bluuebunny/crossref_metadata_2025 huggingface dataset:
Distribution and fate of cocaine‐ and amphetamine‐regulated transcript peptide (CARTp)‐expressing cells in rat urinary bladder: A developmental study
Authors: Zvarova Katarina , Vizzard Margaret A.
Published: July 2005

We examined the distribution and fate of cocaine‐ and amphetamine‐regulated transcript peptide (CARTp)55–102‐immunoreactive (IR) structures in the neonatal and adult rat urinary bladder. Double‐labeling studies examining CARTp with tyrosine hydroxylase (TH), neuronal nitric oxide synthase (nNOS), or choline acetyltransferase (ChAT) were performed in wholemounts of urothelium or detrusor or cryostat sections of the bladder. In younger animals (postnatal day [P]1, P3), CARTp‐IR cell bodies in detrusor smooth muscle were observed in large clusters (∼100 cells/cluster) at the ureteral insertion and along thick bundles of nerve fibers at the bladder base. The total number of CARTp‐IR cells was significantly reduced (by five‐fold) at P14, and this reduced number persisted into adulthood. The decrease in the number of CARTp‐expressing cells was complemented with positive staining for cleaved caspase‐3, suggesting that apoptosis contributed to this decrease. At birth (P1), all CARTp‐IR cells expressed the neuronal marker Hu. After birth, CARTp was expressed by some neurons (CARTp‐IR, Hu‐IR) that represent intramural ganglion cells and by cells that lacked a neuronal phenotype (CARTp‐IR, Hu‐) but did express TH. Neither of these cell populations expressed ChAT immunoreactivity in adult bladder. These cells (CARTp‐IR, Hu‐, TH‐IR) may represent paraganglion or small intensely fluorescent (SIF) cells. The percentage of colocalization of CARTp‐IR and nNOS or TH was dependent on postnatal age and showed an inverse relationship. At P1, 67.1 % of CARTp‐IR cells expressed nNOS immunoreactivity. Decreased colocalization was observed with increasing postnatal age. In contrast, 19.5% of CARTp‐IR cells expressed TH at P1, but colocalization increased with postnatal age. The suburothelial plexus lacked CARTp‐IR nerve fibers until P14, when nerve fibers with varicosities were observed in the urethra and bladder neck region. In summary, we demonstrate 1) a decrease in the number of CARTp‐IR cells in rat detrusor in early postnatal development; 2) apoptotic events in the bladder during early postnatal development; 3) rostral migration of CARTp‐IR cells from the ureteral insertion toward the bladder body during postnatal development; 4) the presence of different populations of CARTp‐IR cells, some with and others without a neuronal phenotype; and (5) age‐dependent changes in chemical coding of CARTp‐IR cells with postnatal development. This study demonstrates that CARTp‐IR intramural ganglia and CARTp‐IR paraganglion or SIF cells exist in the postnatal and adult rat bladder, although the role of these cell types remains to be determined. J. Comp. Neurol. 489:501–517, 2005. © 2005 Wiley‐Liss, Inc.
Region control and approximation of a weighted rational interpolating curves
Authors: Duan Qi , Zhang Yunfeng , Wang Liqiu , Twizell E. H.
Published: July 2005

A weighted rational cubic spline interpolation has been constructed using two kinds of rational cubic spline with quadratic denominator. The sufficient conditions that constrain the interpolant curves to be in the given region are derived, also the error estimate formulas of this interpolation are obtained. Copyright © 2005 John Wiley & Sons, Ltd.
Levels of gli3 repressor correlate with bmp4 expression and apoptosis during limb development
Authors: Bastida Maria Félix , Delgado M. Dolores , Wang Baolin , Fallon John F. , Fernandez‐Teran Marian , Ros Maria A.
Published: July 2005

The original article to which this Erratum refers was published in Developmental Dynamics 231:148–160Developmental Dynamics(2004) 231(1) 148–160
Formation of C–C Bonds in Diiron Complexes by Addition of Carbanions to Alkynyl(methoxy)carbene Ligands
Authors: Busetto Luigi , Marchetti Fabio , Zacchini Stefano , Zanotti Valerio
Published: July 2005

Addition of cyanide ions to the alkynyl(methoxy)carbene complexes [Fe2{μ‐CN(Me)(R)}(μ‐CO)(CO){Cα(OMe)Cβ≡CγR'}(Cp)2]+ (R = Xyl, R' = Tol, 1a; R = Xyl, R' = Ph, 1b; R = Xyl, R' = Me3Si, 1c; R = Me, R' = Tol, 1d; R = Me, R' = Ph, 1e) occurs selectively at Cα to afford the 1,1‐disubstituted σ‐propargyl complexes [Fe2{μ‐CN(Me)(R)}(μ‐CO)(CO){C(OMe)(CN)(C≡CR')}(Cp)2] (R = Xyl, R' = Tol, 2a; R = Xyl, R' = Ph, 2b; R = Xyl, R' = Me3Si, 2c; R = Me, R' = Tol, 2d; R = Me,R' = Ph, 2e). Conversely, the stabilised carbanaions[CH(R)2]– (R = CN, CO2Me) add at the Cγ position with subsequent hydrogen migration to Cβ to give the 1‐σ‐buta‐1,3‐dienyl complexes [Fe2{μ‐CN(Me)(Xyl)}(μ‐CO)(CO){Cα(OMe)=CβHCγ(Tol)=Cδ(R)2}(Cp)2] (R = CN, 3a; CO2Me, 3b). No migration is possible in the absence of hydrogen atoms at Cδ, therefore addition of [C(Me)(CO2Me)2]– to 1a results in the formation of the σ‐allenyl complex [Fe2{μ‐CN(Me)(Xyl)}(μ‐CO)(CO){Cα(OMe)=Cβ=Cγ(Tol)Cδ(Me)(CO2Me)2}(Cp)2] (4). Protonation of the neutral complexes 3b and 4affords the vinyl(methoxy)carbene complexes [Fe2{μ‐CN(Me)(Xyl)}(μ‐CO)(CO){Cα(OMe)CβH=Cγ(Tol)Cδ(R)(CO2Me)2}]+ (R = H, 5; Me, 6), which exist in solution as mixtures of (E)‐ and (Z)‐isomers in dynamic equilibrium, as shown by VT NMR studies. The cationic complex 6 shows electrophilic behaviour. Thus, addition of CN– results in the σ‐allyl complex [Fe2{μ‐CN(Me)(Xyl)}(μ‐CO)(CO){Cα(OMe)(CN)[CβH=Cγ(Tol)Cδ(Me)(CO2Me)2]}(Cp)2] (7), whereas the reaction with Me2NH affords the vinyl acyl complex [Fe2{μ‐CN(Me)(Xyl)}(μ‐CO)(CO){Cα(O)CβH=Cγ(Tol)Cδ(Me)(CO2Me)2}(Cp)2] (8). The crystal structures of 2b and 3a·CH2Cl2 have been determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Extended Networks of Co2+ and Mn2+ Bridged by NCS–/N3– Anions and Flexible Long Spacers: Syntheses, Structures, and Magnetic Properties
Authors: Wang Xin‐Yi , Li Bao‐Long , Zhu Xia , Gao Song
Published: July 2005

Four new metal‐organic polymers with SCN–/N3– anion bridges and flexible long spacers L {L = bim [1,2‐bis(imidazol‐1‐yl)ethane] and bte [1,2‐bis(1,2,4‐triazol‐1‐yl)ethane]}, [Co(SCN)2(bim)] (1‐Co), [Co(SCN)2(bte)] (2‐Co), [Mn(N3)2(bte)] (3‐Mn), and [Mn(N3)2(bim)] (4‐Mn), were synthesized and characterized by single‐crystal X‐ray diffraction studies and their magnetic properties were investigated. Complex 1‐Co is a triple‐bridging chain complex with double end‐to‐end SCN– anions and single gauche‐bim spacers as bridges. Complexes 2‐Co and 3‐Mn both contain 1D chains bridged by double end‐to‐end SCN– or N3– anions and these chains are further extended to 2D (4,4) layers by the anti‐bte spacers. Complex 4‐Mn has a topological 3D diamond structure constructed through 1D double end‐on azide‐bridged MnII chains and extended through the anti‐bim spacers. Magnetic measurements reveal that 1‐Co and 3‐Mn remain paramagnetic; the dominant magnetic coupling between CoII is weak ferromagnetic and that between MnII is strong antiferromagnetic. As for 2‐Co and 4‐Mn, they show metamagnetic behavior below TN = 2.9 and 3.0 K, respectively. Our results show that a combination of the short anion bridges (SCN–/N3–) and flexible bidentate long spacers can be used to construct coordination polymers with novel topologies and interesting magnetic properties. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Lanthanide(III)‐Induced Conversion of 12‐Metallacrown‐4 to 5‐Metallacrown‐5 Complexes in Solution
Authors: Pacco Antoine , Parac‐Vogt Tatjana N. , van Besien Els , Pierloot Kristine , Görller‐Walrand Christiane , Binnemans Koen
Published: July 2005

The conversion of 12‐metallacrown‐4 complexes with copper(II) in the central cavity to 15‐metallacrown‐5 complexes with lanthanide(III) ions in the central cavity upon addition of trivalent lanthanide ions was analysed in solution by electrospray ionisation mass spectrometry (ESI‐MS), absorption spectrophotometry, circular dichroism and proton NMR spectroscopy. In all cases, copper(II) ions were the ring metals. The lanthanide‐induced shifts of the proton resonances in the NMR spectra of different lanthanide(III)‐containing 15‐metallacrown‐5 complexes with tyrosinehydroximate ligands were studied. The dynamics of ligand exchange of α‐aminohydroximate‐based lanthanide(III)‐containing 15‐metallacrown‐5 complexes were studied in methanol solutions. The ring structure of the 12‐metallacrown‐4 complex that acts as starting compound for the formation of the 15‐metallacrown‐5 complexes was optimized by DFT methods using alaninehydroximate as a model ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Recent Developments in the Chemistry of Beryllocenes
Authors: Fernández Rafael , Carmona Ernesto
Published: July 2005

Synthetic studies on substituted beryllocenes have provided new representatives of this family of compounds. Knowledge of their structures gives a better understanding of the long‐standing problem of the structure of the parent beryllocene, Be(C5H5)2. Theoretical calculations offer a clear picture of their bonding properties, while spectroscopic and reactivity investigations have clarified their dynamic behaviour. Beryllocenes of the type BeCp'2 (Cp' = methyl‐substituted cyclopentadienyl group) and half‐sandwich cyclopentadienylberyllium compounds are considered. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Unimolecular Fragmentation of CH3NH2: Towards a Mechanistic Description of HCN Formation
Authors: Roithová Jana , Schröder Detlef , Schwarz Helmut
Published: July 2005

The mechanism of the consecutive fragmentation of methylamine, CH3NH2, is studied by means of neutralization‐reionization mass spectrometry (NRMS), labeling experiments, and calculations employing density functional theory. It is shown that under the conditions of NRMS the fragmentations proceed by a radical mechanism that involves four distinct X–H bond cleavages (X = C, N). In the first step, a hydrogen atom is eliminated from the methyl group; next, homolytic cleavage of an N–H bond occurs. The so‐formed CH2NH intermediate then, in competition, releases a hydrogen atom either from the nitrogen or the carbon part, resulting in the formation of the radicals H2CN· and HCNH·, respectively. The reaction sequence is terminated by yet another homolytic bond cleavage to produce HCN. An alternative pathway proceeding by an initial 1,1‐elimination of H2 from the methyl group of CH3NH2, followed by a 1,1‐elimination of H2 from the amino function, is also considered, but found to be more energy‐demanding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Preparation of Intact Hexahydrobenzofuran Subunits of Ivermectin by Selective Ozonolysis of the Δ3,4‐Intermediate Secoester
Authors: Rouge dos Santos Anderson , Garcia Ferreira Maria de Lourdes , Kaiser Carlos R. , Férézou Jean‐Pierre
Published: July 2005

Avermectins, and especially their semi‐synthetic partial hydrogenation adduct Ivermectin, constitute a potent endectocide family of worldwide veterinary use that has been known for more than twenty years and has also demonstrated a great efficacy in the treatment of various human filariasis diseases. In a program to design new access to cost‐effective analogues with a new or optimised medical profile, we decided to develop a practical synthetic strategy starting from southern subunits cut from commercial Ivermectin, which is now easily available at a reasonable price. We describe here the first process for preparing intact hexahydrobenzofuran subunits by controlled degradation of Ivermectin in a basically three‐step process that totally preserves the integrity of the Δ3 unsaturated pattern of the unit, which is a requisite feature for the biological activity of this family of molecules. The two crucial steps of the sequence, developed here on a gram scale, involve a transesterification reaction in the presence of titanium(IV) alkoxide that allows the macrolactone opening without isomerisation in 55–70 % yields, followed by the selective ozonolysis of the C10–C11 double bond in the presence of different reducting agents to afford the expected southern unit in reasonable yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Facile Regio‐ and Diastereoselective Syntheses of Hydroxylated2‐Aminocyclohexanecarboxylic Acids
Authors: Fülöp Ferenc , Palkó Márta , Forró Enikő , Dervarics Máté , Martinek Tamás A. , Sillanpää Reijo
Published: July 2005

By means of total regio‐ and diastereoselective functionalizations of cis‐ and trans‐2‐amino‐4‐cyclohexenecarboxylic acid derivatives 1, 9, 12 and 16, isomers of 2‐amino‐4‐hydroxycyclohexanecarboxylic acid 8 and 11, and 2‐amino‐5‐hydroxycyclohexanecarboxylic acid 15 and 19 were prepared in good yields, via 1,3‐oxazine or γ‐lactone intermediates. The enantiomers of 8 and 15 were also prepared by the same pathway, resulting in products with ee > 99 %. The structures, stereochemistry and relative configurations of the synthesized compounds were proved by NMR, using some key vicinal couplings and characteristic NOEs. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Efficient Heterogeneous Asymmetric Transfer Hydrogenation Catalyzed by Recyclable Silica‐Supported Ruthenium Complexes
Authors: Liu Pei‐Nian , Gu Pei‐Ming , Deng Jin‐Gen , Tu Yong‐Qiang , Ma Ya‐Ping
Published: July 2005

Easily accessible N‐(p‐tolylsulfonyl)‐1,2‐diphenylethylenediamine‐(TsDPEN‐)derived organic–inorganic hybrid ligands were prepared and applied to the heterogeneous asymmetric transfer hydrogenation in traditional HCO2H/NEt3 and in water with HCO2Na as the hydrogen source and sodium dodecyl sulfate (SDS) as the phase‐transfer catalyst. The reactions demonstrated high catalytic activities and excellent enantioselectivities for most aromatic ketones and the imine tested, with results similar to those in homogeneous catalysis.In particular, this heterogeneous catalyst can be readily recovered and used in multiple consecutive catalytic runs with the high enantioselectivity maintained both in HCO2H/NEt3 and in water. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
From Vetiver to Patchouli: Discovery of a NewHigh‐Impact Spirocyclic Patchouli Odorant
Authors: Kraft Philip , Eichenberger Walter , Frech David
Published: July 2005

In the course of synthetic work on new vetiver odorants, a new, potent patchouli odorant was discovered. Its structure was elucidated as 1‐hydroxy‐1,4,7,7,9‐pentamethylspiro[4.5]decan‐2‐one (15/16), and both diastereoisomers were synthesized from the previously reported 4,7,7,9‐tetramethyl‐1‐methylenespiro[4.5]decan‐2‐one by epoxidation with m‐chloroperoxybenzoic acid, reduction with lithium aluminum hydride, and subsequent oxidation with pyridinium chlorochromate or Dess–Martin periodinane. The 1,4‐unlike‐isomer 15 was found to be the diastereoisomer with the most powerful odor, and its excellent odor threshold of 0.067 ng/L air triggered the synthesis of the derivatives 19, 22, 23, and 26 possessing a different methyl substitution pattern or ring size. Glycol cleavage in the oxidation step was circumvented by Swern oxidation. Three further 4‐demethylated derivatives, 32, 33, and 34, were prepared by a short sequence consisting of Diels–Alder reaction with 4‐methylene‐5‐oxohexanenitrile (28), reductive radical cyclization mediated by the titanocene(III) complex Cp2Ti(Ph)(iPr), and standard hydrogenation. Finally, the enantiomers of 15 were separated by forming their SAMP hydrazones, which were subsequently cleaved by ozonolysis. The odor of the racemate 15 was shown to be exclusively due to the (+)‐(1S,4R,5R,9S)‐configured enantiomer 38, the stereocenters of which superimpose well with those of (–)‐patchoulol (3), the odorous principle of patchouli oil. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Syntheses of New Chiral Phosphane Ligands by Diastereoselective Conjugate Addition of Phosphides to Enantiomerically Pure Acceptor‐Substituted Olefins from the Chiral Pool
Authors: Wiese Burkhard , Knühl Guido , Flubacher Dietmar , Prieß Jan W. , Ulriksen (nee Laursen) Bolette , Brödner Kerstin , Helmchen Günter
Published: July 2005

A variety of new chiral phosphanes were prepared by highly diastereoselective additions of phosphanes to α,β‐unsaturated carbonyl compounds and related acceptor‐substituted olefins derived from myrtenal as ex chiral pool source. Monophosphanes with astereogenic as well as stereogenic phosphorus are described. In addition diphosphanes were prepared by a highly diastereoselective double conjugate addition of a secondary diphosphane. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Synthesis of a αMan(1→3)αMan(1→2)αMan Glycocluster Presented on aβ‐Cyclodextrin Scaffold
Authors: Carpenter Clare , Nepogodiev Sergey A.
Published: July 2005

Application of 6‐thio‐α‐ and β‐cyclodextrins as the core component for the construction of multivalent carbohydrate structures is described. The method employed for the attachment of monomeric glycosides to a cyclodextrin core is based on the efficient nucleophilic displacement of bromide from an N‐bromoacetamido functionality. The N‐bromoacetyl group was positioned at the end of a spacer arm of glycosides and reacted with thiol groups present on the primary face of thiolated cyclodextrins. This coupling reaction led to perfunctionalised cyclodextrins which were thiother‐linked to appended saccharides through a short spacer arm. Both components of the key conjugation step — 6‐thiocyclodextrins and monomeric glycosides — were used without protecting groups, thus facilitating isolation and purification of target compounds. Glycoclusters incorporating six and seven α‐D‐mannopyranose or β‐D‐glucopyranose residues linked to cyclodexrin cores were synthesized in 57–75 % yield. Using the same technique, 3‐(2‐bromoacetamido)propyl trioside, incorporating a synthetic Man‐α‐(1→3)‐Man‐α‐(1→2)‐Man fragment of antigenic yeast mannan, was attached to per‐6‐thio‐β‐cyclodextrin to afford a heptavalent glycocluster. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Palladium‐Catalyzed Suzuki Coupling with Terminal Alkynes – Application to the Synthesis of 2,3‐Disubstituted Benzo[b]furans
Authors: Colobert Françoise , Castanet Anne‐Sophie , Abillard Olivier
Published: July 2005

The Suzuki coupling reaction between alkynylboronic esters (generated in situ from acetylenic derivatives) and aryl bromides, pyridyl bromides or vinyl bromides is reported. 5‐endo‐dig‐iodocyclisation of o‐alkynylanisoles, generated by this palladium‐catalyzed Suzuki coupling reaction, was performed with N‐iodosuccinimide (NIS) in the presence of BCl3. 2‐Substituted 3‐iodobenzo[b]furans were synthesized and transformed into 2,3‐disubstituted benzo[b]furans by Suzuki coupling reactions in high yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
One‐Pot Synthesis of Novel Enantiomerically Pure and Racemic 4‐Ferrocenyl‐β‐lactams and Their Reactivity in Acidic Media
Authors: Bernardi Luca , Bonini Bianca F. , Comes‐Franchini Mauro , Dessole Gabriella , Fochi Mariafrancesca , Ricci Alfredo
Published: July 2005

A series of 4‐ferrocenyl‐ and 4‐[(SFc)‐2‐(p‐tolylsulfanyl)ferrocenyl]‐β‐lactams has been synthesized in good yields by a one‐pot reaction of achiral and planar‐chiral ferrocenylimines with substituted acetic acids. The acid‐induced stereoconvergent transformation of cis‐ and trans‐4‐ferrocenyl‐β‐lactams into (Z)‐α,β‐unsaturated amides by protonation, N–C‐4 cleavage and subsequent exo‐H elimination and the lack of reaction of the ortho‐S‐tolylsulfanyl analogs are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Methods for the Cleavage of Allylic and Propargylic C–N Bonds in Amines and Amides – Selected Alternative Applications of the 1,3‐Hydrogen Shift
Authors: Escoubet Stéphanie , Gastaldi Stéphane , Bertrand Michèle
Published: July 2005

The aim of this article is to provide an updated review on the various methodologies that allow allylic C–N bonds (and by extension propargylic C–N bonds) to be cleaved. Since selectivity is crucial for synthetic planning, as far as possible, the relative reactivity of the various allylic groups is examined, and the discrimination between O‐allyl and N‐allyl derivatives is discussed. A special development is devoted to reactions leading to enamines through a 1,3‐hydrogen shift, even though some of these reactions were not originally performed for the purpose of cleaving the N‐allyl bond. Some selected applications are discussed. In addition to preparative deprotection methods, reactions such as the enzyme‐mediated cleavage of allylic C–N bonds are also mentioned, although these reactions may not have any practical synthetic interest at the moment. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Cycloadditions with Cyclic Seven‐Membered Ketene Imines
Authors: Giera Henry , Huisgen Rolf , Polborn Kurt
Published: July 2005

The cyclic seven‐membered ketene imines 8 – isolable despite ring strain – are available by reactions of thiocarbonyl ylides 3 with 2,3‐bis(trifluoromethyl)fumaronitrile (4). In contrast to open‐chain ketene imines, 8A–8C underwent (2+2) cycloadditions with ethyl vinyl ether at the C=N double bond; the diastereomeric cycloadducts 10 and 11 were characterized by their spectra, and 10A by X‐ray analysis. The corresponding adduct 12 from 8A and 2‐methoxypropene easily hydrolyzed to give 14. When 8A–8C were treated with diazomethane, (2+3) cycloadditions took place side by side to the C=C and C=N bond of 8. A supposed adduct at the C=C bond, 18A, lost N2, and 19A was formed which contained a cyclopropylideneamine group; at 50 °C, cheletropic elimination produced the isocyanide 22A. Diazomethane addition to the C=N bond of 8 gave rise to condensed 1,2,3‐triazoles 21; the HF elimination from the pyrazolines 20 as primary adducts was probably induced by the excess of diazomethane. The structure of 21B was confirmed by X‐ray. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Cover Picture: Divergent and Linear Solid‐Phase Synthesis of PNA Containing Thiazole Orange as Artificial Base (Eur. J. Org. Chem. 15/2005)
Authors: Jarikote Dilip V. , Köhler Olaf , Socher Elke , Seitz Oliver
Published: July 2005

The cover picture shows the divergent synthesis of peptide nucleic acid based probes in which the DNA intercalator dye thiazole orange serves as a base surrogate. The so‐called FIT (Forced Intercalation of Thiazole orange) PNA probes can provide information about the hybridization to complementary DNA by enhancement of fluorescence. The graphical representation depicted in the bottom left corner gives an idea of the structure of FIT PNA complexed by DNA. In this model, FIT PNA has been hybridized to DNA that contains an abasic site opposite to thiazole orange. The article by O. Seitz et al. on p. 3187 ff. describes the details of linear and divergent solid‐phase syntheses of FIT PNAs. Both methods provide very rapid access and should be applicable to the synthesis of any type of base‐modified PNA molecule.
Optimal design of an induction motor for an electric vehicle
Authors: Faiz Jawad , Sharifian M. B. B.
Published: July 2005

In this paper a squirrel‐cage three‐phase induction motor, selected as the driving power of an electric vehicle (EV), is designed optimally using a modified‐Hooke–Jeeves optimization technique. The optimal designs are analyzed and compared with varying pole number, rated base speed and slot shapes. This optimization technique has the same advantages such as simple programming, non‐gradient, short convergence time and independent variation of each parameter. Variation of design parameters of optimally designed motors versus rated base speed for 2‐ and 4‐pole motors are presented and discussed. The results show that a 2‐pole motor with parallel‐sided stator and rotor slots and rated speed 1800 rpm has the best performance. Copyright © 2005 John Wiley & Sons, Ltd.
Fast computation evolutionary programming algorithm for the economic dispatch problem
Authors: Somasundaram P. , Kuppusamy K. , Kumudini Devi R. P.
Published: July 2005

This paper essentially aims to propose a new EP based algorithm for solving the ED problem. The ED problem is solved using EP with system lambda as decision variable and power mismatch as fitness function. The algorithm is made fast through judicious modifications in initialization of the parent population, offspring generation and selection of the normal distribution curve. The proposed modifications reduce the search region progressively and generate only effective offsprings. The proposed algorithm is tested on a number of sample systems with quadratic cost function and also on a 10‐unit system with piecewise quadratic cost function. The computational results reveal that the proposed algorithm has an excellent convergence characteristic and is superior to other EP based methods in many respects. Copyright © 2005 John Wiley & Sons, Ltd.
A systematic approach to nuclear microscopy of water trees for a large number of field‐aged HV cable samples
Authors: Ahmed M. , Al‐Ohali M. , Garwan M. , Al‐Hamouz Z. , Al‐Soufi K. , Minqin R. , Rajta I. , Watt F.
Published: July 2005

In order to perform micro‐PIXE measurements on water trees in underground HV cables when a large number of cable samples are involved, a sequence of tests has been devised to minimize time and effort for sample preparation, water tree detection and analysis. These tests include electrical diagnostic tests to predict the possible presence of water trees, optical microscopy on cable insulation to detect water trees in the samples screened by the electrical tests, scanning electron microscopy for detailed surface topography of water trees, and nuclear microscopy for elemental composition and distribution maps of water trees. Correlations among the results of the four types of measurements are discussed to evaluate the usefulness of the methodology. Copyright © 2005 John Wiley & Sons, Ltd.
Unstructured lattice Boltzmann method in three dimensions
Authors: Rossi N. , Ubertini S. , Bella G. , Succi S.
Published: July 2005

Over the last decade, the lattice Boltzmann method (LBM) has evolved into a valuable alternative to continuum computational fluid dynamics (CFD) methods for the numerical simulation of several complex fluid‐dynamic problems. Recent advances in lattice Boltzmann research have considerably extended the capability of LBM to handle complex geometries. Among these, a particularly remarkable option is represented by cell‐vertex finite‐volume formulations which permit LBM to operate on fully unstructured grids. The two‐dimensional implementation of unstructured LBM, based on the use of triangular elements, has shown capability of tolerating significant grid distortions without suffering any appreciable numerical viscosity effects, to second‐order in the mesh size. In this work, we present the first three‐dimensional generalization of the unstructured lattice Boltzmann technique (ULBE as unstructured lattice Boltzmann equation), in which geometrical flexibility is achieved by coarse‐graining the lattice Boltzmann equation in differential form, using tetrahedrical grids. This 3D extension is demonstrated for the case of 3D pipe flow and moderate Reynolds numbers flow past a sphere. The results provide evidence that the ULBE has significant potential for the accurate calculation of flows in complex 3D geometries. Copyright © 2005 John Wiley & Sons, Ltd.
2‐Halogeno‐1,3,2‐diazaarsolenes and 2‐halogeno‐1,3,2‐diazastibolenes: Examples for spontaneous EX bond heterolysis or not?
Authors: Gans‐Eichler Timo , Gudat Dietrich , Nieger Martin
Published: July 2005

2‐X‐1,3,2‐diazaarsolenes and 2‐X‐1,3,2‐ stibolenes (X = Cl, Br) were prepared from appropriate α‐amino‐aldimine precursors via transamination with ClSb(NMe2)2or via base‐induced dehydrohalogenation with EX3(E = As, Sb). The products were further converted into 2‐iodo‐derivatives via halide exchange with Me3SiI, or into 1,3,2‐diazaarsolenium or 1,3,2‐stibolenium salts via halide abstraction using E′X3(E′ = Al, Ga, Sb) or Me3SiOTf. All compounds synthesized were characterized by spectroscopic data and several of them by single‐crystal X‐ray diffraction studies. The results of these investigations confirmed that diazaarsolenium or stibolenium cations are stabilized by similar π‐delocalization effects as the corresponding diazaphospholenium cations. 2‐Halogeno‐1,3,2‐diazaarsolenes and 2‐halogeno‐132‐stibolenes are best addressed as molecular species whose covalent EX bonds are as in 2‐chloro‐diazaphospholenes weakened by intramolecular π(C2N2) → σ*(EX) and, in the case of the Sb‐containing heterocycles, inter‐ molecular n(X′) → σ*(EX) hyperconjugation between the σ* (EX) orbital and a lone‐pair of electrons on the halogen atom of a neighboring molecule. Correlation of structural and spectroscopic data and the evaluation of halide transfer reactions allowed to conclude that the extent of EX bond weakening in the 2‐X‐substituted heterocycles decreases and thus the Lewis acidity of the cations increases, with increasing atomic number of the pnicogen atom. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:327–338, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20098
Crystal structures of dibenzo[ce]‐1,2‐dithiine and its related oxides
Authors: Aucott Stephen M. , Milton Heather L. , Robertson Stuart D. , Slawin Alexandra M. Z. , Woollins J. Derek
Published: July 2005

The X‐ray structures of dibenzo[ce]‐1,2‐dithiine, dibenzo[ce]‐1,2‐dithiine‐5,5‐dioxide, diben‐ zo[ce]‐1,2‐dithiine‐5,5,6‐trioxide, and dibenzo[ce]‐1, 2‐dithiine‐5,5,6,6‐tetraoxide are reported and compared with the related “constrained'' naphthalene deri‐ vatives. The S‐S distances vary upon oxidation of the S centers in the order S‐S < SO‐S > SO2‐S < SO2‐SO > SO2‐SO2 i.e. the most oxidized sulfur atoms do not lead to the longest bond lengths. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:346–351, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20101
Synthesis and structure of the scandium‐rich indides Sc5Ni2In4 and Sc5Rh2In4
Authors: Lukachuk Mar'yana , Heying Birgit , Rodewald Ute Ch. , Pöttgen Rainer
Published: July 2005

The ternary indides Sc5 Ni2 In4 and Sc5 Rh2 In4 were synthesized by arc‐melting of the elements and subsequent annealing. A structural investigation by X‐ray powder and single crystal diffraction revealed: Lu5 Ni2 In4 type, Pbam, a = 1716.3(2), b = 755.1(1), c = 335.22(5) pm, wR2 = 0.0721, 844 F2 values for Sc5 Ni2 In4, and a = 1754.3(3), b = 765.0(1), c = 332.97(6) pm, wR2 = 0.0363, 1107 F2 values for Sc5 Rh2 In4 with 36 variables per refinement. Both structures can be described as intergrowths of distorted AlB2‐ and CsCl‐related slabs, where the transition metal (T) atoms have a trigonal prismatic and the indium atoms a distorted square prismatic coordination. The shortest interatomic distances occur for ScT and TIn. The crystal chemistry and chemical bonding in these intermetallics are briefly discussed. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:364–368, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20106
On the electronic structure and bonding of the intriguing mixed Fe2+/Fe3+ [{Cp(CO)2Fe}tBuPO2FeCl2]2‐Complex
Authors: Lorenz Ingo‐Peter , Maier Markus , Schulz Axel
Published: July 2005

The structure and bonding of [{Cp(CO)2Fe}tBuPO2FeCl2]2(2) have been investigated theoretically and experimentally. The molecular orbitals of 2 have been calculated to investigate the question why this type of complex forms a planar ring system. The electronic configuration of different electronic states, spin polarization, and bonding of 2 are discussed. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:398–405, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20109
Patterns of emotional availability among young mothers and their infants: A dydaic, contextual analysis
Authors: Easterbrooks M. Ann , Chaudhuri Jana H. , Gestsdottir Steinunn
Published: July 2005

The aim of this study was to examine patterns of emotional availability among 80 young mothers (under 21 years at their child's birth) and their infants, and to identify contextual and individual factors associated with different patterns of emotional availability. To operationalize the dyadic aspect of emotional availability, cluster analysis of the Emotional Availability Scales, third edition (EAS; Biringen, Robinson, & Emde, 1998) was conducted on mother and infant scales simultaneously. Four distinct groups of emotional availability patterns emerged, reflecting synchrony and asynchrony between maternal and child behavior: (a) low‐functioning dyads, (b) average dyads, (c) average parenting/disengaged infants, and (d) high‐functioning dyads. Further analyses revealed that mothers in different clusters differed on outcomes such as depressive symptomatology, social support, and relationships with their own mothers. The clusters and the variables related to them demonstrate the various challenges in integrating the dual tasks of adolescent and parenting development among young mothers. The clinical implications of these patterns of emotional availability and live context are discussed.
A study of biologically active peptide sequences (P‐15) on the surface of an ABM scaffold (PepGen P‐15™) using AFM and FTIR
Authors: Hole Bhushan B. , Schwarz James A. , Gilbert Jeremy L. , Atkinson Brent L.
Published: July 2005

Cellular response to any biomaterial surface is governed by a number of factors including topography, surface chemistry, surface charge, structural heterogeneity, and physiological conditions. Understanding these factors at the nanoscale level is crucial to develop improved biomaterials. Any changes in these properties due to surface modifications need to be addressed properly, as they could have significant impact on the cellular interaction with biomaterials. In this study, the topography and surface chemistry of commercially available tissue engineered xenograft, PepGen P‐15™ [comprised of a synthetic peptide P‐15 irreversibly attached to anorganic bovine bone mineral (OsteoGraf/‐N®)] was studied using Atomic Force Microscopy (AFM), and Fourier Transform Infrared Spectroscopy (FTIR). FTIR confirmed the presence of the peptide on the surface of PepGen P‐15™. Changes in the peptide conformation, which includes a decrease in the β‐strand accompanied by an increase in unordered structures/random coil structures after attachment on OsteoGraf/‐N® is observed. Specific functional groups, which are involved in the binding mechanism, are identified. The results suggest that the attachment of the peptide on OsteoGraf/‐N® occurs via a specific surface docking ionic interaction involving the C‐terminal carboxylic group on the peptide with positive domains generated by hydroxyl vacancies on the apatite surface. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res, 2005
Design of functionally graded dental implant in the presence of cancellous bone
Authors: Hedia H. S.
Published: July 2005

In a previous work by the author [Hedia HS, Mahmoud NA. Biomed Mater Eng 2004;14(2):133–143], a functionally graded material (FGM) dental implant was designed without cancellous bone in the model. In this investigation, the effect of the presence of cancellous bone as a thin layer around the dental implant was investigated. It is well known that the main inorganic component of natural bone is hydroxyapatite (HAP) and that the main organic component is collagen (Col). HAP implants are not bioabsorbable, and because induction of bone into and around the artificially made HAP is not always satisfactory, loosening or breakage of HAP implants might occur after implantation in the clinical application. The development of a new material that is bioabsorbable and that has osteoconductive activity is needed. Therefore, the aim of the current investigation was to design an implant, in the presence of cancellous bone as a thin layer around it, from FGM. In this study, a novel biomaterial, Col/HAP, as a FGM, was developed using the finite element and optimization techniques that are available in the ANSYS package. These materials have a self‐organized character similar to that of natural bone. The investigations have shown that the maximum stress in the cortical bone and cancellous bone for the Col/HAP functionally graded implant has been reduced by about 40% and 19%, respectively, compared with currently used titanium dental implants. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005
Using pH‐sensitive hydrogels containing cubane as a crosslinking agent for oral delivery of insulin
Authors: Mahkam Mehrdad
Published: July 2005

The goal of oral insulin delivery devices is to protect the sensitive drug from proteolytic degradation in the stomach and upper portion of the small intestine. Copolymers of 2‐hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAA) based hydrogels containing 2, 4, and 6% of a crosslinking agent (CA) were studied as drug delivery systems. Cubane‐1, 4‐dicarboxylic acid (CDA) was linked to two HEMA groups as CA. Radical copolymerizations of HEMA and MAA with the various ratios of CA were performed at 70°C. The compositions of the crosslinked three‐dimensional polymers were determined using Fourier transform infrared spectroscopy. Glass‐transition temperature of the network polymers was determined calorimetrically. The effect of copolymer composition on the swelling behavior and hydrolytic degradation was studied in simulated gastric fluid (pH 1) and simulated intestinal fluid (pH 7.4). The swelling and hydrolytic behavior of the copolymers was dependent on the content of MAA groups and caused a decrease in gel swelling in simulated gastric fluid or an increase in gel swelling in simulated intestinal fluid. The drug‐release profiles indicate that the amount of drug release depends on their degree of swelling and crosslinking. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005
Bone compaction enhances fixation of hydroxyapatite‐coated implants in a canine gap model
Authors: Kold Søren , Rahbek Ole , Zippor Berit , Bechtold Joan E. , Søballe Kjeld
Published: July 2005

Primary cementless joint replacement depends partly on the ability of bone to heal into those areas of an inserted implant where a gap to surrounding bone initially exists. A new bone preparation technique, compaction, has enhanced gap‐healing around grit‐blasted implants without osteoconductive properties. However, hydroxyapatite (HA) porous‐coated implants with osteoconductive properties are often inserted clinically to enhance gap healing and implant fixation. It is unknown whether the osteoconductive properties of HA porous‐coated implants might overwhelm the beneficial effects of compaction on gap healing. Therefore, we compared the compaction technique with the conventional bone‐removing technique, drilling, using HA porous‐coated implants in a canine gap model. HA porous‐coated titanium implants were bilaterally inserted into oversized cavities of the proximal humeri of seven dogs. Each dog served as its own control. Thus, one humerus had the implant cavity prepared with compaction, the other with drilling. Two weeks after surgery push‐out test and histomorphometry was performed. Compaction significantly increased ultimate shear strength, energy absorption, apparent shear stiffness, bone implant contact, and peri‐implant bone density. The results of this study suggest that compaction may enhance gap healing when osteoconductive HA porous coated implants are inserted in joint replacements. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005
Effect of niobium content on the microstructure and thermal properties of fluorapatite glass‐ceramics
Authors: Denry I. L. , Holloway J. A. , Nakkula R. J. , Walters J. D.
Published: July 2005

Niobium oxide has been shown to improve biocompatibility and promote bioactivity. The purpose of this study was to evaluate the effect of niobium oxide additions on the microstructure and thermal properties of fluorapatite glass‐ceramics for biomedical applications. Four glass‐ceramic compositions with increasing amounts of niobium oxide from 0 to 5 wt % were prepared. The glass compositions were melted at 1525°C for 3 h, quenched, ground, melted again at 1525°C for 3 h and furnace cooled. The coefficient of thermal expansion was measured by dilatometry. The crystallization behavior was evaluated by differential thermal analysis. The nature of the crystalline phases was investigated by X‐ray diffraction. The microstructure was studied by SEM. In addition, the cytotoxicity of the ceramics was evaluated according to the ASTM standard F895‐84. The results from X‐ray diffraction analyses showed that fluorapatite was the major crystalline phase in all glass‐ceramics. Differential thermal analyses revealed that fluorapatite crystallization occurred between 800 and 934°C depending on the composition. The coefficient of thermal expansion varied from 7.6 to 9.4 × 10−6/°C. The microstructure after heat treatment at 975°C for 30 min consisted of submicroscopic fluorapatite crystals (200–300 nm) for all niobium‐containing glass‐ceramics, whereas the niobium‐free glass‐ceramic contained needle‐shaped fluorapatite crystals, 2 μm in length. None of the glass‐ceramics tested exhibited any cytotoxic activity as tested by ASTM standard F895‐84. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005
Skin regeneration using keratinocytes and dermal fibroblasts cultured on biodegradable microspherical polymer scaffolds
Authors: Kim Sang‐Soo , Gwak So‐Jung , Choi Cha Yong , Kim Byung‐Soo
Published: July 2005

Bioartificial skin sheet grafts have been utilized to treat large burns and chronic ulcers. However, the trypsinization step to harvest cultured skin grafts from culture dishes damages the cells by breaking the anchoring proteins and lowers their uptake ratio after transplantation. In addition, epidermal sheet grafts require a long fabrication period. To overcome these limitations, we utilized biodegradable poly(lactide‐co‐glycolide) (PLGA) microspheres as both cell culture matrix and transplantation vehicle of skin cells for skin regeneration in this study. This method could avoid the trypsinization step and have a relatively short preparation period. Human keratinocytes and dermal fibroblasts cultured on PLGA microspheres in spinner flasks proliferated by 3.0‐fold and 9.4‐fold, respectively, after 10 days. When both types of cells cultured on PLGA microspheres were reinoculated onto culture dishes, the cells migrated from the PLGA microspheres to the culture dish surface, grew, and formed a confluent cell layer within 5 days, showing the growth and migration abilities of the cells cultured on PLGA microspheres. Full‐thickness skin wounds created on the back of athymic mice were either treated with transplantation of keratinocytes and dermal fibroblasts cultured on microspheres (cell‐transplanted group), treated with PLGA microspheres alone (microsphere‐implanted group), or covered with dressing materials without treatment (untreated group). Three weeks after the treatments, differentiated epithelium that stained positively for cytokeratin, a marker of epidermis, was observed in the cell‐transplanted group, while the microsphere‐implanted group and untreated group showed incomplete reepithelialization. Dermal regeneration with positive staining for vimentin, a marker of dermal fibroblast, was observed in the cell‐transplanted group. Regenerated dermis with positive staining for vimentin was partly observed in the microsphere‐implanted group and untreated group. These results suggest that transplantation of keratinocytes and dermal fibroblasts cultured on PLGA microspheres could be potentially useful as an alternative to bioartificial skin grafts for the treatment of skin wounds. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005
Free volume study on calcification process in an intraocular lens after cataract surgery
Authors: Ramani R. , Parihar J.K.S. , Ranganathaiah C. , Awasthi P. , Alam S. , Mathur G.N.
Published: July 2005

An opacified intraocular lens explanted from a patient in the postoperative period after phacoemulsification was investigated to find the cause of opacification. From the UV‐visible and energy dispersive X‐ray spectroscopy (EDS) measurements, the opacification in the present case seems to be due to calcification of the intraocular lens and not due to modification in the UV absorber material of the lens. The average free volume size of the intraocular lens both in unimplanted and explanted state were obtained from positron lifetime spectroscopy (PLS). Further, the combined FTIR and PLS results indicate that calcium gets into the free volume cavities of the intraocular lens matrix as a cationic moiety, may be in the form of Ca++. The small decrease in glass transition temperature of the calcified lens seems to indicate the plasticizing action of calcium ions. The present results could be of some use in the design of the intraocular lens material in which calcification would be minimum. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005
A class of 2D graphical representations of RNA secondary structures and the analysis of similarity based on them
Authors: Yao Yu‐Hua , Nan Xu‐Ying , Wang Tian‐Ming
Published: July 2005

Based on the concepts of cell and system of graphical representation, a class of 2D graphical representations of RNA secondary structures are given in terms of classifications of bases of nucleic acids. The representations can completely avoid loss of information associated with crossing and overlapping of the corresponding curve. As an application, we make quantitative comparisons for a set of RNA secondary structures at the 3′‐terminus of different viruses based on the graphical representations. The examination of similarities/dissimilarities illustrates the utility of the approach. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1339–1346, 2005
Are AM1 ligand‐protein binding enthalpies good enough for use in the rational design of new drugs?
Authors: Villar R. , Gil M. J. , García J. I. , Martínez‐Merino V.
Published: July 2005

We have examined the performance of semiempirical quantum mechanical methods in solving the problem of accurately predicting protein‐ligand binding energies and geometries. Firstly, AM1 and PM3 geometries and binding enthalpies between small molecules that simulate typical ligand‐protein interactions were compared with high level quantum mechanical techniques that include electronic correlation (e.g., MP2 or B3LYP). Species studied include alkanes, aromatic systems, molecules including groups with hypervalent sulfur or with donor or acceptor hydrogen bonding capability, as well as ammonium or carboxylate ions. B3LYP/6‐311+G(2d,p) binding energies correlated very well with the BSSE corrected MP2/6‐31G(d) values. AM1 binding enthalpies also showed good correlation with MP2 values, and their systematic deviation is acceptable when enthalpies are used for the comparison of interaction energies between ligands and a target. PM3 otherwise gave erratic energy differences in comparison to the B3LYP or MP2 approaches. As one would expect, the geometries of the binding complexes showed the known limitations of the semiempirical and DFT methods. AM1 calculations were subsequently applied to a test set consisting of “real” protein active site‐ligand complexes. Preliminary results indicate that AM1 could be a valuable tool for the design of new drugs using proteins as templates. This approach also has a reasonable computational cost. The ligand‐protein X‐ray structures were reasonably reproduced by AM1 calculations and the corresponding AM1 binding enthalpies are in agreement with the results from the “small molecules” test set. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1347–1358, 2005