bluuebunny/crossref_metadata_2025_split huggingface dataset:
Liquid Crystals Anchored on Mixed Monolayers of Chiral versus Achiral Molecules: Continuous Change in Orientation as a Function of Enantiomeric Excess
Authors: Bai Yiqun , Abbasi Reza , Wang Chenxuan , Abbott Nicholas L. 
Published: May 2014

AbstractThe orientations of liquid crystals (LCs) anchored on monolayers formed from mixtures of chiral versus achiral molecules were compared. Changes in the enantiomeric excess of mixed monolayers of chiral dipeptides gave rise to continuous changes in the orientations of nematic LCs, allowing arbitrary tuning of the azimuthal orientations of LCs over a range of ≈100°. In contrast, the same LCs exhibited discontinuous changes in orientation on surfaces presenting mixtures of achiral molecules. These striking differences in the anchoring of LCs on surfaces presenting chiral versus achiral molecules provide insights into the molecular origins of ordering transitions of LCs, and provide new principles based on chiral monolayers for the rational design of surfaces that permit continuous tuning of the orientations of LCs.
Highly Stable, Water‐Dispersible Metal‐Nanoparticle‐Decorated Polymer Nanocapsules and Their Catalytic Applications
Authors: Yun Gyeongwon , Hassan Zahid , Lee Jiyeong , Kim Jeehong , Lee Nam‐Suk , Kim Nam Hoon , Baek Kangkyun , Hwang Ilha , Park Chan Gyung , Kim Kimoon 
Published: May 2014

AbstractA facile synthesis of highly stable, water‐dispersible metal‐nanoparticle‐decorated polymer nanocapsules (M@CB‐PNs: M=Pd, Au, and Pt) was achieved by a simple two‐step process employing a polymer nanocapsule (CB‐PN) made of cucurbit[6]uril (CB[6]) and metal salts. The CB‐PN serves as a versatile platform where various metal nanoparticles with a controlled size can be introduced on the surface and stabilized to prepare new water‐dispersible nanostructures useful for many applications. The Pd nanoparticles on CB‐PN exhibit high stability and dispersibility in water as well as excellent catalytic activity and recyclability in carbon–carbon and carbon–nitrogen bond‐forming reactions in aqueous medium suggesting potential applications as a green catalyst.
Enantioselective Haloetherifications Catalyzed by 1,1′‐Bi‐2‐naphthol (BINOL) Phosphates: From Symmetrical Alkenediols to Simple Alkenols
Authors: Müller Christian H. , Rösner Christian , Hennecke Ulrich 
Published: May 2014

AbstractAsymmetric haloetherifications can be conducted using 1,1′‐bi‐2‐naphthol (BINOL) phosphates as catalyst. In combination with simple N‐haloamides such as N‐iodopyrrolidinone or N‐bromosuccinimide, good enantioselectivities can be achieved. However, depending on the substrate, the choice of BINOL phosphate is important, and different catalysts show remarkably different selectivities.
Induced pluripotent stem cells for modeling of pediatric neurological disorders
Authors: Jang Jiho , Quan Zhejiu , Yum Yunjin J. , Song Hyo Sook , Paek Seonyeol , Kang Hoon‐Chul 
Published: May 2014

AbstractThe pathophysiological mechanisms underlying childhood neurological disorders have remained obscure due to a lack of suitable disease models reflecting human pathogenesis. Using induced pluripotent stem cell (iPSC) technology, various neurological disorders can now be extensively modeled. Specifically, iPSC technology has aided the study and treatment of early‐onset pediatric neurodegenerative diseases such as Rett syndrome, Down syndrome, Angelman syndrome. Prader–Willi syndrome, Friedreich's ataxia, spinal muscular atrophy (SMA), fragile X syndrome, X‐linked adrenoleukodystrophy (ALD), and SCN1A gene‐related epilepsies. In this paper, we provide an overview of various gene delivery systems for generating iPSCs, the current state of modeling early‐onset neurological disorders and the ultimate application of these in vitro models in cell therapy through the correction of disease‐specific mutations.
In vitro model to study the biomaterial-dependent reaction of macrophages in an inflammatory environment
Authors: Grotenhuis N , vd Toom H F E , Kops N , Bayon Y , Deerenberg E B , Mulder I M , van Osch G J V M , Lange J F , Bastiaansen-Jenniskens Y M 
Published: May 2014

Abstract

Background
Macrophages play an important role in the reaction to biomaterials, which sometimes have to be used in a surgical field at risk of contamination. The macrophage phenotype in reaction to biomaterials in an inflammatory environment was evaluated in both an in vivo and in vitro setting.

Methods
In the in vivo setting, polypropylene (PP) biomaterial was implanted for 28 days in the contaminated abdominal wall of rats, and upon removal analysed by routine histology as well as immunohistochemistry for CD68 (marker for macrophages), inducible nitric oxide synthase (iNOS – a marker for proinflammatory M1 macrophages) and CD206 (marker for anti-inflammatory M2 macrophages). For the in vitro model, human peripheral blood monocytes were cultured for 3 days on biomaterials made from PP, collagen (COL), polyethylene terephthalate (PET) and PET coated with collagen (PET+COL). These experiments were performed both with and without lipopolysaccharide and interferon γ stimulation. Secretion of both M1- and M2-related proteins was measured, and a relative M1/M2 index was calculated.

Results
In vivo, iNOS- and CD206-positive cells were found around the fibres of the implanted PP biomaterial. In vitro, macrophages on both PP and COL biomaterial had a relatively low M1/M2 index. Macrophages on the PET biomaterial had a high M1/M2 index, with the highest increase of M1 cytokines in an inflammatory environment. Macrophages on the PET+COL biomaterial also had a high M1/M2 index.

Conclusion
Macrophages in an inflammatory environment in vitro still react in a biomaterial-dependent manner. This model can help to select biomaterials that are tolerated best in a surgical environment at risk of contamination.

Surgical relevance
Biomaterials in an environment at risk of contamination are often not tolerated owing to a high risk of postoperative infection, which may ultimately lead to removal of the biomaterial.
An in vitro model with primary human macrophages was used to provide insight into the acute reaction of macrophages to a biomaterial in an inflammatory environment simulated with lipopolysaccharide and interferon γ. The reaction of macrophages in such an inflammatory environment was still biomaterial-dependent.
This in vitro model can be used to study the reaction of macrophages to different biomaterials in an inflammatory environment in more detail, and thereby help to select biomaterials that are tolerated best in a surgical environment at risk of contamination.
Surgical treatment of primary breast cancer in the neoadjuvant setting
Authors: Kümmel S , Holtschmidt J , Loibl S 
Published: May 2014

AbstractBackgroundNeoadjuvant chemotherapy (NACT) is a standard treatment option for primary operable breast cancer when adjuvant chemotherapy is indicated.MethodsThis article reviews the use of NACT in breast cancer treatment.ResultsPathological complete response (pCR) rates of up to 60 per cent have been reached for certain breast cancer subgroups. Patients achieving a pCR have a lower locoregional recurrence rate. Nevertheless, the rate of breast-conserving surgery seems to be stable at around 65–70 per cent, although more than 80 per cent of patients respond to NACT. The risk of local relapse does not appear to be higher after NACT, which supports the recommendation to operate within the new margins, as long as there is no tumour in the inked area of the surgical specimen. However, tumours do not shrink concentrically and the re-excision rate is higher after NACT. Mastectomy rates for lobular carcinomas remain high irrespective of tumour response. The role of sentinel lymph node biopsy (SLNB) in the context of NACT has been studied in recent years, and it is not yet completely clear which type of axillary staging is the most suitable. SLNB before NACT in clinically node-negative patients has been the preferred option. However, this practice is currently changing, and it seems advisable to have the SLNB after NACT to reduce the risk of a false-negative SLNB.ConclusionOverall, patients do benefit from NACT, especially those with human epidermal growth factor receptor 2-positive and triple-negative breast cancer, but surgical/local procedures need to be adapted.
Positive outcomes of social norm transgressions
Authors: Popa Monica , Phillips Barbara J. , Robertson Courtney 
Published: May 2014

ABSTRACTNorm transgressions occur when consumers behave outside social expectations; such transgressions often cause embarrassment for the perpetrator and negative responses from witnesses. This study asks if norm violations can lead to positive audience responses. The study relies on 246 written reports from norm breakers and finds positive audience responses occurring almost 17 per cent of the time, with an additional 26 per cent of cases providing a mix of both positive and negative reactions. A content analysis of influence factors suggests that the emergence of a positive outcome depends on the importance of the norm, the position of the perpetrating behavior relative to the broader scope of the norm, and the rewards received by the audience as a result of the norm transgression. These factors are illustrated by representative participant quotes. The findings have implications for theory as well as marketing practice. Copyright © 2014 John Wiley & Sons, Ltd.
Entertainment events in shopping malls—profiling passive and active participation behaviors
Authors: Sit Jason Kokho , Birch Dawn 
Published: May 2014

ABSTRACTThis paper presents an empirical framework for operationalizing passive versus active participation in the context of shopping mall entertainment events (e.g., school holiday events and fashion shows) and assesses the framework's utility for segmenting and profiling shopping mall entertainment audiences. Exploratory factor analysis of data collected at shopping mall events revealed two distinct dimensions, “relax and be entertained” and “socialize and explore,” reflecting passive and active participation, respectively. From nine activities operationalizing passive versus active participation, two distinct audience segments reporting different levels of immediate and future shopping behaviors were identified. The “engage me” segment (active‐dominant audience) was more likely to stay longer at the mall, purchase food and nonfood items, share the event experience with others, and attend similar entertainment events in the future than the “entertain me” segment (passive‐dominant audience). The activities operationalizing passive versus active participation were tested with 280 participants at two family‐oriented shopping mall entertainment events. This paper extends the knowledge in the retail event marketing literature whereby it confirms passive versus active participation levels at retailing events, and verifies that passive and active participation levels can be measured and differentiated operationally. The findings provide insights on the utility of shopper participation level as a meaningful segmentation variable, pertinent to both the marketing and management of shopper experiences within a retailing entertainment event. Managerial implications and limitations of this paper are discussed. Copyright © 2014 John Wiley & Sons, Ltd.
Electrochemical Characterization of an Oleyl‐coated Magnetite Nanoparticle‐Modified Electrode
Authors: Murugappan Krishnan , Silvester Debbie S. , Chaudhary Deeptangshu , Arrigan Damien W. M. 
Published: May 2014

AbstractThe electrochemical behavior of oleyl‐coated Fe3O4 nanoparticles synthesized by chemical co‐precipitation is investigated. An approach based on the formation of a film of nanoparticles on an electrode surface is employed together with cyclic voltammetry. Characterization by scanning electron microscopy, confocal Raman spectroscopy, and X‐ray photoelectron spectroscopy shows that Fe3O4 nanoparticles with a particle size of 20 nm coated with oleic acid are synthesized. These nanoparticles show superparamagnetic behavior and form a homogeneous film from their solution when dried in air. The nanoparticle film electrodes display redox behavior in acidic media but not in alkaline media, which suggests that protons take part in the electrochemical reaction. It is estimated that there are about 240 layers of nanoparticles deposited on the surface and that only around 1 % of these nanoparticles are electrochemically active. This is attributed to either the long‐chain surfactant or the large number of layers of nanoparticles inhibiting the electron‐transfer process.
Sequential Activation and Oscillations of Globally Coupled Microelectrodes during a Bistable Reaction
Authors: Crespo‐Yapur D. Alfonso , Bonnefont Antoine , Schuster Rolf , Krischer Katharina , Savinova Elena R. 
Published: May 2014

AbstractThe cooperative behavior of globally coupled Pt microelectrodes during the bistable CO bulk electrooxidation is explored as a function of the concentration of the H2SO4 supporting electrolyte and the capacitance of the electrochemical system. By measuring the individual currents flowing through each of the microelectrodes, different kinds of cooperative behavior can be evidenced. In addition to the sequential activation of the microelectrodes arising when the applied reaction current value is linearly increased, the emergence of two types of spontaneous potential oscillations are observed in dilute sulfuric acid: 1) low‐amplitude potential oscillations, resulting from the coherent synchronization of noisy microelectrodes, and 2) large‐amplitude passivation–activation potential oscillations, which are only observed at high electrode capacitance. These cooperative behaviors are discussed with the help of a mean‐field model for CO oxidation.
Synthesis of Unsymmetrically Substituted Phosphane Oxides (R1R2P(O)H) and Phosphinous Acids (R1R2POH)
Authors: Allefeld Nadine , Grasse Michael , Ignat'ev Nikolai , Hoge Berthold 
Published: May 2014

AbstractThis paper describes the synthesis of unsymmetrically substituted phosphinous acids and phosphane oxides featuring at least one electron‐withdrawing pentafluoroethyl group. The presence of a diethylamino function as a protecting group allows a selective reaction of RClPNEt2 (R=CF3, C6F5, C6H5) with LiC2F5. On treatment with para‐toluenesulfonic acid the isolated aminophosphanes R(C2F5)PNEt2 are readily converted into the corresponding phosphinous acids or phosphane oxides, respectively. Investigation of the tautomeric equilibrium between oxide and acid tautomer revealed (CF3)(C2F5)POH as a stable phosphinous acid, whereas the pentafluorophenyl and phenyl derivatives constitute a solvent dependent equilibrium between the acid and the oxide tautomer.
SiIV Incorporation into a [28]Hexaphyrin That Triggered Formation of Möbius Aromatic Molecules
Authors: Ishida Shin‐ichiro , Tanaka Takayuki , Lim Jong Min , Kim Dongho , Osuka Atsuhiro 
Published: May 2014

AbstractIncorporation of SiIV into an expanded porphyrin has been achieved for the first time. Treatment of [28]hexaphyrin 1 with CH3SiCl3 and N,N‐diisopropylethylamine gave SiIV complex 2 and its N‐fused product 4 that both have Möbius aromatic nature. In both complexes, the coordinated Si atom is satisfied in a typical trigonal bipyramidal coordination. SiIV incorporation induces conformational rigidification and redshifted absorption profiles due to σ–π conjugation between the Si atom and hexaphyrin macrocycle. Tamao–Fleming oxidation of 2 with H2O2 gave β‐hydroxy [28]hexaphyrin 5, which exists as a ruffled rectangular shape in the solid state, yet it has been revealed to exist predominantly as a twisted Möbius aromatic conformer in CH2Cl2.
Nitrogen‐Enriched Eutrophication Promotes the Invasion of Spartina alterniflora in Coastal China
Authors: Zhao Hui , Yang Wen , Xia Lu , Qiao Yajun , Xiao Yan , Cheng Xiaoli , An Shuqing 
Published: May 2014

AbstractPollution‐driven eutrophication is a significant by‐product of rapid economic growth in China. Such environmental changes have huge consequences on local biodiversity and ecosystem functions through the spread of invasive introduced species. Spartina alterniflora has been spreading quickly and extensively throughout China since the mid 1980s, soon after its intentional introduction from the eastern United States. The range expansion of S. alterniflora coincides with a significant increase in the per unit standing biomass of the species in the Chinese coastal wetlands from the 1980s to 2000s. Here we showed that the long term per m2 biomass of S. alternifolia changes are significantly correlated with human‐induced increases of the inorganic nitrogen level in the Chinese coastal water. We established this causal relationship by showing that reproduction, growth, and biomass of individual S. alterniflora, grown in experimental tanks, increased with higher levels of soil inorganic nitrogen. Competition experiments indicated that S. alterniflora out competed Phragmites australis at both low and high soil nitrogen levels. These field and experimental based results support the hypothesis that nitrogen‐enriched eutrophication contributed significantly to the successful invasion of S. alterniflora in China.
High‐risk human papillomavirus infection associated with telomere elongation in patients with esophageal squamous cell carcinoma with poor prognosis
Authors: Zhang Dong‐Hong , Chen Jiong‐Yu , Hong Chao‐Qun , Yi De‐Qing , Wang Fei , Cui Wei 
Published: May 2014

BACKGROUNDTelomere maintenance is crucial in carcinogenesis and tumor progression. The results of a previous study from the authors indicated that infection with high‐risk human papillomavirus (HR‐HPV) types 16, 18, and 58 was a risk factor for esophageal squamous cell carcinoma (ESCC) in the Shantou region of China. In the current study, the authors explored the association between HR‐HPV infection, telomere length (TL), and DNA methylation and their significance in the prognosis of patients with ESCC.METHODSTL and DNA methylation were analyzed by real‐time polymerase chain reaction and methylation‐specific polymerase chain reaction in 70 cases of ESCC tumor (T) and paired nontumor (NT) tissues and 50 cases of normal esophagus (NE). The prognostic value of TL and DNA methylation in ESCC was analyzed.RESULTSTL gradually decreased from NE to NT to T tissue. TL in tumor tissue (T‐TL) was found to be longer in tissue that was positive for HR‐HPV compared with negative tissue and was found to be positively associated with viral load (Spearman correlation, 0.410; P = .037) and integration (represented by the ratio of HR‐HPV E2 to E6/E7 genes; P = .01). The DNA methylation ratio of human telomerase reverse transcriptase was more prevalent with long (≥ 0.7) compared with short (< 0.7) T‐TL and was positively correlated with T‐TL (Spearman correlation, 0.318; P = .007) and HR‐HPV integration (P = .036). Furthermore, Cox proportional hazards modeling revealed a high ratio of T‐TL to NT‐TL (≥ 0.80) as a factor of poor prognosis, independent of other clinicopathologic variables.CONCLUSIONSHR‐HPV infection and integration related to telomere elongation and DNA methylation of human telomerase reverse transcriptase may be a potential biomarker of prognosis in patients with ESCC. Cancer 2014;120:2673–2683. © 2014 American Cancer Society.
Coordination mechanisms for decentralized parallel systems
Authors: Cohen Johanne , Cordeiro Daniel , Trystram Denis 
Published: May 2014

SummaryOn resource sharing platforms, the execution of the jobs submitted by users is usually controlled by a centralized global scheduler. It determines efficient schedules regarding some common objective function that all organizations agree with (for instance, maximizing the utilization of the entire platform). However, in practice, each organization is mostly interested in the performance obtained for its own jobs. We study the price that the collectivity must pay in order to allow independence to selfish, self‐governing organizations, so they can choose the best schedules for their own jobs. In other words, we are interested in analyzing the costs on the global performance inflicted by the decentralization of scheduling policies. We present a game‐theoretic model for the problem and the associated coordination mechanisms developed to reduce the cost of the decentralization of the decision‐making process. The main contribution is to show (in theory and practice) how to devise pure Nash equilibria configurations for every instance of the problem and to prove that the price paid by the collectivity depends on the local scheduling policy and on the characteristics of the workload executed on such platforms. Copyright © 2014 John Wiley & Sons, Ltd.
Parallel Water/Aromatic Interactions of Non‐Coordinated and Coordinated Water
Authors: Vojislavljević‐Vasilev Dubravka Z. , Janjić Goran V. , Medaković Vesna B. , Blagojević Jelena P. , Zarić Snežana D. 
Published: May 2014

AbstractThe parallel interactions of non‐coordinated and coordinated water molecules with an aromatic ring were studied by analyzing data in the Cambridge structural database (CSD) and by using quantum chemical calculations. The CSD data show that water/aromatic contacts prefer parallel to OH/π interactions, which indicates the importance of parallel interactions. The results reveal the influence of water coordination to a metal ion; the interactions of aqua complexes are stronger. Coordinated water molecules prefer a parallel‐down orientation in which one OH bond is parallel to the aromatic ring, whereas the other OH bond points to the plane of the ring. The interactions of aqua complexes with parallel‐down water/benzene orientation are as strong as the much better known OH/π orientations. The strongest calculated interaction energy is −14.89 kcal mol−1. The large number of parallel contacts in crystal structures and the quite strong interactions indicate the importance of parallel orientation in water/benzene interactions.
Formic Acid Dehydrogenation with Bioinspired Iridium Complexes: A Kinetic Isotope Effect Study and Mechanistic Insight
Authors: Wang Wan‐Hui , Xu Shaoan , Manaka Yuichi , Suna Yuki , Kambayashi Hide , Muckerman James T. , Fujita Etsuko , Himeda Yuichiro 
Published: May 2014

AbstractHighly efficient hydrogen generation from dehydrogenation of formic acid is achieved by using bioinspired iridium complexes that have hydroxyl groups at the ortho positions of the bipyridine or bipyrimidine ligand (i.e., OH in the second coordination sphere of the metal center). In particular, [Ir(Cp*)(TH4BPM)(H2O)]SO4 (TH4BPM: 2,2′,6,6′‐tetrahydroxyl‐4,4′‐bipyrimidine; Cp*: pentamethylcyclopentadienyl) has a high turnover frequency of 39 500 h−1 at 80 °C in a 1 M aqueous solution of HCO2H/HCO2Na and produces hydrogen and carbon dioxide without carbon monoxide contamination. The deuterium kinetic isotope effect study clearly indicates a different rate‐determining step for complexes with hydroxyl groups at different positions of the ligands. The rate‐limiting step is β‐hydrogen elimination from the iridium–formate intermediate for complexes with hydroxyl groups at ortho positions, owing to a proton relay (i.e., pendent‐base effect), which lowers the energy barrier of hydrogen generation. In contrast, the reaction of iridium hydride with a proton to liberate hydrogen is demonstrated to be the rate‐determining step for complexes that do not have hydroxyl groups at the ortho positions.