bluuebunny/crossref_metadata_2025 huggingface dataset:
Sulfur- and Carbon-Bonded Forms of the Cobalt(III) Complex With the Ligands 2-Aminoethyl 3-Aminopropyl Sulfide and 1,1,1-Tris(aminomethyl)ethane
Authors: Kofod P , Larsen E , Springborg J , Larsen S , Larsen TA , Geue RJ , Searle GH
Published: September 2010

The new sulfur-bonded compound [Co(tame)( aeaps )] Cl3.H2O has been synthesized by the reaction of aeaps with Co(tame)Cl3 [tame = 1,1,1-tris( aminomethyl )ethane, and aeaps = 2- aminoethyl 3-aminopropyl sulfide or 3-thiahexane-1,6-diamine]. The Co(tame)( aeaps )3+ ion equilibrates in basic solution with the corresponding carbon-bonded species: Co(tame)( aeaps )3++HO-↔ Co(tame)(C-aeaps )2++H2O A salt of the carbon-bonded species, [Co(tame)(C- aeaps )](S2O6), has been isolated and its structure solved by X-ray diffraction analysis ( C- aeaps = 1,6-diamino-3-thiahexan-4-ide). The crystals are orthorhombic, Pna21, with cell dimensions a 20.455(10), b 9.960(10), c 8.982(10) Ǻ at 122(2) K. Preliminary thermodynamic and kinetic data are similar to the recently reported values for the corresponding coordination ion Co( tacn )( aeaps )3+ ( tacn = 1,4,7-triazacyclononane). In basic solution the Co(tame)( aeaps )3+ species exchanges one of its methylene protons orders of magnitude faster than any other methylene protons and also much faster than it forms the alkyl complex as shown by 13C n.m.r. measurements.
Structural Systematics of Rare Earth Complexes. I. Structural Characterization of Lanthanoid(III) Picrate Hydrates: Monoclinic (P21/C) (Quasi-)Dodecahydrates of the Related La → Pr and Nd → Tb Families
Authors: Harrowfield JM , Lu WM , Skelton BW , White AH
Published: September 2010

Single-crystal room-temperature X-ray studies on hydrated specimens (deposited from aqueous solutions) of the sequence of trivalent lanthanoid picrates La → Tb have shown, with certain qualifications/reservations discussed herein and in Parts III and IV following, their existence as dodecahydrates in two closely related but subtly different monoclinic P21/c structural types. Nd → Tb generally conform to a 'low-β' type: a 7.767(1) → 7.603(3), b 27.525(9) → 27.440(10), c 18.198(11) → 18.182(8) Ǻ, β 105.11(3) → 105.18(4)°, V 3712(3) → 3674(3) Ǻ3, Z = 4 formula units, while La → Pr are a 'higher-β' type: a 7.933(1) → 7.9435(9), b 26.856(6) → 26.74(1), c 18.244(6) → 18.215(2) Ǻ, β 107.96(2) → 108.238(8)°, V 3697(2) → 3675(2) Ǻ3, Z = 4 formula units; the latter form is frequently found partially desolvated toward the undecahydrate without loss of crystal integrity, as water is lost from tunnels in the lattice, with the actual hydrate stoichiometry dependent on the history of the specimen. In both sets of compounds, similar complex species [ Ln ( pic )2(OH2)6]+ are observed, with one picrate uncoordinated as counter ion, and six lattice water molecules. The lanthanoid ion is >8-coordinate, one of the coordinated picrate moieties being quasi-bidentate , with an ortho-nitro group oxygen atom having a long contact to the metal atom in both series.
Experiments Directed Towards the Synthesis of Anthracyclinones. XIX. Elaboration of 2-Formylquinizarin Through a Wittig Reaction
Authors: Boniface PJ , Cambie RC , Carroll DR , Marsh NF , Milbank JBJ , Rutledge PS , Woodgate PD
Published: September 2010

Reaction of 2-formylquinizarin dimethyl ether (3) with the dimethoxy ylide (6) gives an α,β -unsaturated ester (8) which on hydrogenation, reduction and methylation gives the tetramethoxyanthracene diester (18). When linked to work by Dotz and Popall this sequence provides a route to (�)-4-demethoxydaunomycinone.
New Macrocyclic Complexes Derived From Cobalt(III) Cage Complexes
Authors: Creaser II , Komorita T , Sargeson AM , Willis AC , Yamanari K
Published: September 2010

The synthesis and partial characterization of several green complexes, derived from the products of the reactions between [Co(Cl2-sar)]3+ (Cl2-sar = 1,8-dichloro-3,6,10,13,16,19- hexaazabicyclo [6.6.6] icosane ) and zinc powder in water, are described. Most of the complexes appear to have [CoCl2(N4)] chromophores , where N4 denotes the tetraaza macrocyclic ligand , 6,13-dimethylene-1,4,8,11-tetraazacyclotetradecane (L1). For trans-[CoCl2(L1)]+, three isomers due to different configurations about the asymmetric nitrogen donor centres were obtained and characterized by the electronic absorption and 13C n.m.r. spectra. Their stereochemistry is discussed and compared with that of 1,4,8,11-tetraazacyclotetradecane on the basis of strain energy minimized calculations. A trans-[CoCl2(H2L2)]3+ complex containing a related macrocycle with a pendant ethane-1,2-diamine arm [H2L2+, 6-(4-ammonio-2-azoniabutyl)-13-methylene-1,4,8,11-tetraazacyclotetradecane] was also isolated and characterized by X-ray crystallographic analysis. All these molecules are derived from the decomposition of zinc alkyl complexes formed by oxidative addition of zinc to the parent [CoII(Cl2-sar)]2+ ion in aqueous solution.
A Study of Chemical Reactions in Molten Sodium Hydrogen Sulfate Potassium Hydrogen Sulfate Eutectic. V. The Reactions of Eleven Acetates
Authors: Mohamed N , Tariq SA
Published: September 2010

The reactions of the acetates of lithium, sodium, potassium, magnesium, calcium, strontium, barium, manganese, cobalt, zinc and lead with molten sodium hydrogen sulfate-potassium hydrogen sulfate eutectic were investigated by means of thermogravimetry, differential thermal analysis, X-ray diffraction, mass spectral and infrared methods. In these acid-base reactions, the metal acetates were found to be converted into the corresponding metal sulfates, and acetic acid was the volatile product of each reaction. The temperatures and stoichiometries of the reactions have been determined.
The Conformations of the Hexaammineruthenium(III) Ion in Simple Salts
Authors: Engelhardt LM , Reynolds PA , Sobolev AN
Published: September 2010

Single-crystal X-ray diffraction results are presented for six hexaammineruthenium (III) salts, viz. [ Ru (NH3)6]2(SO4)35H2O, [ Ru (NH3)6] CdCl5, [ Ru (NH3)6]ZnCl5, [ Ru (NH3)6]Cl2SCN, [ Ru (NH3)6]2(S2O6)3.H2O, and a salt of approximate formula [ Ru (NH3)6]2 [POF5]3.4H2O. The 11 independent cations in these and other published structures do not adopt a single conformation in respect of hydrogen atom disposition. Analysis of the N- Ru -N-H dihedral angles and their correlations strongly suggests that the conformation is random, given the crystallographic site symmetry. The structure with torsional energy calculated at a minimum by ab initio methods is not observed. This suggests that there are only a limited number of interionic geometries feasible in crystallization. Such a limitation suggests that computing crystal structures, with no assumptions as to space group or any other assumption, is not an open-ended problem with excessive alternatives.
13C N.M.R. and Single-Crystal X-Ray Structural Investigation of the Fluoroquinolone Antimicrobial Drug Norfloxacin 2DCl.D2O
Authors: Wallis SC , Gahan LR , Charles BG , Hambley TW
Published: September 2010

The sites of deuteronation of the molecule norfloxacin.2DCl.D2O have been investigated by 13C n.m.r. and a single-crystal structure determination. The 13C n.m.r. spectrum of norfloxacin (3 M DCl ) displays 14 lines, seven of which display 19F-13C coupling. The observation of 19F-13C coupling for the resonance at 171.0 ppm (J 3.9 Hz) allows positive assignment of this resonance to the keto carbon atom. The position of this resonance was found to be sensitive to [D+]. The crystals of norfloxacin.2DCl.D2O are monoclinic, space group P21/c, with a 8.536(2), b 14.379(3), c 14.985(4) Ǻ, β 93.40(2)°, V 1836.0(7) Ǻ3, and Z = 4. The structure was refined to R 0.039 and Rw 0.041. The n.m.r. study, combined with the structural analysis permits assignment of the sites of deuteronation for this molecule as an oxygen of the carboxylic acid, the external nitrogen of the piperazine ring and the keto oxygen atom.
Synthesis of a Phosphinic Acid Transition State Analog Inhibitor of Dihydroorotase
Authors: Cao Y , Christopherson RI , Elix JA , Gaul KL
Published: September 2010

The synthesis of the phosphinic acid 4-hydroxy-6-oxo-1,4-azaphosphinane-2-carboxylic acid 4-oxide (11) is described. The phosphinic acid (11) was designed as a transition state analogue inhibitor of dihydroorotase.
Synthesis of Phthalide Derivatives of Podocarpic Acid Via Directed ortho Metalation: a Route to Highly Substituted Octahydrochrysene Derivatives
Authors: Cambie RC , Rutledge PS , Stevenson RJ , Woodgate PD
Published: September 2010

Two phthalide derivatives (7) and (8) have been prepared from podocarpic acid (1) via directed ortho metallation. The ring-c aromatic 16-oxa-17-oxo androstane analogue (8) was reacted with dimethyl acetylenedicarboxylate to give the 1,4-epoxy decahydrochrysene derivatives (9) and (10). The stereoisomer (10) was aromatized under acidic conditions to give the chrysen-1-ol derivative (11).
Pyrolysis of Aryl Azides. XII. Mechanistic Implications of the Very Small Neighboring Group Effects Across the 2,3-Bond of 2-Azidonaphthalene
Authors: Dyall LK , Ferguson JA
Published: September 2010

2-Azidonaphthalenes with nitro, acetyl, benzoyl and methoxycarbonyl substituents in the 3-position have been synthesized and then pyrolysed in nitrobenzene solution. At 120°, the rates (relative to 2-azidonaphthalene) are respectively 27.9, 24.8, 5.00 and 3.67. These very small neighbouring group effects are consistent with a transition state which has considerable quinonoid character. No evidence of cyclic products was obtained from the two azides with nitro and ester neighbouring groups. With the two azido ketones there was infrared spectroscopic evidence of clean cyclization in dilute solution, to form the corresponding naphth [2,3-c] isoxazole. Our attempts to isolate these two naphthisoxazoles led to decomposition, though 3-methylnaphth[2,3-c] isoxazole has been reported previously ( Friedrichsen and Kaschner 1977).
New Macrocyclic Ligands. V. Synthetic, Crystallographic and Computational Studies of a New N2O6-Heteroatom Cage
Authors: Atkinson IM , Lindoy LF , Matthews OA , Meehan GV , Sobolev AN , White AH
Published: September 2010

The synthesis, characterization and X-ray structure of a new cage molecule containing six phenoxy and two nitrogen heteroatoms is reported. Semiempirical MO calculations have been used to probe the topological rigidity of the cage relative to related aliphatic systems.
The Chemistry of 5-Oxodihydroisoxazoles. VIII. Photolysis of 2-(Heterocyclyl)isoxazol-5(2H)-ones
Authors: Prager RH , Singh Y , Weber B
Published: September 2010

Photolysis of 2-( heterocyclyl )isoxazol-5(2H)-ones occurs readily at 300 nm. In alcohol the products are the corresponding 2-alkoxy-3-heterocyclylaminoacrylates, and, in the presence of 1 M trifluoroacetic acid, the corresponding imidazole annulated heterocycle . Examples are reported where the heterocycle is quinolin-2-yl (10 examples), isoquinolin-1-yl, benzoxazol-2-yl, benzothiazol-2-yl, quinazolin-1-yl and pyrimidin-2-yl.
The Preparation and Crystal Structure of the Bismuth(III) Catecholate Complex Adduct (NH4)2[Bi2(C6H4O2)4].(C6H6O2)2.2H2O
Authors: Smith G , Reddy AN , Byriel KA , Kennard CHL
Published: September 2010

(NH4)2[Bi2(C6H4O2)4].(C6H6O2)2.2H2O, a bismuth(III)-catechol complex adduct, has been prepared and its structure determined by X-ray diffraction methods. The complex anion is a centrosymmetric dimer comprising two five-coordinate [ bis ( catecholato (2-)) bismuthate (III)] centres [Bi-O, 2.177(4), 2.222(4) Ǻ and 2.150(3), 2.322(4)Ǻ], bridged by one of the catechol oxygens [Bi-O, 2.653(3)Ǻ]. In addition, the structure is stabilized by hydrogen bonding involving the ammonium ions, the lattice waters and the two adduct catechol molecules.
Solvent Polarity Studies of the Water+t-Butyl Alcohol and Water+t-Butylamine Binary Systems With the Solvatochromic Dyes Nile Red and Pyridinium-N-phenoxide Betaine, Refractometry and Permittivity Measurements
Authors: Kipkemboi PK , Easteal AJ
Published: September 2010

The empirical solvent polarity parameters ENR and ET for the solvatochromic compounds Nile Red (1) and pyridinium-N-phenoxide betaine (2), respectively, have been determined as a function of composition for water+t -butyl alcohol and water+t-butylamine binary mixtures, over the whole composition range at 298 K. For both systems the two parameters vary with composition in a strongly non-linear fashion, and the polarity of the mixture decreases with increasing proportion of the organic cosolvent. The non-linear variation of the polarity parameters is attributed to water-cosolvent hydrophobic interactions at low cosolvent contents, and hydrogen-bonding interactions at higher cosolvent contents. Permittivity and refractive index have also been measured at 298 K for both systems, and both properties are strongly non-linear functions of composition.
Synthesis of Bridgehead Substituted Bicyclo[2.2.1]Heptanes. Radical Cyclization of an Oxime Ether and an α,β-Unsaturated Ester
Authors: Della EW , Knill AM
Published: September 2010

The synthesis of bicyclo[2.2.1]heptanes with useful functionality at each bridgehead is achieved by radical cyclization of appropriately substituted 4-methylene- and 4-benzyloxyimino- cyclohexylmethyl radicals. The latter process, for example, leads to a bridgehead amine. Optimum yields are achieved when the reactions are conducted at 110� with slow addition of tributyltin hydride; under these conditions, the uncyclized isomer is either not detected, or formed in very small quantity. Production of a mixture of five- and six-membered cycloalkanones from similar treatment of the analogous 4-oxocyclohexylmethyl radicals reveals that the reaction is medicated by the corresponding 1-norbornyloxy radical.
Attempted Heterocyclic Syntheses Through Electrophilic Ring Closure Reactions of 2-Allylaniline Systems Containing Larger Side Chains
Authors: Francis CL , Ward AD
Published: September 2010

The electrophile-initiated cyclization of some 2-allylanilines and their amide derivatives has been further investigated. Although 2-allylanilines with small, allylic substituents such as methyl reacted with iodine to yield 3-iodo-1,2,3,4-tetrahydroquinolines the 2-allylanilines with larger substituents related to those of virantmycin provided low yields of the tetrahydroquinoline as part of a complex product mixture.
Reactivities of Monomers Towards the 1-Methyl-1-(methoxycarbonyl)ethyl Radical
Authors: Lyons RA , Senogles E
Published: September 2010

The relative reactivities of acrylonitrile, methyl acrylate , methyl methacrylate and styrene towards the 1-methyl-1-( methoxycarbonyl )ethyl radical have been determined at 60°C, and the results compared with those for the poly (methyl methacrylate ) radical. The results for methyl acrylate suggest that the copolymerization of this monomer with methyl methacrylate is adequately described by a terminal mechanism. Those for styrene show that the presence of a penultimate styrene or methyl methacrylate unit in a poly(methyl methacrylate ) radical leads to a slightly greater preference for this radical to add styrene over methyl methacrylate compared to the 1-methyl-1-( methoxycarbonyl )ethyl radical. The results for methyl methacrylate and acrylonitrile suggest that the copolymerization of these monomers is probably best represented by a penultimate mechanism.
Studies Directed Towards the Total Synthesis of Anticapsin and Related Compounds. IV. Competitive Reaction of Amino and Carboxy Substituents in the Halohydrination of 2-Aminobicyclo[2.2.2]oct-5-ene-2-carboxylic Acid Derivatives
Authors: Crossley MJ , Davies SR , Hambley TW
Published: September 2010

Bromohydrination of benzyl (1RS,2SR,4SR)-2-benzyloxycarbonylamino-1-trimethylsilyloxy-bicyclo[2.2.2]oct-5-ene-2-carboxylate (6a) and the (1RS,2RS,4SR)- diastereomer (6b) with N- bromoacetamide in aqueous dioxan has been investigated. These reactions are highly regio-and stereo-selective and give the corresponding bromohydrins (9a) and (9b), but in moderate to low yield. These bromohydrins have the necessary stereochemistry for conversion into anticapsin. The other products from the reaction are tricyclic compounds formed by capture of the anti- bromonium cation intermediates or resultant bromohydrins by interaction with the proximal protected carboxy and amino groups within the molecules. Thus the carbolactone (11) is formed from the endo -adduct (6a), and the carbonimidic acid derivative (12) and the cyclic urethane (13) are formed from the exo-adduct (6b). Cleavage of the trimethylsilyl group from the tricyclic compound (12) gives benzyl (1RS,2RS,3RS,7RS,8RS)-5-benzyloxy-2-bromo-8-hydroxy-4-oxa-6-azatricyclo[5.3.1.03,8]undec-5-ene-7-carboxylate(14), the structure of which was determined by X-ray diffraction methods and refined to a residual of 0.035 for 1549 independent observed reflections. The crystals of (14) are monoclinic, P21/c, a 12.954(3), b 6.197(3), c 26.784(7) Ǻ, β 95.33(2)°, Z 4. Reactions attempting to generate iodohydrins from the alkenes (6) were also highly regioselective and gave detrimethylsilylated iodo analogues of (11) and (13).
Erratum to: DNA sequences from three genomes reveal multiple long-distance dispersals and non-monophyly of sections in Australasian Plantago (Plantaginaceae)
Authors: Tay Mei Lin , Meudt Heidi M. , Garnock-Jones Philip J. , Ritchie Peter A.
Published: August 2010

We examined the geographic origins and taxonomic placements of New Zealand and Australian Plantago (Plantaginaceae) by using molecular phylogenetic data. Plantago comprises over 200 species distributed worldwide. Analyses of three markers from the nuclear (ITS), chloroplast (ndhF?rpl32) and mitochondrial (coxI) genomes showed that the New Zealand species form three distinct, well supported clades that are not each others' closest relatives, and were each derived relative to the sampled Australian species. Therefore, at least three long-distance directional dispersal events into New Zealand can be inferred for Plantago, likely from Australian ancestors. This result differs from the biogeographic pattern often reported for New Zealand plant genera of a single dispersal event followed by rapid radiation, and may be attributed to ready biotic dispersal of mucilaginous seeds and habitat similarities of the Australasian species. Molecular dating placed the arrival time and diversification of the New Zealand species between 2.291 and 0.5�million years ago, which coincides with the geological dates for the uplift of mountain ranges in New Zealand. The mitochondrial DNA substitution rate of the Australasian clade relative to the rest of the genus is discussed, as well as implications of the non-monophyly of sections Oliganthos, Mesembrynia and Plantago within subgenus Plantago.
Arrangement of Kv1 α subunits dictates sensitivity to tetraethylammonium
Authors: Al-Sabi Ahmed , Shamotienko Oleg , Dhochartaigh Sorcha Ni , Muniyappa Nagesh , Le Berre Marie , Shaban Hamdy , Wang Jiafu , Sack Jon T. , Dolly J. Oliver
Published: August 2010

Shaker-related Kv1 channels contain four channel-forming α subunits. Subfamily member Kv1.1 often occurs oligomerized with Kv1.2 α subunits in synaptic membranes, and so information was sought on the influence of their positions within tetramers on the channels’ properties. Kv1.1 and 1.2 α genes were tandem linked in various arrangements, followed by expression as single-chain proteins in mammalian cells. As some concatenations reported previously seemed not to reliably position Kv1 subunits in their assemblies, the identity of expressed channels was methodically evaluated. Surface protein, isolated by biotinylation of intact transiently transfected HEK-293 cells, gave Kv1.1/1.2 reactivity on immunoblots with electrophoretic mobilities corresponding to full-length concatenated tetramers. There was no evidence of protein degradation, indicating that concatemers were delivered intact to the plasmalemma. Constructs with like genes adjacent (Kv1.1-1.1-1.2-1.2 or Kv1.2-1.2-1.1-1.1) yielded delayed-rectifying, voltage-dependent K+ currents with activation parameters and inactivation kinetics slightly different from the diagonally positioned genes (Kv1.1-1.2-1.1-1.2 or 1.2–1.1-1.2-1.1). Pore-blocking petidergic toxins, α dendrotoxin, agitoxin-1, tityustoxin-Kα, and kaliotoxin, were unable to distinguish between the adjacent and diagonal concatamers. Unprecedentedly, external application of the pore-blocker tetraethylammonium (TEA) differentially inhibited the adjacent versus diagonal subunit arrangements, with diagonal constructs having enhanced susceptibility. Concatenation did not directly alter the sensitivities of homomeric Kv1.1 or 1.2 channels to TEA or the toxins. TEA inhibition of currents generated by channels made up from dimers (Kv1.1-1.2 and/or Kv1.2-1.1) was similar to the adjacently arranged constructs. These collective findings indicate that assembly of α subunits can be directed by this optimized concatenation, and that subunit arrangement in heteromeric Kv channels affects TEA affinity.
Room Decontamination with UV Radiation
Authors: Rutala William A. , Gergen Maria F. , Weber David J.
Published: August 2010

Objective.

To determine the effectiveness of a UV-C-emitting device to eliminate clinically important nosocomial pathogens in a contaminated hospital room.

Methods.

This study was carried out in a standard but empty hospital room (phase 1) and in a room previously occupied by a patient with methicillin-resistant Staphylococcus aureus (MRSA) or vancomycin-resistant Enterococcus (VRE) infection (phase 2) in an acute care tertiary hospital in North Carolina from January 21 through September 21, 2009. During phase 1, 8 × 8 cm Formica sheets contaminated with approximately 104-105 organisms of MRSA, VRE, multidrug-resistant (MDR) Acinetobacter baumannii, or Clostridium difficile spores were placed in a hospital room, both in direct line of sight of the UV-C device and behind objects. After timed exposure, the presence of the microbes was assessed. During phase 2, specific sites in rooms that had housed patients with MRSA or VRE infection were sampled before and after UV-C irradiation. After timed exposure, the presence of MRSA and VRE and total colony counts were assessed.

Results.

In our test room, the effectiveness of UV-C radiation in reducing the counts of vegetative bacteria on surfaces was more than 99.9% within 15 minutes, and the reduction in C. difficile spores was 99.8% within 50 minutes. In rooms occupied by patients with MRSA, UV-C irradiation of approximately 15 minutes duration resulted in a decrease in total CFUs per plate (mean, 384 CFUs vs 19 CFUs; P < .001), in the number of samples positive for MRSA (81 [20.3%] of 400 plates vs 2 [0.5%] of 400 plates; P < .001 ), and in MRSA counts per MRSA-positive plate (mean, 37 CFUs vs 2 CFUs; P < .001).

Conclusions.

This UV-C device was effective in eliminating vegetative bacteria on contaminated surfaces both in the line of sight and behind objects within approximately 15 minutes and in eliminating C. difficile spores within 50 minutes.
Seroprevalence of Measles Antibodies among High-Risk Healthcare Workers in Auckland, New Zealand: Additional Justification for Assumption of Age-Determined Immunity Based on Local Data
Authors: Williamson Deborah , Freeman Joshua , Austin Paul , Allum Caroline , Roberts Sally
Published: August 2010

An outbreak of measles in another region of New Zealand prompted our organization to review the measles immunity of healthcare workers. Some studies suggest that age-specific immunity cannot be assumed. In our local setting, however, we found that 893 (98%) of 912 healthcare workers more than 40 years old tested seropositive for measles immunoglobulin G.
Illusionary Progress in Loyalty Programs: Magnitudes, Reward Distances, and Step-Size Ambiguity
Authors: Bagchi Rajesh , Li Xingbo
Published: August 2010

Loyalty programs offer rewards via mediums of different magnitudes (e.g., “$6 off when you accumulate 1,000 [100] points. Earn 10 [1] points/dollar”). The program medium presents two key pieces of information: reward distance (points required to redeem reward) and step size (points earned per dollar). In higher-magnitude (vs. lower-magnitude) programs, both reward distances (1,000 vs. 100) and step sizes (10 vs. 1 point[s]/dollar) are larger. How do these two pieces of information affect consumers' postenrollment inferences of progress, store loyalty, and recommendation likelihood? Do consumers always integrate both pieces? We identify a moderator, step-size ambiguity, and show that when ambiguity is high, only reward distance affects inferences. When ambiguity is lower, consumers integrate step size with reward distance, but in a biased manner. Implications arise in goal following and in physical and psychological distance estimation contexts (e.g., weight loss, savings) where distances and step sizes can vary (e.g., as a function of units: kilograms vs. pounds), but especially in loyalty rewards contexts.
Notes on complex hyperbolic triangle groups
Authors: Kamiya Shigeyasu , Parker John , Thompson James
Published: August 2010

We first demonstrate a family of isomorphisms between complex hyperbolic triangle groups and outline a systematic approach classifying the groups. Then we describe conditions that determine the discreteness of certain groups, in particular we prove a slightly weaker version of a conjecture given by Schwartz. Finally we collect together a list of known discrete triangle groups and propose some good candidates for discrete groups.
A Reduced Phytate Diet Does Not Reduce Endogenous Fecal Zinc in Children on a Habitual High‐Phytate Diet
Authors: Kennedy Gregg , Hambidge K Michael , Manary Mark
Published: September 2010

Ten Malawian children, ages 3 to 5 years, at risk for zinc deficiency and receiving a habitual maize‐based high‐phytate diet, received maize after phytate reduction for 40 days and had their endogenous fecal zinc (EFZ) measured using stable isotope techniques before and after phytate reduction. The phytate:Zn of the diet before reduction was 23.0 and afterward was 7.6. EFZ was similar before and after dietary phytate reduction, 1.15 ± 0.33 and 1.17 ± 0.16 mg/day, respectively. EFZ was not affected by dietary phytate in this population.
An effective programme is not enough: a review of factors associated with poor attendance and engagement with parenting support programmes
Authors: Whittaker Karen A. , Cowley Sarah
Published: September 2010

The provision of parenting support is a key feature of wealthier nations’ health and social care services. However, attendance and engagement by the neediest parents remains poor. Barriers experienced by parents include personal life factors (beliefs, lifestyles and limited resources) and programme‐specific factors (delivery, content and support arrangements). Here we give consideration to these issues, drawing on published reviews of parenting programme effectiveness identified through a comprehensive search of electronic databases. We suggest ways of improving attendance and engagement, by providing programmes as part of a comprehensive framework of family support.
Long‐term study of infliximab in Japanese patients with plaque psoriasis, psoriatic arthritis, pustular psoriasis and psoriatic erythroderma
Authors: TORII Hideshi , NAKAGAWA Hidemi ,   THE JAPANESE INFLIXIMAB STUDY INVESTIGATORS
Published: September 2010

The efficacy and safety of infliximab in patients with plaque psoriasis, psoriatic arthritis, pustular psoriasis (excluding localized type) and psoriatic erythroderma were assessed in clinical practice. Without washout of the existing treatment of psoriasis, treatment was switched to infliximab, which was given at a dose of 5 mg/kg at weeks 0, 2 and 6 and then every 8 weeks up to week 46. The primary end‐points were 75% improvement in Psoriasis Area and Severity Index score (PASI 75 response rate) for plaque psoriasis, 20% improvement in American College of Rheumatology criteria (ACR 20 response rate) for psoriatic arthritis, and global improvement in pustular psoriasis and psoriatic erythroderma. The PASI 75 response rate in plaque psoriasis was 72.2% at week 10 and 53.6% at week 50. The ACR 20 response rate in psoriatic arthritis was 66.7% at week 14 and 80.0% at week 46. The response defined as global improvement in pustular psoriasis was between 66.7% and 100.0% during the 2–50‐week period. The response defined as global improvement in psoriatic erythroderma was between 75.0% and 100.0% during the week‐2–50 period. There were 14 discontinued patients. The most frequently reported reason for discontinuation was the development of adverse events. However, there were no serious respiratory diseases, infections or infusion reactions. In patients with plaque psoriasis, psoriatic arthritis, pustular psoriasis and psoriatic erythroderma, infliximab was well tolerated, regardless of prior treatment, and also showed superior efficacy over a period of approximately 1 year.
Phase I/II study of the pharmacokinetics, safety and efficacy of S‐1 in patients with advanced hepatocellular carcinoma
Authors: Furuse Junji , Okusaka Takuji , Kaneko Shuichi , Kudo Masatoshi , Nakachi Kohei , Ueno Hideki , Yamashita Tatsuya , Ueshima Kazuomi
Published: August 2010

S‐1, an oral fluoropyrimidine derivative, has been shown to be clinically effective against various solid tumors, and preclinical studies have demonstrated activity against hepatocellular carcinoma. We conducted a phase I/II study in patients with advanced hepatocellular carcinoma to examine the pharmacokinetics, recommended dose, safety and efficacy of S‐1. In phase I, the administered dose of S‐1 was approximately 64 mg/m2 per day in three patients (level 1) and approximately 80 mg/m2 per day in six patients (level 2). There was no dose‐limiting toxicity at level 1, but two patients had dose‐limiting toxicity at level 2 (grade 3 anorexia and grade 2 rash requiring eight or more consecutive days of rest). The recommended dose was finally estimated to be 80 mg/m2 per day. There were no significant differences in the pharmacokinetics of S‐1 between patients with Child‐Pugh A and those with B. In phase II, five of 23 patients (21.7%) had partial responses. The median progression‐free survival and overall survival were 3.7 and 16.6 months, respectively. The most common toxicities of grade 3 or 4 were elevated serum aspartate aminotransferase levels, hypochromia and thrombocytopenia. In conclusion, S‐1 showed an acceptable toxicity profile and promising antitumor activity for hepatocellular carcinoma, warranting further evaluation in randomized clinical trials. (Cancer Sci 2010; 101: 2606–2611)
Physico‐chemical features of the environment affect the protein conformation and the immunoglobulin E reactivity of kiwellin (Act d 5)
Authors: Bernardi M. L. , Picone D. , Tuppo L. , Giangrieco I. , Petrella G. , Palazzo P. , Ferrara R. , Tamburrini M. , Mari A. , Ciardiello M. A.
Published: September 2010

Background
Allergy diagnostic systems sometimes give false positive or negative results. In this respect, the influence of protein conformational changes on the allergen–IgE interaction sites is worthy to be investigated.

Objective
To investigate the influence of different experimental conditions on the structural properties and IgE reactivity of kiwellin (Act d 5) as a model system.

Methods
Act d 5 was purified from the natural source. To study its conformational features, experiments of circular dichroism (CD) in different media were performed. The IgE reactivity was investigated by skin testing, immunoblotting and ISAC microarray system, in a population of kiwifruit allergic subjects.

Results
CD experiments indicated that Act d 5 has a mainly helical structure and the conformation is strongly affected by the experimental conditions. The protein is more structured in low polarity media and at acidic pH values, similar to those of the natural source. Eleven subjects of 29 (38%) allergic to kiwifruit were positive to purified natural Act d 5 by skin test. Among them, three patients (10%) showed a reaction only to Act d 5 at pH 4.5, and three (10%) showed a reaction only to the allergen in standard neutral conditions. No one of the 11 subjects with positive skin test recognized Act d 5 immobilized on the ISAC system. Eight of nine subjects detected Act d 5 by IgE immunoblotting. One subject did not recognize the sequence epitopes of Act d 5 in IgE immunoblotting experiments and reacted to the skin test only when the allergen was in acidic conditions.

Conclusions and Clinical Relevance
The conformation and IgE reactivity of Act d 5 are affected by the physico‐chemical characteristics of the solvent. These findings suggest that the assay conditions influence the results of the diagnostic systems by modulating the pattern of exposed antigenic epitopes.

Cite this as: M. L. Bernardi, D. Picone, L. Tuppo, I. Giangrieco, G. Petrella, P. Palazzo, R. Ferrara, M. Tamburrini, A. Mari and M. A. Ciardiello, Clinical & Experimental Allergy, 2010 (40) 1819–1826.
Serum neopterin levels in spontaneous urticaria and atopic dermatitis
Authors: Ciprandi G. , De Amici M. , Berardi L. , Vignini M. , Caimmi S. , Marseglia A. , Marseglia G. , Fuchs D.
Published: August 2010

Serum neopterin may be considered a diagnostic marker of the degree of activation of the immune system. This preliminary study was performed to measure serum neopterin levels in patients with acute spontaneous urticaria (ASU), chronic spontaneous urticaria (CSU) and atopic dermatitis (AD). In total, 180 patients [96 men, 84 women; mean age 23.1 years; 41 with spontaneous urticaria (13 ASU and 28 CSU), 48 with AD] and 96 healthy controls were enrolled in the study. Patients with ASU had the highest neopterin levels, and all three groups of patients (ASU, CSU and AD) had higher values than normal subjects. This preliminary study demonstrates that serum neopterin could be a biomarker of immune activation in patients with SU or AD.
Versican targeting by RNA interference suppresses aggregative growth of dermal papilla cells
Authors: Feng M. , Yang G. , Wu J.
Published: August 2010

Background. Dermal papilla cells (DPCs) are specialized fibroblasts found in the hair follicle papilla, which are associated with the development and cycle regulation of hair follicles (HFs). DPCs exhibit a multilayer aggregative growth character, which is closely related to induction of HF formation. Versican, a large chondroitin sulphate proteoglycan and one of the major components of the extracellular matrix, is involved in the formation of HF.

Methods. To confirm the relationship between versican and the aggregative growth of DPCs, we first induced and established an aggregative cell model in DPCs in vitro, with cells taken to passage 8. Simultaneously, aggregative passage 2 DPCs and nonaggregative passage 8 DPCs were selected as parallel controls. RNA interference (RNAi) targeted to versican was used in passage 2 DPCs using a lentiviral vector. Reverse transcriptase (RT)-PCR and western blotting were used to assay the expression of versican in DPCs.

Results. RNAi targeted to versican efficiently suppressed the aggregative growth of passage 2 DPCs, and the inhibitory effect was significant 3 days after RNAi treatment. The mRNA and protein levels of versican were also downregulated in passage 2 DPCs, and were lower than levels in nonaggregative passage 8 DPCs. Notably, the aggregative growth of nonaggregative passage 8 DPCs was restored after induction in a 1 : 1 v/v mixture of fresh DMEM and medium recycled from a previous passage.

Conclusion. Versican is a key gene for the aggregative growth of DPCs, and might be significant in the regeneration of HF.
Apoptosis and cell proliferation correlated with tumour grade in peritoneal fluids of patients with serous ovarian cancer
Authors: Kalogeraki A. , Karvela‐Kalogeraki I. , Petraki P. E. , Zois I. , Tamiolakis D. , Stathopoulos E. N.
Published: August 2010

A. Kalogeraki, I. Karvela‐Kalogeraki, P. E. Petraki, I. Zois, D. Tamiolakis and E. N. Stathopoulos  Apoptosis and cell proliferation correlated with tumour grade in peritoneal fluids of patients with serous ovarian cancer

Objective:  Apoptosis and cell proliferation in peritoneal fluids of patients with ovarian serous adenocarcinoma have not been well described in cytology. To investigate the contribution of cell death to the growth of this tumour we analysed both apoptosis and cell proliferation in peritoneal fluids of patients with ovarian serous adenocarcinoma.

Methods:  We studied 40 tumours from 40 patients with ovarian serous adenocarcinoma. Twelve tumours were high grade, 13 were moderately differentiated and 15 were poorly differentiated. The detection of DNA fragments in situ using the terminal deoxyribonucleotidy transferase (TDT)‐mediated dUTP‐digoxigenin nick‐end labelling (TUNEL) assay was applied to investigate active cell death (apoptosis), and the MIB‐1 antigen was used to investigate cell proliferation.

Results:  The TUNEL indices were 0.29 ± 0.05, 0.79 ± 0.10 and 2.1 ± 0.90 in Grade I, Grade II and Grade III ovary carcinomas, respectively. The MIB‐1 antigen labelling indices were 6.5 ± 0.09, 12.9 ± 3 and 25.8 ± 6.2, respectively, in the same order of tumour differentiation. The differences in both TUNEL and MIB‐1 labelling indices were statistically significant between Grade I, Grade II and Grade III carcinomas and there was a positive correlation between the two indices (P < 0.001).

Conclusions:  Apoptosis and cell proliferation increased as the grade of tumour increased in ovarian serous adenocarcinoma, suggesting a rapid turnover of the tumour cells in tumours of higher grade, and may play an important role in the growth and the extension of such cancer cells in the peritoneal cavity.
Identifying non‐responsive bleeding episodes in patients with haemophilia and inhibitors: a consensus definition
Authors: BERNTORP E. , COLLINS P. , D’OIRON R. , EWING N. , GRINGERI A. , NÉGRIER C. , YOUNG G.
Published: September 2010

Summary.  Assessing response to treatment with bypassing agents presents a substantial challenge in the treatment of patients with haemophilia and inhibitors. Rapid and accurate identification of bleeding episodes that are non‐responsive to bypassing therapy with either Factor Eight Inhibitor Bypassing Activity (FEIBA; Baxter AG) or recombinant activated factor VII (rFVIIa; NovoSeven®, Novo Nordisk A/S) is essential to guide treatment decisions and optimize patient outcomes through early intervention. Although both bypassing agents are effective, differential responses to therapy necessitate multiple therapeutic options. This article provides a consensus definition for non–life‐threatening joint and muscle bleeds that are non‐responsive to bypassing agents. An international panel of seven physicians met in December 2008 to develop the consensus definition using a modified National Institutes of Health Consensus Development Conference method. The consequent definition of non–life‐threatening bleeding episodes that are non‐responsive to bypassing treatment provides a global picture of the condition of the patient during such an event. Identification of non‐responsiveness is based on various criteria: pain, swelling/tension, mobility, patient perception and laboratory parameters. Criteria can be assessed subjectively by the patient/parent and/or objectively by the clinician. Although the precise timing of each determination should be at the discretion of the physician, bleeds should be considered non‐responsive if the clinical situation meets the specified criteria 24 h from the start of treatment. Although it is not intended to replace clinical judgment, this definition can guide the optimal course of treatment for patients with haemophilia and inhibitors.
Relationship between total hip replacement appropriateness and surgical priority instruments
Authors: Allepuz Alejandro , Quintana José M , Espallargues Mireia , Escobar Antonio , Moharra Montse , Arostegui Inmaculada
Published: August 2010

Rationale  Variability in indications for total hip replacement (THR) and unequal waiting times may limit health care access.

Objective  To analyse the relationship between appropriateness and previously developed surgical priority instruments.

Method  Multicentre cross‐validation study of patients placed on the waiting list for THR. Information on surgical priority, surgeons' evaluation of priority through a visual analogue scale (VAS) and health‐related quality of life (HRQOL) (Health Utilities Index mark 3, EQ‐5D, Western Ontario McMaster Osteoarthritic Index) was collected. THR indications were considered appropriate, uncertain or inappropriate according to appropriateness criteria. Statistical differences and clinically important differences in surgical priority, VAS and HRQOL between appropriateness categories were analysed with the Mann–Whitney U‐test and effect size (ES), respectively. Surgical priority score's ability to discriminate appropriate and inappropriate indications was evaluated through the area under the receiver‐operating characteristic curve (AUC) and its 95% confidence interval (95% CI).

Results  49.4% (87) of the THR indications were deemed appropriate, 39.8% (70) uncertain and 10.8% (19) inappropriate. Differences in surgical priority score, VAS and HRQOL between appropriateness categories were statistically significant. Clinically important differences were generally small (ES, 0.2–0.5) between inappropriate and uncertain, moderate (ES, 0.5–0.8) between uncertain and appropriate, and large (ES > 0.8) between inappropriate and appropriate categories. The AUC to discriminate appropriate and inappropriate indications was 0.97 (95% CI: 0.96–0.99) and 0.90 (95% CI: 0.83–0.97), respectively.

Conclusions  The relationship between the surgical priority and appropriateness instruments reinforces their validity and could improve waiting list management by establishing maximum waiting periods based on patients' characteristics.
Shr of group A streptococcus is a new type of composite NEAT protein involved in sequestering haem from methaemoglobin
Authors: Ouattara Mahamoudou , Bentley Cunha Elizabeth , Li Xueru , Huang Ya‐Shu , Dixon Dabney , Eichenbaum Zehava
Published: August 2010

A growing body of evidence suggests that surface or secreted proteins with NEAr Transporter (NEAT) domains play a central role in haem acquisition and trafficking across the cell envelope of Gram‐positive bacteria. Group A streptococcus (GAS), a β‐haemolytic human pathogen, expresses a NEAT protein, Shr, which binds several haemoproteins and extracellular matrix (ECM) components. Shr is a complex, membrane‐anchored protein, with a unique N‐terminal domain (NTD) and two NEAT domains separated by a central leucine‐rich repeat region. In this study we have carried out an analysis of the functional domains in Shr. We show that Shr obtains haem in solution and furthermore reduces the haem iron; this is the first report of haem reduction by a NEAT protein. More specifically, we demonstrate that both of the constituent NEAT domains of Shr are responsible for binding haem, although they are missing a critical tyrosine residue found in the ligand‐binding pocket of other haem‐binding NEAT domains. Further investigations show that a previously undescribed region within the Shr NTD interacts with methaemoglobin. Shr NEAT domains, however, do not contribute significantly to the binding of methaemoglobin but mediate binding to the ECM components fibronectin and laminin. A protein fragment containing the NTD plus the first NEAT domain was found to be sufficient to sequester haem directly from methaemoglobin. Correlating these in vitro findings to in vivo biological function, mutants analysis establishes the role of Shr in GAS growth with methaemoglobin as a sole source of iron, and indicates that at least one NEAT domain is necessary for the utilization of methaemoglobin. We suggest that Shr is the prototype of a new group of NEAT composite proteins involved in haem uptake found in pyogenic streptococci and Clostridium novyi.
OsEDR1 negatively regulates rice bacterial resistance via activation of ethylene biosynthesis
Authors: SHEN XIANGLING , LIU HONGBO , YUAN BIN , LI XIANGHUA , XU CAIGUO , WANG SHIPING
Published: August 2010

Rice OsEDR1 is a sequence ortholog of Arabidopsis EDR1. However, its molecular function is unknown. We show here that OsEDR1‐suppressing/knockout (KO) plants, which developed spontaneous lesions on the leaves, have enhanced resistance to Xanthomonas oryzae pv. oryzae (Xoo) causing bacterial blight disease. This resistance was associated with increased accumulation of salicylic acid (SA) and jasmonic acid (JA), induced expression of SA‐ and JA‐related genes and suppressed accumulation of 1‐aminocyclopropane‐1‐carboxylic acid (ACC), the direct precursor of ethylene, and expression of ethylene‐related genes. OsEDR1‐KO plants also showed suppressed production of ethylene. Knockout of OsEDR1 suppressed the ACC synthase (ACS) gene family, which encodes the rate‐limiting enzymes of ethylene biosynthesis by catalysing the formation of ACC. The lesion phenotype and enhanced bacterial resistance of the OsEDR1‐KO plants was partly complemented by the treatment with ACC. ACC treatment was associated with decreased SA and JA biosynthesis in OsEDR1‐KO plants. In contrast, aminoethoxyvinylglycine, the inhibitor of ethylene biosynthesis, promoted expression of SA and JA synthesis‐related genes in OsEDR1‐KO plants. These results suggest that ethylene is a negative signalling molecule in rice bacterial resistance. In the rice–Xoo interaction, OsEDR1 transcriptionally promotes the synthesis of ethylene that, in turn, suppresses SA‐ and JA‐associated defence signalling.
Supra‐optimal expression of the cold‐regulated OsMyb4 transcription factor in transgenic rice changes the complexity of transcriptional network with major effects on stress tolerance and panicle development
Authors: PARK MYOUNG‐RYOUL , YUN KIL‐YOUNG , MOHANTY BIJAYALAXMI , HERATH VENURA , XU FUYU , WIJAYA EDWARD , BAJIC VLADIMIR B. , YUN SONG‐JOONG , DE LOS REYES BENILDO G.
Published: August 2010

The R2R3‐type OsMyb4 transcription factor of rice has been shown to play a role in the regulation of osmotic adjustment in heterologous overexpression studies. However, the exact composition and organization of its underlying transcriptional network has not been established to be a robust tool for stress tolerance enhancement by regulon engineering. OsMyb4 network was dissected based on commonalities between the global chilling stress transcriptome and the transcriptome configured by OsMyb4 overexpression. OsMyb4 controls a hierarchical network comprised of several regulatory sub‐clusters associated with cellular defense and rescue, metabolism and development. It regulates target genes either directly or indirectly through intermediary MYB, ERF, bZIP, NAC, ARF and CCAAT‐HAP transcription factors. Regulatory sub‐clusters have different combinations of MYB‐like, GCC‐box‐like, ERD1‐box‐like, ABRE‐like, G‐box‐like, as1/ocs/TGA‐like, AuxRE‐like, gibberellic acid response element (GARE)‐like and JAre‐like cis‐elements. Cold‐dependent network activity enhanced cellular antioxidant capacity through radical scavenging mechanisms and increased activities of phenylpropanoid and isoprenoid metabolic processes involving various abscisic acid (ABA), jasmonic acid (JA), salicylic acid (SA), ethylene and reactive oxygen species (ROS) responsive genes. OsMyb4 network is independent of drought response element binding protein/C‐repeat binding factor (DREB/CBF) and its sub‐regulons operate with possible co‐regulators including nuclear factor‐Y. Because of its upstream position in the network hierarchy, OsMyb4 functions quantitatively and pleiotrophically. Supra‐optimal expression causes misexpression of alternative targets with costly trade‐offs to panicle development.