bluuebunny/crossref_metadata_2025 huggingface dataset:
Phosphonopropionic acid as a building block in supramolecular chemistry: salts with organic diamines
Authors: Bowes Katharine F. , Ferguson George , Lough Alan J. , Glidewell Christopher
Published: March 2003

The structures of seven salts formed by phosphonopropionic acid with organic diamines are reported; in these salts, the hydrogen-bonded substructures formed by the anions can be zero-, one- or two-dimensional, while the overall hydrogen-bonded supramolecular structures are three-dimensional. The 1:1 adduct, compound (1), formed between 1,2-bis(4′-pyridyl)ethene and phosphonopropionic acid is a salt, [{(C12H10N2)H2}2+]·[(C12H10N2)]·[(C3H6O5P)−]2, in which both diamine components lie across centres of inversion in space group P21/c. The anions form hydrogen-bonded head-to-head dimers, and these are linked by the two diamine units into sheets, which are themselves linked by C—H...O hydrogen bonds. With 2,2′-dipyridylamine the acid forms the hydrated salt [{(C10H9N3)H}+]·[(C3H6O5P)−]·H2O (2), in which all components are disordered with occupancy 0.5 in space group Fmm2. The anions form head-to-tail dimers, which are linked into sheets by the cations, and the sheets are linked into a three-dimensional framework by the water molecules. The piperazine salt [{(C4H10N2)H2}2+]·[(C3H5O5P)2−] (3) contains simple anion chains linked into a three-dimensional framework by the two independent cations, both of which are centrosymmetric. In the hydrated salt formed by N,N′-dimethylpiperazine, [{(MeNC4H8NMe)H2}2+]·[(C3H6O5P)−]2·(H2O)2 (4), head-to-tail anion chains combine with the water molecules to form a three-dimensional framework, which encloses voids that contain the cations. In the 4,4′-bipyridyl adduct [{(C10H8N2)H0.72}0.72+]·[{(H0.5O)3PCH2CH2COOH0.78}0.72−] (5), there is extensive disorder of the H atoms that are bonded to N and O atoms, and the anion chains are linked by the cations into sheets, which are themselves linked by C—H...O hydrogen bonds. In the 1:2 adduct formed with 1,2-bis(4′-pyridyl)ethane, [{(C12H12N2)H2}2+]·[(C3H6O5P)−]2 (6), where the cation lies across an inversion centre, the anions form molecular ladders. These ladders are linked into sheets by the cations, which are themselves linked by C—H...O hydrogen bonds. In the methanol-solvated salt formed with 2,6-dimethylpiperazine, [{(C6H14N2)H2}2+]·[(C3H6O5P)−]2· (CH4O)0.34 (7), the anions form sheets that are linked into a three-dimensional framework by the cations. The supramolecular structures are compared with those of analogous salts formed by phosphonoacetic acid.
Molecular structures of the inclusion complexes β-cyclodextrin–1,2-bis(4-aminophenyl)ethane and β-cyclodextrin–4,4′-diaminobiphenyl; packing of dimeric β-cyclodextrin inclusion complexes
Authors: Giastas Petros , Yannakopoulou Konstantina , Mavridis Irene M.
Published: March 2003

The present investigation is part of an ongoing study on the influence of the long end-functonalized guest molecules DBA and BNZ in the crystal packing of β-cyclodextrin (βCD) dimeric complexes. The title compounds are 2:2 host:guest complexes showing limited host–guest hydrogen bonding at the primary faces of the βCD dimers. Within the βCD cavity the guests exhibit mutual π...π interactions and between βCD dimers perpendicular NH...π interactions. The DBA guest molecule exhibits one extended and two bent conformations in the complex. The BNZ guest molecule is not planar inside βCD, in contrast to the structure of BNZ itself, which indicates that the cavity isolates the molecules and forbids the π...π stacking of the aromatic rings. NMR spectroscopy studies show that in aqueous solution both DBA and BNZ form strong complexes that have 1:1 stoichiometry and structures similar to the solid state ones. The relative packing of the dimers is the same in both complexes. The axes of two adjacent dimers form an angle close to 20° and have a lateral displacement ≃2.45 Å, both of which characterize the screw-channel mode of packing. Although the βCD/BNZ complex indeed crystallizes in a space group characterizing the latter mode, the βCD/DBA complex crystallizes in a space group with novel dimensions not resembling any of the packing modes reported so far. The new lattice is attributed to the three conformations exhibited by the guest in the crystals. However, this lattice can be transformed into another, which is isostructural to that of the βCD/BNZ inclusion complex, if the conformation of the guest is not taken into account.
Molecular orbital study of the bond-valence sum rule using Lewis-electron pair theory
Authors: Mohri Fumihito
Published: March 2003

The bond-valence sum rule has been examined by molecular-orbital methods related to spin-coupling matrix theory [Okada & Fueno (1976). Bull. Chem. Soc. Jpn, 49, 1524–1530], to give a new formulation of the Lewis-electron pair concept. It is shown that the `pair-coupling population' between atoms M and X exhibits the same behaviour as the bond valence between them. A quantum chemical definition for bond valence is proposed and successfully applied to Al2Cl6, Te4Cl16 and Al2Be3(SiO3)6 (beryl). Using an alternative bond-valence definition it is shown that for oxides the bond valence can possibly be taken as the double pair-coupling population.
Providing Web access to a catalogue of British newspaper cartoons
Authors: Bovey J.D.
Published: March 2003

This paper describes how the University of Kent Cartoon Centre catalogue was made accessible on the World Wide Web and analyses the effectiveness of the search site during the four years it has been online. The Cartoon Centre catalogue covers a wide range of British newspaper cartoon drawings and is unusual in being a substantial (over 90,000 records) online catalogue that also includes digital images of all the catalogued material. The paper describes some of the decisions that were made in putting the catalogue on the Web and then uses the evidence of the Web server logs to draw some conclusions about how successful the Web interface has been and how it might be improved in the future.
Polarographic Study of the Systems Pb(II)-Valine and Pb(II)-Valinate Ion Under Physiological Conditions
Authors: Rodríguez Placeres Jesús C. , Castro Macias Josefa , Lemus Sánchez Mercedes , Borges Miquel Teresa M. , Ruiz-Morales Juan C.
Published: March 2003

The polarographic method has been used to the study of the systems Pb(II)-valine and Pb(II)-valinate ion in aqueous medium, atI= 0.15 mol l-1(NaClO4) and 37 °C. The stabilized complexes were found: [Pb(HV)]2+, β10= 9.0; [Pb(HV)2]2+, β20= 12; [Pb(V)]+, β01= 1.8 × 104; and [Pb(V)2], β02= 1.7 × 106.
A Facile Synthesis of Selectively Protected Linear Oligoamines
Authors: Koščová Simona , Buděšínský Miloš , Hodačová Jana
Published: March 2003

A convenient multi-gram preparative method for the synthesis of linear oligoamines having the terminal primary amino groups unprotected and the central secondary amino functions protected with tert-butoxycarbonyl groups is presented. At the same time, simple one-pot preparation of the α,ω-bis(trifluoroacetamide) intermediates 2 has been developed. NMR spectra of the novel selectively protected oligoamines are also discussed.
A Facile Synthesis of 9-Deaza Analogue of Olomoucine
Authors: Čapek Petr , Otmar Miroslav , Masojídková Milena , Votruba Ivan , Holý Antonín
Published: March 2003

Heating of 6-(benzylamino)-2-chloro-9-deazapurine (3) with ethanolamine afforded 6-(benzylamino)-2-[(2-hydroxyethyl)amino]-9-deazapurine (8). Its treatment with formaldehyde in alkaline solution, after protection of the OH group with DMTr, led to hydroxymethylation at position 9. Conversion of the hydroxymethyl group to methyl was performed by catalytic hydrogenation under simultaneous deprotection, which resulted in the formation of the 9-deaza analogue 1 of olomoucine. Compound 1 does not exhibit any significant in vitro cell growth inhibition of CCRF-CEM, HeLa and L-1210 cell lines. Cytostatic activity was found in 6-(benzylamino)-9-deazapurine (2) and its 2-chloro derivative 3 in CCRF-CEM cells with IC50 13.3 and 15.8 μM, respectively.
Synthesis of 4-Nitrophenyl 2-Acetamido-2-deoxy-β-D-mannopyranoside and 4-Nitrophenyl 2-Acetamido-2-deoxy-α-D-mannopyranoside
Authors: Krist Pavel , Kuzma Marek , Pelyvás István F. , Simerská Pavla , Křen Vladimír
Published: March 2003

The title compounds were synthesized by the selective reduction of the azido group in 4-nitrophenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (8) and 4-nitrophenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-β-D-mannopyranoside (11), and by subsequent acetylation. Compound8was prepared by opening of the epoxide ring in methyl 2,3-anhydro-4,6-O-benzylidene-α-D-glucopyranoside (1) with sodium azide, followed by inversion of the configuration at C-3 in the resulting altropyranoside and glycosidation with 4-nitrophenol.
STRUCTURAL ACOUSTIC OPTIMIZATION USING THE COMPLEX METHOD
Authors: CUNEFARE KENNETH A. , DATER BRIAN S.
Published: March 2003

An optimization program based on M. J. Box's Complex Method was implemented in a computational design tool for constrained optimization of acoustic environments produced by vibrating structures. The tool can treat interior and exterior environments, and can consider acoustic and structural excitations. The tool integrates finite element and boundary element methods to perform the requisite structural acoustic analyses. The new optimization component described in this paper contains unique additions to Box's original algorithm. The optimizer executes stand-alone, or can be used as a starting point generator for another optimizer, thus creating a hybrid algorithm. This paper describes the new optimizer's algorithm and the results of an example optimization to reduce the interior noise levels within an unstiffened cylindrical shell. Design variables were selected as the shell thicknesses, subject to upper and lower bounds. All analyses were performed at a single excitation frequency. The results demonstrate effective performance of the optimizer, and the potential to obtain significant noise level reductions though the use of other-than-uniform thickness distributions.
ORBITAL NOISE OF THE EARTH CAUSES INTENSITY FLUCTUATION IN THE GEOMAGNETIC FIELD
Authors: LIU H. S. , KOLENKIEWLCZ R. , WADE C.
Published: March 2003

Orbital noise of Earth's obliquity can provide an insight into the core of the Earth that causes intensity fluctuations in the geomagnetie field. Here we show that noise spectrum of the obliquity frequency have revealed a series of frequency periods centered at 250-, 100-, 50-, 41-, 30-, and 26-kyr which are almost identical with the observed spectral peaks from the composite curve of 33 records of relative paleointensity spanning the past 800 kyr (Sint–800 data). A continuous record for the past two million years also reveals the presence of the major 100 kyr periodicity in obliquity noise and geomagnetic intensity fluctuations. These results of correlation suggest that obliquity noise may power the dynamo, located in the liquid outer core of the Earth, which generates the geomagnetic field.
QUANTITATIVE DYNAMICS IN GEOPHYSICAL PARAMETERS SIMULTANEOUSLY RECORDED IN THE SOOS NATURE PARK (CZECH REPUBLIC)
Authors: TELESCA LUCIANO , COLANGELO GERARDO , LAPENNA VINCENZO , HEINICKE JENS , KOCH ULRICH
Published: March 2003

Time dynamics of self-potential, geochemical and meteorological parameters, simultaneously recorded in a CO 2 degassing area at Soos, NW-Bohemia (Czech Republic), have been investigated. The power spectra, behaving as power-law function of the frequency, show the presence of colored-noise-type dynamics. The Higuchi analysis reveals the observed geophysical signals to have the property of fractal curves, with the identification of different scaling regimes. The Detrended Fluctuation Analysis, removing trends and non-stationarities, has shown that the signals present clear fingerprints of long-range correlated fluctuations.
AN S-PLUS IMPLEMENTATION OF CONTRACTION MAPPING FOR FREQUENCY ESTIMATION
Authors: FOKIANOS KONSTANTINOS , KEDEM BENJAMIN
Published: March 2003

A classical time series problem is that of estimating unknown frequencies for a given sinusoidal regression model. Existing methods include nonlinear least squares and periodogram analysis. An alternative method is offered by the contraction mapping algorithm whose implementation in S-Plus is outlined.
Function and Structure of Complex II of the Respiratory Chain
Authors: Cecchini Gary
Published: March 2003

▪ Abstract  Complex II is the only membrane-bound component of the Krebs cycle and in addition functions as a member of the electron transport chain in mitochondria and in many bacteria. A recent X-ray structural solution of members of the complex II family of proteins has provided important insights into their function. One feature of the complex II structures is a linear electron transport chain that extends from the flavin and iron-sulfur redox cofactors in the membrane extrinsic domain to the quinone and b heme cofactors in the membrane domain. Exciting recent developments in relation to disease in humans and the formation of reactive oxygen species by complex II point to its overall importance in cellular physiology.
The Many Faces of Vitamin B12: Catalysis by Cobalamin-Dependent Enzymes
Authors: Banerjee Ruma , Ragsdale Stephen W.
Published: March 2003

▪ Abstract  Vitamin B12is a complex organometallic cofactor associated with three subfamilies of enzymes: the adenosylcobalamin-dependent isomerases, the methylcobalamin-dependent methyltransferases, and the dehalogenases. Different chemical aspects of the cofactor are exploited during catalysis by the isomerases and the methyltransferases. Thus, the cobalt-carbon bond ruptures homolytically in the isomerases, whereas it is cleaved heterolytically in the methyltransferases. The reaction mechanism of the dehalogenases, the most recently discovered class of B12enzymes, is poorly understood. Over the past decade our understanding of the reaction mechanisms of B12enzymes has been greatly enhanced by the availability of large amounts of enzyme that have afforded detailed structure-function studies, and these recent advances are the subject of this review.
Red cell adenylate kinase deficiency: molecular study of 3 new mutations (118G>A, 190G>A, and GAC deletion) associated with hereditary nonspherocytic hemolytic anemia
Authors: Corrons Joan-Lluis Vives , Garcia Estefania , Tusell Joan J. , Varughese Kottayil I. , West Carol , Beutler Ernest
Published: March 2003

We report here 2 patients with chronic nonspherocytic hemolytic anemia (CNSHA) and severe red blood cell (RBC) adenylate kinase (AK) deficiency. One of these patients, a boy of Spanish origin, exhibited a neonatal icterus and splenomegaly and required blood transfusions until the age of 2 years. The other patient was a white, American infant born to parents who were first cousins; he also presented with neonatal icterus and anemia. In neither case was psychomotor impairment observed. The first patient was found to be a compound heterozygote for 2 different missense mutations, 118G>A(Gly40Arg) and 190G>A(Gly64Arg) (cDNA sequence first described by Matsuura et al, 1989). The second patient was homozygous for an in-frame deletion (GAC) from nucleotide (nt) 498 to 500 or nt 501 to 503 of the cDNA sequence, predicting deletion of either aspartic acid (Asp) 140 or 141. The crystal structure of porcine cytosolic AK was used as a molecular model to investigate how these mutations may affect enzyme structure and function. (Blood. 2003;102:353-356)
Depsipeptide (FR901228) induces histone acetylation and inhibition of histone deacetylase in chronic lymphocytic leukemia cells concurrent with activation of caspase 8–mediated apoptosis and down-regulation of c-FLIP protein
Authors: Aron Jennifer L. , Parthun Mark R. , Marcucci Guido , Kitada Shinichi , Mone Andrew P. , Davis Melanie E. , Shen Tiansheng , Murphy Timothy , Wickham Joseph , Kanakry Chris , Lucas David M. , Reed John C. , Grever Michael R. , Byrd John C.
Published: March 2003

Depsipeptide is in clinical trials for chronic lymphocytic leukemia (CLL) on the basis of earlier observations demonstrating selective in vitro activity in CLL. We sought to determine the relationship of histone H3 and H4 acetylation, inhibition of histone deacetylase, and apoptosis observed in CLL cells to justify a pharmacodynamic end point in these clinical trials. We demonstrate that in vitro depsipeptide induces histone H3 and H4 acetylation and histone deacetylase enzyme inhibition at concentrations corresponding to the LC50 (concentration producing 50% cell death) for cultured CLL cells (0.038 μM depsipeptide). The changes in histone acetylation are lysine specific, involving H4 K5, H4 K12, and H3 K9, and to a lesser extent H4 K8, but not H4 K16 or H3 K14. Depsipeptide-induced apoptosis is caspase dependent, selectively involving the tumor necrosis factor (TNF) receptor (extrinsic pathway) initiating caspase 8 and effector caspase 3. Activation of caspase 8 was accompanied by the down-regulation of cellular FLICE-inhibitory protein (c-FLIP, I-FLICE) without evidence of Fas (CD95) up-regulation. Changes in other apoptotic proteins, including Bcl-2, Bax, Mcl-1, and X-linked inhibitor of apoptosis (XIAP), were not observed. Our results demonstrate a relationship between target enzyme inhibition of histone deacetylase, histone H3 and H4 acetylation, and apoptosis involving the TNF-receptor pathway of apoptosis that is not used by other therapeutic agents in CLL. These data suggest use of histone H3 and H4 acetylation, inhibition of histone deacetylase, and down-regulation of FLIP as pharmacodynamic end points for further evaluation of this drug in patients.
Antisense Protein Tyrosine Phosphatase 1B Reverses Activation of p38 Mitogen-Activated Protein Kinase in Liver of ob/ob Mice
Authors: Gum Rebecca J. , Gaede Lori L. , Heindel Matthew A. , Waring Jeffrey F. , Trevillyan James M. , Zinker Bradley A. , Stark Margery E. , Wilcox Denise , Jirousek Michael R. , Rondinone Cristina M. , Ulrich Roger G.
Published: March 2003

Phosphorylation of stress-activated kinase p38, a MAPK family member, was increased in liver of ob/ob diabetic mice relative to lean littermates. Treatment of ob/ob mice with protein tyrosine phosphatase 1B (PTP1B) antisense oligonucleotides (ASO) reduced phosphorylation of p38 in liver—to below lean littermate levels—and normalized plasma glucose while reducing plasma insulin. Phosphorylation of ERK, but not JNK, was also decreased in ASO-treated mice. PTP1B ASO decreased TNFα protein levels and phosphorylation of the transcription factor cAMP response element binding protein (CREB) in liver, both of which can occur through decreased phosphorylation of p38 and both of which have been implicated in insulin resistance or hyperglycemia. Decreased p38 phosphorylation was not directly due to decreased phosphorylation of the kinases that normally phosphorylate p38—MKK3 and MKK6. Additionally, p38 phosphorylation was not enhanced in liver upon insulin stimulation of ASO-treated ob/ob mice (despite increased activation of other signaling molecules) corroborating that p38 is not directly affected via the insulin receptor. Instead, decreased phosphorylation of p38 may be due to increased expression of MAPK phosphatases, particularly the p38/ERK phosphatase PAC1 (phosphatase of activated cells). This study demonstrates that reduction of PTP1B protein using ASO reduces activation of p38 and its substrates TNFα and CREB in liver of diabetic mice, which correlates with decreased hyperglycemia and hyperinsulinemia.
Dechlorination of o-Dichlorobenzene with Various Hydrogen Donors
Authors: Yasuda Kensei , Shinoda Kiyonori
Published: March 2003

o-Dichlorobenzene (o-DCB) was perfectly converted into benzene and hydrogen chloride by dechlorination with cyclohexane at 300 °C over activated carbon-supported palladium(II) chloride and cerium(III) chloride. The long term stability of catalyst was assessed.
Thermoresponsive Hydrogels Based on Biodegradable Poly(amino acid)s
Authors: Tachibana Yoichi , Kurisawa Motoichi , Uyama Hiroshi , Kakuchi Toyoji , Kobayashi Shiro
Published: March 2003

Thermoresponsive hydrogels based on biodegradable poly(amino acid)s have been developed by crosslinking of poly(N-(ω-hydroxyalkyl) α/β-asparagine)s with diisocyanate. The poly(amino acid) hydrogels showed a thermoresponsive release of a model drug.
Poisson–Boltzmann Continuum Solvation Models for Nonaqueous Solvents I. 1-Octanol
Authors: Park Insook , Jang Yun Hee , Hwang Sungu , Chung Doo Soo
Published: March 2003

A Poisson–Boltzmann continuum solvation model coupled with ab initio quantum calculation was developed for 1-octanol. It was applied to the calculation of the solvation free energies of various solutes consisting of C, H, and O in 1-octanol and their 1-octanol/water partition coefficients.
Michael Addition of Cyanide to Cyclohex-1-enyliodonium Salts
Authors: Fujita Morifumi , Kim Wan Hyeok , Okuyama Tadashi
Published: March 2003

Reaction of 4-substituted cyclohex-1-enyliodonium salt with cyanide in chloroform produces three isomeric cyanocyclohexenes, ipso and two cine products. Deuterium labeling experiments showed that the allylic cine product is formed via the Michael addition of cyanide, followed by elimination of the iodonio group and a 1,2-H shift.
Successful chemotherapy in a male patient with malignant lymphoma and Leber's hereditary optic neuropathy (LHON)
Authors: Zanssen Stefanie , Buse Gerhard
Published: March 2003

Leber's hereditary optic neuropathy (LHON) is a bilateral subacute optic neuropathy caused by hereditary missense mutations of the mitochondrial genome. Primary mutations are located at nucleotide positions 11778, 3460, and 14484 in genes encoding subunits of complex I of the respiratory chain. It has been suggested that degenerative changes in the optic nerve might be mediated by apoptosis. Therefore, we hypothesized that patients affected with LHON might show altered sensitivity to cytotoxic drugs. Here we report the case of a LHON patient carrying the 11778 mutation who required chemotherapy for malignant lymphoma. Using in vitro assays, we found that the patient's peripheral blood mononuclear cells did not show altered vulnerability to cytotoxic drugs. The patient was treated with combination chemotherapy and consolidating radiotherapy, leading to complete remission without inappropriately severe acute or chronic side effects. These data indicate that the 11778 mutation does not change cellular response to cytotoxic drugs in a clinically apparent manner. Am. J. Hematol. 72:263–266, 2003. © 2003 Wiley‐Liss, Inc.
Gene profiling in spinal cord injury shows role of cell cycle in neuronal death
Authors: Di Giovanni Simone , Knoblach Susan M. , Brandoli Cinzia , Aden Sadia A. , Hoffman Eric P. , Faden Alan I.
Published: March 2003

Spinal cord injury causes secondary biochemical changes leading to neuronal cell death. To clarify the molecular basis of this delayed injury, we subjected rats to spinal cord injury and identified gene expression patterns by high‐density oligonucleotide arrays (8,800 genes studied) at 30 minutes, 4 hours, 24 hours, or 7 days after injury (total of 26 U34A profiles). Detailed analyses were limited to 4,300 genes consistently expressed above background. Temporal clustering showed rapid expression of immediate early genes (30 minutes), followed by genes associated with inflammation, oxidative stress, DNA damage, and cell cycle (4 and 24 hours). Functional clustering showed a novel pattern of cell cycle mRNAs at 4 and 24 hours after trauma. Quantitative reverse transcription polymerase chain reaction verified mRNA changes in this group, which included gadd45a, c‐myc, cyclin D1 and cdk4, pcna, cyclin G, Rb, and E2F5. Changes in their protein products were quantified by Western blot, and cell‐specific expression was determined by immunocytochemistry. Cell cycle proteins showed an increased expression 24 hours after injury and were, in part, colocalized in neurons showing morphological evidence of apoptosis. These findings suggest that cell cycle–related genes, induced after spinal cord injury, are involved in neuronal damage and subsequent cell death. Ann Neurol 2003
Continuous growth of mean tumor diameter in a subset of grade II gliomas
Authors: Mandonnet Emmanuel , Delattre Jean‐Yves , Tanguy Marie‐Laure , Swanson Kristin R. , Carpentier Antoine F. , Duffau Hugues , Cornu Philippe , Van Effenterre Rémy , Alvord Ellsworth C. , Capelle Laurent
Published: March 2003

Serial magnetic resonance images of 27 patients with untreated World Health Organization grade II oligodendrogliomas or mixed gliomas were reviewed retrospectively to study the kinetics of tumor growth before anaplastic transformation. Analysis of the mean tumor diameters over time showed constant growth. Linear regression, using a mixed model, found an average slope of 4.1mm per year (95% confidence interval, 3.8–4.4mm/year). Untreated low‐grade oligodendrogliomas or mixed gliomas grow continuously during their premalignant phase, and their pattern of growth can be predicted within a relatively narrow range. These findings could be of interest to optimize patients management and follow‐up. Ann Neurol 2003;53:524–528
Age‐dependent changes in the ability to encode a novel elementary motor memory
Authors: Sawaki Lumy , Yaseen Zaneb , Kopylev Leonid , Cohen Leonardo G.
Published: March 2003

In healthy individuals, motor training elicits cortical plasticity that encodes the kinematic details of the practiced movements and is thought to underlie recovery of function after stroke. The influence of age on this form of plasticity is incompletely understood. We studied 55 healthy subjects and identified a substantial decrease in training‐dependent plasticity as a function of age in the absence of differences in training kinematics. These results suggest that the ability of the healthy aging motor cortex to reorganize in response to training decreases with age. Ann Neurol 2003;53:521–524
Synthesis, Structure, and Antibacterial Activity of 4‐Imino‐1, 4‐dihydrocinnoline‐3‐carboxylic Acid and 4‐Oxo‐1, 4‐dihydrocinnoline‐3‐carboxylic Acid Derivatives as Isosteric Analogues of Quinolones
Authors: Stańczak Andrzej , Ochocki Zbigniew , Martynowski Dariusz , Główka Marek , Nawrot Ewa
Published: March 2003

Chemical modification of cinnoxacin was studied with the aim of improving its antibacterial activity and spectrum. A series of 4‐imino‐1, 4‐dihydrocinnoline‐3‐carboxylic acid derivatives was synthesized and their in vitro antibacterial activity was evaluated. These derivatives were designed as isosteric analogues of fluoroquinolones and are characterized by the presence of an imine group instead of an oxo group at the 4‐position and a nitrogen atom in position 2. The crystal structure of one analogue determined by X‐ray diffraction shows the dipolar formof the compound in the solid state. The in vitro antibacterial activity of the synthesized compounds against Gram‐positive and Gram‐negative bacteria was examined. The MIC of the most active compounds lies in the range of the first generation of quinolones such as nalidixic acid. The compounds with dichlorobenzyl substituent show enhanced activity against Gram‐positive bacteria.
Comparative enantiocontrol with allyl phenyldiazoacetates in asymmetric catalytic intramolecular cyclopropanation
Authors: Doyle Michael P. , Hu Wenhao , Weathers Thomas M.
Published: March 2003

Dirhodium(II) azetidinone‐carboxylates are effective asymmetric catalysts for diazo decomposition of allyl diazoacetates and their subsequent intramolecular cyclopropanations. The effect of alkene substituents on enantiocontrol has been examined and modest selectivities have been achieved. Steric influences from substituents on the diazo carbon are seen to diminish enantioselectivities. Chirality 15:369–373, 2003. © 2003 Wiley‐Liss, Inc.
Configurational stability of chiral lithiated cyclopropylnitriles: A density functional study
Authors: Carlier Paul R.
Published: March 2003

Chiral, configurationally stable lithiated nitriles would be valuable intermediates for asymmetric carbon–carbon bond‐forming reactions. To gain insight into the design of such species, Walborsky's attempted enantioselective deprotonation/trapping reactions of a chiral cyclopropylnitrile were studied computationally up to the MP2(fc)/6‐31+G* and B3LYP/6‐31+G* levels. Investigation of cyclopropylnitrile/LiNH2 deprotonation transition structures demonstrated a significant (20–23 kcal/mol) kinetic preference for N‐lithiation, and a facile (4–6 kcal/mol barrier) “conducted tour” racemization pathway for the N‐lithiated nitrile product. Addition of a model directing group (formyl) to the β‐carbon of the cyclopropyl ring is predicted to significantly favor C‐lithiation over N‐lithiation, both kinetically and thermodynamically. Thus, chiral β‐Lewis base substituted cyclopropylnitriles may serve as precursors to chiral, configurationally stable organolithium reagents. Chirality 15:340–347, 2003. © 2003 Wiley‐Liss, Inc.
Interior structure of a quality control center at the low‐voltage side considering power conditioning by SMES
Authors: Sasaki Takashi , Kita Hiroyuki , Hara Ryoichi , Tanaka Eiichi , Hasegawa Jun
Published: March 2003

The authors have proposed FRIENDS—Flexible, Reliable and Intelligent Electrical eNergy Delivery System—as a future electric power distribution system. The most important idea of FRIENDS is to install new facilities called Quality Control Centers (QCCs) between the distribution substation and customers. By controlling QCCs appropriately, various purposes of FRIENDS can be achieved.

It is indispensable to design the concrete interior structure of QCC in order to realize FRIENDS. This paper proposes the interior structure and control methods of QCC from the viewpoint of power conditioning functions by energy storage system in QCC. In this paper, it is assumed that SMES is used as the energy storage system in QCC. The proposed interior structure is based on the concept of UPS (Uninterruptable Power Supply). In this paper, SMES is installed in the DC side of UPS. Further, this paper proposes control methods of SMES and PWM converters. The proposed control methods are used to satisfy various purposes, such as load fluctuation compensation, load leveling, and cooperation with dispersed‐type generator. Finally, the validity of these control methods is confirmed through transient analysis PSCAD/EMTDC. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 143(3): 20–28, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.10056
A self‐commutated back‐to‐back system and its performance under a single line‐to‐ground fault condition
Authors: Hagiwara Makoto , Akagi Hirofumi , Fujita Hideaki
Published: March 2003

This paper deals with a self‐commutated BTB (Back‐To‐Back) system for the purpose of power flow control and/or frequency change in transmission systems. Each BTB unit consists of two sets of 16 three‐phase voltage‐source converters, and their AC terminals are connected in series to each other via 16 three‐phase transformers. Hence, the BTB unit uses totally 192 switching devices capable of achieving gate commutation. This results in a great reduction of voltage and current harmonics without performing PWM control. Simulation results verify the validity of the proposed system configuration and control scheme not only under a normal operating condition but also under a single line‐to‐ground fault condition. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 143(3): 68–78, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.10124
MHD flow simulation in subsonic disk MHD generator driven by a shock tube facility
Authors: Nabara Yoshihiro , Okuno Yoshihiro
Published: March 2003

The MHD flow behavior and the performance of an experimental nonequilibrium subsonic disk MHD generator driven by a shock‐tube facility have been examined with time‐dependent r−z two‐dimensional and r−θ−z three‐dimensional Large Eddy Simulation for the first time. The calculation region is extended and covers a hot duct through a downstream duct including the subsonic MHD generator with two throats. For optimal and high load operations, the flow chokes at the downstream throat and the subsonic flow is maintained in the generator channel. The discharge structure is uniform in the θ direction, and suitable fluid flow is realized in the generator channel, although the large boundary layer separations and eddies are observed behind the downstream throat. For low load operations, the flow chokes at the upstream throat and the flow becomes supersonic, where pseudo‐shock waves and large eddies are observed in the generator channel and the downstream duct. The ionization instability in the r−θ plane occurs in the generator channel, which deteriorates the generator performance. Asymmetric flow at the generator inlet, which is attributed to the change of flow direction from the hot duct, seems not to be significant for the generator performance. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 143(3): 1–8, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.10130
A compensation method for the end effect of a linear induction motor
Authors: Fujii Nobuo , Harada Toshiyuki , Sakamoto Yasuaki , Kayasuga Takeshi
Published: March 2003

For the end effect of a linear induction motor (LIM), the authors propose a new concept that the end effect can be compensated for only by the supply of secondary current synchronized with the current of the LIM in front of the entry end of the LIM, without considering the flux density distribution in the LIM primary region. As a concrete method to supply the secondary current in front of the LIM, the authors propose the rotator with rare‐earth‐type permanent magnets which has a strong flux density without ohmic loss, and does not cause the power factor problem even for the influence of end effect. The results of analytical study on the numerical example of LIM designed for subways are as follows. This method can make the flux density and thrust density distribution in the LIM primary region almost entirely agree with those of the case without end effects. This method can compensate for the thrust, power factor, and efficiency of the LIM at the rated speed to coincide with the characteristics without end effect. There is no problem in the slip characteristic curves of the LIM with the compensator, although the compensator only rotates synchronizing with the frequency of the LIM. The effect of compensation becomes large in the lower slip. The force to rotate the compensator is very small in the suitable design. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 143(3): 58–67, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.10132
The phase reversal effect of a fiber Bragg grating and its application to optical switches
Authors: Morimura Shun , Kurono Masahiro
Published: March 2003

We propose an interferometer‐type multistate optical switch and an interferometer‐type digital performance switch using a fiber Bragg grating (FBG) and the phase reversal effect. The effect is a reversing phenomenon of optical phase difference between the reflected and transmitted light from an FBG on a reflectivity spectrum dip between the main reflection band and first sideband. By combining this effect and reflectivity change, the multistate switch including only a single FBG can perform as a four‐state switch. In this paper we describe the principle of the phase reversal effect and some novel optical switch structures, and also the results of experimental examination. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 143(3): 38–48, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.10136
A degree‐of‐damage estimation model of earthquake damage using interferometric SAR data
Authors: Ito Yosuke , Hosokawa Masafumi
Published: March 2003

This paper presents a damage estimation model of an earthquake using a pair of interferometric SAR data. Coherence is defined as a correlation function of two SLC (Single Look Complex) data. The coherence derived from multi‐temporal SLCs before and after the earthquake includes a temporal decorrelation in disturbed regions. To estimate a degree of damage using the temporal decorrelation, the proposed model employs a coherence ratio, which is the ratio of the coherence derived from the SLCs before and after the event to the coherence derived from a pair of SLCs before the event. The temporal coherence ratio is computed by compensating the coherence ratio with the spatial decorrelation. The degrees of damage are defined by the logarithmic probability range of the ratio of the damage areas. It is shown that there is a significant relationship between the temporal coherence ratio and the probability of the degree of damage. In the case of the Hyogoken–Nanbu earthquake, its relationship can be represented by a linear function. The parameters of regression lines are set by applying the least‐squares method. We have succeeded in estimating the cumulative probability of the degree of damage from the temporal coherence ratio. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 143(3): 49–57, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.10138
A Facile Direct Synthesis of Bimetallic CuIIZnII Complexes with Ethylenediamine Revealing Different Types of Chain Crystal Structures
Authors: Pryma Oksana V. , Petrusenko Svitlana R. , Kokozay Volodymyr N. , Skelton Brian W. , Shishkin Oleg V. , Teplytska Tetyana S.
Published: March 2003

Unactivated copper metal powder and zinc oxide readily react with ethylenediamine (en) in nonaqueous [methanol, dimethylformamide (dmf), dimethyl sulfoxide (dmso), acetonitrile] solutions of ammonium salts under ambient conditions producing, in high yields, a series of heterobimetallic complexes of general formula [Cu(en)2ZnX4]·(Solv), where X = Cl, Br, NCS, CH3COO (OAc); Solv = dmf, dmso, CH3CN, H2O. The single‐crystal X‐ray analysis of the complexes reveals chain structures, which are based on the completion of the octahedral coordination of CuII by two bridging X atoms from ZnX42−. The ZnX42− is shown to be a distorted tetrahedron (Cl, Br, NCS) or a very distorted octahedron (OAc) and to behave as a one‐ or two‐linking centre bridging ligand. The chains are found to be zigzag [Cu(en)2ZnCl4]·dmso (1), [Cu(en)2ZnCl4]·dmf (2), [Cu(en)2Zn(NCS)4]·CH3CN (3), quasi linear [Cu(en)2Zn(OAc)4] (4), or helical, [Cu(en)2Zn(NCS)4]· 0.5H2O (5), depending on the nature of the anion and solvent. Complex 4 represents the first compound containing Zn(OAc)42− to be crystallographically authenticated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis and Characterization of Five‐Coordinate Gallium and Indium Complexes Stabilized by Tridentate, Substituted Pyrrole Ligands
Authors: Kuo Pei‐Cheng , Huang Jui‐Hsien , Hung Chen‐Hsiung , Lee Gene‐Hsiang , Peng Shie‐Ming
Published: March 2003

Five‐coordinate gallium and indium complexes stabilized by tridentate, substituted pyrrole ligands have been synthesized and characterized. The reaction of MCl3 with 1 equiv. of Li[NC4H2(CH2NMe2)2‐2,5] in diethyl ether affords [{NC4H2(CH2NMe2)2‐2,5}MCl2] [M = Ga (1), In (2)] in high yield. Reaction of 1 with 2 equiv. of MeLi in diethyl ether at −78 °C followed by heating to reflux for 30 min affords the alkylated product [{NC4H2(CH2NMe2)2‐2,5}GaMe2] (3). Similarly, the reaction of 2 with 2 equiv. of MeLi or nBuLi affords the dialkylated complexes 4 and 5, respectively. Complex 2 is a strong Lewis acid which readily absorbs H2O forming [{[C4H2N(CH2NMe2)2‐2,5]InCl2}2(μ‐OH2)] (6). Complexes 3, 4, and 6 have been characterized by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Cyclopropanation of Olefins with Diazoalkanes, Catalyzed by CoII(porphyrin) Complexes − A Synthetic and Mechanistic Investigation and the Molecular Structure of CoIII(TPP)(CH2CO2Et) (TPP = Dianion of meso‐Tetraphenylporphyrin)
Authors: Penoni Andrea , Wanke Riccardo , Tollari Stefano , Gallo Emma , Musella Danilo , Ragaini Fabio , Demartin Francesco , Cenini Sergio
Published: March 2003

Cobalt(II) porphyrin complexes catalyze reactions between ethyl diazoacetate (EDA) and styrenes to give the corresponding cyclopropanes with trans selectivity. The reactions of other diazoalkanes and other olefins have also been carried out, and the mechanism of the reaction has been investigated. Kinetic data and stoichiometric reactions support the formation of a diazoalkane cobalt‐porphyrin complex that reacts with the olefins to generate the cyclopropane. Diethyl maleate and fumarate are not formed in the presence of an excess of olefin. On treatment of EDA with CoII(TPP) (TPP = dianion of meso‐tetraphenylporphyrin) in the absence of the olefin, an alkyl cobalt(III) complex CoIII(TPP)(CH2CO2Et) was isolated, and its structure has been solved by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Does assessment make a difference for people with dementia? The effectiveness of the Aged Care Assessment Teams in Australia
Authors: Howe Anna L. , Kung Francis
Published: March 2003

The needs of individuals with dementia and other psychiatric problems of old age have received increased attention in Australia over the last decade. This paper reports on the role of Aged Care Assessment Teams (ACATs) in managing these clients, and the extent to which they are differentiated from other clients in the assessment process and outcomes recommended. Data on some 26,500 clients seen by ACATs in Victoria in the second half of 1999 are analysed to show (1) the relationship between a diagnosis of dementia and reporting of disability in orientation, (2) characteristics of clients with and without a diagnosis of dementia and (3) outcomes for groups of clients defined on the basis of a diagnosis of dementia and disability in orientation. Copyright © 2003 John Wiley & Sons, Ltd.
The long term care insurance law in Japan: impact on institutional care facilities
Authors: Ikegami Naoki , Yamauchi Keita , Yamada Yukari
Published: March 2003

Background

Following the introduction of the public long‐term care (LTC) insurance in Japan on 1 April 2000, funding that had been split between the health and social welfare sectors was unified. All elderly people 65 and over have become entitled to receive benefits according to their eligibility level, regardless of income or family support. Except for those assessed as in the least dependent group, individuals can choose either community care or institutional care, with only the cost of food an additional payment for the latter.

Method

Review of the development and implications of long term care insurance provision for older people and analysis of quality based on resident level data.

Results

Despite the structural changes, the impact of the new programme has had minimal impact upon the providers of institutional care. The three types of facilities that had provided LTC have continued to function independently, basically retaining the same staffing requirements and charges. For indicators adjusted for risk, the quality of care tended to be higher in designated LTC hospital beds.

Conclusions

Appropriate balance between institutional and community care and triaging among the three different types of facilities remains difficult because decisions rest with the individual. Indicators of quality must take into account differences in case‐mix among the facility types. However, there are few incentives for providers to improve quality because demand is likely to be increasingly greater than supply. Whether the generous provisions of the new programme will prove to be sustainable remains to be seen. Copyright © 2003 John Wiley & Sons, Ltd.
An attachment perspective on grandparents raising their very young grandchildren: Implications for intervention and research
Authors: Poehlmann Julie
Published: March 2003

The purpose of this article is to apply an attachment perspective to the growing number of families with grandparents raising grandchildren to increase our understanding of the complexity of intergenerational relationship processes in these families and to guide early intervention and research. It is proposed that, as grandparents take responsibility for their grandchildren, three relationship processes simultaneously occur: (1) disruptions in attachments potentially occur, especially in relationships involving parents, (2) attachment relationships between grandchildren and grandparents develop or are revised, and (3) family members' internal working models of attachment and caregiving are challenged and shaped. To address these processes, attachment theory and research focusing on the formation, disruption, and intergenerational transmission of attachment relationships are reviewed. Conclusions suggest that when grandparents assume responsibility for grandchildren, families may need and be particularly open to a range of interventions. In addition, research focusing on attachment relationships in families of grandparents raising grandchildren is needed. ©2003 Michigan Association for Infant Mental Health.
Maternal self‐efficacy beliefs, competence in parenting, and toddlers' behavior and developmental status
Authors: Coleman Priscilla K. , Karraker Katherine Hildebrandt
Published: March 2003

This study was designed to examine parenting self‐efficacy beliefs as correlates of mothers' competence in parenting toddlers and as predictors of toddlers' behavior and development. Sixty‐eight predominantly middle‐class mother–toddler pairs participated in this study. Mothers completed questionnaires, toddlers were administered the Bayley Scales of Infant Development (BSID‐II), and each dyad participated in the Crowell Procedure, which is designed to observe parent and toddler behaviors in a semistructured laboratory context. Although domain‐general and domain‐specific parenting self‐efficacy beliefs were not associated with parenting competence, domain‐specific beliefs were significantly related to toddlers' scores on the Mental Scale of the BSID‐II and several behaviors observed during the Crowell Procedure (Affection Towards Mother, Avoidance of Mother, Compliance, Enthusiasm, and Negativity). Implications of the findings are discussed. ©2003 Michigan Association for Infant Mental Health.
Ontological modelling of e‐services to ensure appropriate mobile transactions
Authors: Terziyan Vagan
Published: March 2003

The main goal of this paper is to provide simple ontological support to mobile electronic commerce. The description of an ontology‐driven Transaction Monitor (TM) for mobile business applications is considered. The approach is based on the assumption that the transaction management tool can be implemented in a mobile terminal, allowing integration of different distributed external e‐services. We use the ontology‐based framework for transaction management so that the TM will be able to manage transaction across multiple e‐services and we consider management of distributed location‐based services as an example of such ontology‐based TM implementation. The core of the approach is very simple service ontologies. Ontologies should be ‘placed’ both in mobile terminals and in e‐services. They define common multiple clients—multiple services standards and vocabularies for the use of the names, types, schemas, default values for parameters, atomic service actions with appropriate structure of action's input and output. In our implementation ontologies help to the TM to deal with multiple services during transactions and to simplify the appropriate user interface. Copyright © 2003 John Wiley & Sons, Ltd.
A new synthesis of [26,28‐2H6]brassinolide and [26,28‐2H6]castasterone via an unusual methyl migration
Authors: Kolbe A. , Porzel A. , Schmidt J. , Adam G.
Published: March 2003

Deuterium‐labelled brassinosteroids, namely [26,28‐2H6]castasterone, 8, and [26,28‐2H6]brassinolide, 9, were synthesized starting from 6,6‐ ethylenedioxy‐20‐formyl‐2α,3α‐isopropylidenedioxy‐5α‐pregnane, 1, and 3‐[2H3]methyl‐but‐1‐yne‐[4,4,4‐2H3], 11. Upon alkylating cleavage of the epoxide 6 with trimethylaluminium‐n‐butyllithium an unusual migration of a neighbouring [2H3]methyl group takes place to afford deuteriation at positions 26 and 28. Copyright © 2002 John Wiley & Sons, Ltd.