bluuebunny/crossref_metadata_2025 huggingface dataset:
Regioselective Synthesis of Prenylisoflavones. Syntheses of Allolicoisoflavone A, 2,3-Dehydrokievitone, and Related Compounds
Authors: Tsukayama Masao , Li He , Tsurumoto Ken , Nishiuchi Masaki , Kawamura Yasuhiko
Published: June 2006

The palladium-catalyzed coupling reaction of 2′,4′,5,7-tetrakis(benzyloxy)-5′-iodoisoflavone (12), synthesized from the 5-iodochalcone 9, with 2-methyl-3-butyn-2-ol gave the corresponding 5′-(3-hydroxy-3-methyl-1-butynyl)isoflavone 13. The catalytic hydrogenation of 13 gave 2′,4′,5,7-tetrahydroxy-5′-(3-hydroxy-3-methylbutyl)isoflavone (2). Dehydration of the benzoate 14 of 2 afforded a mixture of 5′-(3-methyl-2-butenyl)isoflavone 15 and the isomer 5′-(3-methyl-3-butenyl)isoflavone 16. The separation of 15 was accomplished by a treatment of the mixture (15 and 16) with mercury(II) nitrate. Hydrolysis of 15 afforded 2′,4′,5,7-tetrahydroxy-5′-prenylisoflavone (allolicoisoflavone A) (1). In a similar manner, 2′,4′,5,7-tetrahydroxy-8-prenylisoflavone (2,3-dehydrokievitone) (3) and 2′,4′,5,7-tetrahydroxy-8-(3-hydroxy-3-methylbutyl)isoflavone (2,3-dehydrokievitone hydrate) (4) were synthesized from the corresponding 8-iodoisoflavone 22. The tetramethyl ether 5 of 3 was also prepared from the 8-iodotetramethoxyisoflavone 32.
Substitution for Apoprotein of Neocarzinostatin by Self-Aggregate of Cholesterol-Bearing Pullulan
Authors: Taniguchi Ikuo , Fujiwara Masashi , Akiyoshi Kazunari , Sunamoto Junzo
Published: June 2006

A nanoparticle of cholesterol-bearing pullulan (CHP) self-aggregates effectively complexed with a neocarzinostatin chromophore (NCS-chr) in 0.5 M (1 M = 1 mol dm−3) AcONa/AcOH (pH 4.7) at 2 °C in the dark. The complex so obtained was very colloidally stable even after 4 d at 37 °C in a weak acidic medium. The complexed NCS-chr still maintained in vitro cytotoxicity to HeLa, HepG2, and 3′-mRLh-2 cells. In all cases, the cytotoxicity of the complex was higher than that of free NCS-chr itself. When the galactose moiety was additionally conjugated to CHP, the modified complex showed high cytotoxicity to a 3′-mRLh-2 cell. This cytotoxicity of the complex was almost comparable to that of intact NCS, which is ascribed to the galactose specific receptor-mediated endocytosis of the modified complex. This is the first finding to show that the complexed NCS-chr so obtained still maintains the strong cytotoxicity in vitro, and that the self-aggregate of hydrophobized polysaccharide (HPS) can nicely substitute for the apoprotein of NCS.
Facile Synthesis of α-Fluoroalkyl Sulfides under the Oxidative Desulfurization–Fluorination Conditions
Authors: Furuta Satoru , Kuroboshi Manabu , Hiyama Tamejiro
Published: June 2006

Upon treatment with n-Bu4NH2F3 and 1,3-dibromo-5,5-dimethylhydantoin, various organic sulfides underwent a Pummerer-type rearrangement, followed by fluorination, to give α-fluoro sulfides. The fluoro-Pummerer rearrangement, when applied to RCH(SMe)CF2SMe, gave trifluoro sulfides RCF(SMe)CF2SMe. When an HF-pyridine reagent was used as the fluorinating agent, an oxidative desulfurization–fluorination reaction occurred depending on the structure of the substrates.
Syntheses of Tungsten Diazoalkane Complexes from a Dinitrogen Complex and Diketones. Conversion of Molecular Nitrogen into Pyrazoles via the Diazoalkane Complexes as Intermediates
Authors: Harada Yuji , Mizobe Yasushi , Ishii Youichi , Hidai Masanobu
Published: June 2006

The hydrazido(2-) complexes [WCl2(NNH2)(L)(PMe2Ph)2] (L = PMe2Ph, CO), derived from the dinitrogen complex cis-[W(N2)2(PMe2Ph)4] (1), reacted with β-diketones R1COCHR2COR3 (R1 = Me, But, Ph; R2 = H, Me; R3 = Me, Et, But, Ph) to afford a series of diazoalkane complexes [WCl2(NN=CR1CHR2COR3)(L)(PMe2Ph)2]. The detailed structure of cis,mer-[WCl2(NN=CMeCH2COPh)(PMe2Ph)3] has been determined by X-ray analyses. These diazoalkane complexes were treated with a KOH/EtOH mixture to produce pyrazoles in moderate yields, whereas the reaction of 1 with a MeCOCH2COPh/KOH/EtOH mixture resulted in the direct formation of 5-methyl-3-phenylpyrazole.
Irradiation Effects of Excimer Laser Light on Poly(vinylidene fluoride) (PVdF) Film
Authors: Izumi Yoshinobu , Kawanishi Shunichi , Hara Shinji , Yoshikawa Daishi , Yamamoto Tadashi
Published: June 2006

The irradiation effects of intense ultraviolet (UV) light from ArF and KrF excimer lasers on poly(vinylidene fluoride) (PVdF) were studied. The optical absorption spectroscopy made it clear that irradiation with ArF and KrF excimer laser light mainly caused the formation of diene and triene structures, respectively. From the dependence on the laser intensity it was found that ArF and KrF laser-induced reactions proceeded via single-photon and multi-photon processes, respectively. The wavelength dependence was explained by photochemical and photothermal effects of ArF and KrF excimer lasers, respectively. These results indicate that the distinction of the photo-reaction between the two is closely related to the difference in the absorption sites.
Synthesis and Characterization of an Ultramicroporous Cesium Hydrogen Salt of 12-Tungstophosphoric Acid, Cs2.1H0.9PW12O40
Authors: Yamada Takashi , Yoshinaga Yusuke , Okuhara Toshio
Published: June 2006

An ultramicroporous heteropoly compound, Cs2.1H0.9PW12O40, was synthesized by a titration method using aqueous solutions of H3PW12O40 and Cs2CO3. Concentrations of the starting materials and the drop rate of Cs2CO3 solution were determined to synthesize Cs2.1H0.9PW12O40 having nearly uniform micropores and very low external surface area. The Dollimore-Heal method of N2 isotherms showed that Cs2.1H0.9PW12O40 prepared by the controlled conditions has no mesopores. Adsorption of various molecules having different sizes revealed that the micropore size of Cs2.1H0.9PW12O40 was in the range from 0.43 to 0.59 nm and the fraction of the external surface area was less than 3% of the total surface area. A model for the unique ultramicropores has been proposed on the basis of the pore size, pore volume, and the primary crystallite size, in which the ultramicropores are spaces formed between the crystal faces of the mcirocrystallites as the primary particles of Cs2.1H0.9PW12O40.
Hydration Structure of Na+ in Concentrated Aqueous Solutions
Authors: Kameda Yasuo , Sugawara Kentaro , Usuki Takeshi , Uemura Osamu
Published: June 2006

X-Ray diffraction and Raman spectroscopic measurements have been carried out for aqueous 10 mol% NaX (X = Cl, Br, ClO4, and NO3) solutions in order to determine the hydration structure of Na+ in concentrated aqueous solutions. Isotropic Raman spectra for NaX–H2O solutions exhibit a polarized peak centered at 183—187 cm−1. The corresponding peak in the isotropic spectra for NaX–D2O solutions is shifted to the lower frequency side by ca. 10 cm−1, indicating that the peak can be assigned to the totally symmetric vibrational mode of hydrated Na+, Na+(H2O)n. The least-squares fitting analysis was applied to the X-ray interference term observed for these solutions in order to discuss the hydration number of Na+ in concentrated aqueous solutions.
89Y-Static and -MAS NMR, and 27Al-MAS NMR in Green Phosphor, Tb-Doped Y3Al5O12 and Luminous Characteristics
Authors: Harazono Toshie , Yokota Etsuzo , Uchida Hiroshi , Watanabe Tokuko
Published: June 2006

Luminous properties of a green phosphor, Tb-doped Y3Al5O12, have been studied by 89Y (nuclear spin 1/2)-static and -magic angle spinning (MAS) NMR and 27Al (nuclear spin 5/2)-MAS NMR. In pure Y3Al5O12, a sharp signal at 239 ppm was observed in 89Y-MAS NMR spectrum, which was expected from a powder pattern due to 8O-coordinated Y in D2 symmetry in 89Y-static NMR spectrum. In the 27Al-MAS NMR spectrum of Y3Al5O12, two typical signals were observed, i.e., a sharp signal at 0 ppm due to 6O-coordinated Al in the octahedral site and a characteristic signal due to 4O-coordinated Al in the tetrahedral site. These 89Y and 27Al signals became broader in Tb-Y3Al5O12 with increasing in content of the doped Tb. In addition to the main peak at 239 ppm, furthermore, extra peaks appeared in the bottom of the main peak in 89Y-MAS NMR; these were assigned to the second nearest to the fifth nearest neighboring Y (Y2 to Y5) atoms to Tb atom substituted in the site of Y atom. Shifts of these Y atoms were reasonably explained by a pseudocontact shift via a paramagnetic Tb3+ ion. Incorporation of Tb3+ ions caused a large reduction in 89Y nuclear spin-lattice relaxation time from 4000s (pure Y3Al5O12) to several hundred seconds (3% Tb-Y3Al5O12) as well.

The line-broadening of the signals was mainly dominated by the dipole–dipole interaction mechanism between the Al or Y resonating nucleus and a Tb3+ ion. The signals of Y atoms in the sites where either one of the nearest neighboring Y1 atoms was replaced by Tb atom were not detected because of the large line-broadening.

The stronger brightness was obtained in the specimens which showed the much broader linewidth in 27Al-MAS signals and in 89Y-static NMR signals under the same Tb content. So we concluded that the homogeneous distribution of Tb3+ ions in Tb-Y3Al5O12 plays a key role for the higher brightness in the green phosphor as in the red phosphor.
Variation of Thermodynamic Parameters in the Adduct Formation of β-Diketonato Chelates with 1,10-Phenanthroline across the Lanthanoid Series
Authors: Yajima Setsuko , Hasegawa Yuko
Published: June 2006

The enthalpy change in the adduct formation of tris[1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato]lanthanoids (LnA3) with 1,10-phenanthroline (phen) as well as the formation constant of the adduct has been determined in chloroform across the lanthanoid series at 298 K by calorimetric titration and solvent-extraction techniques. The enthalpy change in the first adduct formation changes remarkably from light lanthanoids (endothermic) to heavy ones (exothermic), while the entropy change decreases largely from the middle to the heavy lanthanoids along with a small change from light to the middle of the series. Such a trend has been explained on the basis of the difference in the dehydration from lanthanoid(III) chelates and in the strength of the new bonding of chelates formed between tris(β-diketonato) lanthanoid(III) and phen across the lanthanoid series.
Synthesis and Characterization of Palladium(II)-Phosphole and -Biphosphole Complexes. Regulation of the Homoleptic Coordination Environment of Square-Planar Palladium(II)
Authors: Kojima Takahiko , Saeki Kaoru , Ono Kazuhiro , Matsuda Yoshihisa
Published: June 2006

A series of novel square-planar palladium(II)-phosphole complexes was synthesized in good yields by a ligand-substitution reaction of [Pd(CH3CN)4](BF4)2 with 3,4-dimethyl-1-phenylphosphole (dmpp) and/or 3,3′4,4′-tetramethyl-1,1′-diphenyl-2,2′-biphosphole (bidmpp) in CH2Cl2; [Pd(dmpp)4](BF4)2 (1), [Pd(bidmpp)(dmpp)2](BF4)2 (2), and [Pd(bidmpp)2](BF4)2 (3). Those complexes were characterized by 1H and 31P NMR spectroscopies and X-ray crystallography for 3. The crystal structure of 3 revealed that the configurations of the phosphorus atoms were (R, R, S, S), indicating that the structure was a meso form with an intramolecular π–π interaction between the phenyl groups. 1H NMR spectroscopy suggested the structures of 1 and 2: Complex 1 has a water wheel-like C4h structure and complex 2 is C2 symmetric. In the 31P NMR spectra of those complexes, each resonance showed a smaller downfield shift than that observed for [Pd(dppe)2]Cl2 (dppe = 1,2-bis(diphenylphosphino)ethane), indicating that the palladium-phosphole interaction is governed by mainly a σ-donation, and that there is a small contribution from a π-back bonding interaction.
Dehydrative Glycosylation by Diethylaminosulfur Trifluoride (DAST)–Tin(II) Trifluoromethanesulfonate–Tetrabutylammonium Perchlorate–Triethylamine System
Authors: Hirooka Motoko , Koto Shinkiti
Published: June 2006

Dehydrative glycosylation using 2,3,4,6-tetra-O-benzyl-d-glucopyranose was carried out by the use of a condensing reagent system composed of diethylaminosulfur trifluoride (DAST), tin(II) triflate, tetrabutylammonium perchlorate, and triethylamine. Using this system, two tetrasaccharides, O-α-d-glucopyranosyl-(1→4)-O-α-d-glucopyranosyl-(1→3)-O-α-d-glucopyranosyl-(1→4)-d-glucopyranose and O-α-d-glucopyranosyl-(1→3)-O-α-d-glucopyranosyl-(1→4)-O-α-d-glucopyranosyl-(1→4)-d-glucopyranose, were synthesized.
Synthesis of An Azobenzene Derivative Bearing Two Stable Nitronyl Nitroxide Radicals as Substituents and Its Magnetic Properties
Authors: Hamachi Kiyoe , Matsuda Kenji , Itoh Tetsuji , Iwamura Hiizu
Published: June 2006

3,4′-Bis(4,5-dihydro-4,4,5,5-tetramethyl-3-oxido-1-oxyl-3-imidazolio-2-yl)azobenzene (1) was synthesized starting from 3,4′-dimethylazobenzene via the diformyl derivative. Biradical 1 crystallized as dark blue-green needles; its crystal structure was determined by the X-ray crystallography. X-band ESR spectra of biradical 1 in the degassed toluene solution were measured in the temperature range 10—300 K. At 300 K the ESR spectrum showed nine lines centered at g = 2.006 (aN = 3.7 G). At 10 K the ESR spectrum showed a fine structure with zero-field splitting (zfs) parameters |D/hc| = 0.0026 cm−1and |E/hc| = 0.00014 cm−1. Magnetic susceptibility measurements revealed that the two radical centers coupled in a ferromagnetic way and the through-bond exchange interaction was determined to be 2J/kB = 8.36 ± 0.26 K with a Weiss constant θ = −0.39 ± 0.01 K. Photochromic reaction was monitored by ESR and UV-vis spectroscopy.
Photo-Induced Intermolecular Radical β-Addition to Chiral α-(Arylsulfinyl) Enones
Authors: Mase Nobuyuki , Watanabe Yoshihiko , Toru Takeshi
Published: June 2006

The reactions of α-(arylsulfinyl) enones with alkyl radicals having a hydroxy or acetal group were examined under photo-irradiation in the presence of benzophenone. High diastereoselectivity was observed in the photo-induced radical reaction of 2-(arylsulfinyl)-2-cyclopentenones having a bulky aryl group, such as the 2,4,6-triisopropylphenyl or 2,4,6-trimethylphenyl group. The photo-induced reaction of 3-[(2,4,6-triisopropylphenyl)sulfinyl]-3-pentene-2-one in 1,3-dioxolane also gave a single diastereomer of the 1,3-dioxolan-2-yl adduct.
Syntheses and Properties of Isocyanatodisiloxanes and Their Alkoxy-Substituted Derivatives
Authors: Gunji Takahiro , Setogawa Akira , Asakura Kazue , Abe Yoshimoto
Published: June 2006

Isocyanatooligosiloxanes and their alkoxy derivatives were synthesized. The hydrolysis of triisocyanato(methyl)silane followed by distillation provided 1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane in good yield. The reaction of 1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane with ethanol, isopropyl alcohol, and t-butyl alcohol proceeded selectively to afford partially alkoxy substituted isocyanatodimethyldisiloxanes, (RO)n(NCO)4−nMe2Si2O (R = Et, n = 1—4; R = Pri, n = 1—4; and R = But, n = 1—2). On the other hand, the hydrolysis of tetraisocyanatosilane provided a mixture of isocyanatooligosiloxanes. Hexaisocyanatodisiloxane was isolated by distillation from the reaction mixture with some impurities produced by the disproportionation of hexaisocyanatodisiloxane on heating. The reaction of hexaisocyanatodisiloxane with alcohols provided partially alkoxy-substituted isocyanatodisiloxanes, [(RO)n(NCO)3−nSi]2O (R = Et, n = 2—3; R = Pri, n = 1—3; and R = But, n = 1—2), selectively and in high yield.
A Quartz-Crystal Microbalance Study of Adsorption Behaviors of Artificial Glycoconjugate Polymers onto Chemically Modified Gold Surfaces and Their Interactions with Lectins
Authors: Matsuura Kazunori , Tsuchida Akiko , Okahata Yoshio , Akaike Toshihiro , Kobayashi Kazukiyo
Published: June 2006

Adsorption behaviors of two different types of lactose-carrying polystyrenes, poly(p-vinylbenzamido-β-lactose) (PNLA, 1) and poly(N-p-vinylbenzyllactonamide) (PVLA, 2), onto cast films of polystyrene and self-assembled monolayers (SAMs) of 1-octadecanethiol and cystamine were investigated by applying a quartz-crystal microbalance (QCM). The amphiphilic artificial glycoconjugate polymers were strongly adsorbed on the hydrophobic surfaces, i.e. a polystyrene cast film and a SAM of 1-octadecanethiol, from their aqueous solution according to the Langmuir adsorption isotherm (the apparent association constant: Ka ≈ 107 M−1). On the other hand, they were adsorbed little on a hydrophilic SAM of cystamine. The saturated adsorption amounts of the polymers on the hydrophobic surfaces were 2—5 times larger than that calculated on the basis of an assumption of closed-packing monolayer adsorption, which suggests that the adsorbed polymers may take a loop-train-tail conformation. A SAM of 1-octadecanethiol adsorbed two times more of each polymer than a polystyrene cast film did. β-Galactoside-specific RCA120 and PNA lectins bound to the surfaces coated with the galactose-bearing polymers according to the Langmuir adsorption isotherm (Ka ≈ 106 M−1). The binding was stronger than that observed by the inhibition of hemagglutinating activity (about 104 M−1).
A New Three-Component Photoresist Based on Calix[4]resorcinarene Derivative, a Cross-linker, and a Photo-acid Generator
Authors: Nakayama Tomonari , Nomura Masayoshi , Haga Kohji , Ueda Mitsuru
Published: June 2006

Calix[4]resorcinarene (2,8,14,20-tetramethylcalix[4]arene-4,6,10,12,16,18,22,24-octol, abbrev. to C4-RA) derivative (4) having p-hydroxybenzyl groups on its exterior was prepared by the condensation of C4-RA and p-(allyloxy)benzyl bromide, followed by the cleavage of allyl groups with palladium catalyst and ammonium formate. Compound 4 having high transparency to UV-light above 300 nm was considered for a new resist matrix. A three-component photoresist consisting of 4, 2,6-bis(hydroxymethyl)-4-methylphenol (BHMP), and diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DIAS) showed a sensitivity of 19 mJ cm−2 (D1/2) and a contrast of 3.0 (γ1/2) when it was exposed to 365 nm light and post-exposure baked (PEB) at 110 °C for 5 min, followed by developing with a 0.2 wt% aqueous tetramethylammonium hydroxide (TMAH) solution. A fine negative image featuring 1 μm of minimum line and space patterns was observed on film of the photoresist exposed to 40 mJ cm−2 of UV-light at 365 nm with a scanning electron microscope.
A Novel Receptor-based Surface-plasmon-resonance Affinity Biosensor for Highly Sensitive and Selective Detection of Dopamine
Authors: Kumbhat Sunita , Shankaran Dhesingh Ravi , Kim Sook Jin , Gobi K Vengatajalabathy , Joshi Vinod , Miura Norio
Published: June 2006

We have established a new surface-plasmon-resonance (SPR) based affinity biosensor for highly sensitive and selective detection of dopamine (DA) employing a D3 dopamine receptor (D-RC) and a home-made DA-bovine serum albumin (DA-BSA) conjugate. The proposed biosensor is simple, reproducible and exhibit excellent sensitivity for DA (detection limit = 85 pg/mL (ppt)) without any significant interference from ascorbic acid (AA), uric acid (UA), and other DA analogues.
Structure and Electrochemical Capacitance of Nitrogen-enriched Mesoporous Carbon
Authors: Kodama Masaya , Yamashita Junya , Soneda Yasushi , Hatori Hiroaki , Kamegawa Katsumi , Moriguchi Isamu
Published: June 2006

Nitrogen-enriched mesoporous carbon which has been successfully prepared from quinoline-polymerized pitch using mesoporous silica as a template denoted ordered hexagonal assembly of fibrous carbon having ca. 6–7 nm in diameter and higher capacitance amounting to 200–300 F·g−1 in H2SO4 electrolyte than ordinary mesoporous carbons prepared using divinylbenzene as a carbon precursor (<180 F·g−1).
Interactions of Flexible Diamine-bridged Dinuclear Ruthenium(II)–2,2′-Bipyridine Complexes with Mononucleotides and DNA
Authors: Nakabayashi Yasuo , Iwamoto Nobuaki , Inada Hiroyuki , Yamauchi Osamu
Published: June 2006

A series of new flexible diamine-bridged dinuclear ruthenium(II) complexes [{RuCl(bpy)2}2(μ-BL)]2+ (bpy = 2,2′-bipyridine; BL = H2N(CH2)nNH2 (n = 4 ([1]2+), 8 ([2]2+), 12 ([3]2+))) were prepared. Time-course spectroscopic experiments revealed that these dinuclear ruthenium(II) complexes selectively bind to guanine residues in calf thymus (CT) DNA and the degree of binding of [2]2+ or [3]2+ to CT-DNA relative to [1]2+ is high.
A New Hexanuclear Manganese Complex Exhibits Superparamagnetic Behavior
Authors: Yang Chen-I , Chung George , Kuo Ting-Shen , Shieh Minghuey , Tsai Hui-Lien
Published: June 2006

A new mixed-valence hexanuclear manganese(II,III) complex, [Mn6O2(O2CPh)8(L)3] (HL = 1-phenyl-3-pyridin-2-ylpropane-1,3-dione), has been synthesized and characterized structurally and magnetically. The complex contains a new [MnII3MnIII3O2]11+ structural topology. The frequency dependence of out-of-phase component in alternating current magnetic susceptibilities for the complex indicates superparamagnetic behavior.
Persistent Spectral Hole Burning in Eu3+-doped Calcium Oxide- and Calcium Fluoride-based Aluminoborate Glasses
Authors: Liang Hailian , Hanzawa Hiromasa , Horikawa Takashi , Machida Ken-ichi
Published: June 2006

Eu3+-doped oxyfluoride glasses with composition of 30CaF2–10Al2O3–60B2O3 (mol %) and oxide glasses of 30CaO–10Al2O3–60B2O3 (mol %) were prepared in a reducing atmosphere. The persistent spectral hole burning (PSHB) was characterized over a temperature range from 10 to 300 K, and the hole-burning efficiency between Eu3+-doped glass matrix of 30CaF2–10Al2O3–60B2O3 and 30CaO–10Al2O3–60B2O3 was compared.
Preparation and Characterization of Amine-modified Gradient Polyethylene Surfaces
Authors: Kim Moon Suk , Cho Young Ho , Lee Soo Young , Khang Gilson , Lee Tae Geol , Moon Dae Won , Lee Hai Bang
Published: June 2006

A gradient polyethylene (PE) surface was created through corona treatment, in which the corona power increased along the 5-cm length of the PE. The gradient PE surface was treated by amines with varying molecular weights. TOF–SIMS results exhibited the gradient surface images and intensities before and after amine modification on the corona-treated PE surface.
Peri-selectivity in Thermolysis of Acyloxybenzocyclobutenes Possessing α,β-Unsaturated Carbonyl Group: Synthesis of 2-Benzoxocin Derivatives
Authors: Hamura Toshiyuki , Kawano Nobuyuki , Matsumoto Takashi , Suzuki Keisuke
Published: June 2006

1-Acyloxybenzocyclobutenes, having an α,β-unsaturated carbonyl group at C1 position, undergo the periselective thermal ring expansion to give 2-benzoxocin derivatives in high yields.
Biomass-assisted Hydrothermal Synthesis of Ceria Nanoparticle —A New Application of Lignin as a Bio-nanopool—
Authors: Umetsu Mitsuo , Man Xin , Okuda Kazuhide , Tahereh Mousavand , Ohara Satoshi , Zhang Jing , Takami Seiichi , Adschiri Tadafumi
Published: June 2006

We introduced a nanometer-sized reaction pool in the hydrothermal synthesis of ceria (CeO2). The addition of a heat-stable biopolymer, lignosulfate, in the hydrothermal synthesis resulted in the drastic downsizing of CeO2 particle to 5 nm. We, further, show that the lignosulfate functions as an accelerator for the CeO2 nanoparticle synthesis.
Deactivation of Ru/Al2O3 Catalyst for Preferential CO Oxidation in the Presence of Low-concentration NH3 by Nitrosyl Species
Authors: Wakita Hidenobu , Ukai Kunihiro , Takeguchi Tatsuya , Ueda Wataru
Published: June 2006

The behavior of a Ru/Al2O3 catalyst for the preferential CO oxidation in the presence of low-concentration NH3 (21–75 ppm) was investigated. In contrast to the results in the absence of NH3, the catalyst was rapidly deactivated at higher [O2]/[CO] ratios in the presence of NH3. NH3 was oxidized to nitrosyl species, which was strongly adsorbed on Ru and suppressed the activation of both oxygen and CO. At low [O2]/[CO] ratios, the catalyst exhibited a stable activity even in the presence of NH3, and the deactivated catalyst was rapidly regenerated.
Sidewall Modification of Single-walled Carbon Nanotubes with Sulfur-containing Functionalities and Gold Nanoparticle Attachment
Authors: Nakamura Takako , Ohana Tsuguyori , Ishihara Masatou , Tanaka Akihiro , Koga Yoshinori
Published: June 2006

Photolysis of cyclic disulfides with single-walled carbon nanotubes led to a sidewall modification of the surfaces to introduce sulfur-containing functional groups, as confirmed by means of Raman, XPS, FT-IR, mass, and UV–vis–NIR measurements. A subsequent treatment of sulfur-containing substituents modified SWNTs with gold nanoparticles gave an attachment of gold on the surface of SWNTs through thioalkylthiol linkage.
2-Picolinoylpyrrole: A New Entry to Metal-complexing Agent
Authors: Ono Yuki , Furuta Hiroyuki
Published: June 2006

The Pd(II) and Pt(II) complexes of 2-picolinoylpyrrole were synthesized and the 2:1 square-planar coordination, wherein each pyrrole and pyridine moieties are in trans positions, respectively, were characterized by means of X-ray single-crystal analyses.
Dinuclear Addition of the Pd–Pd Moieties to 1,3-Dienes
Authors: Murahashi Tetsuro , Nagai Tomoki , Nakashima Hiromitsu , Tomiyasu Sadayuki , Kurosawa Hideo
Published: June 2006

The reaction of a substitutionally labile dipalladium(I) complex [Pd2(CH3CN)6][BF4]2 with isoprene or 1,3-butadiene in acetonitrile afforded [Pd2(μ-η3:η1-C5H8)(CH3CN)5][BF4]2 or [Pd2(μ-η3:η1-C4H6)(CH3CN)5][BF4]2. The structure of the isoprene complex was determined by X-ray crystallographic analyses. The interconversion between the [Pd2(μ-η3:η1-C5H8)(CH3CN)5][BF4]2 and [Pd2(μ-η2:η2-C5H8)(μ-Cl)Cl2][PPh4] occurred facilely.
Mesoscopic Photonic Crystals Made of TiO2 Hollow Spheres Connected by Cylindrical Tubes
Authors: Zhu Yong-zheng , Chen Hong-bo , Wang Yan-ping , Li Zhi-hui , Cao Yan-ling , Chi Yuan-bin
Published: June 2006

The face-centered cubic (fcc) photonic crystals of titanium dioxide (TiO2) hollow spheres connected by TiO2 cylindrical tubes have been fabricated using silica template. The preparation process is based on the vertical deposition method, thermal sintering and selective etching techniques. In the crystal, the lowest energy pseudogaps at points U and K of the Brillouin zone have been opened.
Double Ortho-lithiation of (Diethylamino)diphenylphosphine Oxide and tert-Butyldiphenylphosphine Oxide
Authors: Tsuji Hayato , Komatsu Shigeo , Kanda Yasuhisa , Umehara Teruhiko , Saeki Tomoyuki , Tamao Kohei
Published: June 2006

We have developed the double ortho-lithiation of a (diethylamino)diphenylphosphine oxide and tert-butyldiphenylphosphine oxide. The resulting doubly lithiated species can be converted to various ortho-difunctionalized products as well as phosphorus heterocycles, such as dibenzophospholes and 9-phospha-10-metalla-9,10-dihydroanthracene derivatives. The structure and photophysical properties of the prepared 9-phospha-10-sila-9,10-dihydroanthracene derivative were also studied.
A School Curriculum–Based Exercise Program Increases Bone Mineral Accrual and Bone Size in Prepubertal Girls: Two-Year Data From the Pediatric Osteoporosis Prevention (POP) Study
Authors: Linden Christian , Ahlborg Henrik G , Besjakov Jack , Gardsell Per , Karlsson Magnus K
Published: June 2006

This 2-year prospective controlled exercise intervention trial in 99 girls at Tanner stage 1, evaluating a school curriculum–based training program on a population-based level, showed that the annual gain in BMC, aBMD, and bone size was greater in the intervention group than in the controls.

Introduction: Most exercise intervention studies in children, evaluating the accrual of BMD, include volunteers and use specifically designed osteogenic exercise programs. The aim of this study was to evaluate a 2-year general school-based exercise intervention program in a population-based cohort of girls at Tanner stage 1.

Materials and Methods: Forty-nine girls 7–9 years of age in grades 1 and 2 in one school were included in a school curriculum–based exercise intervention program of general physical activity for 40 minutes per school day (200 minutes/week). Fifty healthy age-matched girls in three neighboring schools, assigned to the general Swedish school curriculum of physical activity (60 minutes/week), served as controls. All girls were premenarchal, remaining in Tanner stage 1 during the study. BMC (g) and areal BMD (aBMD; g/cm2) were measured with DXA of the total body (TB), the lumbar spine (L2–L4 vertebrae), the third lumbar vertebra (L3), the femoral neck (FN), and the leg. Volumetric BMD (vBMD; g/cm3) and bone size were calculated at L3 and FN. Total lean body mass and total fat mass were estimated from the total body scan. Height and weight were also registered. Baseline measurements were performed before the intervention was initiated. Follow-up was done after 2 years.

Results: No differences between the groups were found at baseline in age, anthropometrics, or bone parameters. The annual gain in BMC was greater in the intervention group than in the controls: L2–L4, mean 3.8 percentage points (p = 0.007); L3 vertebra, mean 7.2 percentage points (p < 0.001); legs, mean 3.0 percentage points (p = 0.07). The intervention group had a greater annual gain in aBMD: total body, mean 0.6 percentage points (p = 0.006), L2–L4, mean 1.2 percentage points (p = 0.02), L3 vertebra, mean 1.6 percentage points (p = 0.006); legs, mean 1.2 percentage points (p = 0.007). There was also a greater mean annual gain in bone size in the L3 vertebra (mean 1.8 percentage points; p < 0.001) and in the FN (mean 0.3 percentage points; p = 0.02).

Conclusions: A general school-based exercise program for 2 years for 7- to 9-year-old girls (baseline) enhances the accrual of BMC and BMD and increases bone size.
Association of Geometric Factors and Failure Load Level With the Distribution of Cervical vs. Trochanteric Hip Fractures
Authors: Pulkkinen Pasi , Eckstein Felix , Lochmüller Eva-Maria , Kuhn Volker , Jämsä Timo
Published: June 2006

We experimentally studied the distribution of hip fracture types at different structural mechanical strength. Femoral neck fractures were dominant at the lowest structural strength levels, whereas trochanteric fractures were more common at high failure loads. The best predictor of fracture type across all failure loads and in both sexes was the neck-shaft angle.

Introduction: Bone geometry has been shown to be a potential risk factor for osteoporotic fractures. Risk factors have been shown to differ between cervical and trochanteric hip fractures. However, the determinants of cervical and trochanteric fractures at different levels of structural mechanical strength are currently unknown. In addition, it is not known if the distribution of fracture types differs between sexes. The aim of this experimental study on excised femora was to investigate whether there exist differences in the distribution of cervical and trochanteric fractures between different structural mechanical strength levels and different sexes and to identify the geometric determinants that predict a fracture type.

Materials and Methods: The sample was comprised of 140 cadavers (77 females: mean age, 81.7 years; 63 males: mean age, 79.1 years) from whom the left femora were excised for analysis. The bones were radiographed, and geometrical parameters were determined from the digitized X-rays. The femora were mechanically tested in a side impact configuration, simulating a sideways fall. After the mechanical test, the fracture patterns were classified into cervical and trochanteric.

Results: The overall proportion of cervical fractures was higher in females (74%) than in males (49%) (p = 0.002). The fracture type distribution differed significantly across load quartiles in females (p = 0.025), but not in males (p = 0.205). At the lowest load quartiles, 94.7% of fractures in female and 62.5% in males were femoral neck fractures. At the highest quartiles, in contrast, only 52.6% of fractures in females and 33.3% in males were cervical fractures. Among geometric variables, the neck-shaft angle was the best predictor of fracture type, with higher values in subjects with cervical fractures. This finding was made in females (p < 0.001) and males (p = 0.02) and was consistent across all failure load quartiles.

Conclusions: Femoral neck fractures predominate at the lowest structural mechanical strength levels, whereas trochanteric fractures are more common at high failure loads. Females are more susceptible to femoral neck fractures than males. The best predictor of fracture type across all structural strength levels and both sexes was the neck-shaft angle.
Vitamin D–Resistant Rickets and Type 1 Diabetes in a Child With Compound Heterozygous Mutations of the Vitamin D Receptor (L263R and R391S): Dissociated Responses of the CYP-24 and rel-B Promoters to 1,25-Dihydroxyvitamin D3
Authors: Nguyen Minh , d'Alesio Arnold , Pascussi Jean Marc , Kumar Rajiv , Griffin Matthew D , Dong Xiangyang , Guillozo Huguette , Rizk-Rabin Marthe , Sinding Christiane , Bougnères Pierre , Jehan Frédéric , Garabédian Michèle
Published: June 2006

We report here the first association between vitamin D–resistant rickets, alopecia, and type 1 diabetes in a child with compound heterozygous mutations in the VDR gene. Transfection studies suggest dissociated effects of VDR gene mutations on the regulation of genes involved in vitamin D metabolism and dendritic cell maturation.

Introduction: Whereas vitamin D may play a role in the immune tolerance process, no patient has been reported to associate hereditary vitamin D–resistant rickets (HVDRR) and an autoimmune disease, and no attempt has been made to delineate the outcome of mutations of the vitamin D receptor (VDR) on the transcription of genes controlling immune tolerance.

Materials and Methods: The VDR gene was analyzed in a child with vitamin D–resistant rickets, total alopecia, and early childhood–onset type 1 diabetes. Patient's fibroblasts and COS-7 cells transfected with wildtype or mutant VDRs were studied for ligand-binding capacity, transactivation activity using two gene promoters [CYP-24, a classical 1,25(OH)2D3-responsive gene, and relB, a critical NF-κB component for regulation of dendritic cell differentiation], VDR-RXR heterodimers association to CYP 24 VDREs by gel mobility shift assays, and co-activator binding by Glutathione-S-transferase pull-down assays.

Results: Two novel compound heterozygous mutations (L263R and R391S) were identified in the VDR ligand-binding domain in this child. Both mutations significantly impaired VDR ligand-binding capacity but had dissociated effects on CYP-24 and RelB promoter responses to vitamin D. CYP 24 response binding to SRC-1 and RXR-heterodimer binding to CYP24 VDREs were abolished in L263R mutants but normal or partially altered in R391S mutants. In the opposite, RelB responses to vitamin D were close to normal in L263R mutants but abolished in R391S mutants.

Conclusions: We report the first clinical association between HVDRR, total alopecia, and early childhood–onset type 1 diabetes. Mutations in the VDR ligand-binding domain may hamper the 1,25(OH)2D3–mediated relB responses, an effect that depends on the site of the VDR mutation and cannot be anticipated from VDR ligand-binding ability or CYP-24 response. Based on these results, we propose to survey the immune function in patients with HVDRR, including those with moderate features of rickets.
RANKL-Induced Expression of Tetraspanin CD9 in Lipid Raft Membrane Microdomain Is Essential for Cell Fusion During Osteoclastogenesis
Authors: Ishii Masaru , Iwai Kaori , Koike Masato , Ohshima Shiro , Kudo-Tanaka Eriko , Ishii Taeko , Mima Toru , Katada Yoshinori , Miyatake Kunio , Uchiyama Yasuo , Saeki Yukihiko
Published: June 2006

We showed that CD9, a member of tetraspanin superfamily proteins, is expressed in a specific membrane microdomain, called “lipid raft,” and is crucial for cell fusion during osteoclastogenesis after activation of the RANK/RANKL system.

Introduction: Osteoclasts are bone-resorbing multinuclear polykaryons that are essential for bone remodeling and are formed through cell fusion of mononuclear macrophage/monocyte lineage precursors. Although osteoclastogenesis has been shown to be critically regulated by the RANK/RANKL system, the mechanism how precursor cells fuse with each other remains unclear. We examined the function of CD9, a member of tetraspanin superfamily, which has previously been shown to form macromolecular membrane microdomains and to regulate cell–cell fusion in various cell types.

Materials and Methods: We used RAW264.7, a macrophage/monocyte lineage cell line, which can differentiate into osteoclast-like polykaryons on the application of RANKL. Expression and distribution of CD9 was assessed by Western blotting, fluorescence-assorted cell sorting (FACS) and immunohistochemistry with light and electron microscopy. A specific neutralizing antibody and RNA interference were used to inhibit the function of CD9, and green fluorescent protein (GFP)-CD9 was exogenously expressed to enhance the effect of CD9. The distribution of CD9 in lipid microdomain was examined by biochemical (sucrose density gradient) isolation and imaging technique.

Results: CD9 is expressed on cell surfaces of RAW264.7, which is enhanced by RANKL. Targeted inhibition of CD9 decreases the number of osteoclast-like cells. On the other hand, overexpression of CD9 promotes spontaneous cell fusion even in the absence of RANKL. CD9 is localized in detergent-insoluble “lipid raft” microdomain in RANKL stimulation, and disruption of lipid rafts markedly reduces the formation of osteoclast-like polykaryons. Immunohistochemical studies of bone tissues revealed the expression of CD9 in osteoclasts in vivo.

Conclusions: These data suggest that function of tetraspanin CD9 and its expression in lipid rafts are crucial for cell fusion during osteoclastogenesis.
Deletion of a Single Allele of the Dkk1 Gene Leads to an Increase in Bone Formation and Bone Mass
Authors: Morvan Frederic , Boulukos Kim , Clément-Lacroix Philippe , Roman Sergio Roman , Suc-Royer Isabelle , Vayssière Béatrice , Ammann Patrick , Martin Patrick , Pinho Sonia , Pognonec Philippe , Mollat Patrick , Niehrs Christof , Baron Roland , Rawadi Georges
Published: June 2006

Wnt/β-catenin signaling has been proven to play a central role in bone biology. Unexpectedly, the Wnt antagonist Dkk2 is required for terminal osteoblast differentiation and mineralized matrix formation. We show that Dkk1, unlike Dkk2, negatively regulates osteoblast differentiation and bone formation.

Introduction: The Wnt co-receptor LRP5 is a critical regulator of bone mass. Dickkopf (Dkk) proteins act as natural Wnt antagonists by bridging LRP5/6 and Kremen, inducing the internalization of the complex. Wnt antagonists are thus expected to negatively regulation bone formation. However, Dkk2 deficiency results in increased bone, questioning the precise role of Dkks in bone metabolism.

Materials and Methods: In this study, we investigated specifically the role of Dkk1 in bone in vitro and in vivo. Using rat primary calvaria cells, we studied the effect of retroviral expression of Dkk1 on osteoblast differentiation. In addition, the effect of Dkk1 osteoblast was studied in MC3T3-E1 cells by means of recombinant protein. Finally, to address the role of Dkk1 in vivo, we analyzed the bone phenotype of Dkk1+/− animals.

Results: Retroviral expression of Dkk1 in rat primary calvaria cells resulted in a complete inhibition of osteoblast differentiation and formation of mineralized nodules, with a marked decrease in the expression of alkaline phosphatase. Dkk1 expression also increased adipocyte differentiation in these cell cultures. Recombinant murine Dkk1 (rmDkk1) inhibited spontaneous and induced osteoblast differentiation of MC3T3-E1 cells. To determine the role of Dkk1 in vivo and overcome the embryonic lethality of homozygous deletion, we studied the bone phenotype in heterozygous Dkk1-deficient mice. Structural, dynamic, and cellular analysis of bone remodeling in Dkk1+/− mice showed an increase in all bone formation parameters, with no change in bone resorption, leading to a marked increase in bone mass. Importantly, the number of osteoblasts, mineral apposition, and bone formation rate were all increased several fold.

Conclusions: We conclude that Dkk1 protein is a potent negative regulator of osteoblasts in vitro and in vivo. Given that a heterozygous decrease in Dkk1 expression is sufficient to induce a significant increase in bone mass, antagonizing Dkk1 should result in a potent anabolic effect.
Effects of Conjugated Equine Estrogen on Risk of Fractures and BMD in Postmenopausal Women With Hysterectomy: Results From the Women's Health Initiative Randomized Trial
Authors: Jackson Rebecca D , Wactawski-Wende Jean , LaCroix Andrea Z , Pettinger Mary , Yood Robert A , Watts Nelson B , Robbins John A , Lewis Cora E , Beresford Shirley AA , Ko Marcia G , Naughton Michelle J , Satterfield Suzanne , Bassford Tamsen
Published: June 2006

Further analyses from the Women's Health Initiative estrogen trial shows that CEE reduced fracture risk. The fracture reduction at the hip did not differ appreciably among risk strata. These data do not support overall benefit over risk, even in women at highest risk for fracture.

Introduction: The Women's Health Initiative provided evidence that conjugated equine estrogen (CEE) can significantly reduce fracture risk in postmenopausal women. Additional analysis of the effects of CEE on BMD and fracture are presented.

Materials and Methods: Postmenopausal women 50–79 years of age with hysterectomy were randomized to CEE 0.625 mg daily (n = 5310) or placebo (n = 5429) and followed for an average 7.1 years. Fracture incidence was assessed by semiannual questionnaire and verified by adjudication of radiology reports. BMD was measured in a subset of women (N = 938) at baseline and years 1, 3, and 6. A global index was used to examine whether the balance of risks and benefits differed by baseline fracture risk.

Results: CEE reduced the risk of hip (hazard ratio [HR], 0.65; 95% CI, 0.45–0.94), clinical vertebral (HR, 0.64; 95% CI, 0.44–0.93), wrist/lower arm (HR, 0.58; 95% CI, 0.47–0.72), and total fracture (HR, 0.71; 95% CI, 0.64–0.80). This effect did not differ among strata according to age, oophorectomy status, past hormone use, race/ethnicity, fall frequency, physical activity, or fracture history. Total fracture reduction was less in women at the lowest predicted fracture risk in both absolute and relative terms (HR, 0.86; 95% CI, 0.68–1.08). CEE also provided modest but consistent positive effects on BMD. The HRs of the global index for CEE were relatively balanced across tertiles of summary fracture risk (lowest risk: HR, 0.81; 95% CI, 0.62–1.05; mid risk: HR, 1.09; 95% CI, 0.92–1.30; highest risk: HR, 1.04; 95% CI, 0.88–1.23; interaction, p = 0.42).

Conclusions: CEE reduces the risk of fracture and increases BMD in hysterectomized postmenopausal women. Even among the women with the highest risk for fractures, when considering the effects of estrogen on other important health outcomes, a summary of the burden of monitored effects does not indicate a significant net benefit.
Mice Lacking Cathepsin K Maintain Bone Remodeling but Develop Bone Fragility Despite High Bone Mass
Authors: Li Chao Yang , Jepsen Karl J , Majeska Robert J , Zhang Jian , Ni Rujing , Gelb Bruce D , Schaffler Mitchell B
Published: June 2006

Bone microstructural and biomechanical properties were analyzed in mice genetically lacking cathepsin K (CatK). CatK deficiency (CatK−/−) produced mild osteopetrosis, elevated numbers of osteoclasts, regions of disorganized bone microstructure, and increased bone fragility, showing how chronic alteration of enzyme activity during skeletal development dramatically affects bone organization and function.

Introduction: Mouse models of CatK deficiency recapitulate the osteopetrosis of human pyknodysostosis and allow study of clinically relevant issues: how inhibition of this enzyme activity affects bone integrity structurally and biomechanically. To address these questions, we generated CatK-deficient mice by targeted disruption of the Ctsk gene and compared their bone structural and mechanical properties with wildtype (WT) controls.

Materials and Methods: Standard histomorphometric and biomechanical analyses were performed on femora from C57BL/6J male and female CatK−/−, CatK+/−, and WT mice.

Results: CatK−/− femora exhibited the mild metaphyseal osteopetrosis, a greater cortical bone area and thickness, normal bone strength, but a high degree of brittleness (nearly 50–70% decrease in postyield displacement versus WT) and a 30–40% reduction in the work-to-failure. In cancellous bone, osteoclast numbers and resorption surface were increased markedly (∼150% and 50%, respectively), despite the overall decrease in net bone resorption for CatK-deficient mice. Bone formation indices were altered in CatK−/− mice as well, with significant increases in mineral appositional rate, but not in bone formation surface; these data suggest difference in osteoblast work but not in their recruitment in CatK deficiency. CatK-deficient cortical bones had large areas of woven bone and intracortical resorption spaces within the disorganized tissue. Bone phenotype in CatK−/− was similar in males and females.

Conclusions: Genetic CatK deficiency in mice results not only in the impairment of osteoclast function and osteopetrosis, but also altered osteoblast function, defective tissue organization, and very brittle bones. Whether this bone fragility in CatK deficiency results entirely from indirect effects of suppressed bone turnover because of impaired osteoclast function or perhaps represents a previously unappreciated more direct role for CatK in bone formation remains to be established.
Contracting Female Marriage in Anthony Trollope's Can You Forgive Her?
Authors: MARCUS SHARON
Published: June 2006

This essay demonstrates that Anthony Trollope was one of several Victorians aware of"female marriage," a term that Elizabeth Barrett Browning used to describe committed unions between women. After establishing that Trollope knew women in female marriages at the time that he was composing his novel Can You Forgive Her? (1864-65), the essay analyzes how female marriage inscribes itself within the form of the marriage plot. Trollope's novel aligns female marriage with contractual marriage, associated with feminist demands to make unions between men and women more egalitarian as well as dissoluble. The novel works to discredit contractual forms of marriage and to celebrate indissoluble hierarchical marriage by associating the first with primitive savagery, the second with an ideal of civilization that can accommodate male violence.
Jo March's Love Poems
Authors: DOYLE JENNIFER
Published: June 2006

At key moments in Louisa May Alcott's novel Little Women (1868-69) we encounter poetry written by the tomboy heroine, Jo March. This essay considers the place of those poems in a lesbian reading of the novel.
Death and Translation
Authors: SAUSSY HAUN
Published: June 2006

ABSTRACT A poem by Baudelaire, rendered by its first Chinese translator in language that recalls the early Daoist philosopher Zhuangzi, resembles less amimesis of the total work than an assimilative digestion of the work's fragments. This practice of translation operates in counterpoint to the rhetoric of decay prominent in the original poem, here decoded with the help of Aristotle and Dante.
Sacrifice, Mimesis, and the Theorizing of Victimhood (A Speculative Essay)
Authors: CHOW REY
Published: June 2006

ABSTRACT This essay is an attempt to identify and elaborate the inextricable mutual implications between mimesis and sacrifice in considerations of victimhood (understood as dominated or stigmatized existence), especially as found in prominent examples of contemporary cultural theory. The authors discussed include Giorgio Agamben, Luce Irigaray, Homi Bhabha, and René Girard.
Orienting Mimesis: Marriage and the Book of Songs
Authors: CHIN TAMARA
Published: June 2006

ABSTRACT Modern critics generally locate the beginning of the Chinese aesthetic tradition in the Confucian commentarial repression of the “love and marriage” poems of the Book of Songs. This article argues that these commentators were actually using the Songs to engage with Han dynasty debates about desire, and in doing so formulated a new, gendered way of presenting poems as parables.