bluuebunny/crossref_metadata_2025 huggingface dataset:
Determinants of price mark‐up tolerance for green electricity – lessons for environmental marketing strategies from a study of residential electricity customers in Germany
Authors: Gerpott Torsten J. , Mahmudova Ilaha
Published: March 2009

This paper develops hypotheses on the effects of various attitudinal and perceptual variables as well as socio‐demographic characteristics of residential electricity customers on an individual's willingness to pay a mark‐up for electricity generated from renewable energy sources compared with the price due for electricity from conventional sources. The hypotheses are tested with data from a standardized telephone survey of 238 household electricity consumers in Germany. 53.4% of the participants are willing to pay a mark‐up for green electricity. 26.1% report a price tolerance equal to a 5–10% increase in their current electricity bill. Binary logistic and ordinal regression analyses indicate that price tolerance for green electricity is particularly influenced by attitudes (1) towards environmental issues and (2) towards one's current power supplier, (3) perceptions of the evaluation of green energy by an individual's social reference groups, (4) household size and (5) current electricity bill level. The findings are used to derive suggestions for energy related informational activities of public institutions, green marketing strategies of energy companies and future consumer research regarding demand for pro‐environmental goods. Copyright © 2009 John Wiley & Sons, Ltd and ERP Environment.
Surface‐Treated Activated Carbon for Removal of Aromatic Compounds from Water
Authors: Li B. , Lei Z. , Huang Z.
Published: March 2009

Modifications of commercial activated carbons by chemical treatment with HNO3 or HCl and HF and the adsorption behavior of simple aromatic compounds (aniline, pyridine, phenol, and benzene) on activated carbon and modified activated carbon were investigated. The results show that the textural properties change a little after these modifications, but the surface acidity (mainly oxygen‐containing groups) of activated carbon modified with HNO3 increases greatly. The effect of ash of activated carbon on adsorption of the organic compounds mentioned above is insignificant. However, addition of surface acidity (mainly surface oxygen‐containing groups) decreases the adsorption capacity of compounds significantly. The adsorption uptake of compounds on activated carbon with oxidation of HNO3 is low possibly due to dispersive interaction, water cluster blocking, or competition between water and compounds adsorbed on activated carbon's surface because of hydrophilic increase of the activated carbon surface. The solubility of aromatic compounds in water has an important effect on the adsorption capacity of activated carbon. qm and KL (Langmuir adsorption parameters) for the aromatic compounds vary similarly.
Palladium(0)‐Mediated Rapid Methylation and Fluoromethylation on Carbon Frameworks by Reacting Methyl and Fluoromethyl Iodide with Aryl and Alkenyl Boronic Acid Esters: Useful for the Synthesis of [11C]CH3C‐ and [18F]FCH2C‐Containing PET Tracers (PET=Positron Emission Tomography)
Authors: Doi Hisashi , Ban Ikuya , Nonoyama Akihito , Sumi Kengo , Kuang Chunxiang , Hosoya Takamitsu , Tsukada Hideo , Suzuki Masaaki
Published: March 2009

A new synthetic methodology for the rapid methylation and fluoromethylation on aryl and alkenyl frameworks by using methyl and fluoromethyl iodide with an organoboronic acid ester has been developed under the simple and mild conditions of [Pd2(dba)3]/P(o‐CH3C6H4)3/K2CO3 (dba= dibenzylideneacetone) in DMF at 60 °C for 5 min (see scheme). This boron protocol provides a firm chemical basis for the synthesis of 11C‐ and 18F‐incorporated PET tracers.

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The rapid methylation and fluoromethylation on aryl and alkenyl carbon frameworks by reacting methyl and fluoromethyl iodide with aryl and alkenyl boronates have been studied with the focus on the realization of the synthesis of [11C]CH3‐ and [18F]FCH2‐labeled positron emission tomography (PET) tracers. The coupling of methyl iodide and pinacol phenylboronate (40 equiv) is accomplished in >91 % yield within 5 min at 60 °C under the conditions of [Pd2(dba)3]/P(o‐CH3C6H4)3/K2CO3 (0.5:2:2; dba=dibenzylideneacetone) in DMF. The reaction shows a high generality and is applicable to various types of aryl and alkenyl boronates, giving the corresponding methylated derivatives in high yields (80–99 %). This reaction is also useful for the rapid incorporation of the fluoromethyl group. Thus, this boron protocol provides a firm chemical basis for the synthesis of 11C‐ and 18F‐incorporated PET tracers and can be used as a complementary method for [11C]methylation together with our previous and ongoing processes using organotributylstannanes.
Adducts between Dansylated Poly(propylene amine) Dendrimers and Anthracene Clips Mediated by ZnII Ions: Highly Efficient Photoinduced Energy Transfer
Authors: Branchi Barbara , Ceroni Paola , Balzani Vincenzo , Bergamini Giacomo , Klärner Frank‐Gerrit , Vögtle Fritz
Published: March 2009

A family of poly(propylene amine) dendrimers, decorated at their periphery with 4, 16, and 32 dansyl units and a molecular clip, composed of two anthracene sidewalls and a disulfate benzene bridging unit, show intense UV absorption and strong fluorescence in the visible region when in a CH3CN/CH2Cl2 (1:1, v/v) solvent mixture. Both these classes of compounds are good ligands for ZnII ions, as demonstrated by the changes in the absorption and fluorescence spectra upon addition of metal ions. These coordinating properties have been exploited in the self‐assembly of complex structures in which the interaction between a dansylated dendrimer and anthracene‐functionalized clips is mediated by ZnII ions. The self‐assembly process is reversible and the number of metal ions and molecular clips associated with each dendrimer increases with the generation number. In these adducts, an energy transfer process from the anthracene to yield the fluorescent excited state of dansyl takes place with almost unitary efficiency.
Dendrimeric Oligo(phenylenevinylene)‐Extended Dithieno[3,2‐b:2′,3′‐d]phospholes—Synthesis, Self‐Organization, and Optical Properties
Authors: Romero‐Nieto Carlos , Merino Sonia , Rodríguez‐López Julián , Baumgartner Thomas
Published: March 2009

A boost from the branches: Incorporation of the dithieno[3,2‐b:2′,3′‐d]phosphole system as a core in oligo(phenylenevinylene) dendrimers (an example is shown here) provides materials that exhibit energy‐transfer features relaying incoming photons from the dendrons towards the core, which in turn shows enhanced emission intensity. The optical properties and self‐assembly features of the dendrimers can be impacted by the terminal groups (‐H, ‐CF3, or ‐NPh2) employed.

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To establish this system as a fluorescent core in π‐conjugated dendrimers, a series of oligo(phenylenevinylene) (OPV)‐extended dithieno[3,2‐b:2′,3′‐d]phospholes has been prepared by means of a Wittig–Horner protocol with a dithienophosphole dialdehyde and appropriately functionalized phosphonates. The “zero‐generation” model compounds have provided the general accessibility of OPV‐functionalized dithienophospholes, and show varying emission colors covering the optical spectrum from green to red. Expansion of the synthetic strategy towards the corresponding first‐generation dendrimers has provided materials that show intriguing self‐organization features in case of the phenyl‐terminated dendrimer, forming large one‐dimensional microfibres, as well as desirable energy‐transfer processes from the dendrons to the dithienophoshole core resulting in an enhanced emission intensity for the latter. The present study has revealed that the terminal end‐groups of the OPV branches have significant impact on the optical features of the OPV dendrimers as a whole.
A Bisfullerene–Bis(dipyrrinato)zinc Complex: Electronic Coupling and Charge Separation in an Easy‐to‐Assemble Synthetic System
Authors: Rio Yannick , Sánchez‐García David , Seitz Wolfgang , Torres Tomás , Sessler Jonathan L. , Guldi Dirk M.
Published: March 2009

Getting connected: The use of a bis(dipyrrinato)zinc(II)) linker allows the facile tethering of two C60 subunits and gives rise to an electronically coupled system that allows effective charge separation following photoexcitation (see figure).

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Rapid and Tunable Patterning of High Purity ZnO Nanoarrays without Template or Catalyst
Authors: Wang Xiaolei , Zhu Hui , Yang Wen , Yang Fan , Yang Xiurong
Published: March 2009

Arrays of endless possibility: Without template or catalyst, high‐purity ZnO nanoarrays were patterned though a rapid, tunable and repeatable method (see picture). Their potential contributions in both electrical and biomedical fields were also discussed and demonstrated.

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Overlap domain decomposition method for bioluminescence tomography (BLT)
Authors: Wang Tao , Gao Shuping , Zhang Ling , Wu Yan , He Xiaowei , Hou Yanbin , Huang Heyu , Tian Jie
Published: March 2009

Bioluminescence tomography (BLT) allows in vivo localization and quantification of bioluminescent sources inside a small animal to reveal various molecular and cellular activities. In this paper, the overlap domain decomposition method (ODDM) of BLT is proposed, which refers to divide and conquer techniques for solving BLT by iteratively solving sub‐problems on smaller sub‐domains. Here, two triangulations of the region are adopted. We can obtain the photon density distribution on the object surface, as well as reconstruct the position of the light source by using ODDM and genetic algorithm. The numerical simulations have shown that ODDM is computationally efficient and fairly robust. Copyright © 2009 John Wiley & Sons, Ltd.
Dynamic regulation of the P2X4 receptor in alveolar macrophages by phagocytosis and classical activation
Authors: Stokes Leanne , Surprenant Annmarie
Published: March 2009

ATP‐gated P2X4 receptors (P2X4R) in macrophages and microglia have been implicated in neuropathic and inflammatory pain by currently unidentified mechanisms. P2X4R are found predominantly in intracellular lysosomal compartments but can be rapidly trafficked to the surface membrane by procedures that induce endolysosomal secretion. We studied total and surface membrane P2X4R protein expression by Western blot and biotinylation assays and functional expression by whole‐cell patch clamp assays in human and rat alveolar macrophages in response to phagocytosis of zymosan and opsonized zymosan bioparticles and to classical and alternative macrophage activation. Unstimulated macrophages showed high total protein expression but very low functional expression. Phagocytosis rapidly (within 4 h) increased functional P2X4R expression by 2‐ to 7‐fold as did chloroquine, an agent known to induce lysosomal secretion. In contrast, classical activation of macrophage for 48 h with IFN‐γ and TNF‐α or IFN‐γ and LPS reduced surface and functional P2X4R expression by 3‐fold without altering total P2X4R protein levels. Alternative activation with IL‐4 or IL‐13 did not alter total, surface or functional expression of P2X4R. This is the first study of the regulation of P2X4R in macrophages by physiological stimuli and presents a picture whereby P2X4R become functional in response to initial phagocytic stimuli but return to a non‐functional state during sustained activation by classical macrophage activation.
Loss of FOXP3 expression in natural human CD4+CD25+ regulatory T cells upon repetitive in vitro stimulation
Authors: Hoffmann Petra , Boeld Tina J. , Eder Ruediger , Huehn Jochen , Floess Stefan , Wieczorek Georg , Olek Sven , Dietmaier Wolfgang , Andreesen Reinhard , Edinger Matthias
Published: March 2009

The adoptive transfer of CD4+CD25+ natural regulatory T cells (Treg) is a promising strategy for the treatment of autoimmune diseases and the prevention of alloresponses after transplantation. Clinical trials exploring this strategy require efficient in vitro expansion of this rare cell population. Protocols developed thus far rely on high‐grade purification of Treg prior to culture initiation, a process still hampered by the lack of Treg cell‐specific surface markers. Depletion of CD127+ cells was shown to separate activated conventional T cells from natural Treg cell populations allowing the isolation of highly enriched FOXP3+ cells with all functional and molecular characteristics of natural Treg. Here, we demonstrate that upon in vitro expansion, CpG methylation in a conserved region within the FOXP3 gene locus increased in CD4+CD25+CD127low Treg, correlating with loss of FOXP3 expression and emergence of pro‐inflammatory cytokines. Further analysis identified CD45RA−FOXP3+ memory‐type Treg as the main source of converting cells, whereas CD45RA+FOXP3+ Treg from the same donors showed no conversion within 3 wk of in vitro expansion. Thus, Treg cell lineage differentiation does not seem to represent a final fate decision, as natural Treg can lose their cell‐type‐specific characteristics after repetitive TCR stimulation.
IL‐17/Th17 in anti‐fungal immunity: What's new?
Authors: Zelante Teresa , De Luca Antonella , D' Angelo Carmen , Moretti Silvia , Romani Luigina
Published: March 2009

How the immune system tailors protective responses to suit the infectious challenge while limiting damage to the host is an emerging theme in T‐cell biology. Although many studies have focused on the pathological aspects of IL‐17‐producing T cells in many autoimmune diseases, their role in protective anti‐microbial immunity has also been increasingly recognized. This increased recognition also applies to their role in anti‐fungal immunity; however, the role of IL‐17‐producing T cells in protection versus pathology in fungal infections is still controversial. Although both positive and negative effects on immune resistance have been attributed to the IL‐23/Th17 axis in experimental models of fungal infections, defective Th17 cell differentiation has been linked to recurrent pneumonia by filamentous fungi and the occurrence of mucocutaneous candidiasis in patients with primary immunodeficiencies. Here we discuss how recent findings in experimental candidiasis and aspergillosis shed new lights on the contribution of Th17 cells to resistance and pathology to fungi.
Novel therapeutic targets along the Th17 pathway
Authors: Ouyang Wenjun , Filvaroff Ellen , Hu Yan , Grogan Jane
Published: March 2009

The recent discovery of IL‐17‐producing CD4+ Th subset significantly revised the Th1/Th2 dichotomy model proposed by Mosmann and Coffman almost two decades ago. Th17 cells are involved in the pathogenesis of many human autoimmune diseases. Th17 cells, their developmental pathways and their effector functions, therefore, provide novel therapeutic targets.
Thymus‐specific serine protease regulates positive selection of a subset of CD4+ thymocytes
Authors: Gommeaux Julien , Grégoire Claude , Nguessan Prudence , Richelme Mireille , Malissen Marie , Guerder Sylvie , Malissen Bernard , Carrier Alice
Published: March 2009

Thymus‐specific serine protease (TSSP) was initially reported as a putative protease specifically expressed in the endosomal compartment of cortical thymic epithelial cells (cTEC). As such, TSSP is potentially involved in the presentation of the self‐peptides that are bound to MHC class II molecules expressed at the cTEC surface and are involved in the positive selection of CD4+ thymocytes. We tested this hypothesis by generating mutant mice deprived of Prss16, the gene encoding TSSP. TSSP‐deficient mice produced normal numbers of T cells, despite a decrease in the percentage of cTEC expressing high surface levels of MHC class II. By using sensitive transgenic models expressing MHC class II‐restricted TCR transgenes (Marilyn and OT‐II), we showed that the absence of TSSP markedly impaired the selection of Marilyn and OT‐II CD4+ T cells. In contrast, selection of CD8+ T cells expressing an MHC class I‐restricted TCR transgene (OT‐I) was unaffected. Therefore, TSSP is involved in the positive selection of some CD4+ T lymphocytes and likely constitutes the first serine protease to play a function in the intrathymic presentation of self‐peptides bound to MHC class II complexes.
Environmental control of Th17 differentiation
Authors: Quintana Francisco J. , Weiner Howard L.
Published: March 2009

Th17 cells participate in the control of extracellular bacteria and fungi, but dysregulated Th17 cell activity can result in immunopathology. Thus, the generation and the activity of Th17 cells should be tightly regulated, and simultaneously it should be able to respond to the challenges presented by a changing environment. In this viewpoint, we discuss some of the mechanisms by which microbes, dietary components and environmental toxins influence the Th17 response.
Host versus pathogen: Two sides of the same challenge in the TB world
Authors: Cooper Andrea M.
Published: March 2009

Humans have studied tuberculosis for many thousands of years. For most of this time investigations were focused on describing patient symptoms with the hope of ameliorating them and perhaps limiting the spread of disease. At the end of the 19th century, however, the association between the bacterium and disease was demonstrated 1 – a discovery recognized annually on 24 March by World TB Day, a day that also highlights efforts to eliminate the disease. Following the discovery, the study of the disease split in two directions: the nature of the pathogen and the nature of the host response. A key advance to be celebrated this World TB Day 2009 is that we are now in a position to integrate the study of the bacteria with that of the host response and thereby create a more complete understanding of how this pervasive disease develops. With this improved understanding more efficient and targeted intervention will be forthcoming.
Gold(I) Complexes of N‐Heterocyclic Carbenes and Pyridines
Authors: Chiou Josh Y. Z. , Luo Shih C. , You Wan C. , Bhattacharyya Amitabha , Vasam C. Sekhar , Huang Cyong H. , Lin Ivan J. B.
Published: March 2009

Overall ten ionic [Au(NHC)(Py)][PF6]‐ and [Au2(NHC)2(Py)2][PF6]2‐type complexes [NHC = N,N′‐dialkylbenzimidazol‐2‐ylidene, denoted as R2‐bimy with alkyl (R) being methyl (Me) or ethyl (Et), and Py = 4‐substituted pyridine or 4,4′‐bipyridine] have been prepared by incorporating various Pys into the AuI‐NHC core with Au(NHC)Cl as starting material. Their crystal structures characterized by X‐ray diffraction indicate a linearly coordinated AuI center and exhibit secondary forces such as Au···Au, Au···π, or π···π interactions. The luminescent properties of these compounds were studied in the solid state. Density‐functional theory calculations on [Au(Me2‐bimy)(4‐dmapy)][PF6] [4‐dmapy = 4‐(dimethylamino)pyridine] predict the lowest electronic transition with nonzero oscillator strength is the fourth HOMO–LUMO transition. Whereas the fourth HOMO is mainly associated with the Py ligands, the LUMO is predominantly aurophilic. Four AuI‐NHC compounds were examined for their catalytic activity towards the oxidation of benzyl alcohol to aldehyde, in which the starting material [Au(Et2‐bimy)Cl] gave the highest yield. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Structural Evidence for an Unusual Conformation and Weak Interligand Interactions in Two Copper Chelates with (o‐Nitrophenyl)ethylenediaminediacetic Acid
Authors: Allali Mustapha , Jaud Joël , Habbadi Nouzha , Dartiguenave Michèle , Beauchamp André L. , Benoist Eric
Published: March 2009

Two mixed‐ligand copper(II) complexes, [Cu(L1)(H2O)]·H2O (1) and [Cu(L1)(bipy)]·2H2O (2), containing the title N‐substituted iminodiacetate (IDA) derivative (L12–) as primary ligand with and without 2,2′‐bipyridine as auxiliary ligand, have been synthesised. Both have been fully characterised by means of IR spectroscopy, mass spectrometry, elemental analysis and conductimetry, as well as X‐ray crystallography. The dominant structural feature of these complexes is the presence of a flexible coordinating arm on the IDA skeleton which controls the conformation of the resulting complexes. The CuII centre in complex 1 exhibits a distorted square‐pyramidal [4+1] coordination in which the apical site is unexpectedly occupied by the N(2) atom of the coordinating arm instead of a water molecule. The IDA skeleton adopts a tridentate mer‐O2N arrangement in 1, whereas in 2 it exhibits an unusual fac‐O2N(apical) configuration, which is observed for the first time for a tridentate IDA unit bearing a flexible arm containing a coordinating atom. The o‐nitro aromatic group in the flexible arm gives rise to different inter‐ and/or intramolecular stacking interactions. Classic intermolecular “nitrophenyl‐nitrophenyl” π‐π stacking interactions are observed between pairs of complex molecules in crystals of 1, whereas intramolecular “nitrophenyl‐pyridyl” interactions alternate with unprecedented interligand π‐π “nitrophenyl–metal chelate ring” interactions in crystals of 2.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
The Nature of the Metal–Carbene Bond in Normal and Abnormal Pyridylidene, Quinolylidene and Isoquinolylidene Complexes
Authors: Heydenrych Greta , von Hopffgarten Moritz , Stander Elzet , Schuster Oliver , Raubenheimer Helgard G. , Frenking Gernot
Published: March 2009

Quantum chemical calculations using DFT at the BP86/TZ2P level of theory are reported for the complexes (PH3)2ClM‐L where L is an N‐heterocyclic ligand and M a group‐10 metal Ni, Pd and Pt. The ligands comprise pyridyl groups or carbenes derived from the pyridine, quinolidine or isoquinolidine systems wherein the nitrogen atom is either adjacent to the carbene carbon atom or it is in a remote (meta or para, or in the adjacent ring) position. Comparative calculations include the isomeric ligands of the well‐known five‐membered N‐heterocyclic carbene. The nature of the metal–ligand interactions are investigated by energy decomposition analysis (EDA). The EDA results suggest that the nature of the metal–carbene bonds in the complexes shows little variation when the position of the nitrogen atom in pyridylidenes is adjacent (ortho) or remote (meta or para). It changes even very little when the nitrogen atom is in an adjacent ring to the cyclic carbene moiety. The most significant differences between the bond strengths come from the energy level of the σ‐HOMO of the carbene ligand which depends largely on the position of the nitrogen atom. An energetically higher‐lying σ lone‐pair orbital of the carbene ligand yields stronger orbital interactions but also stronger electrostatic attraction because of better overlap with the metal nucleus. This holds also for the isomers of the five‐membered N‐heterocyclic carbenes. An excellent correlation is established between the ϵ(HOMO) values of the ligands and the metal–ligand interaction energies, ΔEint.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Polyhedral Boranes for Medical Applications: Current Status and Perspectives
Authors: Sivaev Igor B. , Bregadze Vladimir V.
Published: March 2009

This review focuses on the current status and perspectives of the application of polyhedral boron hydrides in medicine. The main topics discussed are boron neutron capture therapy for cancer and radionuclide diagnostics and therapy. X‐ray contrast diagnostics, antitumor activity of some metal derivatives of carboranes, and drug design including carborane fragments are discussed as well.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
A New Class of Stable, Saturated N‐Heterocyclic Carbenes with N‐Naphthyl Substituents: Synthesis, Dynamic Behavior, and Catalytic Potential
Authors: Vieille‐Petit Ludovic , Luan Xinjun , Mariz Ronaldo , Blumentritt Sascha , Linden Anthony , Dorta Reto
Published: March 2009

A new family of easily accessible and stable imidazolin‐2‐ylidenes has been synthesized, where the side chains are comprised of substituted naphthyl units. This generates C2‐symmetric (anti) and Cs‐symmetric (syn) atropisomers. The interconversion between the isomers is studied in detail both for the N‐heterocyclic carbene salts and the free carbenes through variable‐temperature 1H NMR spectroscopic studies; activation free energies are calculated and can be linked to the substitution pattern of the naphthyl moieties. Palladium complexes comprising the new N‐heterocyclic carbenes are synthesized and preliminary data show that these compounds behave well as precatalysts in the Buchwald–Hartwig amination reaction of aryl bromides and aryl chlorides. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Insight into cis‐to‐trans Olefin Isomerisation Catalysed by Group 4 and 6 Cyclopentadienyl Compounds
Authors: Chahboun Ghaita , Petrisor Cristina E. , Gómez‐Bengoa Enrique , Royo Eva , Cuenca Tomás
Published: March 2009

Intramolecular isomerisation of the pendant allyl unit present in the model compound [MoH(η5‐C5H4SiMe2CH2CH=CH2)(CO)3] reported before was investigated by DFT calculations. The coordination of CO and the splitting of the agostic Mo–H interactions found in metallacyclic transition states stabilise the cis and trans hydride compounds [MoH(η5‐C5H4SiMe2CH=CHCH3)(CO)3] relative to the corresponding tricarbonyl molybdenum alkyl metallacycles. A comparison with an analogous zirconium system is included. To contrastthese results with the behaviour of metal hydride cyclopentadienyl compounds, which have no intramolecular alkene functionality, group 4 and 6 derivatives such as [Zr(η5‐C5H4SiMe2‐η1‐NtBu)(η5‐C5H4SiMe2CH2CH2‐η1‐CH2)] (2), [MH(η5‐C5HMe4)(CO)3] [M = Mo (3), W (4)], and [ZrH(η5‐C5H4SiMe2‐η1‐NtBu)(η5‐C5H4R)] [R = H (5), SiMe3 (6)] were examined as selective catalysts for the intermolecular isomerisation of the terminal olefins allyltrimethylsilane (A) and 4‐methyl‐1‐pentene (B). Zirconium hydride compounds were the most efficient catalysts. Compound 4 catalysed the same reaction but required heating at 140 °C, whereas compound 3 was inactive due to a dehydrogenation process, which produced the dinuclear compound [Mo(η5‐C5HMe4)(CO)3]2 (7). Reaction of 4 and 5 with the internal alkenes trimethyl(1‐propenyl)silane (C) and 4,4‐dimethyl‐2‐pentene (D) favoured cis‐to‐trans isomer conversion with poor production of the corresponding terminal olefins. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Highly Efficient Visible‐Light‐Induced Photocleavage of DNA by a Ruthenium‐Substituted Fluorinated Porphyrin
Authors: Cunningham Michelle , McCrate Anna , Nielsen Mark , Swavey Shawn
Published: March 2009

A new porphyrin, meso‐5‐(pentafluorophenyl)‐10,15,20‐tris(4‐pyridyl)porphyrin, has been synthesized. Coordination of two [Ru(bipy)2Cl]+ moieties (where bipy = 2,2′‐bipyridine) to the pyridyl nitrogen atoms in the 10,15‐positions gives the target complex. Electronic transitions associated with the ruthenium–porphyrin include an intense Soret band and four less intense Q‐bands in the visible region of the spectrum. An intense π–π* transition in the UV region associated with the bipyridyl groups and a metal‐to‐ligand charge‐transfer (MLCT) band appearing as a shoulder to the Soret band are also observed. Electrochemical properties associated with the complex include a redox couple in the cathodic region with E1/2 = –0.84 V vs. Ag/AgCl attributed to the porphyrin and a redox couple in the anodic region at E1/2 = 0.79 V vs. Ag/AgCl due to the RuIII/II couple. DNA titrations and ethidium bromide displacement experiments indicate the ruthenium porphyrin interacts with DNA potentially through a partial intercalation mechanism. Irradiation of aqueous solutions of the ruthenated complex and supercoiled DNA at a 100:1 base pair/complex ratio with visible light above 400 nm indicates that the complex causes double‐strand breaks of the DNA.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Biodiesel from canola oil using a 1 : 1 molar mixture of methanol and ethanol
Authors: Joshi Hem , Toler Joe , Moser Bryan R. , Walker Terry
Published: March 2009

Canola oil was transesterified using a 1 : 1 molar mixture of methanol and ethanol (M/E) with potassium hydroxide (KOH) catalyst. The effects of catalyst concentration (0.5–1.5 wt‐%), molar ratio of M/E to canola oil (3 : 1 to 20 : 1) and reaction temperature (25–75 °C) on the percentage yield measured after 2.5 and 5.0 min were optimized using a central composite design. A maximum percentage yield of 98% was obtained for a catalyst concentration of 1.1 wt‐% and an M/E to canola oil molar ratio of 20 : 1 at 25 °C at 2.5 min, whereas a maximum percentage yield of 99% was obtained for a catalyst concentration of 1.15 wt‐% and all molar ratios of reactants at 25 °C at 5 min. Statistical analysis demonstrated that increasing catalyst concentration and molar ratio of reactants resulted in curvilinear and linear trends in percentage yield, both at 2.5 and 5 min. However, reaction temperature, which affected the percentage yield at 2.5 min linearly, was insignificant at 5 min. The resultant mixed methyl/ethyl canola esters exhibited enhanced low‐temperature performance and lubricity properties in comparison to neat canola oil methyl esters and also satisfied ASTM D6751 and EN 14214 standards with respect to oxidation stability, kinematic viscosity, and acid value.
The effect of dehydroepiandrosterone on lipogenic gene mRNA expression in cultured primary chicken hepatocytes
Authors: Tang Xue , Ma Haitian , Huang Guoqing , Miao Jinfeng , Zou Sixiang
Published: March 2009

The effects of dehydroepiandrosterone (DHEA) on lipogenic gene mRNA expression were examined using cultured primary chicken hepatocytes. Cell samples were equilibrated to culture conditions for 24 h and then exposed to DHEA (1, 10 and 100 µM) dissolved in DMSO. The expression of sterol regulatory element‐binding protein‐1 (SREBP‐1) mRNA in cultured primary hepatocytes did not vary with time, except for a significant decrease in gene expression when cells were treated with 10 or 100 µM DHEA for either 1 or 2 h. A similar tendency toward decreased gene expression was evident for acetyl CoA carboxylase. The expression of peroxisome proliferator‐activated receptor α (PPARα) and carnitine palmitoyl transferase I mRNA was dramatically enhanced subsequent to treatment with 10 or 100 µM DHEA for periods of time from 6 to 48 h, while there was a decrease in the expression of PPARα in the presence of 10 µM DHEA after 1 and 2 h of exposure, and in the presence of 100 µM DHEA after 2 h of exposure. Hepatocytes treated with 10 or 100 µM DHEA contained more mitochondria and mitochondria with a higher electron density than did untreated hepatocytes. Furthermore, cell survival was significantly inhibited by treatment with 100 µM DHEA at 24, 48 and 72 h. In contrast, 1 µM DHEA administration significantly increased cell survival after 72 h; however, 10 µM DHEA treatment had no pronounced effect on cell survival. Overall, the results reported here indicate that DHEA accelerates lipid catabolism by direct regulation of hepatic gene expression and by induction of changes in hepatocyte mitochondria.
Cyclic Endiamino Peptides: A New Synthesis of Imidazopyrazines
Authors: Kogon Yael , Goren Lee , Pappo Doron , Rudi Amira , Kashman Yoel
Published: March 2009

By applying the cyclic endiamino cyclisation methodology to linear tripeptides embodying a β‐turn‐directing amino acid, the imidazopyrazine ring system was afforded. A mechanism involving the originally desired nine‐membered cyclic endiamine is suggested. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Electrochemical Cholesterol Sensor Based on Tin Oxide‐Chitosan Nanobiocomposite Film
Authors: Ansari Anees A. , Kaushik Ajeet , Solanki Pratima R. , Malhotra B. D.
Published: March 2009

A chitosan (CS)‐tin oxide (SnO2) nanobiocomposite film has been deposited onto an indium‐tin‐oxide glass plate to immobilize cholesterol oxidase (ChOx) for cholesterol detection. The value of the Michaelis–Menten constant (Km) obtained as 3.8 mM for ChOx/CS‐SnO2/ITO is lower (8 mM) than that of a ChOx/CS/ITO bioelectrode revealing enhancement in affinity and/or activity of ChOx towards cholesterol and also revealing strong binding of ChOx onto CS‐SnO2/ITO electrode. This ChOx/CS‐SnO2/ITO cholesterol sensor retains 95% of enzyme activity after 4–6 weeks at 4 °C with response time of 5 s, sensitivity of 34.7 μA/mg dL−1 cm2 and detection limit of 5 mg/dL.
Disposable Electrodes for Capacitive Immunosensor
Authors: Teeparuksapun Kosin , Kanatharana Proespichaya , Limbut Warakorn , Thammakhet Chongdee , Asawatreratanakul Punnee , Mattiasson Bo , Wongkittisuksa Booncharoen , Limsakul Chusak , Thavarungkul Panote
Published: March 2009

Disposable electrodes were fabricated by coating chromium (5 nm) and gold (200 nm) on glass strips (5.0 mm×25.4 mm) and used in a label‐free immunosensor. Human serum albumin (HSA) and its antigen (anti‐HSA) were used as a model system. Electropolymerization of o‐phenylenediamine was used for the immobilization of anti‐HSA by covalent binding. A linear relationship was obtained in the range from 1.0×10−14 to 1.0×10−9 M with a limit of detection of 8.0×10−15 M. Each modified electrode can be reused up to 30 times. The developed system was applied for human serum samples and compared to Albumin BCG method.
Comparison of DNA‐Reactive Metabolites from Nitrosamine and Styrene Using Voltammetric DNA/Microsomes Sensors
Authors: Krishnan Sadagopan , Bajrami Besnik , Mani Vigneshwaran , Pan Shenmin , Rusling James F.
Published: March 2009

Voltammetric sensors made with films of polyions, double‐stranded DNA and liver microsomes adsorbed layer‐by‐layer onto pyrolytic graphite electrodes were evaluated for reactive metabolite screening. This approach features simple, inexpensive screening without enzyme purification for applications in drug or environmental chemical development. Cytochrome P450 enzymes (CYPs) in the liver microsomes were activated by an NADPH regenerating system or by electrolysis to metabolize model carcinogenic compounds nitrosamine and styrene. Reactive metabolites formed in the films were trapped as adducts with nucleobases on DNA. The DNA damage was detected by square‐wave voltammetry (SWV) using Ru(bpy)$\rm{ {_{3}^{2+}}}$ as a DNA‐oxidation catalyst. These sensors showed a larger rate of increase in signal vs. reaction time for a highly toxic nitrosamine than for the moderately toxic styrene due to more rapid reactive metabolite‐DNA adduct formation. Results were consistent with reported in vivo TD50 data for the formation of liver tumors in rats. Analogous polyion/ liver microsome films prepared on 500 nm silica nanoparticles (nanoreactors) and reacted with nitrosamine or styrene, provided LC‐MS or GC analyses of metabolite formation rates that correlated well with sensor response.
A Novel Thin‐Film Copper Array Based on an Organic/Inorganic Sensor Hybrid: Microfabrication, Potentiometric Characterization, and Flow‐Injection Analysis Application
Authors: Arida Hassan , Turek Monika , Rolka David , Schöning Michael J.
Published: March 2009

A first step towards the microfabrication of a thin‐film array based on an organic/inorganic sensor hybrid has been realized. The inorganic microsensor part incorporates a sensor membrane based on a chalcogenide glass material (Cu‐Ag‐As‐Se) prepared by pulsed laser deposition technique (PLD) combined with an PVC organic membrane‐based organic microsensor part that includes an o‐xylyene bis(N,N‐diisobutyl‐dithiocarbamate) ionophore. Both types of materials have been electrochemically evaluated as sensing materials for copper(II) ions. The integrated hybrid sensor array based on these sensing materials provides a linear Nernstian response covering the range 1×10−6–1×10−1 mol L−1 of copper(II) ion concentration with a fast, reliable and reproducible response. The merit offered by the new type of thin‐film hybrid array includes the high selectivity feature of the organic membrane‐based thin‐film microsensor part in addition to the high stability of the inorganic thin‐film microsensor part. Moreover, the thin‐film sensor hybrid has been successfully applied in flow‐injection analysis (FIA) for the determination of copper(II) ions using a miniaturized home‐made flow‐through cell. Realization of the organic/inorganic thin‐film sensor hybrid array facilitates the development of a promising sophisticated electronic tongue for recognition and classification of various liquid media.
Fluorescent isotope‐coded affinity tag 2: Peptide labeling and affinity capture
Authors: Rivera‐Monroy Zuly , Bonn Guenther K. , Guttman András
Published: March 2009

Fluorescent isotope‐coded affinity tag (FCAT) is a novel reagent to label cysteine‐containing peptides. The fluorescein group on the tag enables absolute quantification by fluorescence detection, also supporting affinity capture of the labeled peptides. In this paper we report the synthesis of the heavy isotopic form of the FCAT reagent and its use in labeling tryptic peptides. The heavy form of the reagent exhibited the same reactivity and chromatographic behavior that of the light version. Effective labeling of tryptic peptides from α‐lactalbumin, fetuin, BSA and phosphorylase b was attained by using both the heavy and light FCAT tags. Selective capture of the FCAT‐labeled peptides was easily performed by pipette tips containing either anti‐FITC antibody or iminodiacetic‐acid‐coated beads. The differently labeled peptides were separated by RP HPLC and analyzed by MALDI‐TOF MS.
Intersymbol interference in DQPSK fibre‐optic systems
Authors: Zhao Hongxia , Agrell Erik , Karlsson Magnus
Published: March 2009

The limited bandwidth of high‐speed transmitter and receiver hardware gives rise to intersymbol interference (ISI) in digital communication systems. The influence of such ISI is investigated in a low‐complexity fibre‐optical setting, using differential quaternary phase‐shift keying (DQPSK) modulation. The ISI is approximated by a memoryless, stochastic model, for use in applications where neither equalisation nor sequence detection can be afforded. The channel capacity of this model is calculated and shown to depend strongly on the transmitter calibration. More than 3dB is gained, at a target bit error rate (BER) of 10−6, by allowing the transmitted phase levels to deviate from their nominal multiples of π/2 by up to 7%. Copyright © 2009 John Wiley & Sons, Ltd.
A hybrid FVM–LBM method for single and multi‐fluid compressible flow problems
Authors: Joshi Himanshu , Agarwal Arpit , Puranik Bhalchandra , Shu Chang , Agrawal Amit
Published: March 2009

The lattice Boltzmann method (LBM) has established itself as an alternative approach to solve the fluid flow equations. In this work we combine LBM with the conventional finite volume method (FVM), and propose a non‐iterative hybrid method for the simulation of compressible flows. LBM is used to calculate the inter‐cell face fluxes and FVM is used to calculate the node parameters. The hybrid method is benchmarked for several one‐dimensional and two‐dimensional test cases. The results obtained by the hybrid method show a steeper and more accurate shock profile as compared with the results obtained by the widely used Godunov scheme or by a representative flux vector splitting scheme. Additional features of the proposed scheme are that it can be implemented on a non‐uniform grid, study of multi‐fluid problems is possible, and it is easily extendable to multi‐dimensions. These features have been demonstrated in this work. The proposed method is therefore robust and can possibly be applied to a variety of compressible flow situations. Copyright © 2009 John Wiley & Sons, Ltd.
Predictors of neuropsychiatric symptoms in nursing home patients: influence of gender and dementia severity
Authors: Zuidema Sytse U. , de Jonghe Jos F. M. , Verhey Frans R. J. , Koopmans Raymond T. C. M.
Published: March 2009

Introduction

The aim of the study was to assess the influence of dementia severity and gender on neuropsychiatric symptoms in demented nursing home patients.

Methods

Neuropsychiatric symptoms were assessed in a large sample of 1319 Dutch nursing home patients using the Cohen‐Mansfield Agitation Inventory (CMAI) and the Neuropsychiatric Inventory–Nursing Home version (NPI‐NH). The influence of gender and severity of cognitive decline, assessed with the Global Deterioration Scale (GDS), was investigated using logistic regression analysis and subsequently corrected for possible confounders, such as age, duration of institutionalization and psychoactive medication use.

Results

While physically aggressive behaviour was more common in patients with very severe cognitive deterioration (GDS stage 7), disinhibition, irritability, physically non‐aggressive and verbally agitated behaviour were more common in patients in GDS stage 5 or 6. Physically aggressive behaviour was more common in men, whereas female patients demonstrated more verbally agitated behaviour. With respect to other neuropsychiatric symptoms, delusions and depression were also more common in patients in GDS stage 5 and 6, while prevalences of anxiety and apathy further increased in severely demented patients (GDS stage 7). Apathy was more prevalent in male patients, while depression and anxiety were more common in females.

Conclusion

In nursing home patients, neuropsychiatric symptoms were associated with the severity of dementia, with most symptoms occurring in patients showing (moderately) severe cognitive decline. Only physical aggression, anxiety and apathy were more common in patients with very severe cognitive decline. Dementia severity and gender were important predictors of neuropsychiatric symptoms in this patient cohort. Copyright © 2009 John Wiley & Sons, Ltd.
Use of physical restraints and antipsychotic medications in nursing homes: a cross‐national study
Authors: Feng Zhanlian , Hirdes John P. , Smith Trevor F. , Finne‐Soveri Harriet , Chi Iris , Du Pasquier Jean‐Noel , Gilgen Ruedi , Ikegami Naoki , Mor Vincent
Published: March 2009

Objectives

This study compares inter‐ and intra‐country differences in the prevalence of physical restraints and antipsychotic medications in nursing homes, and examines aggregated resident conditions and organizational characteristics correlated with these treatments.

Methods

Population‐based, cross‐sectional data were collected using a standardized Resident Assessment Instrument (RAI) from 14,504 long‐term care facilities providing nursing home level services in five countries participating in the interRAI consortium, including Canada, Finland, Hong Kong (Special Administrative Region, China), Switzerland, and the United States. Facility‐level prevalence rates of physical restraints and antipsychotic use were examined both between and within the study countries.

Results

The prevalence of physical restraint use varied more than five‐fold across the study countries, from an average 6% in Switzerland, 9% in the US, 20% in Hong Kong, 28% in Finland, and over 31% in Canada. The prevalence of antipsychotic use ranged from 11% in Hong Kong, between 26–27% in Canada and the US, 34% in Switzerland, and nearly 38% in Finland. Within each country, substantial variations existed across facilities in both physical restraint and antipsychotic use rates. In all countries, neither facility case mix nor organizational characteristics were particularly predictive of the prevalence of either treatment.

Conclusions

There exists large, unexplained variability in the prevalence of physical restraint and antipsychotic use in nursing home facilities both between and within countries. Since restraints and antipsychotics are associated with adverse outcomes, it is important to understand the idiosyncratic factors specific to each country that contribute to variation in use rates. Copyright © 2009 John Wiley & Sons, Ltd.
Buried anterolateral thigh flap for pharyngoesophageal reconstruction: Our method for monitoring
Authors: Spyropoulou Georgia‐Alexandra Ch. , Kuo Yur‐Ren , Chien Chih‐Yen , Yang Johnson Chia‐Shen , Jeng Seng‐Feng
Published: March 2009

Background.

A noninvasive method for monitoring in cases of pharyngoesophageal defects reconstruction with the anterolateral thigh flap is presented.

Methods.

Seventeen patients underwent reconstruction from 2005 to 2007. In 16 patients, the distal stump of the descending branch of lateral circumflex femoral artery (LCFA) was left on the skin surface covered with a transparent film dressing and monitoring was performed by direct observation of the pulsation. In the 17th patient, the pedicle emerged from the transverse branch of the LCFA and dissection of the distal stump for monitoring was impossible; therefore, he was excluded from the study.

Results.

Cessation of the pulsation of the stump was noticed immediately postoperatively in 1 patient because of occlusion of the arterial anastomosis and in a second case 15 hours postoperatively due to a neck hematoma that caused collapse of the vein of the pedicle. Both flaps were salvaged.

Conclusion.

The proposed method of monitoring is simple, reliable, costless, and easily interpreted by the nursing staff. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Preclinical models of HPV+ and HPV− HNSCC in mice: An immune clearance of HPV+ HNSCC
Authors: Williams Robin , Lee Dong Wook , Elzey Bennett D. , Anderson Mary E. , Hostager Bruce S. , Lee John H.
Published: March 2009

Background.

To investigate whether human papilloma virus (HPV)‐specific immune mechanisms can result in tumor clearance, we have created HPV+ and HPV− tonsil cells that form squamous cancers in immune‐competent mice. Here, we determine that an immune‐specific response can clear HPV+ tumor cells and the cellular requirements to mediate this tumor clearance.

Methods.

Through the benefit of this model, we use in vitro and in vivo methods to better understand how HPV+ cells are rejected.

Results.

The data show that an in vivo antigen‐specific antitumor response is generated to HPV+ transformed cells and that this response requires CD4+ and CD8+ cells to mount this antitumor response.

Conclusion.

The findings from this preclinical model will have implications not only in understanding human disease but also as a valuable model for testing immunotherapeutic strategies for HPV+ head and neck cancer. © 2009 Wiley Periodicals, Inc. Head Neck, 2009
Impact of an integrated care program for patients with head and neck cancer on the quality of care
Authors: Ouwens Mariëlle M. M. T. J. , Hermens Rosella R. P. M. G. , Hulscher Marlies M. E. J. L. , Merkx Matthias A. W. , van den Hoogen Frank J. A. , Grol Richard P. , Wollersheim Hub C. H. , Marres Henri A. M.
Published: March 2009

Background.

The management of patients with head and neck cancer is complex, and implementation of an integrated care program might improve the quality of care.

Methods.

A prospective before–after study was performed in 1 clinic for head and neck oncology on 311 adults with head and neck cancer to evaluate an integrated care program.

Results.

Scores on the integrated care indicators showed that the implementation of the integrated care program led to relevant improvements, eg, waiting time for diagnostic procedures less than 10 days (improvement of 37%), support for stopping smoking (+37%), nutrition support (+44%), assessment of CT and MRI scans by a an expert radiologist (+23%), and number of patients in contact with the specialist nurses (+37%). The program had no relevant effects on the outcome indicators.

Conclusion.

An integrated care program can improve several aspects of the management of patients with head and neck cancer. © 2009 Wiley Periodicals, Inc. Head Neck, 2009