global scale. Realization of this potential is confounded by the considerable uncertainty that exists in deconvolving the multiple ecophysiological processes that can influence the satellite signal. A dominant source of current uncertainty arises from the extent of reductions in chlorophyll fluorescence caused by the high light intensities phytoplankton are typically exposed to when satellite images are captured. In this study, results from over 200 nonphotochemical quenching (NPQ) experiments conducted on cruises spanning from subtropical gyre to Southern Ocean waters have confirmed that satellite fluorescence quantum yields have the potential to reveal broad regions of iron (Fe) stress. However, our results suggest significant variability in phytoplankton NPQ behavior between oceanic regimes. Dynamic NPQ must therefore be considered to achieve a reliable interpretation of satellite fluorescence in terms of Fe stress. Specifically, significantly lower NPQ was found in stratified subtropical gyre‐type waters than in well‐mixed Southern Ocean waters. Such variability is suggested to result from differences in incident irradiance fluctuation experienced by phytoplankton, with highly variable irradiance conditions likely driving phytoplankton to acclimate or adapt toward a higher dynamic NPQ capacity. Sea surface temperature empirically demonstrated the strongest correlation with NPQ parameters and is presented as a means of correcting the chlorophyll fluorescence signature for the region studied. With these corrections, a decadal composite of satellite austral summer observations is presented for the Southern Ocean, potentially reflecting spatial variability in the distribution and extent of Fe stress.
Balanced dynamics of deep and shallow Hadley circulations in the tropics
Authors: Gonzalez Alex O. , Rojas Gabriela Mora
Published: May 2014

This paper examines the dynamics of large‐scale overturning circulations in the tropical atmosphere using an idealized zonally symmetric model on the equatorial β‐plane. Under certain simplifications of its coefficients, the elliptic partial differential equation for the transverse circulation can be solved by first performing a vertical transform to obtain a horizontal structure equation, and then using Green's function to solve the horizontal structure equation. When deep diabatic heating is present in the Intertropical Convergence Zone (ITCZ), the deep Hadley circulation is of first‐order importance. In the absence of deep diabatic heating, the interior circulation associated with Ekman pumping cannot penetrate deep into the troposphere because the resistance of fluid parcels to horizontal motion (i.e., inertial stability) is significantly smaller than their resistance to vertical motion (i.e., static stability). In this scenario, only a shallow Hadley circulation exists. The shallow overturning circulation is characterized by meridional velocities as large as 7 m s−1 at the top of the boundary layer, in qualitative agreement with observations in the tropical eastern Pacific. The meridional asymmetry between the winter and summer deep and shallow Hadley cells is attributed to the anisotropy of the inertial stability parameter, and as the ITCZ widens meridionally or as the forcing involves higher vertical wave numbers, the asymmetry between the winter and summer cells increases.
Silica‐Supported Tripod Triarylphosphane: Application to Transition Metal‐Catalyzed C(sp3)H Borylations
Authors: Iwai Tomohiro , Murakami Ryo , Harada Tomoya , Kawamorita Soichiro , Sawamura Masaya
Published: May 2014

A silica‐supported tripod triarylphosphane (Silica‐3p‐TPP), containing a triphenylphosphane‐type core tripodally immobilized on the silica surface, allows rhodium‐ and iridium‐catalyzed C(sp3)H borylations of amide, urea and alkylpyridine derivatives. The 31P CP/MAS NMR studies for the coordination behavior of the tripod phosphane towards a rhodium complex indicate efficient site isolation of the each phosphane center, allowing independent mono‐P‐coordination to the metal center.

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Iron‐Promoted Electrophilic Annulation of Aryl Enynes with Disulfides or Diselenides Leading to Polysubstituted Naphthalenes
Authors: Yang Zhi‐Jun , Hu Bo‐Lun , Deng Chen‐Liang , Zhang Xing‐Guo
Published: May 2014

An iron‐promoted electrophilic annulation of aryl enynes with disulfides or diselenides has been developed. In the presence of iron(III) chloride (FeCl3) and iodine (I2,), a variety of trifluoromethyl‐containing aryl enynes underwent electrophilic annulation with various disulfides or diselenides successfully to afford the corresponding polysubstituted naphthalenes in moderate to excellent yields.

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Influence of environmental conditions on caking mechanisms in individual amorphous food particle contacts
Authors: Haider Christine I. , Hounslow Michael J. , Salman Agba D. , Althaus Tim O. , Niederreiter Gerhard , Palzer Stefan
Published: May 2014

Caking of amorphous powders creates severe problems such as product loss and additional costs in the food industry. Among the main factors causing this unwanted agglomeration process are fluctuations of the environmental conditions, that is, a rise in temperature and humidity. There is correspondingly a need to identify and, if possible, avoid the environmental conditions inducing strong interparticle cohesion based on particle contact mechanisms like viscoelastic flattening and sintering. For this reason, a novel micromanipulation approach focusing on the interactions between individual amorphous food particles in contact under load in a controlled environment is introduced. It was possible to identify the dominant caking mechanism under defined conditions, such as temperature and humidity, particle deformation, as well as contact holding time, and to quantify interparticle cohesion. Furthermore, the mechanical behavior of rubbery spherical model particles is presented and a theoretical approach to describe the contact zone formation kinetics is proposed. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2774–2787, 2014
Refinement of the deletion in 8q22.2–q22.3: The minimum deletion size at 8q22.3 related to intellectual disability and epilepsy
Authors: Kuroda Yukiko , Ohashi Ikuko , Saito Toshiyuki , Nagai Jun‐ichi , Ida Kazumi , Naruto Takuya , Iai Mizue , Kurosawa Kenji
Published: May 2014

Kuechler et al. [2011] reported five patients with interstitial deletions in 8q22.2–q22.3 who had intellectual disability, epilepsy, and dysmorphic features. We report on a new patient with the smallest overlapping de novo deletion in 8q22.3 and refined the phenotype. The proposita was an 8‐year‐old girl, who developed seizures at 10 months, and her epileptic seizure became severe and difficult to control with antiepileptic drugs. She also exhibited developmental delay and walked alone at 24 months. She was referred to us for evaluation for developmental delay and epilepsy at the age of 8 years. She had intellectual disability (IQ 37 at 7 years) and autistic behavior, and spoke two word sentences at 8 years. She had mild dysmorphic features, including telecanthus and thick vermilion of the lips. Array comparative genomic hybridization detected a 1.36 Mb deletion in 8q22.3 that encompassed RRM2B and NCALD, which encode the small subunit of p53‐inducible ribonucleotide reductase and neurocalcin delta in the neuronal calcium sensor family of calcium‐binding proteins, respectively. The minimum overlapping region between the present and previously reported patients is considered to be a critical region for the phenotype of the deletion in 8q22.3. We suggest that the deletion in 8q22.3 may represent a clinically recognizable condition, which is characterized by intellectual disability and epilepsy. © 2014 Wiley Periodicals, Inc.
Azobenzene‐Functionalized Metal–Organic Polyhedra for the Optically Responsive Capture and Release of Guest Molecules
Authors: Park Jinhee , Sun Lin‐Bing , Chen Ying‐Pin , Perry Zachary , Zhou Hong‐Cai
Published: May 2014

Stimuli‐responsive metal–organic polyhedra (srMOPs) functionalized with azobenzene showed UV‐irradiation‐induced isomerization from the insoluble trans‐srMOP to the soluble cis‐srMOP, whereas irradiation with blue light reversed this process. Guest molecules were trapped and released upon cis‐to‐trans and trans‐to‐cis isomerization of the srMOPs, respectively. This study provides a new direction in the ever‐diversifying field of MOPs, while laying the groundwork for a new class of optically responsive materials.
Enzyme‐Catalyzed Oxidation of 5‐Hydroxymethylfurfural to Furan‐2,5‐dicarboxylic Acid
Authors: Dijkman Willem P. , Groothuis Daphne E. , Fraaije Marco W.
Published: May 2014

Furan‐2,5‐dicarboxylic acid (FDCA) is a biobased platform chemical for the production of polymers. In the past few years, numerous multistep chemical routes have been reported on the synthesis of FDCA by oxidation of 5‐hydroxymethylfurfural (HMF). Recently we identified an FAD‐dependent enzyme which is active towards HMF and related compounds. This oxidase has the remarkable capability of oxidizing [5‐(hydroxymethyl)furan‐2‐yl]methanol to FDCA, a reaction involving four consecutive oxidations. The oxidase can produce FDCA from HMF with high yield at ambient temperature and pressure. Examination of the underlying mechanism shows that the oxidase acts on alcohol groups only and depends on the hydration of aldehydes for the oxidation reaction required to form FDCA.
Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball
Authors: Edwards Alison J. , Dhayal Rajendra S. , Liao Ping‐Kuei , Liao Jian‐Hong , Chiang Ming‐Hsi , Piltz Ross O. , Kahlal Samia , Saillard Jean‐Yves , Liu C. W.
Published: May 2014

The syntheses of the first rhombicuboctahedral copper polyhydride complexes [Cu28(H)15(S2CNR)12]PF6 (NR=NnPr2 or aza‐15‐crown‐5) are reported. These complexes were analyzed by single‐crystal X‐ray and one by neutron diffraction. The core of each copper hydride nanoparticle comprises one central interstitial hydride and eight outer‐triangular‐face‐capping hydrides. A further six face‐truncating hydrides form an unprecedented bridge between the inner and outer copper atom arrays. The irregular inner Cu4 tetrahedron is encapsulated within the Cu24 rhombicuboctahedral cage, which is further enclosed by an array of twelve dithiocarbamate ligands that subtends the truncated octahedron of 24 sulfur atoms, which is concentric with the Cu24 rhombicuboctahedron and Cu4 tetrahedron about the innermost hydride. For these compounds, an intriguing, albeit limited, H2 evolution was observed at room temperature, which is accompanied by formation of the known ion [Cu8(H)(S2CNR)6]+ upon exposure of solutions to sunlight, under mild thermolytic conditions, and on reaction with weak (or strong) acids.
Unusual Structural Features in the Lysozyme Derivative of the Tetrakis(acetato)chloridodiruthenium(II,III) Complex
Authors: Messori Luigi , Marzo Tiziano , Sanches Rute Nazaré Fernandes , Hanif‐Ur‐Rehman  , de Oliveira Silva Denise , Merlino Antonello
Published: May 2014

The reaction between the paddle‐wheel tetrakis(acetato)chloridodiruthenium(II,III) complex, [Ru2(μ‐O2CCH3)4Cl] and hen egg‐white lysozyme (HEWL) was investigated through ESI‐MS and UV/Vis spectroscopy and the formation of a stable metal–protein adduct was unambiguously demonstrated. Remarkably, the diruthenium core is conserved in the adduct while two of the four acetate ligands are released. The crystal structure of this diruthenium–protein derivative was subsequently solved through X‐ray diffraction analysis to 2.1 Å resolution. The structural data are in agreement with the solution results. It was found that HEWL binds two diruthenium moieties, at Asp101 and Asp119, respectively, with the concomitant release of two acetate ligands from each diruthenium center.
Copper‐Catalyzed Regioselective ortho CH Cyanation of Vinylarenes
Authors: Yang Yang , Buchwald Stephen L.
Published: May 2014

A copper‐based catalytic technique for the regioselective ortho CH cyanation of vinylarenes has been developed. This method provides an effective means for the selective functionalization of vinylarene derivatives. A copper‐catalyzed cyanative dearomatization mechanism is proposed to account for the regiochemical course of this reaction.
Alkyne Cycloaddition to a Titanocene Oxide as a Route to Cyclopentadienyl Modification
Authors: Pappas Iraklis , Chirik Paul J.
Published: May 2014

Addition of terminal or internal alkynes to a base‐free titanocene oxide results in synthesis of the corresponding oxometallocyclobutene. With appropriate cyclopentadienyl substitution, these compounds undergo reversible CC reductive elimination offering a unique approach to cyclopentadienyl modification.
Water‐soluble polymer and photocatalysis for arsenic removal
Authors: Yuksel Suna , Rivas Bernabé L. , Sánchez Julio , Mansilla Héctor D. , Yañez Jorge , Kochifas Pia , Kabay Nalan , Bryjak Marek
Published: May 2014

In this study, the photocatalytic oxidation of hazardous arsenite (As(III)) to arsenate (As(V)) and the sequential removal of arsenate from aqueous solution by liquid‐phase polymer‐based retention (LPR) were investigated. The photocatalytic oxidation of arsenite was performed using TiO2 (P25 Degussa, Germany) under UV‐A light. The optimal photocatalytic conditions to oxidize 10 mg L−1 of arsenite solution were achieved using a 0.5 g L−1 of catalyst at a pH value of 2. The As(III) oxidation reached 100% after 30 min of illumination with UV‐A light. A water‐soluble polymer containing quaternary ammonium groups, poly(3‐acrylamidopropyl)trimethylammonium chloride (P(ClAPTA)), was used as an extracting reagent in the LPR process. To obtain the optimized conditions, the removal experiments were performed at various polymer : As(V) molar ratios using 10 mg L−1 of arsenate solutions. After the oxidation of As(III) to As(V), the removal of arsenate by P(ClAPTA) was obtained in a 99% yield using a 20 : 1 polymer : As(V) molar ratio at a pH value of 9. The results demonstrate that the combination of these methods is highly useful for potential applications related to the treatment of wastewater contaminated with As(III). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40871.
Some Pyrazole and Pyrazolo[3,4‐d]pyrimidine Derivatives: Synthesis and Anticancer Evaluation
Authors: Shamroukh Ahmed H. , Rashad Aymn E. , Abdel‐Megeid Randa E. , Ali Hatem S. , Ali Mamdouh M.
Published: May 2014

5‐Amino‐1‐p‐tolyl‐1H‐pyrazole‐4‐carbonitrile (1) was used for the preparation of some novel pyrazoles and pyrazolo[3,4‐d]pyrimidines 2–10. Moreover, the cytotoxicity and in vitro anticancer activities of the prepared compounds were also assessed against the MCF‐7 breast cancer, HepG2 liver cancer, and A549 lung carcinoma cell lines, along with investigation of the effect of the synthesized compounds on the expression of urokinase plasminogen activator (uPA). The tested compounds exhibited remarkable cytotoxic activity against MCF‐7 and HepG2 cells. Among the tested compounds, 2 and 9 revealed promising anticancer activity compared to the activity of the commonly used anticancer drug, doxorubicin, by inhibiting the expression of uPA.
Synthesis of Oligomeric Mannosides and Their Structure‐Binding Relationship with Concanavalin A
Authors: Li Chen‐Wei , Hon Kai‐Wei , Ghosh Bhaswati , Li Po‐Han , Lin Hsien‐Ya , Chan Po‐Han , Lin Chun‐Hung , Chen Yu‐Chie , Mong Kwok‐Kong Tony
Published: May 2014

Small glycodendrimers with α‐mannosyl ligands were synthesized by using copper‐catalyzed azide–alkyne coupling chemistry and some of these molecules were used as multivalent ligands to study the induction of concanavalin A (Con A) precipitation. The results showed that the monovalent mannose ligand could induce the precipitation of Con A. This unexpected finding initiated a series of studies to characterize the molecular basis of the ligand–lectin interaction. The atypical precipitation is found to be specific to the mannose, fluorescein moiety (FITC), and Con A. Apparently the mannose ligand binds to Con A through hydrogen‐bonding interactions, whereas the binding of FITC is mediated by hydrophobic forces.
Design of Weak‐Donor Alkyl‐Functionalized Push–Pull Pyrene Dyes Exhibiting Enhanced Fluorescence Quantum Yields and Unique On/Off Switching Properties
Authors: Niko Yosuke , Sasaki Shunsuke , Kawauchi Susumu , Tokumaru Katsumi , Konishi Gen‐ichi
Published: May 2014

We designed, synthesized, and evaluated environmentally responsive solvatochromic fluorescent dyes by incorporating weak push–pull moieties. The quantum yields of the push (alkyl)–pull (formyl) pyrene dyes were dramatically enhanced by the introduction of alkyl groups into formylpyrene (1‐formylpyrene: ΦF=0.10; 3,6,8‐tri‐n‐butyl‐1‐formylpyrene: ΦF=0.90; in MeOH). The new dyes exhibited unique sensitivity to solvent polarity and hydrogen‐bond donor ability, and specific fluorescence turn‐on/off properties (e.g., 3,6,8‐tri‐n‐butyl‐1‐formylpyrene: ΦF=0.004, 0.80, 0.37, and 0.90 in hexane, chloroform, DMSO, and MeOH, respectively). Here, the alkyl groups act as weak donors to suppress intersystem crossing by destabilizing the HOMOs of 1‐formylpyrene while maintaining weak intramolecular charge‐transfer properties. By using alkyl groups as weak donors, environmentally responsive, and in particular, pH‐responsive fluorescent materials may be developed in the future.
Rumination and Perceived Impairment Associated With Depressive Symptoms in a Verbal Adolescent–Adult ASD Sample
Authors: Gotham Katherine , Bishop Somer L. , Brunwasser Steven , Lord Catherine
Published: May 2014

The aim of this study was to examine the association between depressive symptoms and several psychosocial constructs (insight into autism symptoms, rumination, desire for social interaction, and satisfaction with social support) that may play a role in the development or maintenance of depression in verbally fluent adolescents and adults with ASD. Participants included 50 individuals with ASD and verbal IQ ≥ 70, aged 16–35 (sample size varied by measure). Elevated depressive symptoms on the Beck Depression Inventory, 2nd edition (BDI‐II), were associated with greater self‐perceived, autism‐related impairments (n = 48), greater rumination (n = 21), and lower perceived social support (n = 37). Rumination tended to moderate the association between self‐perceived autism symptoms and BDI‐II scores (n = 21), and was significantly associated with ASD‐related insistence on sameness behaviors (n = 18). An unexpected relationship between depressive features and social participation and motivation will need to be clarified by longitudinal research. These and similar findings contribute to our understanding of the phenomenology of depression in ASD, which is critical to the development of practical prevention and treatment. Autism Res 2014, 7: 381–391. © 2014 International Society for Autism Research, Wiley Periodicals, Inc.
Structural and Biochemical Analyses of the Catalysis and Potency Impact of Inhibitor Phosphoribosylation by Human Nicotinamide Phosphoribosyltransferase
Authors: Oh Angela , Ho Yen‐Ching , Zak Mark , Liu Yongbo , Chen Xukun , Yuen Po‐wai , Zheng Xiaozhang , Liu Yichin , Dragovich Peter S. , Wang Weiru
Published: May 2014

Prolonged inhibition of nicotinamide phosphoribosyltransferase (NAMPT) is a strategy for targeting cancer metabolism. Many NAMPT inhibitors undergo NAMPT‐catalyzed phosphoribosylation (pRib), a property often correlated with their cellular potency. To understand this phenomenon and facilitate drug design, we analyzed a potent cellularly active NAMPT inhibitor (GNE‐617). A crystal structure of pRib‐GNE‐617 in complex with NAMPT protein revealed a relaxed binding mode. Consistently, the adduct formation resulted in tight binding and strong product inhibition. In contrast, a biochemically equipotent isomer of GNE‐617 (GNE‐643) also formed pRib adducts but displayed significantly weaker cytotoxicity. Structural analysis revealed an altered ligand conformation of GNE‐643, thus suggesting weak association of the adducts with NAMPT. Our data support a model for cellularly active NAMPT inhibitors that undergo NAMPT‐catalyzed phosphoribosylation to produce pRib adducts that retain efficient binding to the enzyme.
AMP‐activated protein kinase is involved in induction of protective autophagy in astrocytes exposed to oxygen‐glucose deprivation
Authors: Gabryel Bożena , Kost Alicja , Kasprowska Daniela , Liber Sebastian , Machnik Grzegorz , Wiaderkiewicz Ryszard , Łabuzek Krzysztof
Published: May 2014

AMP‐activated kinase (AMPK) acts as the intracellular ATP depletion sensor, which detects and limits increases in the AMP/ATP ratio. AMPK may be significantly activated under stress conditions that deplete cellular ATP levels such as ischemia/hypoxia or glucose deprivation. Recent studies strongly suggest that AMPK participates in autophagy regulation, but it is not known whether AMPK activated by ischemia regulates autophagy in astrocytes and the consequence of autophagy activation in ischemic astrocytes are unclear. We have investigated the contribution of AMPK to autophagy activation in rat primary astrocyte cultures subjected to ischemia‐simulating conditions (combined oxygen glucose deprivation, OGD) and its potential effects on astrocyte damage induced by OGD (1–12 h). The evidence supports the conclusion that AMPK activation at early stages of OGD is involved in induction of protective autophagy in astrocytes. Inhibition of AMPK, either by siAMPKα1 or by compound C, significantly attenuated the expression of autophagy‐related proteins and decrease of astrocyte viability following OGD. The findings provide additional data about the role of AMPK in ischemic astrocytes and downstream responses that may be involved in OGD‐induced protective autophagy.
RKHS‐based functional nonparametric regression for sparse and irregular longitudinal data
Authors: Avery Matthew , Wu Yichao , Helen Zhang Hao , Zhang Jiajia
Published: May 2014

This paper focuses on sparse and irregular longitudinal data with a scalar response. The predictor consists of sparse and irregular observations on predictor trajectories, potentially contaminated with measurement errors. For this type of data, Yao, Müller, & Wang (2005a) proposed a principal components analysis through conditional expectation (PACE) approach, which is capable of predicting each predictor trajectory based on sparse and irregular observations. Nonparametric functional data analysis provides an attractive alternative due to its high flexibility. Early work includes functional additive models as in Müller & Yao (2008) and Ferraty & Vieu (2006), which are mainly based on kernel smoothing methods. In this work, we propose a new functional nonparametric regression framework based on reproducing kernel Hilbert spaces (RKHS). The proposed method involves two steps. The first step is to estimate each predictor trajectory based on sparse and irregular observations using PACE. The second step is to conduct a RKHS‐based nonparametric regression using the estimated predictor trajectories. Our approach shows improvement over existing methods in simulation studies as well as in a real data example.The Canadian Journal of Statistics42: 204–216; 2014 © 2014 Statistical Society of Canada
Application of Advanced Oxidation Processes for Polycyclic Aromatic Hydrocarbons Removal from Municipal Treatment Sludge
Authors: Karaca Gizem , Tasdemir Yücel
Published: May 2014

This study was carried out to investigate the removal of polycyclic aromatic hydrocarbons (PAHs) from municipal treatment sludge. The effects of temperature, sunlight, H2O2 and FeSO4 · 7 H2O concentrations on the PAH removal were determined. A UV apparatus was designed for the PAH removal experiments. All experiments were conducted in triplicate. The highest ∑11 PAH removal ratio (71%) was obtained with 4.9 M H2O2 addition to sludge (without FeSO4 · 7 H2O addition) at 17°C. It was concluded that ferrous (Fe2+) and ferric (Fe3+) addition was unnecessary because ferrous and ferric contents of the sludge acted as catalysts. ∑11 PAH concentration was reduced 23% with acid cracking. PAH removal efficiency reached about 63% using the Fenton process. Sixty percent PAH was removed from the sludge with using sunlight in ambient air applications. PAH removal was hindered due to an increase in average temperature (17–36°C) during Fenton and Fenton‐like processes. It was determined that 3‐rings compounds were removed from sludge easier than the heavier compounds. It could also be seen that phenanthrene and anthracene (3‐ring compounds) were removed from sludge with evaporation as 20 and 35%, respectively. It was concluded that the evaporation mechanism became more effective with increasing temperature.
Quantitative Analyses of ROS and RNS Production in Breast Cancer Cell Lines Incubated with Ferrocifens
Authors: Lu Cong , Heldt Jan‐Martin , Guille‐Collignon Manon , Lemaître Frédéric , Jaouen Gérard , Vessières Anne , Amatore Christian
Published: May 2014

Ferrocifens are an original class of ferrocifen‐type breast cancer drugs. They possess anti‐proliferative effects due to the association of the ferrocene moiety and the tamoxifen skeleton. In this work, fluorescence measurements indicated the production of reactive oxygen species (ROS) if hormone‐dependent or ‐independent breast cancer cells were incubated with three hit ferrocifen compounds. Additionally, amperometry at ultramicroelectrodes was carried out to identify and quantify ROS and reactive nitrogen species (RNS) under stress conditions. Videomicroscopy was used to optimize the conditions employed for electrochemical investigations. Amperometry was then performed on two cell lines pre‐incubated with each of the three ferrocifens. Interestingly, these results demonstrate that the presence of an aminoalkyl chain in the ferrocifen structure may confer a unique behavior toward both cell lines, in comparison with the two other compounds that lack this feature.
Patient‐reported symptoms and discontinuation of adjuvant aromatase inhibitor therapy
Authors: Kidwell Kelley M. , Harte Steven E. , Hayes Daniel F. , Storniolo Anna Maria , Carpenter Janet , Flockhart David A. , Stearns Vered , Clauw Daniel J. , Williams David A. , Henry N. Lynn
Published: May 2014

BACKGROUND

Aromatase inhibitor (AI) therapy results in substantial survival benefits for patients with hormone receptor‐positive breast cancer. The rates of poor adherence and discontinuation of AI therapy are high, primarily because of treatment‐related toxicities like musculoskeletal pain. Although pain‐related symptoms may worsen during AI therapy, the authors hypothesized that nonpersistence with AI therapy was associated with symptoms that were present before treatment initiation.

METHODS

Postmenopausal women initiating AI therapy who were enrolled in a prospective clinical trial completed questionnaires at baseline to assess sleep, fatigue, mood, and pain. Reasons for treatment discontinuation during the first year of treatment were recorded. Associations between baseline patient‐reported symptoms and treatment discontinuation because of toxicity were identified using logistic regression.

RESULTS

Four hundred forty‐nine patients were evaluable. The odds of treatment discontinuation were higher in patients who reported a greater number of symptoms before AI initiation. Baseline poor sleep quality was associated with early treatment discontinuation, with an odds ratio (OR) of 1.91 (95% confidence interval [CI], 1.26‐2.89; P = .002). Baseline presence of tired feeling and forgetfulness had similar ORs for discontinuation (tired feeling: OR, 1.76; 95% CI, 1.15‐2.67; P = .009; forgetfulness: OR, 1.66; 95% CI, 1.11‐2.48; P = .015). An increasing total number of baseline symptoms was associated with an increased likelihood of treatment discontinuation, with an OR of 1.89 (95% CI, 1.20‐2.96; P = .006) for 3 to 5 symptoms versus 0 to 2 symptoms.

CONCLUSIONS

Symptom clusters in breast cancer survivors that are present before the initiation of adjuvant AI therapy may have a negative impact on a patient's persistence with therapy. Interventions to manage these symptoms may improve breast cancer outcomes and quality of life. Cancer 2014;120:2403–2411. © 2014 American Cancer Society.
Metabolites of 5F‐AKB‐48, a synthetic cannabinoid receptor agonist, identified in human urine and liver microsomal preparations using liquid chromatography high‐resolution mass spectrometry
Authors: Holm Niels Bjerre , Pedersen Anders Just , Dalsgaard Petur Weihe , Linnet Kristian
Published: May 2014

New types of synthetic cannabinoid designer drugs are constantly introduced to the illicit drug market to circumvent legislation. Recently, N‐​(1‐Adamant​yl)‐​1‐​(5‐​fluoropentyl)‐​1H‐​indazole‐​3‐​carboxamide (5F‐AKB‐48), also known as 5F‐APINACA, was identified as an adulterant in herbal products. This compound deviates from earlier JHW‐type synthetic cannabinoids by having an indazole ring connected to an adamantyl group via a carboxamide linkage. Synthetic cannabinoids are completely metabolized, and identification of the metabolites is thus crucial when using urine as the sample matrix. Using an authentic urine sample and high‐resolution accurate‐mass Fourier transform Orbitrap mass spectrometry, we identified 16 phase‐I metabolites of 5F‐AKB‐48. The modifications included mono‐, di‐, and trihydroxylation on the adamantyl ring alone or in combination with hydroxylation on the N‐fluoropentylindazole moiety, dealkylation of the N‐fluoropentyl side chain, and oxidative loss of fluorine as well as combinations thereof. The results were compared to human liver microsomal (HLM) incubations, which predominantly showed time‐dependent formation of mono‐, di‐, and trihydroxylated metabolites having the hydroxyl groups on the adamantyl ring. The results presented here may be used to select metabolites specific of 5F‐AKB‐48 for use in clinical and forensic screening. Copyright © 2014 John Wiley & Sons, Ltd.
The effect of frying on fat uptake and texture of fried potato products*
Authors: Kita Agnieszka
Published: May 2014

Fat uptake and the characteristic crispy and crunchy texture are the main quality parameters of fried potato products such as the most popular French fries and potato crisps. They are formed during the frying process and depend on different factors, among which frying oil properties and frying conditions were taken under investigation. Quality of frying oils as well as fatty acid composition and degree of degradation affect fat uptake and texture of fried potato products. Technological parameters such as frying temperature and frying conditions were also considered.

Practical applications: Factors affecting fat uptake and texture of fried potato products such as French fries and potato crisps are discussed. The kind and quality of frying medium as well as frying parameters (temperature, using vacuum) influence fat uptake and texture of fried products. Texture of fried potato products is correlated with fat content and composition of frying medium. Higher frying temperature decreases hardness of French fries and potato crisps, which exhibit more crispy and delicate texture in comparison with products fried at lower temperatures.
Syntheses and Photochromic Properties of Diarylethenes with a Naphthalene and a Thiophene Ring
Authors: Takeshita Michinori , Mizukami Erika , Murakami Kazuto , Wada Yuta , Matsuda Yuji
Published: May 2014

Two types of diarylethene, each of which contains a naphthalene and a thiophene ring, were synthesized, and their photochromic properties were studied. The photochromic properties are dependent on the bridge position of the thiophene ring. The cycloreversion of one of the closed forms of some of the diarylethenes occurred almost photon quantitatively, and the photochromic reactions were thermally irreversible, at least at room temperature.
Stereochemistry and Mechanism of Enzymatic and Non‐Enzymatic Hydrolysis of Benzylic sec‐Sulfate Esters
Authors: Toesch Michael , Schober Markus , Breinbauer Rolf , Faber Kurt
Published: May 2014

The substrate scope of inverting alkylsulfatase Pisa1 was extended towards benzylic sec‐sulfate esters by suppression of competing non‐enzymatic autohydrolysis by addition of dimethyl sulfoxide as co‐solvent. Detailed investigation of the mechanism of autohydrolysis in 18O‐labeled buffer by using an enantiopure sec‐benzylic sulfate ester as substrate revealed that from the three possible pathways (i) inverting SN2‐type nucleophilic attack of [OH–] at the benzylic carbon represents the major pathway, whereas (ii) SN1‐type formation of a planar benzylic carbenium ion leading to racemization was a minor event, and (iii) Retaining SN2‐type nucleophilic attack at sulfur took place at the limits of detection. The data obtained are interpreted by analysis of Hammett constants of meta substituents.
Surfactant‐based ionic liquids for extraction of phenolic compounds combined with rapid quantification using capillary electrophoresis
Authors: Huang Fangzhi , Berton Paula , Lu Chengfei , Siraj Noureen , Wang Chun , Magut Paul K. S. , Warner Isiah M.
Published: May 2014

A rapid liquid phase extraction employing a novel hydrophobic surfactant‐based room temperature ionic liquid (RTIL), tetrabutylphosphonium dioctyl sulfosuccinate ([4C4P][AOT]), coupled with capillary electrophoretic‐UV (CE‐UV) detection is developed for removal and determination of phenolic compounds. The long‐carbon‐chain RTIL used is sparingly soluble in most solvents and can be used to replace volatile organic solvents. This fact, in combination with functional‐surfactant‐anions, is proposed to reduce the interfacial energy of the two immiscible liquid phases, resulting in highly efficient extraction of analytes. Several parameters that influence the extraction efficiencies, such as extraction time, RTIL type, pH value, and ionic strength of aqueous solutions, were investigated. It was found that, under acidic conditions, most of the investigated phenols were extracted from aqueous solution into the RTIL phase within 12 min. Good linearity was observed over the concentration range of 0.1–80.0 μg/mL for all phenols investigated. The precision of this method, expressed as RSD, was determined to be within 3.4–5.3% range. The LODs (S/N = 3) of the method were in the range of 0.047–0.257 μg/mL. The proposed methodology was successfully applied to determination of phenols in real water samples.
Derivation of point of departure (PoD) estimates in genetic toxicology studies and their potential applications in risk assessment
Authors: Johnson G.E. , Soeteman‐Hernández L.G. , Gollapudi B.B. , Bodger O.G. , Dearfield K.L. , Heflich R.H. , Hixon J.G. , Lovell D.P. , MacGregor J.T. , Pottenger L.H. , Thompson C.M. , Abraham L. , Thybaud V. , Tanir J.Y. , Zeiger E. , van Benthem J. , White P.A.
Published: May 2014

Genetic toxicology data have traditionally been employed for qualitative, rather than quantitative evaluations of hazard. As a continuation of our earlier report that analyzed ethyl methanesulfonate (EMS) and methyl methanesulfonate (MMS) dose–response data (Gollapudi et al., 2013), here we present analyses of 1‐ethyl‐1‐nitrosourea (ENU) and 1‐methyl‐1‐nitrosourea (MNU) dose–response data and additional approaches for the determination of genetic toxicity point‐of‐departure (PoD) metrics. We previously described methods to determine the no‐observed‐genotoxic‐effect‐level (NOGEL), the breakpoint‐dose (BPD; previously named Td), and the benchmark dose (BMD10) for genetic toxicity endpoints. In this study we employed those methods, along with a new approach, to determine the non‐linear slope‐transition‐dose (STD), and alternative methods to determine the BPD and BMD, for the analyses of nine ENU and 22 MNU datasets across a range of in vitro and in vivo endpoints. The NOGEL, BMDL10 and BMDL1SD PoD metrics could be readily calculated for most gene mutation and chromosomal damage studies; however, BPDs and STDs could not always be derived due to data limitations and constraints of the underlying statistical methods. The BMDL10 values were often lower than the other PoDs, and the distribution of BMDL10 values produced the lowest median PoD. Our observations indicate that, among the methods investigated in this study, the BMD approach is the preferred PoD for quantitatively describing genetic toxicology data. Once genetic toxicology PoDs are calculated via this approach, they can be used to derive reference doses and margin of exposure values that may be useful for evaluating human risk and regulatory decision making. Environ. Mol. Mutagen. 55:609–623, 2014. © 2014 The Authors. Environmental and Molecular Mutagenesis Published by Wiley Periodicals, Inc.
Equilibrium, thermodynamic, and kinetic studies on some metal ions biosorption using black yeast Aureobasidium pullulans biomass
Authors: Ghaedi M. , Brazesh B. , Karimi F. , Ghezelbash G.R.
Published: May 2014

The bioremediation of Pb2+, Cu2+, Ni2+, and Co2+ ions onto Aureobasidium pullulans biomass was studied in batch procedure. The extents to which the experimental variables such as pH, contact time, stirring rate, and temperature affect the efficiency of biosorption were examined. The optimum values of pH (pH = 5), amount of biomass, and contact time (1 day) were found to be 5.0, 1 g, and 24 h, respectively. The equilibrium data were fitted to the Langmuir and Freundlich isotherm models. The Freundlich model showed better (q = 75–82 for different metal ions and R = 1) fit and thus it was more suitable for the interpretation of experimental equilibrium data for Pb2+, Cu2+, Ni2+, and Co2+ ions adsorption onto A. pullulans. The kinetic data at various contact time were analyzed by applying different models which showed that the biosorption process of metal ions onto A. pullulans biomass obeys the first order kinetics Pb2+ and for Co2+ ions while it obeys the second order kinetics for Cu2+ and Ni2+ ions. © 2014 American Institute of Chemical Engineers Environ Prog, 33: 769–776, 2014
Deletion of the MGMT gene in familial melanoma
Authors: Appelqvist Frida , Yhr Maria , Erlandson Anna , Martinsson Tommy , Enerbäck Charlotta
Published: May 2014

The DNA repair gene MGMT (O‐6‐methylguanine‐DNA methyltransferase) is important for maintaining normal cell physiology and genomic stability. Alterations in MGMT play a critical role in the development of several types of cancer, including glioblastoma, lung cancer, and colorectal cancer. The purpose of this study was to explore the function of genetic alterations in MGMT and their connection with familial melanoma (FM). Using multiplex ligation‐dependent probe amplification, we identified a deletion that included the MGMT gene in one of 64 families with a melanoma predisposition living in western Sweden. The mutation segregated with the disease as a heterozygous deletion in blood‐derived DNA, but a homozygous deletion including the promoter region and exon 1 was seen in tumor tissue based on Affymetrix 500K and 6.0 arrays. By sequence analysis of the MGMT gene in the other 63 families with FM from western Sweden, we identified four common polymorphisms, nonfunctional, as predominantly described in previous studies. We conclude that inherited alterations in the MGMT gene might be a rare cause of FM, and we suggest that MGMT contributes to melanoma predisposition. © 2014 Wiley Periodicals, Inc.
The Kabachnik–Fields Reaction Accelerated in External Magnetic Field
Authors: Karpowicz Rafał , Lewkowski Jarosław , Miękoś Ewa , Zieliński Marek
Published: May 2014

The significant acceleration in the Kabachnik–Fields reaction in an external magnetic field has been observed. The phenomenon is explained by the proper orientation of substrate molecules forced by external magnetic field. Diamagnetic dipoles are repulsed to the center by both electromagnet poles, being simultaneously arranged. This phenomenon may then promote the acceleration of the reaction.
Synthesis and Some Properties of Transition Metal Complexes Based on the Octathiophophetane Ammonium Salts
Authors: Kursheva Lidiya I. , Yanberdina Nadezhda V. , Zvereva Elena E. , Vandyukov Aleksandеr E. , Reisenauer Mary Rose , Lujan Jolene D. , Lebrun Robert W. , Edwards Leslie D. , Rogelj Snezna , Frolova Liliya V. , Batyeva Elvira S. , Sinyashin Oleg G.
Published: May 2014

Cyclic octathiotetraphosphetanes, and speciafically their ammonium salt, represent novel polyfunctional heterocyclic ligands that are valuable in the development of organometallic and coordinated chemistry. Coordination features of octathiotetraphosphetane ammonium salts with structures differing only by piperidine and triethylamine substituents in the reaction with transition d‐metals of I and VIII groups [Cu(I), Ag(I), Fe(II), Co(II)] are described. Some similarities and differences in the behavior of piperidinium and triethylammonium salts of the octathiotetraphosphetane upon complexation with metal halides are discussed.
Bromination of a Stable 1,2‐Bis(ferrocenyl)dibismuthene: Synthesis of a 1,2‐Dibromodibismuthane Derivative
Authors: Sasamori Takahiro , Sakagami Michiyasu , Tokitoh Norihiro
Published: May 2014

The bromination reaction of the stable bis(ferrocenyl)dibismuthene, Fc*Bi=BiFc* (1, Fc* = 2,5‐bis(3,5‐di‐t‐butylphenyl)ferrocenyl), with 0.5 equiv of BiBr3 resulted in the formation of the first stable 1,2‐dibromodibismuthane derivative, Fc*(Br)Bi–Bi(Br)Fc* (3). The structure of 3 was revealed by X‐ray crystallographic analysis, showing its unique structure with the bromine atom intramolecularly coordinating to the bismuth atom.
Comparison of interception, forest floor evaporation and transpiration in Pinus radiata and Eucalyptus globulus plantations
Authors: Benyon R. G. , Doody T. M.
Published: May 2014

Studies of evapotranspiration (ET) processes in forests often only measure one component of total ET, most commonly interception. This study examined all three components of annual ET (interception, evaporation from the forest floor and transpiration) and the correlations between them at 18 plantation forest sites in two species. All plantations had closed canopies, and sparse or no understorey. Single‐sided leaf area index averaged 3.5 (standard deviation ±0.5) in Eucalyptus globulus Labill. and 6.1 (±0.8) in Pinus radiata D.Don.

Measurements included annual totals of rainfall in the open and under the canopy, stem flow (four sites only), evaporation from the forest floor and transpiration by the overstorey. Interception (I) averaged 19% (±4.9) of annual rainfall in E. globulus compared with 31% (±11.1) in P. radiata. However, higher annual interception in P. radiata did not result in higher total ET because annual evaporation from the forest floor (E) averaged 29% (±4.9) of rainfall in E. globulus but only 15% (±3.5) in P. radiata. Hence, the relative contribution of annual I plus E to ET did not differ significantly between the two species, averaging 48% (±7.3) of annual rainfall in E. globulus compared with 46% (±11.8) in P. radiata. As reported previously, transpiration did not differ significantly between the two species either, but was strongly related to depth‐to‐groundwater. In closed canopy plantations, mean annual ET did not differ between the two species.

We conclude that when grown in plantations under similar soil and climatic conditions, conifer and broad‐leaved tree species can have similar annual ET, once the canopy of the plantation has closed. Lower average annual interception in broad‐leaved trees was offset by higher soil evaporation. These results highlight the importance of measuring all components of ET in studies of vegetation water use. Copyright © 2014 John Wiley & Sons, Ltd.
Biohydrogen Production from Textile Wastewater by Mixed Microflora in an Intermittent‐flow, Stirred Tank Reactor: Effect of Feeding Frequency
Authors: Lay Chyi‐How , Sen Biswarup , Kuo Szu‐Yu , Chen Chin‐Chao , Lin Chiu‐Yue
Published: May 2014

An intermittent‐flow, stirred tank reactor (IFSTR) was used to produce biohydrogen from textile wastewater (TW) by activated sludge. The IFSTR was operated at pH 5.5 under various feeding frequencies and TW concentrations. The first intermittent peak biogas production rate of 17.5 L biogas/L‐d and HPR of 10 L H2/L‐d were obtained at feeding frequency of 12 times/d with TW concentration of 33.1 g hexoses/L. Butyrate and acetate were the major soluble metabolites at peak HPR, whereas lactate and ethanol accumulation decreased the HPR. Close resemblance of bacterial communities in periods of peak HPR with hydrogen producer Clostridium butyricum was observed.
Synthesis, Characterization, and DNA Binding Studies of a Nickel(II) Complex Containing the 1,3‐Bis(1‐propylbenzimidazol‐2‐yl)‐2‐oxapropane
Authors: Wu Huilu , Shi Furong , Zhang Yanhui , Bai Yuchen , Wang Xiaoli , Kong Jin
Published: May 2014

A complex of formula [Ni(pobb)2](pic)2, (pobb = 1,3‐bis(1‐propylbenzimidazol‐2‐yl)‐2‐oxapropane, pic = 2,4,6‐trinitrophenol), has been synthesized and structurally characterized by physico‐chemical and spectroscopic methods. The crystals crystallize in the monoclinic system, space group C2/c, a = 25.766(11) Å, b = 14.943(7) Å, c = 19.543(14) Å, α = 90°, β = 129.722(4)°, γ = 90°, Z = 4. The coordination environment around nickel(II) atom can be described as a distorted octahedral geometry. The interactions of the ligand pobb and the nickel (II) complex with calf thymus DNA (CT‐DNA) are investigated by using electronic absorption titration, ethidium bromide‐DNA displacement experiments and viscosity measurements. The experimental evidence indicated the compounds interact with calf thymus DNA through intercalation.
Technology and New Fluorescence Flow Cytometry Parameters in Hematological Analyzers
Authors: Arneth Borros M. , Menschikowki Mario
Published: May 2014

Background

Modern hematological analyzers offer a series of new tests in addition to the differential blood cell count. Here, we provide a short overview of the technique and the new tests included in the hematological analyzers manufactured by the company Sysmex (Kobe, Japan). As introduced here, the resulting new extended blood cell count allows for the quantification of DNA‐ and RNA‐rich, activated and/or precursor leukocyte subpopulations.

Methods

To compare the different methods of blood cell counting, repetitive cell counting is carried out by hematological experts using microscopy and using the XE‐5000 hematological analyzer.

Results

The hematological analyzer delivers more‐accurate results with respect to normal cells but microscopy is suited better to recognize and count pathological cells.

Conclusion

With the new hematological analyzers, several new hematological tests are made available as screening tools that were not possible previously using standard cell‐counting procedures.