bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pilot phase III immunotherapy study in early-stage breast cancer patients using oxidized mannan-MUC1 [ISRCTN71711835]
Authors: Apostolopoulos Vasso , Pietersz Geoffrey A , Tsibanis Anastasios , Tsikkinis Annivas , Drakaki Heleni , Loveland Bruce E , Piddlesden Sara J , Plebanski Magdalena , Pouniotis Dodie S , Alexis Michael N , McKenzie Ian F , Vassilaros Stamatis 
Published: June 2006

Abstract
Introduction
Mucin 1 (MUC1) is a high molecular weight glycoprotein overexpressed on adenocarcinoma cells and is a target for immunotherapy protocols. To date, clinical trials against MUC1 have included advanced cancer patients. Herein, we report a trial using early stage breast cancer patients and injection of oxidized mannan-MUC1.

Method
In a randomized, double-blind study, 31 patients with stage II breast cancer and with no evidence of disease received subcutaneous injections of either placebo or oxidized mannan-MUC1, to immunize against MUC1 and prevent cancer reoccurrence/metastases. Twenty-eight patients received the full course of injections of either oxidized mannan-MUC1 or placebo. Survival and immunological assays were assessed.

Results
After more than 5.5 years had elapsed since the last patient began treatment (8.5 years from the start of treatment of the first patient), the recurrence rate in patients receiving the placebo was 27% (4/15; the expected rate of recurrence in stage II breast cancer); those receiving immunotherapy had no recurrences (0/16), and this finding was statistically significant (P = 0.0292). Of the patients receiving oxidized mannan-MUC1, nine out of 13 had measurable antibodies to MUC1 and four out of 10 had MUC1-specific T cell responses; none of the placebo-treated patients exhibited an immune response to MUC1.

Conclusion
The results suggest that, in early breast cancer, MUC1 immunotherapy is beneficial, and that a larger phase III study should be undertaken.
Cation Effects on Infrared Reflection Absorption Spectra of Cyanide Adsorbed on Pt(111) Electrode in Electrolyte Solutions
Authors: Inukai Junji , Morioka Yukiko , Kim Youn-Geun , Yau Shueh-Lin , Itaya Kingo 
Published: June 2006

Abstract
In-situ infrared reflection absorption spectroscopy was applied to the investigation of cation effects on the C–N stretching frequency of cyanide ions on Pt(111) electrode in electrolyte solutions. Only a single absorption peak was observed at ca. 2100 cm−1 in solutions containing H3O+, Li+, Na+, K+, or Cs+. In a KClO4 solution (pH = 9.5), a change in slope was observed in the peak frequency–potential curve at ca. −0.5 V vs. the saturated calomel electrode. It was concluded that in the cathodic region in the KClO4 solution, H3O+ dominates the outer Helmholtz plane as a result of cation exchange. In alkaline solutions, the slope for the frequency shift is dependent on the cations in the order K+ &gt; Na+ &gt; Li+ ≈ Cs+. In HClO4, a change in slope was also observed in the peak frequency-potential curve. In a Mg(ClO4)2 solution, three peaks were observed for CN on Pt(111), indicating that factors other than the simple electrochemical Stark effect must be considered for interpreting the influence of this strongly adsorbed cation.
Quantum Yields of Intramolecular Hydrogen Abstraction Induced by Laser Flash Photolysis of Arene/Cl π-Complexes
Authors: Wu Feng , Shindo Toshihiko , Sawamura Sadashi , Sumiyoshi Takashi 
Published: June 2006

Abstract
Arene/chlorine atom π-complexes were generated by pulse radiolysis of a wide variety of substituted benzenes in carbon tetrachloride at room temperature. Upon laser flash photolysis of the π-complexes, intramolecular hydrogen abstraction was observed in times much shorter than the flash time (6 ns), with quantum yields between 0.05 and 0.18 depending on the sort and the number of the substituents but not on their positions. The effects of substituents on the photochemistry of arene/chlorine atom π-complexes were discussed in connection with the bond dissociation energy of the related atoms and with the structure of the π-complexes.
Dinaionic Ligand Complexes, K2[CuLn] and K2[NiLn] (n = 1, 2; H4L1 = 1,2-Bis(2-hydroxybenzamido)ethane, H4L2 = 1,2-Bis(2-hydroxybenzamido)benzene), and Their Dinuclear Cu(II)–Cu(II) and Ni(II)–Cu(II) Complexes
Authors: Sunatsuki Yukinari , Nakamura Masaaki , Matsumoto Naohide , Kai Fumiaki 
Published: June 2006

Abstract
Copper(II) and nickel(II) complexes with tetraanionic quadridentate ligands, K2[CuLn] and K2[NiLn] (n = 1, 2), have been prepared. We examined whether or not they can function as “ligand complexes”, where H4L1 = 1,2-bis(2-hydroxybenzamido)ethane and H4L2 = 1,2-bis(2-hydroxybenzamido)benzene. One of the ligand complexes, K2[NiL1]·2dmf·2H2O, crystallizes in the monoclinic space group P21/n with the cell dimensions of a = 15.34(8), b = 18.99(8), c = 18.86(5) Å, β = 100.2(3), V = 5406 Å3, and Z = 8. The ligand complex assumes a unique one-dimensional structure consisting of {[KO3][K(NiL1)O]}n as the repeating unit, where each K+ ion is surrounded octahedrally by six oxygen atoms with the distances of 2.672(2)—2.866(9) Å and all the oxygen atoms act as bridging group to K+ ion. Each of the precursor complexes can function as an electrically dianionic bidentate “ligand complex” and reacts with Cu(II) ion and terminal capping ligand (cap) such as 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), ethylenediamine (en), and 1,3-diaminopropane (tn) to give di-μ-phenoxo-bridged dinuclear Cu(II)–Cu(II) and Ni(II)–Cu(II) complexes with the general formula of [(Cu or Ni)LnCu(cap)]. The molar electrical conductivities of the dinuclear complexes measured in the DMF or DMSO solutions are essentially zero, indicating that the dinuclear structures are preserved in the solutions. The electrochemical measurements for a series of [CuL2Cu(cap)] (cap = bpy, phen, tn) demonstrated that the Cu(II/III) redox process of the {CuL2} site exhibits more positive potential (−0.04 — −0.09 V) than that of the mononuclear precursor complex (−0.288 V). One of the dinuclear complexes, [CuL2Cu(phen)(DMSO)], crystallizes in the orthorhombic space group Pna21 with the cell dimensions of a = 19.702(3), b = 15.847(3), c = 9.652(2) Å, V = 3013 Å3, and Z = 4. The complex consists of a discrete di-μ-phenoxo-bridged dinuclear structure, in which two copper(II) ions assume a square planar and square pyramidal coordination geometry and the bridging core of Cu2O2 is unequivalent, as found in the distances of Cu(1)–O(1) = 1.924(4) Å, Cu(1)–O(2) = 1.908(4) Å, Cu(2)–O(2) = 1.964(4) Å and Cu(2)–O(1) = 2.249(4) Å. The magnetic susceptibility is well reproduced with the antiferromagnetic coupling parameter of J = −82 cm−1 by the Bleaney–Boweres equation.
Synthesis and Properties of Tris(octaethylporphyrin)s Connected with Vinylene Groups
Authors: Higuchi Hiroyuki , Shimizu Kenji , Takeuchi Makoto , Ojima Juro , Sugiura Ken-ichi , Sakata Yoshiteru 
Published: June 2006

Abstract
Tris(octaethylporphyrin)s, in which two octaethylporphyrin (OEP) rings are connected with vinylene groups at α,γ- and α,β-meso positions of the central OEP ring, were synthesized. The tris(OEP)s have similar conformational and configurational structures to the corresponding vinylene group-connected bis(OEP). Examination of both 1H NMR and electronic absorption spectra of the tris(OEP)s showed the behavior reflecting the highly symmetrical structure and the mutual interaction between the three OEP rings through the vinylene linkages.
A Chemical Scale for Evaluating the Electron Transfer Ability of Alkylcopper Reagents
Authors: Chounan Yukiyasu , Horino Hiroshi , Ibuka Toshiro , Yamamoto Yoshinori 
Published: June 2006

Abstract
In order to evaluate the electron transfer ability of organocopper reagents, the reactions of appropriate Michael acceptors with methyl- and butylcopper reagents were investigated. The reaction of trimethyl ethylene-1,1,2-tricarboxylate (1a) with methylcopper reagents gave a mixture of the conjugate adduct 2a and reduction product 3a in good to high yields. The ratio of 2a and 3a varied with the copper species and decreased in the following order: MeCu(CN)Li &gt; MeCu &gt; Me2Cu(CN)Li2 &gt;&gt; Me2CuLi &gt; Me3CuLi2. It was confirmed by 13C NMR studies and oxidation experiments of the intermediate copper species that the reduction product 3a was produced via an electron transfer process and that the conjugate adduct 2a was afforded through a nucleophilic attack of MeCuILn. Consequently, the electron transfer ability of methylcopper reagents is in the following order: Me3CuLi2 &gt; Me2CuLi &gt;&gt; Me2Cu(CN)Li2 &gt; MeCu &gt; MeCu(CN)Li. By similar experiments using 3-cyclopropyl-2-methoxycarbonyl-3-phenyl-2-propenoate (9) as a Michael acceptor, we concluded that the electron transfer ability of butylcopper reagents is in the order of Bu2CuLi &gt; BuCu(CN)Li ≈ Bu2Cu(CN)Li2 &gt; BuCu, and that its ability of butylcopper reagents is higher than that of the corresponding methylcopper reagents.
Synthesis of 2-Polyprenyl-Substituted Polyprenols and Their Conversion into Phosphates
Authors: Nagano Hajime , Nagasawa Tomoko , Sakuma Masako 
Published: June 2006

Abstract
Highly Branched polyprenols, {(6E)-2-[(2E)-3,7-dimethyl-2,6-octadienyl]-7,11-dimethyl-3-methylene-6,10-dodecadien-1-ol and (6E,10E)-2-[(2E,6E)-3,7,11-trimethyl-2,6,10-dodecatrienyl]-7,11,15-trimethyl-3-methylene-6,10,14-hexadecatrien-1-ol}, were synthesized (1) from diethyl malate, geranyl bromide, and homogeranyl iodide, and (2) from ethyl acetoacetate and geranyl (or farnesyl) bromide. These alcohols were transformed into disodium phosphates, which have been postulated to be primitive lipids in the evolution of membranes.
Synthesis of Nano-Dimensional Iron–Cobalt Spinel Mixed Oxides from Layered-Type Carbonate Hydroxide Precursors
Authors: Uzunova Elly L , Mitov Ivan G , Klissurski Dimitar G 
Published: June 2006

Abstract
Pyroaurite-like carbonate hydroxide precursors Co1−xFex(CO3)x/2(OH)2·nH2O, where x varies in the range 0.25 ≤ x ≤ 0.75, yield cation deficient mixed oxides with particle dimensions in the nano-scale range. The thermal decomposition and spinel structure formation processes have been studied by thermal analysis and IR spectroscopy, revealing an intermediate of hydroxide oxide type. Mesoporous mixed oxides with cubic spinel structure were synthesised at 300—400 °C with significant contribution of small pores of radii &lt;200 Å. Oxygen desorption from cobalt ferrite, synthesised at 350 °C, suggests the existence of a high content of extraframework oxygen. The temperature-programmed reduction (TPR) with hydrogen occurs in one stage for all cobalt/iron compositions. The peak maxima shift to higher temperatures and a broadening is observed with increasing the iron content. Partly inverse cation distributions of the spinel ferrites are deduced from the Moessbauer spectra.
Molecular Magnets Based on Organic Charge Transfer Complexes
Authors: Enoki Toshiaki , Yamaura Jun-Ichi , Miyazaki Akira 
Published: June 2006

Abstract
Organic charge transfer complexes form a large variety of electronic structures from insulating state to metallic state in low-dimensional frameworks, which are governed by the competition between the transfer integral and the on-site Coulomb interaction. In the insulating regime, the generation of localized magnetic moments of π-electron origin provides low-dimensional magnetic systems having the features of quantum spins. The increase in the transfer integral which works to suppress the effect of on-site Coulomb interaction makes π-electrons delocalized, resulting in the appearance of the systems with the coexistence of magnetism and electron transport as materials classified around the Mott–Hubbard boundary. The introduction of localized magnetic moments of d-electrons in the complexes gives rise to the interaction between the π-electrons and the magnetic moments of d-electrons. Localized magnetic moments of d-electrons embedded in insulating complexes are expected to interact with each other through superexchange interaction mediated by the organic π-electron system, while localized d-spins in metallic complexes are coupled to each other via the π–d interaction, leading to the generation of molecule-based metal magnets. The studies of organic complex-based molecular magnets based on TTF-type donor molecules performed in our group are reviewed.
Behavior of Ruthenium Trisbipyridine–Anthraquinone Conjugates Connected with Alkyl Spacers in Homogeneous and Microheterogeneous Media
Authors: Otsuki Joe , Ogawa Hiroyuki , Okuda Naotoshi , Araki Koji , Seno Manabu 
Published: June 2006

Abstract
A series of mononuclear Ru trisbypiridine complexes connected to an anthraquinone unit by a flexible alkyl chain of varying lengths and a bolaamphiphilic dinuclear ruthenium complex bearing an anthraquinone unit in the middle of alkyl chain spacers were synthesized. Their conformational preference in CH3CN and in dihexadecyl phosphate vesicles was probed by utilizing the intramolecular electron-transfer quenching of the metal-to-ligand charge-transfer excited state of the Ru center by the appended quinone moiety. The length of the alkyl chain spacer had little effect on the quenching efficiency in either medium. A marked difference in the quenching behavior was observed only in the case of the dinuclear Ru complex in vesicles. These results indicate that the bolaamphiphilic structure is necessary and effective for the set of immobilized molecules to take a stretched conformation spanning a bilayer membrane.
The First Structurally Characterized Salen–Indium Complexes
Authors: Atwood David A , Jegier Jolin A , Rutherford Drew 
Published: June 2006

Abstract
In this manuscript are reported the synthesis and characterization of the first complexes of indium incorporating the acen and salen classes of ligands. This includes the compounds of formula LInMe (where L = acen (1) (N,N′-ethylenebis(2-hydroxy-α-methylbenzylidenimine)), salen (2) (N,N′-ethylenebis(2-hydroxybenzylideneimine)), salophen (3) (N,N′-(1,2-phenylene)bis(2-hydroxybenzylidenimine)), salomphen (4) (N,N′-(4,5-dimethyl-1,2-phenylene)bis(2-hydroxybenzylidenimine)). Attempts to prepare the derivatives, [In(R)(salpen)] (salpen = N,N′-propylenebis(2-hydroxybenzylidenimine), R = Me, Et) led to the formation of the bimetallic complexes, [(InMe2)2(salpen)] (5) and [In(Et2)2(salpen)] (6). Dissolution of 5 and 6 in MeOH causes the formation of three unusual products. They are the ligand bridged compounds [{In(μ-OMe)(μ-salpen)}2] (7), [{In(salpen)}2(μ-salpen)] (8) and the methoxy-only bridged complex, [{In(salpen)(μ-OMe)}2] (9). Compounds 7—9 are the first structurally characterized indium–salen complexes. For purposes of comparison, the structure of [{Al(salen)(μ-OMe)}2] (10) will also be described.
Successive Potentiometric Titration of Chromium(VI) and Iron(III) with Cobalt(II) in the Presence of 1,10-Phenanthroline
Authors: Katsumata Hideyuki , Teshima Norio , Kawashima Takuji 
Published: June 2006

Abstract
Studies are made on the effect of 1,10-phenanthroline (phen) on the redox reactions such as chromium(VI) and iron(III) with cobalt(II). In the presence of phen, the conditional redox potential of the Co(III)/Co(II) system is lower than that of the Cr(VI)/Cr(III) and the Fe(III)/Fe(II) systems. Two large potential breaks are thus observed at equivalence points when the titration of 5 × 10−4 mol dm−3 chromium(VI) and 1 × 10−3 mol dm−3 iron(III) with cobalt(II) is carried out in the presence of 8 × 10−2 mol dm−3 phen at pH 1, while in the absence of this ligand no potential break can be observed at equivalence points. By using these redox reactions, we propose successive potentiometric titrations of chromium(VI) and iron (III) with cobalt(II) in a single titration. The proposed method is successfully applied to the determination of chromium and iron in high carbon ferrochromium.
Synthesis of Dichloro(phthalocyaninato)antimony(V) Perchlorate, Tetrafluoroborate, and Hexafluorophosphate and Electrochemical Reinvestigation on the New Complex Salts
Authors: Kagaya Yutaka , Isago Hiroaki 
Published: June 2006

Abstract
The titled new salts were synthesized by exchanging the unknown counter anion of [Sb(pc)Cl2]+ salt (pc2− = phthalocyaninate, C32H16N82−), which was the first product of the reaction of phthalonitrile with antimony(III) trichloride, with perchlorate, tetrafluoroborate, and hexafluorophosphate. Elemental analytical data and infrared spectra of the new salts confirmed that these complexes are composed of one [Sb(pc)Cl2]+ cation and one mononegative counter ion. The introduction of electrochemically inactive counter-anions exerted little effect on the electronic spectrum and the first and second pc-ring reduction potentials of the complex in dichloromethane, but has made it possible to observe the third and fourth reduction processes, which were not observed for the initial salt. Up to four successive reduction processes of a pc-ring were observed for the first time in a noncoordinating solvent. Although the 1Δ2E1/2 (half-wave potential interval between the first and second reduction processes; 0.45 V), and 3Δ4E1/2 (0.58 V) values for [Sb(pc)Cl2]+ were typical of those for the known phthalocyanines, the 2Δ3E1/2 value (0.31 V) was much smaller. The anomaly in the spacing of the reduction processes for [Sb(pc)Cl2]+ is discussed in terms of the lack of a significant Jahn–Teller distortion of the pc-ring upon reduction.
Acid-Catalyzed [4+2] Cycloaddition Reaction of 2-(Alk-2-enyl)amino-3-(N-arylimino)methyl-4-oxo-4H-pyrido[1,2-a]pyrimidines
Authors: Noguchi Michihiko , Mizukoshi Takashi , Nishimura Shigeki 
Published: June 2006

Abstract
The N-arylimines of 2-(alk-2-enyl)amino-4-oxo-4H-pyrido[1,2-a]pyrimidine-3-carbaldehyde undergo the intramolecular [4+2] cycloaddition reaction under Lewis acid-catalyzed conditions to afford diastereomeric tetraazapentaphene derivatives. The diastereoselectivity as well as the scope and limitations of the cycloaddition reactions is discussed.
Linear and Stack Oligostreptocyanines. Effects of Relative Orientation of Chromophores on Redox Potentials of Dye Aggregates
Authors: Katoh Takashi , Inagaki Yoshio , Okazaki Renji 
Published: June 2006

Abstract
Linear and stack pentamethinestreptocyanine oligomers were prepared in which streptocyanines are covalently connected to each other. The absorption bands of the linear oligomers showed bathochromic shifts compared to that of the corresponding monomer, while the absorption band of the stack dimer was hypsochromically shifted. These spectral shifts were reproduced by a calculation with the INDO/S-CI method and are in agreement with those based upon a molecular exciton theory. The redox potentials of the linear oligomers underwent a positive shift due to the Coulombic interaction compared to those of the streptocyanine monomer. The positive shift of the reduction potential and the negative shift of the oxidation potential of the stack dimer are explained in terms of the Coulombic and orbital interactions.
Selectivity in Organic Group Transfer in Reactions of Mixed Diorganomanganese(II) and Triorganomanganate(II) with 2-Cyclohexen-1-one or Cyclohexanecarbaldehyde
Authors: Yorimitsu Hideki , Hayashi Yasuhiro , Tang Jun , Shinokubo Hiroshi , Oshima Koichiro 
Published: June 2006

Abstract
The unsymmetrical diorganomanganeses(II) (R1R2Mn) and magnesium triorganomanganates(II) (R12R2MnMgX) reacted with 2-cyclohexen-1-one to produce the 1,4-addition products in moderate to good yields. The approximate reactivity order obtained from the product distribution was CH2=CHCH2 &gt; PhS &gt; n-Bu &gt; Ph &gt; Me, Me3SiCH2, n-C6H13–C≡C. In contrast, the reactivity order for the addition of these reagents to cyclohexanecarbaldehyde was CH2=CHCH2 &gt; Ph &gt; Me &gt; n-Bu &gt; n-C6H13C≡C &gt; Me3SiCH2.
Molecular Probing for the Microenvironment of Photonics Materials Prepared by the Sol–Gel Process
Authors: Matsui Kazunori , Nozawa Kazuhiro 
Published: June 2006

Abstract
The absorption and fluorescence spectra of the solvatochromic dye 9-diethylamino-5H-benzo[a]phenoxazin-5-one (Nile Red) were studied in modified SiO2 gels prepared from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), triethoxysilane (HTES), and triethoxymethylsilane (MTES). Nile Red showed a remarkable spectral shift during the sol–gel process, the direction and extent of which depended on the gel properties. ENT, empirical parameters of the solvent polarity, were determined based on the spectral shifts. As the precursors for the xerogels changed, ENT of the xerogels decreased in the order TEOS ≈ TMOS &gt; MTES &gt; HTES. ENT of the xerogels were 0.88—0.99 for TMOS and TEOS; this result showed the polarity of the xerogels form TMOS and TEOS to be almost the same as that of water (1.000). On the contrary, the polarity of the xerogels from HTES and MTES were as hydrophobic as haloalkane (0.1—0.3).
Zeolitic Membranes: Synthesis, Properties, and Prospects
Authors: Matsukata Masahiko , Kikuchi Eiichi 
Published: June 2006

Abstract
This article is intended to describe recent progress in the synthesis of zeolitic membranes and their permeation properties. While hydrothermal synthesis has been widely employed for zeolitic-membrane synthesis, the development of a new technique for zeolite synthesis, vapor-phase transport (VPT), has enabled us to prepare pinhole-free, zeolite-porous support composite membranes. This article consists of three sections that describe: a survey of the hydrothermal synthesis of zeolitic membranes, our synthesis results and the formation mechanism of zeolitic membranes by the VPT method as well as some permeation results to show the prospects of zeolitic membranes.
Hydrophobic Hydration Structures of Tris(1,10-phenanthroline)metal and Tris(2,2′-bipyridine)metal Complex Ions and Effect of the Ionic Charge. X-Ray Diffraction Study with Isomorphous Substitution
Authors: Yokoyama Haruhiko , Shinozaki Kazuteru , Hattori Shin , Miyazaki Fumiyo 
Published: June 2006

Abstract
X-Ray diffraction measurements have been made for aqueous solutions of sulfates or chlorides of [Ru(phen)3]2+, [Ni(phen)3]2+, [Ru(bpy)3]2+, [Ni(bpy)3]2+, [Rh(bpy)3]3+, and [Cr(bpy)3]3+ (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine). Radial distribution functions for the metal interactions were obtained by the isomorphous substitution between ruthenium(II) and nickel(II) complexes or between rhodium(III) and chromium(III) complexes. Metal–nitrogen and metal–carbon distances within the complex ions in solution were essentially in agreement with those in the crystals. Regarding the divalent metal complexes, about two water molecules seemed to exist at a distance of 3.5—3.6 Å (1 Å = 10−10 m) from the central metal atom and 10—11 water molecules existed in the region of 5.3 to 6.3 Å, probably in the vicinity of peripheral hollows along the C3 axis of the complex. Further, large broad peaks with high electron density were observed around 7.7 and 11.2 Å for the [Ru(bpy)3]2+ ion and around 8.0 and 11.5 Å for the [Ru(phen)3]2+ ion, almost independent of salt concentration and kinds of counter ions. These were attributed to the hydrophobic hydration shells having the hydrogen-bonded network structure. The hydration structure of the trivalent metal complexes was significantly different from that observed for the divalent ones: 14—15 water molecules existed in the range of 4.7 to 6.0 Å, a part of them presumably in the hollows along the C2 axes of the complex, and only a single broad peak was observed around 7.7 Å as the hydrophobic hydration shell. These results indicated that the hydrophobic hydration structure was reduced by the increase of the ionic charge, as predicted from a comparison of temperature coefficients of the Walden product obtained by the conductivity measurements of dilute solutions.