bluuebunny/crossref_metadata_2025 huggingface dataset:
SHM
of a Tall Building
Authors: Brownjohn James M. W. , Pan Tso‐Chien
Published: September 2009

A long‐term monitoring program on a 280‐m 65‐story office tower began in 1993 when Shimizu Corporation installed stress and strain gauges at the 18th story during construction. Manual static readings were combined with measurements of fundamental mode natural frequencies, and when the building was completed, a full vibration survey was undertaken, after which a remotely operated monitoring system was installed to track wind velocities along with accelerations at basement and roof levels. The system operated for 10 years, and in its final years global positioning system (GPS) receivers for tracking “absolute” displacements were included. The monitoring system showed gradual changes in building performance over time, but more importantly it provided valuable information about the nature of the dynamic loading experienced due to wind and earthquake. Using the building as a super sensor showed the significance of regional seismic hazard in comparison to the benign wind loading. The system also provided a platform for evaluating structural health monitoring technology including GPS, operational modal analysis, and data mining.
Novelty Detection
Authors: Tarassenko Lionel , Clifton David A. , Bannister Peter R. , King Steve , King Dennis
Published: September 2009

Novelty detection is described here as a data‐driven technique in which a probabilistic model of normality is constructed from (normal) training data, so that subsequent departures from expected behavior can be identified as novel events. The first step in constructing the model of normality is to select features that characterize normal behavior, but which are also likely to change during periods of abnormal behavior. Data visualization techniques, such as the NeuroScale dimensionality‐reduction mapping, are helpful in investigating the distribution of the features over the space of normal data, especially at the boundaries of this space. We show, in this article, how the Parzen windows density estimator can be used to characterize normal vibration behavior and identify an unexpected event during the development phase of a three‐shaft jet engine. We discuss how the novelty threshold may be set in principled fashion using extreme value statistics and present results for two types of vibration feature vectors; one is based on the real‐time measurement of vibration levels at harmonically related frequencies and the other, a speed‐based vibration signature, summarizing the entire flight.
Comprehensive process design study for layered‐NOX‐control in a tangentially coal fired boiler
Authors: Zhou Wei , Moyeda David , Nguyen Quang , Payne Roy
Published: September 2009

As emissions regulations for coal‐fired power plants become stricter worldwide, layering combustion modification and post‐combustion NOX control technologies can be an attractive option for efficient and cost‐effective NOX control in comparison to selective catalytic reduction (SCR) technology. The layered control technology approach designed in this article consists of separate overfire air (SOFA), reburn, and selective noncatalytic reduction (SNCR). The combined system can achieve up to 75% NOX reduction. The work presented in this article successfully applied this technology to NRG Somerset Unit 6, a 120‐MW tangential coal‐fired utility boiler, to reduce NOX emissions to 0.11 lb/MMBtu (130 mg/Nm3), well under the US EPA SIP Call target of 0.15 lb/MMBtu. The article reviews an integrated design study for the layered system at Somerset and evaluates the performance of different layered‐NOX‐control scenarios including standalone SNCR (baseline), separated overfire air (SOFA) with SNCR, and gas reburn with SNCR. Isothermal physical flow modeling and computational fluid dynamics simulation (CFD) were applied to understand the boiler flow patterns, the combustible distributions and the impact of combustion modifications on boiler operation and SNCR performance. The modeling results were compared with field data for model validation and verification. The study demonstrates that a comprehensive process design using advanced engineering tools is beneficial to the success of a layered low NOX system. © 2009 American Institute of Chemical Engineers AIChE J, 2010
Development of a mechanistic model for biological nutrient removal activated sludge systems and application to a full‐scale WWTP
Authors: Ni Bing‐Jie , Xie Wen‐Ming , Liu Shao‐Gen , Yu Han‐Qing , Gan Yi‐Ping , Zhou Jun , Hao Er‐Cheng
Published: September 2009

In wastewater treatment plants (WWTPs) the production of nitrite as an intermediate in the biological nutrient removal (BNR) process has been widely observed, but not been taken into account by most of the conventional activated sludge models yet. This work aims to develop a mechanistic mathematical model to evaluate the BNR process after resolving such a problem. A mathematical model is developed based on the Activated Sludge Model No.3 (ASM3) and the EAWAG Bio‐P model with an incorporation of the two‐step nitrification–denitrification, the anoxic P uptake, and the associated two‐step denitrification by phosphorus accumulating organisms. The database used for simulations originates from a full‐scale BNR municipal wastewater treatment plant. The influent wastewater composition is characterized using batch tests. Model predictions are compared with the measured concentrations of chemical oxygen demand (COD), NH‐N, NO‐N, NO‐N, PO‐P, and mixed liquid volatile suspended solids. Simulation results indicate that the calibrated model is capable of predicting the microbial growth, COD removal, nitrification and denitrification, as well as aerobic and anoxic P removal. Thus, this model can be used to evaluate and simulate full‐scale BNR activated sludge WWTPs. © 2009 American Institute of Chemical Engineers AIChE J, 2009
Genomic duplication of PTPN11 is an uncommon cause of Noonan syndrome
Authors: Graham John M. , Kramer Nancy , Bejjani Bassem A. , Thiel Christian T. , Carta Claudio , Neri Giovanni , Tartaglia Marco , Zenker Martin
Published: September 2009

Noonan syndrome (NS) is a genetically heterogeneous disorder caused most commonly by activating mutations in PTPN11. We report a patient with hypotonia, developmental delay and clinical features suggestive of NS. High‐resolution chromosome analysis was normal, and sequence analyses of PTPN11, SOS1, KRAS, BRAF, RAF1, MEK, and MEK2 were also normal. Array CGH revealed a single copy gain of 9 BAC clones at 12q24.11q24.21 (8.98 Mb in size), which encompassed the PTPN11 locus at 12q24.13 and was confirmed by FISH analysis. Shchelochkov et al. [Shchelochkov et al. (2008); Am J Med Genet Part A 146A:1042–1048] reported a similar case and speculated that such duplications might account for 15–30% of NS cases with no detectable mutation in NS genes. We screened more than 250 NS cases without mutation in known NS disease‐causing genes by quantitative PCR, and none of these studies produced results in the duplicated range. We also explored the possibility that de novo changes affecting the untranslated region (UTR) of the PTPN11 transcript might represent an alternative event involved in SHP2 enhanced expression. DHPLC analysis and direct sequencing of the entire 3′ UTR in 36 NS patients without mutation in known genes did not show any disease‐associated variant. These findings indicate that duplications of PTPN11 represent an uncommon cause of NS, and functionally relevant variations within the 3′UTR of the gene do not appear to play a major role in NS. However, recurrent observations of NS in individuals with duplications involving the PTPN11 locus suggest that increased dosage of SHP2 may have dysregulating effects on intracellular signaling. © 2009 Wiley‐Liss, Inc.
Descriptive epidemiology of nonsyndromic omphalocele in Texas, 1999–2004
Authors: Agopian A. , Marengo L. , Mitchell L.E.
Published: September 2009

Omphalocele is a congenital malformation that involves protrusion of abdominal contents into the umbilicus. Though omphalocele may present as a manifestation of several chromosomal and Mendelian syndromes, the etiology for nonsyndromic omphalocele is unknown. The present study sought to estimate the birth prevalence of nonsyndromic omphalocele in offspring of women residing in Texas from 1999 to 2004, and to describe prevalence as a function of parental and infant demographic characteristics. Data on 325 cases with nonsyndromic omphalocele and 2,208,758 live births delivered during 1999–2004 were obtained from the Texas Birth Defects Registry. These data were used to estimate omphalocele birth prevalence and obtain both crude and adjusted prevalence ratios for the association of nonsyndromic omphalocele with parental and infant demographic characteristics. Nonsyndromic omphaloceles were significantly more common among the offspring of women without previous live births (adjusted prevalence ratio: 1.80, 95% CI: 1.41–2.30), compared to the offspring of women with previous live births. The prevalence of nonsyndromic omphalocele was also increased among women aged 25–29 (adjusted prevalence ratio: 1.68, 95% CI: 1.12–2.50) and women aged 40 and older (adjusted prevalence ratio: 4.83, 95% CI: 2.63–8.86) compared to the offspring of women age <20, and in infants of multiple gestation pregnancies compared to singleton infants (adjusted prevalence ratio: 2.03, 95% CI: 1.22–3.37). In addition, among Hispanic women, the prevalence of nonsyndromic omphalocele was higher in the offspring of those born in the U.S. as compared to those born elsewhere (adjusted prevalence ratio: 1.50, 95% CI: 1.12–2.00). These findings augment the existing omphalocele literature. © 2009 Wiley‐Liss, Inc.
Novel mutations in the calreticulin gene core promoter and coding sequence in schizoaffective disorder
Authors: Olad Nabi M. , Mirabzadeh A. , Feizzadeh G. , Khorram Khorshid H.R. , Karimlou M. , Zarif Yeganeh M. , Asgharian A.M. , Najmabadi H. , Ohadi M.
Published: September 2009

We have recently reported the first case of mutation in the core promoter sequence of the human calreticulin gene in a family case of schizoaffective disorder. Remarkably, this gene coincides with a region of suggested linkage at 19p13.2, identified in a whole genome scan [Hamshere et al. (2005); Arch Gen Psychiatry 62;1081–1088]. The identified mutation was located at the conserved position −48 from the transcription start site, and was shown to be of functional effect, resulting in the aberrant expression of the gene. Following screening of the gene in 60 independent cases of schizoaffective disorder, we report novel germ‐line mutations at positions −205 C > T and the conserved exon 5 (c: 682 C > T, pro228ser) in two unrelated cases of schizoaffective disorder. These mutations were disease‐specific, and as for the −48 G > C mutation, neither was detected in a control population of 370 individuals, indicating a contribution of 3.17% in this sample series. To our knowledge, this is the first instance of disease‐specific mutations in schizoaffective disorder, which warrants systematic screening of the regulatory and coding regions of the calreticulin gene in this disorder. © 2009 Wiley‐Liss, Inc.
Biphasic oligomerization of ethylene with nickel complexes immobilized in organochloroaluminate ionic liquids
Authors: Pei Lixia , Liu Xianmei , Gao Haiyang , Wu Qing
Published: September 2009

Ethylene was selectively oligomerized by nickel complexes such as (PPh3)2NiBr2 and (PPh3)2NiCl2 immobilized in chloroaluminate ionic liquid in biphasic catalytic reactions. The influence of reaction parameters such as reaction media, reaction temperature and Et2AlCl:Ni molar ratio was also evaluated. Turnover frequency up to 24000 mol C2H4/(mol Ni h) was achieved under mild reaction conditions (0.5 atm and 40 °C). GC‐MS analyses showed that the obtained oligomers completely consist of C4 and C6. The olefinic products can be easily separated from the catalytic ionic liquid phase by simple decantation, and the nickel catalyst can be reused without a significant decrease in turnover frequency and change of the distribution of the olefinic products. Copyright © 2009 John Wiley & Sons, Ltd.
Ecdysteroids from Cyanotis longifolia Benth. (Commelinaceae)
Authors: Crouzet Sophie , Maria Annick , Dinan Laurence , Lafont René , Girault Jean‐Pierre
Published: September 2009

Cyanotis longifolia Benth. (Commelinaceae) contains ecdysteroids, which are highly concentrated in the roots and flowers, whereas leaves contain only very low amounts and stems intermediate amounts. 20‐Hydroxyecdysone is the major component found in all tissues, but roots also contain large amounts of 20‐hydroxyecdysone 3‐acetate and ajugasterone C. A preparative experiment has shown that roots contain a complex ecdysteroid mixture, and the analysis of minor components has allowed the isolation of several already known ecdysteroids (polypodine B, 2‐deoxy‐20,26‐dihydroxyecdysone, isovitexirone, poststerone) together with five new (ajugasterone C 3‐acetate, 5β‐hydroxy‐poststerone, poststerone 2‐acetate, 14(15)‐dehydro‐poststerone 2‐acetate, 24‐epi‐atrotosterone A [=24‐methyl‐ajugasterone C]) ecdysteroids that have been fully characterized. A preliminary investigation of 55 species belonging to 15 different genera of the Commelinaceae has shown that several of them contain significant concentrations of ecdysteroids, among which some previously uninvestigated ones appear to be very promising sources of ecdysteroids. © 2009 Wiley Periodicals, Inc.
Der Hydraulische Grundbruch – Bemessungsdiagramme zur Ermittlung der erforderlichen Einbindetiefe
Authors: Ziegler Martin , Aulbach Benjamin , Heller Hartmut , Kuhlmann Dieter
Published: September 2009

Für den Nachweis der Sicherheit gegen hydraulischen Grundbruch werden oftmals Näherungsverfahren zur Bestimmung der Strömungskraft verwendet. Nach DIN 1054 ist die Strömungskraft jedoch in der Regel durch Auswertung von Strömungsnetzen zu ermitteln. Im Rahmen eines vom Deutschen Institut für Bautechnik geförderten Forschungsvorhabens wurden am Lehrstuhl für Geotechnik im Bauwesen der RWTH Aachen in Zusammenarbeit mit der Wayss & Freytag Ingenieurbau AG Untersuchungen zur erforderlichen Einbindetiefe zur Gewährleistung der Sicherheit gegen hydraulischen Grundbruch angestellt. Als Ergebnis der auf der Auswertung von Strömungsnetzen beruhenden Untersuchungen entstanden dimensionslose Bemessungsdiagramme, welche es ermöglichen, die erforderliche Einbindetiefe der seitlichen Baugrubenwände in Abhängigkeit der geometrischen Randbedingungen auf einfachem Wege zu ermitteln.

The Hydraulic Heave – Design charts for determining the necessary embedded length.

Often simplified calculation methods are used to determine the seepage force for the proof of safety against hydraulic heave. However, according to DIN 1054 the seepage force normally has to be determined by means of a flow net. Within the framework of a research project, which was funded by Deutsches Institut für Bautechnik, the required embedded length for the safety against hydraulic heave was investigated at the Chair of Geotechnical Engineering at RWTH Aachen University in collaboration with Wayss & Freytag Ingenieurbau AG. As a result of the research dimensionless design charts have been generated based on the analysis of flow nets. These design charts easily allow determining the required embedded length of the lateral wall of a building pit with respect to the geometrical boundary conditions.
Reduktion der Frosthebungen bei der künstlichen Bodenvereisung
Authors: Zhou Guoqing , Zou Yazhou , Boley Conrad
Published: September 2009

Mit dem Ziel der Reduktion der Frosthebungen bei der künstlichen Bodenvereisung wurden die Einflüsse des Temperaturgradienten, der Temperaturänderung sowie der Temperaturänderungsamplitude und ‐periode der Vereisungstemperatur auf die Frosthebungen bei der eindimensionalen Frosteindringung in feinkörnige Böden experimentell im Labor untersucht. Bei der Frosteindringung in feinkörnige Böden ist die Frosthebung infolge der Bildung der untersten Eislinse (letzte Eislinse bei Frostung von oben nach unten) im thermodynamisch stationären Zustand maßgebend. Der Temperaturgradient beeinflusst zwar die Frosteindringtiefe, die Größe der Frosthebung dagegen nur in geringem Maße. Durch zyklische Veränderungen der Vereisungstemperatur kann das Wachstum der letzten Eislinse beschränkt und dadurch die Frosthebung vermindert werden. Die zyklische Veränderung der Vereisungstemperatur bereits vor der Bildung der letzten Eislinse führt dagegen zu einer großen Frosthebung. Zur Minimierung der Frosthebung müssen die Temperaturveränderungsamplitude und ‐periode während der Vereisung auf die Eislinsenbildung abgestimmt werden.

Decreasing frost heaves of artificial frozen soils by intermission freezing.

For decreasing the frost heaves of artificially frozen soils the influences of temperature gradient, its changes as well as the amplitude and period of changing freezing temperature on the one‐dimensional frost heaves of fine‐grained soils were investigated by experiments in the laboratory. During the frost penetration into the fine‐grained soils the frost heaves due to the formation of the final ice lens under thermodynamic stationary condition is decisive. The gradient of temperature influences strongly the depth of frost penetration but only little the total frost heave. Cyclical changes of the freezing temperature can confine the growth of the final ice lens and thereby the frost heave decreases. However, the cyclical changes of the freezing temperature before the formation of the final ice lens can cause a heavy frost heave. For decreasing frost heaves the amplitude und period of changing the freezing temperature must be controlled properly.
Windkraftwerke–Umwelt, Bemessung, Perspektiven
Authors: Noakowski Piotr , Harling Andreas , Breddermann Martin , Rost Markus , Hoffmeister Hermann
Published: September 2009

Die globale Erwärmung wird offensichtlich durch eine Membrane aus Industriegasen verursacht, die bei der konventionellen Energiegewinnung entstehen. Die zur Zeit vorherrschende Meinung besagt, dass die derzeitigen Naturkatastrophen Folgen dieser Umweltverschmutzung sind. Eine der Reaktionen der hochentwickelten Welt ist die Forcierung von erneuerbaren Energiequellen wie Biomasse, Wasser, Sonne und Wind. Wind ist definitive die wichtigste Alternative zu den fossilen Brennstoffen, und deshalb gehören Windkraftanlagen zu den wichtigsten Bauarten der nahen Zukunft.

In diesem Beitrag wird “The state of the art” von Windkraftanlagen behandelt. Entsprechend dem hohen Stellenwert dieser turmartigen Massenbauwerke stehen dabei Lösungen ihrer beiden bautechnischen Fragen – Sicherheit und Wirtschaftlichkeit – im Vordergrund, untermauert durch drei Kernthemen:

– Merkmale, Grundlagen, maßgebliche Tragrichtungen

– vertikale Tragrichtung mit einem Erläuterungsbeispiel

– horizontale Tragrichtung mit einem Erläuterungsbeispiel

Der Aufsatz schließt mit Ausführungen über die aktuellen Herausforderungen und Entwicklungstendenzen der Energiegewinnung aus Windkraft.

Wind Power Plants – Environment, design, outlook and scope.

The today's world is confronted by two global threats: worming effect caused probably by the excessive use of fossil fuels and dependence on these becoming short sources of energy.

The worming effect is caused by a membrane of gases produced among others during the conventional energy generation. There are voices claiming that some of the current natural disasters are consequences of such air pollution.

One of the reactions of the highly developed world is use of renewable energy sources such as bio mass, water, sun and wind. Wind is definitive the most important alternatives to the fossil fuels and so wind mills belong to the most important structures of the near future.

Consequently, the paper addresses the following major issues regarding modern structural design of wind mills:

– Basis of structural design: Structural features, design principles, bearing directions

– vertical bearing direction: Design process, design tools, design example

– horizontal bearing direction: Design process, design tools, design example
Making Epothilones Fluoresce: Design, Synthesis, and Biological Characterization of a Fluorescent N12‐Aza‐Epothilone (Azathilone)
Authors: Gertsch Jürg , Feyen Fabian , Bützberger Alexander , Gerber Barbara , Pfeiffer Bernhard , Altmann Karl‐Heinz
Published: September 2009

A green fluorescent 12‐aza‐epothilone (azathilone) derivative has been prepared through the attachment of the 4‐nitro‐2,1,3‐benzoxadiazole (NBD) fluorophore to the 12‐nitrogen atom of the azamacrolide core structure. While less potent than natural epothilones or different N12‐acylated azathilone derivatives, NBD‐azathilone (3) promotes tubulin assembly, inhibits cancer cell proliferation in vitro and arrests the cell cycle at the G2/M transition. Most significantly, the binding of 3 to cellular microtubules (MTs) could be directly visualized by confocal fluorescence microscopy. Based on competition binding experiments with laulimalide‐stabilized MTs in vitro, the N12‐Boc substituted azathilone 1, Epo A, and NBD‐azathilone (3) all interact with the same tubulin‐binding site. Computational studies provided a structural model of the complexes between β‐tubulin and 1 or 3, respectively, in which the NBD moiety of 3 or the BOC moiety of 1 directly and specifically contribute to MT binding. Collectively, these data demonstrate that the cellular effects of 3 and, by inference, also of other azathilones are the result of their interactions with the cellular MT network.
Controlling the Conformational Changes in Donor–Acceptor [4]‐Dendralenes through Intramolecular Charge‐Transfer Processes
Authors: Kanibolotsky Alexander L. , Forgie John C. , McEntee Greg J. , Talpur M. Munsif A. , Skabara Peter J. , Westgate Thomas D. J. , McDouall Joseph J. W. , Auinger Michael , Coles Simon J. , Hursthouse Michael B.
Published: September 2009

The synthesis of two [4]‐dendralene compounds incorporating thiophene‐(p‐nitrophenyl) donor–acceptor units is presented. The dendralenes adopt two different conformers in solution and solid state and the transformation between the structures can be controlled by light and heat. The electron‐donating components of the dendralenes are represented by bromothienyl (in 13) and ethylenedioxythiophene(EDOT)‐thienyl (in 15) end‐groups. The most facile transformation involves the isomerisation of donor–acceptor conjugated systems (a conformers) into structures in which only the thiophenes are conjugated (b conformers), and this process is driven by ambient light. The structures of the two conformers of compound 13 are confirmed by single‐crystal X‐ray diffraction studies and the structural changes in both compounds have been monitored by 1H NMR spectroscopy and absorption studies. The transformations were found to be first‐order processes with rate constants of k=0.0027 s−1 and k=0.00022 s−1 for 13 and 15, respectively. Density functional theory calculations at the B3LYP/6‐31G* level give credence to the proposed mechanism for the a→b conversion, which involves photoinduced intramolecular charge transfer (ICT) as the key step. The EDOT derivative (15) can be polymerised by electrochemical oxidation and a combination of cyclic voltammetry and UV/Vis spectroelectrochemical experiments indicate that the a conformer can be trapped and stabilised in the solid state.
An Organocatalytic Asymmetric Tandem Reaction for the Construction of Bicyclic Skeletons
Authors: Cao Chun‐Li , Zhou You‐Yun , Zhou Jian , Sun Xiu‐Li , Tang Yong , Li Yu‐Xue , Li Guang‐Yu , Sun Jie
Published: September 2009

Cyclic ketones react with (E)‐2‐nitroallylic acetates in the presence of catalytic pyrrolidine‐thiourea, which affords bicyclic skeletons with four or five stereocenters in one single reaction with up to 98 % eein moderate to high yields. The cooperative effects of both enamine and the Brønsted acid are found to be crucial for the high reactivity and enantioselectivity of this cascade reaction, which is demonstrated by both theoretical calculation and experimental data.
Homoleptic Organoderivatives of High‐Valent Nickel(III)
Authors: Alonso Pablo J. , Arauzo Ana B. , García‐Monforte María Angeles , Martín Antonio , Menjón Babil , Rillo Conrado , Tomás Milagros
Published: September 2009

Homoleptic perhalophenyl derivatives of divalent nickel complexes with the general formula [NBu4]2[NiII(C6X5)4] [X=F (1), Cl (2)] have been prepared by low‐temperature treatment of the halo‐complex precursor [NBu4]2[NiBr4] with the corresponding organolithium reagent LiC6X5. Compounds 1 and 2 are electrochemically related by reversible one‐electron exchange processes with the corresponding organometallate(III) compounds [NBu4][NiIII(C6X5)4] [X=F (3), Cl (4)]. The potentials of the [NiIII(C6X5)4]−/[NiII(C6X5)4]2− couples are +0.07 and −0.11 V for X=F or Cl, respectively. Compounds 3 and 4 have also been prepared and isolated in good yield by chemical oxidation of 1 or 2 with bromine or the amminium salt [N(C6H4Br‐4)3][SbCl6]. The [NiIII(C6X5)4]− species have SP‐4 structures in the salts 3 and 4, as established by single‐crystal X‐ray diffraction methods. The [NiII(C6F5)4]2− ion in the parent compound 1 has also been found to exhibit a rather similar SP‐4 structure. According to their SP‐4 geometry, the NiIII compounds (d7) behave as S=1/2 systems both at microscopic (EPR) and macroscopic levels (ac and dc magnetization measurements). The spin Hamiltonian parameters obtained from the analysis of the magnetic behavior of 3 and 4 within the framework of ligand field theory show that the unpaired electron is centered mainly on the metal atom, with >97 % estimated d contribution. Thermal decomposition of 3 and 4 proceeds with formation of the corresponding C6X5C6X5 coupling compounds.
Modification of Supramolecular Binding Motifs Induced By Substrate Registry: Formation of Self‐Assembled Macrocycles and Chain‐Like Patterns
Authors: Fendt Leslie‐Anne , Stöhr Meike , Wintjes Nikolai , Enache Mihaela , Jung Thomas A. , Diederich François
Published: September 2009

The self‐assembly properties of two ZnII porphyrin isomers on Cu(111) are studied at different coverage by means of scanning tunneling microscopy (STM). Both isomers are substituted in their meso‐positions by two voluminous 3,5‐di(tert‐butyl)phenyl and two rod‐like 4′‐cyanobiphenyl groups, respectively. In the trans‐isomer, the two 4′‐cyanobiphenyl groups are opposite to each other, whereas they are located at right angle in the cis‐isomer. For coverage up to one monolayer, the cis‐substituted porphyrins self‐assemble to form oligomeric macrocycles held together by antiparallel CN⋅⋅⋅CN dipolar interactions and CN⋅⋅⋅H‐C(sp2) hydrogen bonding. Cyclic trimers and tetramers occur most frequently but everything from cyclic dimers to hexamers can be observed. Upon annealing of the samples at temperatures >150 °C, dimeric macrocyclic structures are observed, in which the two porphyrins are bridged by Cu atoms, originating from the surface, under formation of two CN⋅⋅⋅Cu⋅⋅⋅NC coordination bonds. The trans‐isomer builds up linear chains on Cu(111) at low coverage, whereas for higher coverage the molecules assemble in a periodic, densely packed structure. Both cis‐ and trans‐bis(4′‐cyanobiphenyl)‐substituted ZnII porphyrins behave very differently on Cu(111) compared to similar porphyrins in literature on less reactive surfaces such as Au(111) and Ag(111). On the latter surfaces, there is no signal visible between molecular orientation and the crystal directions of the substrate, whereas on Cu(111), very strong adsorbate–substrate interactions have a dominating influence on all observed structures. This strong porphyrin–substrate interaction enables a much broader variety of structures, including also less favorable intermolecular bonding motifs and geometries.
Red‐ and Green‐Emitting Iridium(III) Complexes for a Dual Barometric and Temperature‐Sensitive Paint
Authors: Fischer Lorenz H. , Stich Matthias I. J. , Wolfbeis Otto S. , Tian Nan , Holder Elisabeth , Schäferling Michael
Published: September 2009

A new dual luminescent sensitive paint for barometric pressure and temperature (T) is presented. The green‐emitting iridium(III) complex [Ir(ppy)2(carbac)] (ppy=2‐phenylpyridine; carbac=1‐(9H‐carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐dione) was applied as a novel probe for T along with the red‐emitting complex [Ir(btpy)3], (btpy=2‐(benzo[b]thiophene‐2‐yl)pyridine) which functions as a barometric (in fact oxygen‐sensitive) probe. Both iridium complexes were dissolved in different polymer materials to achieve optimal responses. The probe [Ir(ppy)2(carbac)] was dispersed in gas‐blocking poly(acrylonitrile) microparticles in order to suppress any quenching of its luminescence by oxygen. The barometric probe [Ir(btpy)3], in turn, was incorporated in a cellulose acetate butyrate film which exhibits good permeability for oxygen. The effects of temperature on the response of the oxygen probe can be corrected by simultaneous optical determination of T, as the poly(acrylonitrile) microparticles containing the temperature indicator are incorporated into the film. The phosphorescent signals of the probes for T and barometric pressure, respectively, can be separated by optical filters due to the ≈75 nm difference in their emission maxima. The dual sensor is applicable to luminescence lifetime imaging of T and barometric pressure. It is the first luminescent dual sensor material for barometric pressure/T based exclusively on the use of IrIII complexes in combination with luminescence lifetime imaging.
Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes
Authors: Barrios Leoní A. , Aguilà David , Roubeau Olivier , Gamez Patrick , Ribas‐Ariño Jordi , Teat Simon J. , Aromí Guillem
Published: September 2009

The ligand 1,3‐bis[3‐oxo‐3‐(2‐hydroxyphenyl)propionyl]benzene (H4L), designed to align transition metals into tetranuclear linear molecules, reacts with MII salts (M=Ni, Co, Cu) to yield complexes with the expected [MM⋅⋅⋅MM] topology. The novel complexes [Co4L2(py)6] (2; py=pyridine) and [Na(py)2][Cu4L2(py)4](ClO4) (3) have been crystallographically characterised. The metal sites in complexes 2 and 3, together with previously characterised [Ni4L2(py)6] (1), favour different coordination geometries. These have been exploited for the deliberate synthesis of the heterometallic complex [Cu2Ni2L2(py)6] (4). Complexes 1, 2, 3 and 4 exhibit antiferromagnetic interactions between pairs of metals within each cluster, leading to S=0 spin ground states, except for the latter cluster, which features two quasi‐independent S=1/2 moieties within the molecule. Complex 4 gathers the structural and physical conditions, thus allowing it to be considered as prototype of a two‐qbit quantum gate.
Axially Chiral Facial Amphiphiles with a Dihydronaphthopentaphene Structure as Molecular Tweezers for SWNTs
Authors: Marquis Renaud , Kulikiewicz Krystyna , Lebedkin Sergei , Kappes Manfred M. , Mioskowski Charles , Meunier Stéphane , Wagner Alain
Published: September 2009

Syntheses of chiral 6,15‐dihydronaphtho[2,3‐c]pentaphene derivatives of opposite configurations are reported. Starting from anthracene, the strategy involves two key steps: a Diels–Alder reaction on a prochiral dianthraquinone, and an enantiomeric resolution using (−)‐menthol. The final molecules exhibit very strong optical activity, as shown by their circular dichroism spectra, and are examples of chiral facial amphiphiles. Their adsorption at the surface of single‐walled carbon nanotubes (SWNTs) has also been studied, and has been found to occur preferentially on 0.8–1.0 nm diameter nanotubes among the population of a high‐pressure CO conversion (HiPco) SWNT sample (0.8–1.2 nm). The synthesised facial amphiphiles act as nano‐tweezers for the diameter‐selective solubilisation of SWNTs in water. The expected optical activities of the SWNT samples solubilised by each of the chiral amphiphiles have been studied by circular dichroism spectroscopy, but the results are not yet conclusive.
Total Synthesis of the Bicyclic Depsipeptide HDAC Inhibitors Spiruchostatins A and B, 5′′‐epi‐Spiruchostatin B, FK228 (FR901228) and Preliminary Evaluation of Their Biological Activity
Authors: Narita Koichi , Kikuchi Takuya , Watanabe Kazuhiro , Takizawa Toshiya , Oguchi Takamasa , Kudo Kyosuke , Matsuhara Keisuke , Abe Hideki , Yamori Takao , Yoshida Minoru , Katoh Tadashi
Published: September 2009

The bicyclic depsipeptide histone deacetylase (HDAC) inhibitors spiruchostatins A and B, 5′′‐epi‐spiruchostatin B and FK228 were efficiently synthesized in a convergent and unified manner. The synthetic method involved the following crucial steps: i) a Julia–Kocienski olefination of a 1,3‐propanediol‐derived sulfone and a L‐ or D‐malic acid‐derived aldehyde to access the most synthetically challenging unit, (3S or 3R,4E)‐3‐hydroxy‐7‐mercaptohept‐4‐enoic acid, present in a D‐alanine‐ or D‐valine‐containing segment; ii) a condensation of a D‐valine‐D‐cysteine‐ or D‐allo‐isoleucine‐D‐cysteine‐containing segment with a D‐alanine‐ or D‐valine‐containing segment to directly assemble the corresponding seco‐acids; and iii) a macrocyclization of a seco‐acid using the Shiina method or the Mitsunobu method to construct the requisite 15‐ or 16‐membered macrolactone. The present synthesis has established the C5′′ stereochemistry of spiruchostatin B. In addition, HDAC inhibitory assay and the cell‐growth inhibition analysis of the synthesized depsipeptides determined the order of their potency and revealed some novel aspects of structure–activity relationships. It was also found that unnatural 5′′‐epi‐spiruchostatin B shows extremely high selectivity (ca. 1600‐fold) for class I HDAC1 (IC50=2.4 nM) over class II HDAC6 (IC50=3900 nM) with potent cell‐growth‐inhibitory activity at nanomolar levels of IC50 values.
Supramolecular Architectures by Fullerene‐Bridged Bis(permethyl‐β‐cyclodextrin)s with Porphyrins
Authors: Zhang Ying‐Ming , Chen Yong , Yang Yang , Liu Peng , Liu Yu
Published: September 2009

The Hirsch–Bingel reaction of bis{4‐methyl[1,2,3]triazolyl}malonic ester‐bridged bis(permethyl‐β‐cyclodextrin) 1 with C60 has led to the formation of a new fullerene‐bridged bis(permethyl‐β‐cyclodextrin) 2, which has been comprehensively characterized by NMR spectroscopy, MALDI‐MS, and elemental analysis. Taking advantage of the high affinity between 2 and 5,10,15,20‐tetrakis(4‐sulfonatophenyl)porphyrin (3) or [5,10,15,20‐tetrakis(4‐sulfonatophenyl)porphinato]zinc(II) (4), linear supramolecular architectures with a width of about 2 nm and a length ranging from hundreds of nanometers to micron dimension were conveniently constructed and fully investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM). Significantly, the photoinduced electron‐transfer (PET) process between porphyrin and C60 moieties takes place within the 2⋅3 and 2⋅4 supramolecular architectures under light irradiation, leading to the highly efficient quenching of the porphyrin fluorescence. The PET process and the charge‐separated state were investigated by means of fluorescence spectroscopy, fluorescence decay, cyclic voltammetry, and nanosecond transient absorption measurements.
Efficient Synthesis of Cryptophycin‐52 and Novel para‐Alkoxymethyl Unit A Analogues
Authors: Eißler Stefan , Bogner Tobias , Nahrwold Markus , Sewald Norbert
Published: September 2009

Cryptophycins are a family of highly cytotoxic, cyclic depsipeptides. They display antitumour activity that is largely maintained for multi‐drug‐resistant tumour cells. Cryptophycins are composed of four building blocks (units A–D) that correspond to the respective amino and hydroxy acids. A new synthetic route to unit A allows the selective generation of all four stereogenic centres in a short, efficient and reliable synthesis and contributes to an easier and faster synthesis of cryptophycins. The first two stereogenic centres are introduced by a catalytic asymmetric dihydroxylation, whereas the remaining two stereogenic centres are introduced with substrate control of diastereoselectivity. The stereogenic diol function also serves as the epoxide precursor. The approach was used to synthesise the native unit A building block as well as three para‐alkoxymethyl analogues from which cryptophycin‐52 and three analogous cryptophycins were prepared. Macrocyclisation of the seco‐depsipeptides was based on ring‐closing metathesis.
Estimation in capture–recapture models when covariates are subject to measurement errors and missing data
Authors: Xi Liqun , Watson Ray , Wang Ji‐Ping , Yip Paul S. F.
Published: September 2009

For capture–recapture models when covariates are subject to measurement errors and missing data, a set of estimating equations is constructed to estimate population size and relevant parameters. These estimating equations can be solved by an algorithm similar to the EM algorithm. The proposed method is also applicable to the situation when covariates with no measurement errors have missing data. Simulation studies are used to assess the performance of the proposed estimator. The estimator is also applied to a capture–recapture experiment on the bird speciesPrinia flaviventrisin Hong Kong. The Canadian Journal of Statistics 37: 645–658; 2009 © 2009 Statistical Society of Canada
Distribution of prolactin‐responsive neurons in the mouse forebrain
Authors: Brown Rosemary S.E. , Kokay Ilona C. , Herbison Allan E. , Grattan David R.
Published: September 2009

Prolactin has numerous biological actions in the brain, and transgenic mice are increasingly being used to investigate these actions. The present study aimed to provide a detailed mapping of the prolactin‐responsive neurons in the female mouse forebrain by describing the distribution of prolactin receptor mRNA by in situ hybridization, and measuring prolactin‐induced phosphorylation of signal transducer and activation of transcription 5 (pSTAT5) by immunohistochemistry. For in situ hybridization, a probe designed to detect both long and short receptor isoforms showed mRNA expression in a heterogeneous manner within the forebrain. Strong expression was observed in the rostral hypothalamus, particularly in periventricular regions, as well as in the arcuate and ventromedial nuclei of the mediobasal hypothalamus. There was also significant expression in some nonhypothalamic regions, notably high expression in the choroid plexus, and lower levels of expression in the medial amygdala, bed nucleus of the stria terminalis, and lateral septum. Prolactin‐induced pSTAT5, detected by immunohistochemistry, provided a functional index of prolactin receptor activation in neurons. Prolactin‐induced pSTAT5 was only observed in areas containing prolactin receptor mRNA, and was particularly prominent in the rostral and mediobasal hypothalamus. Most other areas that contained prolactin receptor mRNA also showed positive signal for prolactin‐induced pSTAT5. The major exceptions were paraventricular nucleus and median preoptic nucleus, in which prolactin receptor mRNA was observed, but no induction of pSTAT5 by prolactin. The data provide key neuroanatomical information facilitating the use of the mouse model for furthering our understanding of prolactin actions in the brain. J. Comp. Neurol. 518:92–102, 2010. © 2009 Wiley‐Liss, Inc.
Differential localization of γ‐aminobutyric acid type a and glycine receptor subunits and gephyrin in the human pons, medulla oblongata and uppermost cervical segment of the spinal cord: An immunohistochemical study
Authors: Waldvogel H.J. , Baer K. , Eady E. , Allen K.L. , Gilbert R.T. , Mohler H. , Rees M.I. , Nicholson L.F.B. , Faull R.L.M.
Published: September 2009

Gephyrin is a multifunctional protein responsible for the clustering of glycine receptors (GlyR) and γ‐aminobutyric acid type A receptors (GABAAR). GlyR and GABAAR are heteropentameric chloride ion channels that facilitate fast‐response, inhibitory neurotransmission in the mammalian brain and spinal cord. We investigated the immunohistochemical distribution of gephyrin and the major GABAAR and GlyR subunits in the human light microscopically in the rostral and caudal one‐thirds of the pons, in the middle and caudal one‐thirds of the medulla oblongata, and in the first cervical segment of the spinal cord. The results demonstrate a widespread pattern of immunoreactivity for GlyR and GABAAR subunits throughout these regions, including the spinal trigeminal nucleus, abducens nucleus, facial nucleus, pontine reticular formation, dorsal motor nucleus of the vagus nerve, hypoglossal nucleus, lateral cuneate nucleus, and nucleus of the solitary tract. The GABAAR α1and GlyR α1and β subunits show high levels of immunoreactivity in these nuclei. The GABAAR subunits α2, α3, β2,3, and γ2present weaker levels of immunoreactivity. Exceptions are intense levels of GABAAR α2subunit immunoreactivity in the inferior olivary complex and high levels of GABAAR α3subunit immunoreactivity in the locus coeruleus and raphe nuclei. Gephyrin immunoreactivity is highest in the first segment of the cervical spinal cord and hypoglossal nucleus. Our results suggest that a variety of different inhibitory receptor subtypes is responsible for inhibitory functions in the human brainstem and cervical spinal cord and that gephyrin functions as a clustering molecule for major subtypes of these inhibitory neurotransmitter receptors. J. Comp. Neurol. 518:305–328, 2010. © 2009 Wiley‐Liss, Inc.
Selective long‐term reorganization of the corticospinal projection from the supplementary motor cortex following recovery from lateral motor cortex injury
Authors: McNeal David W. , Darling Warren G. , Ge Jizhi , Stilwell‐Morecraft Kimberly S. , Solon Kathryn M. , Hynes Stephanie M. , Pizzimenti Marc A. , Rotella Diane L. , Tyler Vanadurongvan  , Morecraft Robert J.
Published: September 2009

Brain injury affecting the frontal motor cortex or its descending axons often causes contralateral upper extremity paresis. Although recovery is variable, the underlying mechanisms supporting favorable motor recovery remain unclear. Because the medial wall of the cerebral hemisphere is often spared following brain injury and recent functional neuroimaging studies in patients indicate a potential role for this brain region in the recovery process, we investigated the long‐term effects of isolated lateral frontal motor cortical injury on the corticospinal projection (CSP) from intact, ipsilesional supplementary motor cortex (M2). After injury to the arm region of the primary motor (M1) and lateral premotor (LPMC) cortices, upper extremity recovery is accompanied by terminal axon plasticity in the contralateral CSP but not the ipsilateral CSP from M2. Furthermore, significant contralateral plasticity occurs only in lamina VII and dorsally within lamina IX. Thus, selective intraspinal sprouting transpires in regions containing interneurons, flexor‐related motor neurons, and motor neurons supplying intrinsic hand muscles, which all play important roles in mediating reaching and digit movements. After recovery, subsequent injury of M2 leads to reemergence of hand motor deficits. Considering the importance of the CSP in humans and the common occurrence of lateral frontal cortex injury, these findings suggest that spared supplementary motor cortex may serve as an important therapeutic target that should be considered when designing acute and long‐term postinjury patient intervention strategies aimed to enhance the motor recovery process following lateral cortical trauma. J. Comp. Neurol. 518:586–621, 2010. © 2009 Wiley‐Liss, Inc.
Melanocortin‐4 receptor expression in a vago‐vagal circuitry involved in postprandial functions
Authors: Gautron Laurent , Lee Charlotte , Funahashi Hisayuki , Friedman Jeffrey , Lee Syann , Elmquist Joel
Published: September 2009

Vagal afferents regulate energy balance by providing a link between the brain and postprandial signals originating from the gut. In the current study, we investigated melanocortin‐4 receptor (MC4R) expression in the nodose ganglion, where the cell bodies of vagal sensory afferents reside. By using a line of mice expressing green fluorescent protein (GFP) under the control of the MC4R promoter, we found GFP expression in approximately one‐third of nodose ganglion neurons. By using immunohistochemistry combined with in situ hybridization, we also demonstrated that ∼20% of GFP‐positive neurons coexpressed cholecystokinin receptor A. In addition, we found that the GFP is transported to peripheral tissues by both vagal sensory afferents and motor efferents, which allowed us to assess the sites innervated by MC4R‐GFP neurons. GFP‐positive efferents that co‐expressed choline acetyltransferase specifically terminated in the hepatic artery and the myenteric plexus of the stomach and duodenum. In contrast, GFP‐positive afferents that did not express cholinergic or sympathetic markers terminated in the submucosal plexus and mucosa of the duodenum. Retrograde tracing experiments confirmed the innervation of the duodenum by GFP‐positive neurons located in the nodose ganglion. Our findings support the hypothesis that MC4R signaling in vagal afferents may modulate the activity of fibers sensitive to satiety signals such as cholecystokinin, and that MC4R signaling in vagal efferents may contribute to the control of the liver and gastrointestinal tract. J. Comp. Neurol. 518:6–24, 2010. © 2009 Wiley‐Liss, Inc.
Differentiation of papillae and rostral sensory neurons in the larva of the ascidian Botryllus schlosseri (Tunicata)
Authors: Caicci Federico , Zaniolo Giovanna , Burighel Paolo , Degasperi Valentina , Gasparini Fabio , Manni Lucia
Published: September 2009

During the metamorphosis of tunicate ascidians, the swimming larva uses its three anterior papillae to detect the substrate for settlement, reabsorbs its chordate‐like tail, and becomes a sessile oozooid. In view of the crucial role played by the anterior structures and their nerve relations, we applied electron microscopy and immunocytochemistry to study the larva of the colonial ascidian Botryllus schlosseri, following differentiation of the anterior epidermis during late embryogenesis, the larval stage, and the onset of metamorphosis. Rudiments of the papillae appear in the early tail‐bud stage as ectodermic protrusions, the apexes of which differentiate into central and peripheral bipolar neurons. Axons fasciculate into two nerves direct to the brain. Distally, the long, rod‐like dendritic terminations extend during the larval stage, becoming exposed to sea water. After the larva selects and adheres to the substrate, these neurons retract and regress. Adjacent to the papillae, other scattered neurons insinuate dendrites into the tunic and form the net of rostral trunk epidermal neurons (RTENs) which fasciculate together with the papillary neurons. Our data indicate that the papillae are simple and coniform, the papillary neurons are mechanoreceptors, and the RTENs are chemoreceptors. The interpapillary epidermal area, by means of an apocrine secretion, provides sticky material for temporary adhesion of the larva to the substrate. J. Comp. Neurol. 518:547–566, 2010. © 2009 Wiley‐Liss, Inc.