bluuebunny/crossref_metadata_2025 huggingface dataset:
Switchable Reconfiguration of an Interlocked DNA Olympiadane Nanostructure
Authors: Lu Chun‐Hua , Qi Xiu‐Juan , Cecconello Alessandro , Jester Stefan‐Sven , Famulok Michael , Willner Itamar
Published: May 2014

Interlocked DNA rings (catenanes) are interesting reconfigurable nanostructures. The synthesis of catenanes with more than two rings is, however, hampered, owing to low yields of these systems. We report a new method for the synthesis of catenanes with a controlled number of rings in satisfactory yields. Our approach is exemplified by the synthesis of a five‐ring DNA catenane that exists in four different configurations. By the use of nucleic acids as “fuels” and “antifuels”, the cyclic reconfiguration of the system across four states is demonstrated. One of the states, olympiadane, corresponds to the symbol of the Olympic Games. The five‐ring catenane was implemented as a mechanical scaffold for the reconfiguration of Au NPs. The advantages of DNA catenanes over supramolecular catenanes include the possibility of generating highly populated defined states and the feasibility of tethering nanoobjects to the catenanes, which act as a mechanical scaffold to reconfigure the nanoobjects.
Selektive Funktionalisierung von P4 durch Metall‐vermittelte Bildung einer C‐P‐Bindung
Authors: Heinl Sebastian , Reisinger Sabine , Schwarzmaier Christoph , Bodensteiner Michael , Scheer Manfred
Published: May 2014

Eine neue einstufige und selektive Synthese für den ersten Schritt der Aktivierung von weißem Phosphor wurde unter Verwendung organischer Radikale entwickelt. Die Reaktion von NaCpR mit P4 in Gegenwart von CuX oder FeBr3 führt zur direkten Bildung der organisch substituierten P4‐Butterfly‐Verbindungen CpR2P4 (CpR: CpBIG=C5(4‐nBuC6H4)5 (1 a), Cp′′′=C5H2tBu3 (1 b), Cp*=C5Me5 (1 c) und Cp4iPr=C5HiPr4 (1 d)). Die Reaktion verläuft über die Aktivierung von P4 mittels CpR‐Radikalen, die durch Übergangsmetallen erzeugt wurden. Die neu gebildeten organischen P4‐Derivate wurden durch NMR‐Spektroskopie und Röntgenstrukturanalyse umfangreich charakterisiert.
Carbon–Carbon Cross‐Coupling Reactions Catalyzed by a Two‐Coordinate Nickel(II)–Bis(amido) Complex via Observable NiI, NiII, and NiIII Intermediates
Authors: Lipschutz Michael I. , Tilley T. Don
Published: May 2014

Recently, the development of more sustainable catalytic systems based on abundant first‐row metals, especially nickel, for cross‐coupling reactions has attracted significant interest. One of the key intermediates invoked in these reactions is a NiIII–alkyl species, but no such species that is part of a competent catalytic cycle has yet been isolated. Herein, we report a carbon–carbon cross‐coupling system based on a two‐coordinate NiII–bis(amido) complex in which a NiIII–alkyl species can be isolated and fully characterized. This study details compelling experimental evidence of the role played by this NiIII–alkyl species as well as those of other key NiI and NiII intermediates. The catalytic cycle described herein is also one of the first examples of a two‐coordinate complex that competently catalyzes an organic transformation, potentially leading to a new class of catalysts based on the unique ability of first‐row transition metals to accommodate two‐coordinate complexes.
7‐Aryl‐7‐deazaadenine 2′‐Deoxyribonucleoside Triphosphates (dNTPs): Better Substrates for DNA Polymerases than dATP in Competitive Incorporations
Authors: Kielkowski Pavel , Fanfrlík Jindřich , Hocek Michal
Published: May 2014

A series of 7‐substituted 7‐deazaadenine and 5‐substituted cytosine 2′‐deoxyribonucleoside triphosphates (dNTPs) were tested for their competitive incorporations (in the presence of dATP and dCTP) into DNA by several DNA polymerases by using analysis based on cleavage by restriction endonucleases. 7‐Aryl‐7‐deazaadenine dNTPs were more efficient substrates than dATP because of their higher affinity for the active site of the enzyme, as proved by kinetic measurements and calculations.
Carbon Dioxide Sensitivity of Zeolitic Imidazolate Frameworks
Authors: Mottillo Cristina , Friščić Tomislav
Published: May 2014

Zeolitic imidazolate frameworks of zinc, cobalt, and cadmium, including the framework ZIF‐8 commercially sold as Basolite Z1200, exhibit surprising sensitivity to carbon dioxide under mild conditions. The frameworks chemically react with CO2 in the presence of moisture or liquid water to form carbonates. This effect, which has been previously not reported in metal–organic framework chemistry, provides an explanation for conflicting reports on ZIF‐8 stability to water and is of outstanding significance for evaluating the potential applications of metal–organic frameworks, especially for CO2 sequestration.
Elucidating Diphosphoinositol Polyphosphate Function with Nonhydrolyzable Analogues
Authors: Wu Mingxuan , Chong Lucy S. , Capolicchio Samanta , Jessen Henning J. , Resnick Adam C. , Fiedler Dorothea
Published: May 2014

The diphosphoinositol polyphosphates (PP‐IPs) represent a novel class of high‐energy phosphate‐containing messengers which control a wide variety of cellular processes. It is thought that PP‐IPs exert their pleiotropic effects as allosteric regulators and through pyrophosphorylation of protein substrates. However, most details of PP‐IP signaling have remained elusive because of a paucity of suitable tools. We describe the synthesis of PP‐IP bisphosphonate analogues (PCP‐IPs), which are resistant to chemical and biochemical degradation. While the two regioisomers 1PCP‐IP5 and 5PCP‐IP5 inhibited Akt phosphorylation with similar potencies, 1PCP‐IP5 was much more effective at inhibiting its cognate phosphatase hDIPP1. Furthermore, the PCP analogues inhibit protein pyrophosphorylation because of their inability to transfer the β‐phosphoryl group, and thus enable the distinction between PP‐IP signaling mechanisms. As such, the PCP analogues will find widespread applications for the structural and biochemical characterization of PP‐IP signaling properties.
Allenamides as Orthogonal Handles for Selective Modification of Cysteine in Peptides and Proteins
Authors: Abbas Ata , Xing Bengang , Loh Teck‐Peng
Published: May 2014

In this study, a remarkably simple and direct strategy has been successfully developed to selectively label target cysteine residues in fully unprotected peptides and proteins. The strategy is based on the reaction between allenamides and the cysteine thiol, and proceeds swiftly in aqueous medium with excellent selectivity and quantitative conversion, thus forming a stable and irreversible conjugate. The combined simplicity and mildness of the process project allenamide as robust and versatile handles to target cysteines and has potential use in biological systems. Additionally, fluorescent‐labeling studies demonstrated that the installation of a C‐terminal allenamide moiety onto various molecules of interest may supply a new methodology towards the site‐specific labeling of cysteine‐containing proteins. Such a new labeling strategy may thus open a window for its application in the field of life sciences.
Antagonizing STAT3 Dimerization with a Rhodium(III) Complex
Authors: Ma Dik‐Lung , Liu Li‐Juan , Leung Ka‐Ho , Chen Yen‐Ting , Zhong Hai‐Jing , Chan Daniel Shiu‐Hin , Wang Hui‐Min David , Leung Chung‐Hang
Published: May 2014

Kinetically inert metal complexes have arisen as promising alternatives to existing platinum and ruthenium chemotherapeutics. Reported herein, to our knowledge, is the first example of a substitutionally inert, Group 9 organometallic compound as a direct inhibitor of signal transducer and activator of transcription 3 (STAT3) dimerization. From a series of cyclometalated rhodium(III) and iridium(III) complexes, a rhodium(III) complex emerged as a potent inhibitor of STAT3 that targeted the SH2 domain and inhibited STAT3 phosphorylation and dimerization. Significantly, the complex exhibited potent anti‐tumor activities in an in vivo mouse xenograft model of melanoma. This study demonstrates that rhodium complexes may be developed as effective STAT3 inhibitors with potent anti‐tumor activity.
In situ processing of Nannochloropsis oculata algal biomass using a mixed bed ion‐exchange resin as a heterogeneous catalyst
Authors: Jamal Yousuf , Luo Guofan , Boulanger Bryan O.
Published: May 2014

Ion‐exchange resins have the ability to convert microalgae‐derived lipids into esters and other recoverable organics. The presented research evaluated the use of mixed bed ion‐exchange resins for in situ processing of Nannochloropsis oculata algal biomass to recoverable organics within a co‐solvent system. The impact of various processing conditions (resin loading, resin type, biomass drying, solvent type, solvent volume, and biomass sonication) on the reaction yield of recoverable organics was investigated. Multiple analytical chemical approaches were used to characterize lipids within the biomass and to identify the converted reaction products. Each reaction system studied produced more than 20 recoverable organics in addition to the normally desired ester products. Phytol was observed as predominant reaction product in each system. The highest ester yield (approaching 60% biomass lipid to ester conversion) was observed with air‐dried algae processed at 50 °C at a mixing rate of 550 rpm for 2 h. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
The quantification of reticulocyte maturation and neocytolysis in normal and erythropoietin stimulated rats
Authors: Wiczling Paweł , Krzyzanski Wojciech , Żychlińska Natalia , Lewandowski Krzysztof , Kaliszan Roman
Published: May 2014

A technique has recently been proposed for obtaining the reticulocyte (RET) age distribution from the flow cytometric reticulocyte count. It allows for a quantitative characterization of reticulocyte dynamics. In this work this technique was applied to characterize the blood, bone marrow and spleen reticulocytes in homeostatic and erythropoietically stimulated rats in order to determine the reticulocyte maturation times in the bone marrow and blood; and to confirm the presence of ineffective erythropoiesis (neocytolysis). The latter was done by comparing the reticulocyte removal rate from blood with bilirubin formation after erythropoiesis stimulation. A single subcutaneous dose (4050 IU/kg) of recombinant human erythropoietin (rHuEPO) was administered to rats, then their reticulocytes were stained with thiazole orange and the distribution of the fluorescent signal measured using flow cytometry. The obtained signal distribution of the reticulocytes was transformed to the age distribution and a set of basic parameters reflecting reticulocyte dynamics was determined. Bilirubin concentrations were measured to directly assess the presence of reticulocyte irreversible removal. The bilirubin formation was found to be considerably modulated by rHuEPO and corresponded well to the determined reticulocyte removal rate. The initial increase and subsequent decrease of the reticulocyte maturation time in blood was quantitated and directly linked with RET mobilization from the bone marrow. A substantial number (60%) of reticulocytes is sequestrated during homeostasis in rats. This number increases and then decreases after rHuEPO administration, as also reflected by bilirubin formation. Flow cytometry seems to be an excellent method for studying RET dynamics and the presence of young RBC neocytolysis. Copyright © 2014 John Wiley & Sons, Ltd.
Highly Active and Recyclable Metal Oxide Catalysts for the Prins Condensation of Biorenewable Feedstocks
Authors: Costa Vinícius V. , Bayahia Hossein , Kozhevnikova Elena F. , Gusevskaya Elena V. , Kozhevnikov Ivan V.
Published: May 2014

Metal oxides such as Nb2O5, Cr2O3, and especially a ZnIICrIII mixed oxide are demonstrated to be highly active and recyclable heterogeneous catalysts for Prins condensation, which provides a clean, high‐yielding route for the synthesis of nopol through the condensation of biorenewable β‐pinene with paraformaldehyde. ZnCr mixed oxide with an optimum Zn/Cr atomic ratio of 1:6 gave 100 % nopol selectivity at 97 % β‐pinene conversion, with the catalyst easily recovered and recycled. The acid properties of Nb2O5 and ZnCr mixed oxide were characterized by the diffuse reflectance IR Fourier transform spectroscopy of adsorbed pyridine and ammonia adsorption microcalorimetry. An appropriate combination of acid–base properties of ZnCr mixed oxide is believed to be responsible for its efficiency.
Pillar[5]arene‐Mediated Synthesis of Gold Nanoparticles: Size Control and Sensing Capabilities
Authors: Montes‐García Verónica , Fernández‐López Cristina , Gómez Borja , Pérez‐Juste Ignacio , García‐Río Luis , Liz‐Marzán Luis M. , Pérez‐Juste Jorge , Pastoriza‐Santos Isabel
Published: May 2014

We present a simple procedure for the synthesis of quasi‐spherical Au nanoparticles in a wide size range mediated by macrocyclic host molecules, ammonium pillar[5]arene (AP[5]A). The strategy is based on a seeded growth process in which the water‐soluble pillar[5]arene undergoes complexation of the Au salt through the ammonium groups, thereby avoiding Au nucleation, while acting as a stabilizer. The presence of the pillar[5]arene onto the Au nanoparticle particle surface is demonstrated by surface‐enhanced Raman scattering (SERS) spectroscopy, and the most probable conformation of the molecule when adsorbed on the Au nanoparticles surface is suggested on the basis of theoretical calculations. In addition, we analyze the host–guest interactions of the AP[5]A with 2‐naphthoic acid (2NA) by using 1H NMR spectroscopy and the results are compared with theoretical calculations. Finally, the promising synergetic effects of combining supramolecular chemistry and metal nanoparticles are demonstrated through SERS detection in water of 2NA and a polycyclic aromatic hydrocarbon, pyrene (PYR).
Two C3‐Symmetric Dy3III Complexes with Triple Di‐μ‐methoxo‐μ‐phenoxo Bridges, Magnetic Ground State, and Single‐Molecule Magnetic Behavior
Authors: Hänninen Mikko M. , Mota Antonio J. , Aravena Daniel , Ruiz Eliseo , Sillanpää Reijo , Camón Agustín , Evangelisti Marco , Colacio Enrique
Published: May 2014

Two series of isostructural C3‐symmetric Ln3 complexes Ln3⋅[BPh4] and Ln3⋅0.33[Ln(NO3)6] (in which LnIII=Gd and Dy) have been prepared from an amino‐bis(phenol) ligand. X‐ray studies reveal that LnIII ions are connected by one μ2‐phenoxo and two μ3‐methoxo bridges, thus leading to a hexagonal bipyramidal Ln3O5 bridging core in which LnIII ions exhibit a biaugmented trigonal‐prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self‐consistent field (CASSCF) calculations indicate that the magnetic coupling between the DyIII ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To reduce the electronic repulsion from the coordinating oxygen atom with the shortest DyO distance, the local magnetic moments are oriented almost perpendicular to the Dy3 plane, thus leading to a paramagnetic ground state. CASSCF plus restricted active space state interaction (RASSI) calculations also show that the ground and first excited state of the DyIII ions are separated by approximately 150 and 177 cm−1, for Dy3⋅[BPh4] and Dy3⋅0.33[Dy(NO3)6], respectively. As expected for these large energy gaps, Dy3⋅[BPh4] and Dy3⋅0.33[Dy(NO3)6] exhibit, under zero direct‐current (dc) field, thermally activated slow relaxation of the magnetization, which overlap with a quantum tunneling relaxation process. Under an applied Hdc field of 1000 Oe, Dy3⋅[BPh4] exhibits two thermally activated processes with Ueff values of 34.7 and 19.5 cm−1, whereas Dy3⋅0.33[Dy(NO3)6] shows only one activated process with Ueff=19.5 cm−1.
Phosphorus Centers of Different Hybridization in Phosphaalkene‐Substituted Phospholes
Authors: Öberg Elisabet , Orthaber Andreas , Lescop Christophe , Réau Régis , Hissler Muriel , Ott Sascha
Published: May 2014

Phosphole‐substituted phosphaalkenes (PPAs) of the general formula Mes*PC(CH3)(C4H2P(Ph))R 5 a–c (Mes*=2,4,6‐tBu3Ph; R=2‐pyridyl (a), 2‐thienyl (b), phenyl (c)) have been prepared from octa‐1,7‐diyne‐substituted phosphaalkenes by utilizing the Fagan–Nugent route. The presence of two differently hybridized phosphorus centers (σ2,λ3 and σ3,λ3) in 5 offers the possibility to selectively tune the HOMO–LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of 5 a–c by sulfur proceeds exclusively at the σ3,λ3‐phosphorus atom, thus giving rise to the corresponding thioxophospholes 6 a–c. Similarly, 5 a is selectively coordinated by AuCl at the σ3,λ3‐phosphorus atom. Subsequent second AuCl coordination at the σ2,λ3‐phosphorus heteroatom results in a dimetallic species that is characterized by a gold–gold interaction that provokes a change in π conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO–LUMO gap relative to reference phosphole‐containing π systems that lack a PC substituent.
“Click” Chemistry Mildly Stabilizes Bifunctional Gold Nanoparticles for Sensing and Catalysis
Authors: Li Na , Zhao Pengxiang , Liu Na , Echeverria María , Moya Sergio , Salmon Lionel , Ruiz Jaime , Astruc Didier
Published: May 2014

A large family of bifunctional 1,2,3‐triazole derivatives that contain both a polyethylene glycol (PEG) chain and another functional fragment (e.g., a polymer, dendron, alcohol, carboxylic acid, allyl, fluorescence dye, redox‐robust metal complex, or a β‐cyclodextrin unit) has been synthesized by facile “click” chemistry and mildly coordinated to nanogold particles, thus providing stable water‐soluble gold nanoparticles (AuNPs) in the size range 3.0–11.2 nm with various properties and applications. In particular, the sensing properties of these AuNPs are illustrated through the detection of an analogue of a warfare agent (i.e., sulfur mustard) by means of a fluorescence “turn‐on” assay, and the catalytic activity of the smallest triazole–AuNPs (core of 3.0 nm) is excellent for the reduction of 4‐nitrophenol in water.
Sequential Hydroformylation/Diels–Alder Processes: One‐Pot Synthesis of Polysubstituted Cyclohexenes, Cyclohexadienes, and Phthalates from Alkynes
Authors: Fang Xianjie , Jackstell Ralf , Beller Matthias
Published: May 2014

A novel, one‐pot hydroformylation/Diels–Alder sequence for the synthesis of multisubstituted cyclohexenes, cyclohexadienes, and phthalates has been developed. Various alkynes were efficiently converted into the corresponding products in good yields and with excellent diastereoselectivity through palladium‐catalyzed hydroformylation followed by an AAD‐type reaction (AAD: Amides–Aldehydes–Dienophiles). In view of the availability of the substrates, the atom‐efficiency of the overall process, and the convenient introduction of substituents in the cyclohexene ring, this method complements current methods for the preparation of polysubstituted cyclohexane derivatives.
Electrophilic Trifluoromethylthiolation of Carbonyl Compounds
Authors: Alazet Sébastien , Zimmer Luc , Billard Thierry
Published: May 2014

A general method for the α‐trifluoromethylthiolation of carbonyl compounds, without prefunctionalization, has been developed. Aldehydes, ketones, esters, amides, keto‐esters, alkaloids, and steroids have been trifluoromethylthiolated with good yields. This work, proposing a new reagent for electrophilic trifluoromethylthiolation, provides a route towards the original synthesis of various trifluoromethylthiolated molecules for further applications.
Rapeseed Proteins for Paperboard Coating
Authors: Oviedo Jesus Palomino , Metz Robert , Schulz John , Tressel Ralf‐Peter , Pudel Frank
Published: May 2014

Protein samples of rapeseed were prepared with different compositions as protein isolate, protein concentrate and acetylated protein concentrate. They showed functional properties which are consolidated in the coating. The manufactured protein samples were tested in a pilot‐scale paperboard coating plant. The results indicated that the use of rapeseed proteins in the coating preparation is technically feasible and that the color and roughness of the coated paperboard show no negative effect on the quality. Industry printing experiments with this coated paperboard achieved the standard quality.
Orbital Effect‐Induced Anomalous Anion–π Interactions between Electron‐Rich Aromatic Hydrocarbons and Fluoride
Authors: Shi Guosheng , Yang Jinrong , Ding Yihong , Fang Haiping
Published: May 2014

Anion–π interactions generally exist between an anion and an electron‐deficient π‐ring because of the electron‐accepting character of the ring. In this paper, we report orbital effect‐induced anomalous binding between electron‐rich π systems and F− through anion–π interactions calculated at the MP2/6‐31+G(d,p) and ωB97X‐D/6‐31+G(d,p) levels of theory. We find that anion–π interactions between F− and electron‐rich π rings increase markedly with increasing number of π electrons and size of the π rings. This is contrary to intuition because anion–π interactions would be expected to gradually decrease because of gradually increasing Coulombic repulsion between the negative charge of the anions and gradually increasing number of π electrons of the aromatic surfaces. Energy decomposition analysis showed that the key to this anomalous effect is the more effective delocalization of negative charge to the unoccupied π* orbitals of larger π rings, which is termed an “orbital effect”.
Ab Initio Study on the Stability of NgnBe2N2, NgnBe3N2and NgBeSiN2Clusters
Authors: Pan Sudip , Moreno Diego , Cabellos José Luis , Merino Gabriel , Chattaraj Pratim K.
Published: May 2014

The global minima of Be2N2, Be3N2and BeSiN2clusters are identified using a modified stochastic kick methodology. The structure, stability and bonding nature of these clusters bound to noble gas (Ng) atoms are studied at the MP2/def2‐QZVPPD level of theory. Positive BeNg bond dissociation energy, which gradually increases down Group 18 from He to Rn, indicates the bound nature of Ng atoms. All of the Ng‐binding processes are exothermic in nature. The Xe and Rn binding to Be2N2and Be3N2clusters and ArRn binding to BeSiN2are exergonic processes at room temperature; however, for the lighter Ng atoms, lower temperatures are needed. Natural population analysis, Wiberg bond index computations, electron density analysis, and energy decomposition analysis are performed to better understand the nature of BeNg bonds.
Renormalization group approach to 1D cellular automata with large updating neighborhoods
Authors: Weaver Iain S. , Prügel‐Bennett Adam
Published: May 2014

We study self‐similarity in one‐dimensional probabilistic cellular automata (PCA) by applying a real‐space renormalization technique to PCA with increasingly large updating neighborhoods. By studying the flow about the critical point of the renormalization, we may produce estimates of the spatial scaling properties of critical PCA. We find that agreement between our estimates and experimental values are improved by resolving correlations between larger blocks of spins, although this is not sufficient to converge to experimental values. However, applying the technique to PCA with larger neighborhoods, and, therefore, more renormalization parameters, results in further improvement. Our most refined estimate produces a spatial scaling exponent, found at the critical point of the five‐neighbor PCA, of ν = 1.056 which should be compared to the experimental value of ν = 1.097. © 2014 Wiley Periodicals, Inc. Complexity 21: 206–213, 2015
Climate Change Agenda at Subnational Level in Mexico: Policy coordination or policy competition?
Authors: Valenzuela Jose Maria
Published: May 2014

The paper analyses the political challenges and opportunities of advancing the climate change agenda in a developing country under constraints and channels imposed by divided authority at the vertical level and political fragmentation within the state. The articles focuses on historical and political institutional arrangements to approach the current framework of climate change agenda‐setting in Mexico, later analysing the potential changes to the outcomes due to the influence of an international climate change regime. On the one hand, the literature suggests that federalism poses serious limitations to government efficacy due to division of competences, and a similar argument is posed about presidentialism under a politically fragmented regime; on the second hand, transnationalism is depicted to enhance subnational state and non‐state actor leadership roles in many areas, including economic and environmental policy setting. Evidence shows that federalism and the political fragmentation of the presidential regime in Mexico has prevented the federal government from taking assertive steps to influence subnational governments, while some of the heads of politically relevant subnational governments have assumed policy leadership roles, enabled by transnational networks and the Kyoto climate change regime. This balance may change according to the nature of the post‐Kyoto regime, either strengthening the federal government if more responsibility on actions and disbursement is placed on national governments; or enabling subnational government to foster their position, if decentralized and transnational networks are strengthened. Copyright © 2014 John Wiley & Sons, Ltd and ERP Environment
Consumer discrimination of Chemlali and Arbequina olive oil cultivars according to their cultivar, geographical origin, and processing system
Authors: Hassine Kaouther Ben , El Riachy Milad , Taamalli Amani , Malouche Dhafer , Ayadi Mohamed , Talmoudi Khouloud , Aouini Maroua , Jlassi Yosra , Benincasa Cinzia , Romano Elvira , Perri Enzo , Kiristakis Apostolos , Hamdi Mokhtar , Grati‐Kammoun Naziha , Hammami Mohamed
Published: May 2014

The chemical composition and consumer preferences according to consumer characteristics of virgin olive oils (VOOs) from “Chemlali” and “Arbequina” cultivars were studied in relation to processing system and geographical origin. Statistical analyses revealed significant differences (p < 0.05) among cultivars in % free acidity, K270, and OSI values, pigments, and antioxidant content and in some FAME content. Significant differences were also found according to the processing system in terms of some quality indices, pigments, antioxidant compounds, and OSI values. The effect of processing system on fatty acid composition was almost not significant except for some of them. The effect of the geographical origin was different in relation to the cultivars: For “Chemlali” cultivar, it was significant (p < 0.05) in all studied parameters except for acidity and total polar phenol content. However, for “Arbequina”, the effect was significant (p < 0.05) for K232, pigments, antioxidant compounds and fatty acid composition except for margaric, margaroleic, linolenic, arachidic, and behenic fatty acids. Consumers were able to discriminate between cultivars with more preference for “Arbequina” oil, but only in case of “Chemlali” they could discriminate between the oils from different locations, with significantly more consumer liking for oils from Sidi Bouzid and Sawef. However, they were not able to discriminate between the processing systems.

A session of sensory analysis that shows consumer preferences according to consumer characteristics. Consumer preferences are defined as the subjective (individual) tastes and flavors, as measured by the satisfaction that a consumer derives from the consumption of different goods, in this study, the Virgin Olive Oil (VOO). VOO sensory analysis permits the consumer to rank the different oils according to the levels of satisfaction they give the consumer.
Contribution to the aroma characteristics of mutton process flavor from oxidized suet evaluated by descriptive sensory analysis, gas chromatography, and electronic nose through partial least squares regression
Authors: Tian Honglei , Zhan Ping , Li Weiguo , Zhang Xiaoming , He Xiaoyan , Ma Yongguang , Guo Zhili , Zhang Deqing
Published: May 2014

Changes in the aroma characteristics of mutton process flavors (MFSs) prepared from non‐oxidized suet and oxidized suet (OS) of different oxidation degrees were assessed by GC–MS, descriptive sensory analysis (DSA), and electronic nose (E‐nose). Six sensory attributes (muttony, meaty, suety, simulate, burnt, and off‐flavor) were selected to assess MFSs. DSA results showed a distinct difference among the sample MFS1 with non‐oxidized suet and other MFS samples with added OS of different oxidation degrees in terms of almost all sensory attributes. Also, MFS4 and MFS5 with moderate OS4 and OS5 showed very strong muttony, meaty, suety, and simulate attributes, but the weakest burnt and off‐flavor attributes. GC–MS analysis of volatiles indicated that MFS5, which had moderate OS5, generated a more appropriate content proportion of the characteristic flavor compounds than the others. Moreover, E‐nose analysis confirmed the results of GC–MS and DSA. Results of correlation analysis among 19 selected odor‐active compounds, DSA, and E‐nose data further confirmed that the moderate OS with a peroxide value (PV) of 103.29–287.61 meqO2 kg−1, the p‐anisidine value (p‐AV) of 61.03–262.52, and the acid value (AV) of 1.98–5.11 mg KOH/g suet may be a desirable precursor for the sensory characteristics of MFS.

Species‐species mutton flavor can be enhanced by heating suet in air through the coordination of Maillard reaction and lipid oxidation. Through the partial least squares regression analysis of the descriptive sensory analysis data, odor‐active compounds and E‐nose data, moderate oxidized suet was recommended for preparing mutton process flavors.
Crude canolol and canola distillate extracts improve the stability of refined canola oil during deep‐fat frying
Authors: Aachary Ayyappan Appukuttan , Chen Yougui , Eskin N. A. Michael , Thiyam‐Hollander Usha
Published: May 2014

Crude canolol (CAN) extracted from canola meal by accelerated solvent extraction and phenolic extracts from canola oil deodistillates (DDL) were assessed for their potential to stabilize canola oil during deep‐fat frying. Phenolics extracted from DDL with methanol ranged from 0 to 323 μg/g of DDL phenolics. French fries were deep fried in canola oil (3 L) enriched with 200 ppm of BHT, DDL, or CAN at 185 ± 5°C for 5 min. Twelve batches of fries (30 g each) were fried each day, 30 min apart for a total of 6 h of frying for 5 days. Both CAN and DDL extracts exhibited protection against frying oil deterioration compared to BHT with a considerable reduction in the hydroperoxides after the first day of frying. The ability to reduce primary oxidation was highest with CAN followed by DDL compared to BHT and the control (CAN>DD>Control). The total oxidation (TOTOX) and conjugated diene/triene values of oils fried with DDL and CAN were significantly (p<0.05) lower than BHT. Oil color correlated with AV (R2 = 0.822–0.985) in an exponential model with no major differences as compared to the control. In conclusion, based on the initial PV, TOTOX, and conjugated dienes, DDL and CAN both proved effective in inhibiting lipid oxidation during deep‐fat frying.

Practical applications: Oil deodistillate is an excellent starting material for the production/recovery of a variety of bioactive components such as tocopherols, phenolics, phytosterols, or squalene. The present study confirms the beneficial effects of canolol and DDL phenolic extracts as antioxidants during the deep‐fat frying of canola oil. DDL is an abundant oil‐refining by‐product and this study demonstrates the value‐added potential of DDL as a crude source of phenolic antioxidants. This will provide new avenues for the value‐added opportunities due to their potent antioxidants. In contrast to the commonly applied synthetic antioxidants, the phenolic extracts tested in this study are part of endogenous oil components either removed from crude oil during refining (DDL) or produced during oil extraction process (canolol).

Crude canolol and deodistillate (DDL) extracts protects canola oil from oxidative deterioration during deep‐frying at 185°C. The protective effect of crude DDL extracts and canolol extracts as indicated from the total oxidation (TOTOX) value of oils indicates potential for value‐addition of DDL.
Arsenolipids in commercial canned cod liver: An occurrence and distribution study
Authors: Arroyo‐Abad Uriel , Mattusch Jürgen , Reemtsma Thorsten , Piechotta Christian
Published: May 2014

Arsenolipids (AsL) of the type arsenic‐containing fatty acids (AsFA) and hydrocarbons (AsHC) are known to occur in seafood and their identification is today a challenge due to the need of data for toxicological assessment. The aim of this investigation was to enhance the data concerning AsL in commercial canned cod liver. Therefore, the present study focuses on the quantification and identification of AsL by LC–ICP‐MS combined with ESI‐MS. The molecular structure of 17 AsL was elucidated on the basis of their exact mass and their product ion spectra and two new AsFA tentatively identified. The total arsenic concentration in four different canned cod liver analyzed by ICP‐MS ranged from 2.6 to 5.5 mg As/kg with an extraction recovery of 98%. The AsL detected by RP‐IPC–MS comprise 58–95% of the total arsenic content, indicating that AsL are a major class of arsenic in canned cod liver. Much of the AsL detected in the canned cod liver extracts are, however, not yet identified.

Practical applications: The results obtained in the present research show the possibility to apply the current extraction and detection method in different biological samples for the determination of AsL. Additionally, this information can be used for further studies to assess the risk of AsL for consumer health. On the other hand, the MS/MS results could be used for the future identification of AsL without the ICP‐MS detection and thus, low the cost of the analysis.

Numerous arsenolipids (AsL) were detected and identified by HPLC hyphenated online with ICP‐MS (element specific detection) and ESI‐Q‐TOF‐MS (molecular structure detection) in commercial canned cod liver. ESI‐MS and ESI‐MS/MS spectra confirmed the proposed molecular structure of two new AsL of the type arsenic‐containing fatty acid identified for the first time in this study.
Geophysical Evaluation of the Richland and Holloway Mounds, Southeastern Louisiana, USA
Authors: Keenan Sarah W. , Ellwood Brooks B.
Published: May 2014

The Mississippi River Valley contains some of the earliest records of Native American earthwork construction, extending back ∼6000 years. Louisiana contains over 700 mounds of cultural significance, most of which have not been examined, leaving significant gaps in our understanding of mound usage in this region. Using geophysical techniques, including magnetic susceptibility (MS) and electrical resistivity, the Richland (16WF183) and Holloway (16TA32) Mounds were examined for anomalies or subsurface features. Based on sediment coring and electrical resistivity profiling across the surface, MS and apparent resistivity (ρa) data are well correlated within each mound, and anomalous ρa zones were identified. The Richland and Holloway Mounds differ markedly in the preserved magnetic features: Richland contained an extensive anomalous area, while Holloway contained two distinct and isolated anomalies. Overall morphology and mound preservation, combined with ρa and MS data, suggest a potential burial or remnants of a burial within Holloway. Richland did not contain evidence of subsurface archaeological material, although there may be fired horizons at depth. A combination of minimally destructive and noninvasive geoarchaeological techniques permitted characterization of these sites without significantly altering site context, expanding upon the limited description of mounds in Louisiana, and provides a framework for future studies at these sites.
Reply to Comment on “Analyses of Seismic Deformation at the Kibyra Roman Stadium, Southwest Turkey”
Authors: Karabacak Volkan , Yönlü Önder , Dökü Eray , Kıyak Nafiye Günenç , Altunel Erhan , Özüdoğru Şükrü , Yalçıner Cahit Çağlar , Akyüz Hüsnü Serdar
Published: May 2014

In their comment, Elitez and Yaltırak (2013) criticize our paper (Karabacak et al. ) by arguing that it contains misinterpretations and unreliable data for a fault cutting the Roman Stadium in the ancient city of Kibyra. However their comments are not based on strong arguments to disprove our geological and archeological field observations or previous data. Here we present additional data supported by new figures which validate the faulting both in the bedrock and in the stadium floor. We reject their comments and uphold our original viewpoint on the faulting at the Stadium.
The influence of medical cost controls implemented by Taiwan's national health insurance program on doctor–patient relationships
Authors: Chiu Jhih‐Ling
Published: May 2014

To prevent medical costs from rising, the National Health Insurance administration implemented the global budget system for financial reform, effective 1 July 2004. Since the implementation of this system, patients have been required to pay for some medicines to limit costs to the system. More recently, as they have faced constant increases in health insurance fees and also faced an increase in the number of medical expenses they must pay during an economic recession and a rise in unemployment, would the economic burden on the people of Taiwan not be increased? Even though National Health Insurance is a form of social insurance, does it guarantee social equality? The value of the healthcare industry is irreplaceable, so the most critical concern is whether worsening doctor–patient relationships will worsen healthcare quality. In short, while the global budget system saves on National Health Insurance costs, whether its implementation has affected healthcare quality is also worth exploring. This commentary also hopes to serve as a reference for the implementation of national health insurance in the United States. Copyright © 2014 John Wiley & Sons, Ltd.
Characterization and Functional Analysis of Voltage‐Dependent Anion Channel 1 (VDAC1) from Orange‐Spotted Grouper (Epinephelus coioides)
Authors: Shi Yan , Zhao Zhe , Hong Xiaoyou , Chen Kunci , Zhu Xinping
Published: May 2014

The voltage‐dependent anion channel (VDAC) is a highly conserved integral protein of mitochondria in different eukaryotic species. It forms a selective channel in the mitochondrial outer membrane that serves as the controlled pathway for small metabolites and ions. In this study, a VDAC gene, EcVDAC1, was isolated from orange‐spotted grouper (Epinephelus coioides). The EcVDAC1 exhibits ubiquitous expression in various tissues of orange‐spotted grouper and is upregulated in liver, gill, and spleen after stimulation with lipopolysaccharides (LPS). Subcellular localization analysis shows that the EcVDAC1 protein colocalized with the mitochondria. A caspase‐3 assay demonstrates that overexpression of the EcVDAC1 induced apoptotic cell death in fathead minnow cells. The data presented in this study provide new information regarding the relationship between LPS and the EcVDAC1 gene, suggesting that the fish VDAC1 gene may play an important role in antibacterial immune response.
Vascular resection during radical resection of pancreatic adenocarcinomas: evolution over the past 15 years
Authors: Ouaïssi Mehdi , Turrini Olivier , Hubert Catherine , Louis Guillaume , Gigot Jean‐François , Mabrut Jean‐Yves
Published: May 2014

This literature review aimed to critically analyze oncological results of vascular resection during pancreatectomy for adenocarcinoma in the light of the concept evolution of locally advanced tumors and microscopic complete resection. The literature search was conducted in PubMed and Medline for the period June 1994 to December 2012, retaining English as the language of publication. The review of 12 publications indicated that mortality and morbidity rates were not significantly different for pancreatectomy with or without venous resection (VR). Six comparative studies showed worse long‐term survival in the VR group, though one meta‐analysis, albeit with a significant population heterogeneity, demonstrated that the overall survival between VR and the control group was similar (12% vs. 17%). The compilation of 13 comparative studies showed a significantly lower rate of complete microscopic resection in the VR patient group compared to controls (63% vs. 77%; P = 0.001). Concerning pancreatectomy combined to arterial resection, the literature review indicated a significantly greater mortality and morbidity rate and a lower survival rate compared to pancreatic resection alone. Conflicting results concerning the long‐term outcome of VR was due to the heterogeneity of the patient population. Since the only chance to cure patients of pancreatic adenocarcinoma is to obtain free resection margins, VR is a valid therapeutic option. But combined arterial resection to pancreatic resection does not appear to be recommended.
An apposition‐like compound eye with a layered rhabdom in the small diving beetle Agabus japonicus (Coleoptera, Dytiscidae)
Authors: Jia Lei‐Po , Liang Ai‐Ping
Published: May 2014

The fine structure of the compound eyes of the adult diving beetle Agabus japonicus is described with light, scanning, and transmission electron microscopy. The eye of A. japonicus is mango‐shaped and consists of about 985 ommatidia. Each ommatidium is composed of a corneal facet lens, an eucone type of crystalline cone, a fused layered rhabdom with a basal rhabdomere, seven retinula cells (including six distal cells and one basal cell), two primary pigment cells and an undetermined number of secondary pigment cells that are restricted to the distalmost region of the eye. A clear‐zone, separating dioptric apparatus from photoreceptive structures, is not developed and the eye thus resembles an apposition eye. The cross‐sectional areas of the rhabdoms are relatively large indicative of enhanced light‐sensitivity. The distal and central region of the rhabdom is layered with interdigitating microvilli suggesting polarization sensitivity. According to the features mentioned above, we suggest that 1) the eye, seemingly of the apposition type, occurs in a taxon for which the clear‐zone (superposition) eye is characteristic; 2) the eye possesses adaptations to function in a dim‐light environment; 3) the eye may be sensitive to underwater polarized light or linearly water‐reflected polarized light. J. Morphol. 275:1273–1283, 2014. © 2014 Wiley Periodicals, Inc.
Identification of endolithic traces on stone monuments and natural outcrops: preliminary evidences
Authors: Casanova Municchia A. , Caneva G. , Ricci M. A. , Sodo A.
Published: May 2014

Four different lithotypes of rock gathered from stone monuments and natural outcrops in Temperate and Mediterranean bioclimates, with endolithic microorganism colonization (cyanobacteria, fungi, and lichens), have been analysed by Raman spectroscopy. Endolithic microorganisms can penetrate actively into the rocks giving rise to biodeterioration phenomena. Often the biological origin of these deterioration phenomena is not recognized and confused with abiotic damages. The aim of this work is to identify by Raman spectroscopy the endolithic traces on stones, due to current or past biological colonization. The Raman spectra show the presence of bio‐markers characteristic of the strategy adopted by microorganisms against strong UV‐radiation and dry conditions, such as scytonemin, anthraquinone compounds, and carotenoids. Moreover, we have identified different geo‐markers such as goethite and lepidocrocite because of the mobilization of iron by lichen metabolic activity. Importantly, we have identified for the first time by Raman spectroscopy, traces of endolithic microorganisms on stone monuments located in Temperate and Mediterranean bioclimate, where extreme climate conditions are not foreseen. Copyright © 2014 John Wiley & Sons, Ltd.
Surgical outcomes in the elderly patient after osteocutaneous free flap transfer
Authors: Weaver Tyler S. , Wester Jacob L. , Gleysteen John P. , Peck Jessica J. , Wax Mark K.
Published: May 2014

Objectives/Hypothesis

Morbidity of free tissue transfer in the elderly patient is controversial. Recent studies have shown no significant difference in elderly fasciocutaneous free‐flap donor site morbidity. The purpose of this study is to assess surgical outcomes in elderly patients receiving osteocutaneous free‐tissue transfer.

Study Design

Retrospective chart review of patients 70 years and older undergoing osteocutaneous free flaps from 2000 to 2013.

Methods

Fibular, radial forearm, and scapular flaps were reviewed. Younger patients randomly selected from the same time period served as controls. Data collected included donor site morbidity, flap complications, feeding tube and tracheostomy dependence, and hospital stay.

Results

Forty‐four osteocutaneous free flaps were performed in elderly patients. Overall, there was no significant difference in donor site morbidity between older and younger patients (P = 0.50) (tendon exposure, P = 1.00; split‐thickness skin graft loss, P = 0.36; infections, P = 0.52; dehiscence, P = 1.00; and seroma, P = 1.00). There was no significant difference between older and younger patients being decannulated (P = 0.61) or the time to decannulation (P = 0.24). There was no difference in those who returned to baseline diet (P = 0.67). All patients returned to baseline ambulatory and shoulder status. Length of postoperative hospitalization (P = 0.78) and intensive care unit stay (P = 0.94) were also equal. The only significant difference was that more elderly patients were discharged to skilled nursing facilities (SNF) (40.9% vs. 15.9%, P < 0.01).

Conclusion

Elderly patients undergoing free tissue transfer have similar flap and donor site outcomes, feeding tube and tracheostomy outcomes, ambulatory status, and hospital stays compared to younger patients. They are, however, more likely to require SNF care posthospitalization.

Level of Evidence

4. Laryngoscope, 124:2484–2488, 2014
Prostaglandin E1 alleviates neuropathic pain and neural dysfunction from entrapment neuropathy associated with diabetes mellitus
Authors: Natsume Tadahiro , Iwatsuki Katsuyuki , Nishizuka Takanobu , Arai Tetsuya , Yamamoto Michiro , Hirata Hitoshi
Published: May 2014

In this report, we present the results of investigation of the effects of prostaglandin E1 (PGE1) on entrapment neuropathy using a diabetic rat. A total of 60 male Sprague‐Dawley rats were used in the study. The model of tibial nerve entrapment neuropathy associated with diabetes mellitus was created by streptozotocin‐induced diabetic rats reared in cages with wire grid flooring. Rats were assigned to four groups: nondiabetic (n = 15), untreated diabetic (n = 15), diabetic treated with 30 μg/kg PGE1 (n = 15), and diabetic treated with 100 μg/kg PGE1 (n = 15). Pain tests and electrophysiological tests were performed at 0, 2, and 4 weeks, and assessments of gait, histology, and mRNA expression levels were performed at 4 weeks after initiating the PGE1 administration. In the 30 and 100 μg groups, the mechanical withdrawal thresholds measured by pain tests at 4 weeks (36.2 ± 16.4 g and 31.7 ± 15.3 g, respectively) and the motor conduction velocity (24.0 ± 0.2 m/s and 24.4 ± 0.3 m/s, respectively) were significantly higher than the untreated diabetic group (all P < 0.05) and lower than the nondiabetic group (all P < 0.001). In the gait analysis, the mean intensities in the 30 and 100 μg group (128.0 ± 20.1 a.u. and 109.0 ± 27.8 a.u., respectively) were significantly higher than the untreated diabetic (P < 0.01) and were not significantly different from the nondiabetic group (P = 0.81). Fiber density (P = 0.46) and fiber diameter (P = 0.15) did not show any significant differences. PGE1 significantly decreased nerve growth factor (NGF) mRNA and increased vascular endothelial growth factor (VEGF) mRNA in the tibial nerve (both P < 0.01). In conclusion, neurological deteriorations of diabetic rats were alleviated with PGE1, which is associated with inhibition of NGF and enhancement of VEGF at the entrapment site. © 2014 Wiley Periodicals, Inc. Microsurgery 34:568–575, 2014.