bluuebunny/crossref_metadata_2025 huggingface dataset:
The Emerging Property Development Pattern in Greece and its Impact on Spatial Development
Authors: Delladetsima P. M.
Published: July 2006

Real estate market and property development dynamics in Greece are undergoing some critical changes, exhibiting a new condition which governs the relationship between capital and landed property in the current phase of capitalist development. A key feature of these changes is the formation of a property development pattern which clearly marks a break with the dominant conventional one (structured upon the small-scale owner occupation and the absence of big capital). The potential impact of this new pattern is difficult to assess as yet. Each pattern – the conventional and the newly emerging one – are affecting spatial development differently (in positive or negative terms). As things stand, however, there does appear to be a contradictory coexistence between the two; this is aggravated by inability of state and planning policy, in particular, to actively intervene in the changing spatial economy and society. Thus, there seems to be an inherent risk in the near future of having to cope only with the negative features produced by the two patterns which in a worstcase scenario could result in: continuous urban sprawl, non-planning and environmental degradation, increases in land values, overborrowing, reduction of public space and other socio-economic, functional and environmental bottlenecks.
Intersectionality and Feminist Politics
Authors: Yuval-Davis Nira
Published: July 2006

This article explores various analytical issues involved in conceptualizing the interrelationships of gender, class, race and ethnicity and other social divisions. It compares the debate on these issues that took place in Britain in the 1980s and around the 2001 UN World Conference Against Racism. It examines issues such as the relative helpfulness of additive or mutually constitutive models of intersectional social divisions; the different analytical levels at which social divisions need to be studied, their ontological base and their relations to each other. The final section of the article attempts critically to assess a specific intersectional methodological approach for engaging in aid and human rights work in the South.
MPL515 mutations in myeloproliferative and other myeloid disorders: a study of 1182 patients
Authors: Pardanani Animesh D. , Levine Ross L. , Lasho Terra , Pikman Yana , Mesa Ruben A. , Wadleigh Martha , Steensma David P. , Elliott Michelle A. , Wolanskyj Alexandra P. , Hogan William J. , McClure Rebecca F. , Litzow Mark R. , Gilliland D. Gary , Tefferi Ayalew
Published: July 2006

Recently, a gain-of-function MPL mutation, MPLW515L, was described in patients with JAK2V617F-negative myelofibrosis with myeloid metaplasia (MMM). To gain more information on mutational frequency, disease specificity, and clinical correlates, genomic DNA from 1182 patients with myeloproliferative and other myeloid disorders and 64 healthy controls was screened for MPL515 mutations, regardless of JAK2V617F mutational status: 290 with MMM, 242 with polycythemia vera, 318 with essential thrombocythemia (ET), 88 with myelodysplastic syndrome, 118 with chronic myelomonocytic leukemia, and 126 with acute myeloid leukemia (AML). MPL515 mutations, either MPLW515L (n = 17) or a previously undescribed MPLW515K (n = 5), were detected in 20 patients. The diagnosis of patients with mutant MPL alleles at the time of molecular testing was de novo MMM in 12 patients, ET in 4, post-ET MMM in 1, and MMM in blast crisis in 3. Six patients carried the MPLW515L and JAK2V617F alleles concurrently. We conclude that MPLW515L or MPLW515K mutations are present in patients with MMM or ET at a frequency of approximately 5% and 1%, respectively, but are not observed in patients with polycythemia vera (PV) or other myeloid disorders. Furthermore, MPL mutations may occur concurrently with the JAK2V617F mutation, suggesting that these alleles may have functional complementation in myeloproliferative disease.
Genetic variability in the precore and core promoter regions of hepatitis B virus strains in Karachi
Authors: Abbas Zaigham , Muzaffar Rana , Siddiqui Arif , Naqvi Syed Ali Anwar , Rizvi Syed Adibul Hassan
Published: July 2006

Background

Hepatitis B virus (HBV) genotypes have distinct geographic distribution. Moreover, much genetic variability has been described in the precore (PC) and basal core promoter (BCP) regions of the HBV genome. The local prevalence of HBV genotypes and mutations has not been well studied. The aim of the present study is to determine the prevalence of HBV genotypes and mutations in the PC and BCP region in HBV strains in Karachi.

Methods

A total of 109 chronic hepatitis B patients with detectable HBV DNA by a PCR assay were enrolled in the study. Sera were tested for HBeAg, anti-HBe antibody and liver profile. HBV genotypes and mutations in the PC and BCP regions were detected by INNO-LiPA line-probe assays.

Results

Of the 109 patients investigated, 38 (35%) were HBeAg positive while 71 (65%) were HBeAg negative. Genotype D was present in 100% of the patients. Two patients had co-infection with genotype A. There was no significant difference in the baseline characteristics, mean ALT levels, and presence of clinical cirrhosis in patients with HBeAg positive or negative strains with or without PC and BCP mutations. Of the 38 HBeAg positive patients, 9 (24%) had PC and BCP mutations. In the HBeAg negative patient group, mutations were detected in 44 (62%) of the strains investigated. More than one mutation was common, seen in 26 (37%) patients with HBeAg negative disease and 6 (16%) patients with HBeAg positive disease. Twelve (17%) HBeAg negative patients had dual T1762 and A1764 mutations. None of the HBeAg positive patients had T1762 mutation. Mutations were undetectable in 27 (38%) of patients with HBeAg negative disease.

Conclusion

Our study shows that type D is the main HBV genotype in Karachi, Pakistan. Significant numbers of patients infected with this genotype have PC and BCP variants. Mutations at more than one site are common. Patients harboring these mutants do not differ significantly in their clinical presentation from patients having wild type infection.
Porcine congenital splayleg is characterised by muscle fibre atrophy associated with relative rise in MAFbx and fall in P311expression
Authors: Ooi Peck-Toung , da Costa Nuno , Edgar Julia , Chang Kin-Chow
Published: July 2006

Background

Porcine congenital splayleg (PCS) is the most important congenital condition of piglets, associated with lameness and immobility, of unknown aetiology and pathogenesis, hence the need to better understand the condition by defining, in the first instance, its histopathology and molecular pathology.

Results

Semitendinosus, longissimus dorsi, and gastrocnemius muscles were removed from 4 sets of 2-day-old splayleg piglets, each with a corresponding normal litter mate. Based on immunohistochemistry and histological image analysis, PCS piglets showed significantly smaller fibre size without any accompanying sign of inflammation. Although there was no dramatic change in fibre type composition in affected muscles, several structural myosin heavy chain genes were significantly down-regulated. MAFbx, a major atrophy marker, was highly up-regulated in nearly all PCS muscles, in comparison with controls from normal litter mates. In contrast, P311, a novel 8 kDa protein, was relatively down-regulated in all the PCS muscles. To investigate a functional role of P311 in skeletal muscle, its full-length cDNA was over-expressed in murine C2C12 muscle cells, which resulted in enhanced cell proliferation with reduced myotube formation. Hence, reduced P311 expression in PCS piglets might contribute to atrophy through reduced muscle cell proliferation. P311, predictably, was down-regulated by the over-expression of calcineurin, a key signalling factor of muscle differentiation.

Conclusion

We demonstrated that PCS is a condition characterised by extensive fibre atrophy and raised fibre density, and propose that the combined differential expression of MAFbx and P311 is of potential in the diagnosis of subclinical PCS.
The cnidarian-bilaterian ancestor possessed at least 56 homeoboxes: evidence from the starlet sea anemone, Nematostella vectensis
Authors: Ryan Joseph F , Burton Patrick M , Mazza Maureen E , Kwong Grace K , Mullikin James C , Finnerty John R
Published: July 2006

Background

Homeodomain transcription factors are key components in the developmental toolkits of animals. While this gene superclass predates the evolutionary split between animals, plants, and fungi, many homeobox genes appear unique to animals. The origin of particular homeobox genes may, therefore, be associated with the evolution of particular animal traits. Here we report the first near-complete set of homeodomains from a basal (diploblastic) animal.

Results

Phylogenetic analyses were performed on 130 homeodomains from the sequenced genome of the sea anemone Nematostella vectensis along with 228 homeodomains from human and 97 homeodomains from Drosophila. The Nematostella homeodomains appear to be distributed among established homeodomain classes in the following fashion: 72 ANTP class; one HNF class; four LIM class; five POU class; 33 PRD class; five SINE class; and six TALE class. For four of the Nematostella homeodomains, there is disagreement between neighbor-joining and Bayesian trees regarding their class membership. A putative Nematostella CUT class gene is also identified.

Conclusion

The homeodomain superclass underwent extensive radiations prior to the evolutionary split between Cnidaria and Bilateria. Fifty-six homeodomain families found in human and/or fruit fly are also found in Nematostella, though seventeen families shared by human and fly appear absent in Nematostella. Homeodomain loss is also apparent in the bilaterian taxa: eight homeodomain families shared by Drosophila and Nematostella appear absent from human (CG13424, EMXLX, HOMEOBRAIN, MSXLX, NK7, REPO, ROUGH, and UNC4), and six homeodomain families shared by human and Nematostella appear absent from fruit fly (ALX, DMBX, DUX, HNF, POU1, and VAX).
Housing Reconstruction in Northern Sumatra after the December 2004 Great Sumatra Earthquake and Tsunami
Authors: Meisl Christopher S. , Safaie Sahar , Elwood Kenneth J. , Gupta Rishi , Kowsari Reza
Published: July 2006

The 26 December 2004 earthquake and tsunami resulted in over 100,000 damaged or destroyed homes and over 500,000 internally displaced people in northern Sumatra. Reconstruction and recovery from these massive losses requires the coordination of many stakeholders, including multiple levels of government, nongovernment relief organizations, donors, and the people of northern Sumatra. Although efforts have been taken by the Government of Indonesia to develop standards for the reconstruction of houses and establish a coordinating body, the reconstruction effort in Sumatra still faces many challenges. A broad range of housing types, with varying degrees of construction quality, have been constructed as part of the recovery effort. A field study team visited Banda Aceh, Meulaboh, and Nias seven months after the December event and documented the process of reconstruction, the interaction of the stakeholders, and the types of housing construction.
The Coast of Kenya Field Survey after the December 2004 Indian Ocean Tsunami
Authors: Weiss Robert , Bahlburg Heinrich
Published: July 2006

A field survey of the coast of Kenya was conducted after the 26 December 2004 Indian Ocean tsunami. We visited the coast between Mombasa and the Ngomeni Peninsula north of Malindi from 25 February to 4 March 2005. The tsunami struck the coast during the rising tide, but it caused little damage because warnings had been issued effectively and because large stretches of the coast are protected by reefs. These large stretches of protected coast end at Malindi, and the coasts to the north include sandy beaches and spits like the Ngomeni Peninsula. The maximum recorded runup at this peninsula was 3 m at 43 m from the water level at the time of the tsunami impact.
Survey of Geotechnical Engineering Aspects of the December 2004 Great Sumatra Earthquake and Indian Ocean Tsunami and the March 2005 Nias–Simeulue Earthquake
Authors: Sengara I. Wayan , Puspito Nanang , Kertapati Engkon , Hendarto
Published: July 2006

Reconnaissance surveys of building and infrastructure damage related to geotechnical engineering aspects were conducted four to six weeks after the 26 December 2004 earthquake and five weeks after the 28 March 2005 earthquake. These surveys identified many instances of building collapse and infrastructure damage that were probably caused by strong ground shaking and/or liquefaction-induced foundation or embankment failures. The survey results suggest the need for earthquake engineering research that identifies likely future earthquakes and their ground motion characteristics. Because of the observed variation in the level of damage, a seismic microzonation study should be performed to identify the spatial variability of strong ground shaking for the purpose of reconstruction and future planning of cities in Nangroe Aceh Darrusalam Province and Nias Island.
Social and Political Prerequisites for Recovery in Sri Lanka after the December 2004 Indian Ocean Tsunami
Authors: Godavitarne Chandra , Udu-gama Natasha , Sreetharan Mathini , Preuss Jane , Krimgold Frederick
Published: July 2006

On 26 December 2004, a devastating tsunami struck the coasts of 12 nations on the Indian Ocean. Over 300,000 people in 12 countries died in the wake of the tsunami, millions of housing units were damaged or destroyed, economies were devastated, and ecosystems were disrupted. The lessons from this catastrophe have worldwide implications, but the tragedies were local. Sri Lanka and the Aceh province of Indonesia suffered most of the casualties. The Sri Lankan experience illustrates that the recovery can be hindered by a country's social and political conditions. Challenges to recovery include the need for centralized coordination and organization, planning and development control, gathering planning data, political leadership, equitable distribution of recovery assistance, and disaster education.
Synthetic Studies of Rifamycins. VIII. An Improved Practical Synthesis of the Ansa-chain Compounds for the Rifamycin W Synthesis
Authors: Nakata Masaya , Toshima Kazunobu , Kai Toshiyuki , Kinoshita Mitsuhiro
Published: July 2006

The improved practical synthesis of 6,8,10-tri-O-acetyl-3-C-(acetoxymethyl)-3,5,7,9,11-pentadeoxy-1,2-O-isopropylidene-5,7,9,11-tetra-C-methyl-l-erythro-d-altro-β-l-talo-dodecodialdofuranose-(1,4) 12-(diethyl acetal) (3), a useful synthetic segment for the rifamycin W ansa-chain, is described. The key intermediate, 3-O-benzyl-2,4,7-trideoxy-5,6-O-isopropylidene-2,4-di-C-methyl-aldehydo-d-allo-heptose (22), was synthesized in a 29.4% yield from methyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-α-d-altropyranoside (8) in 15 steps. The coupling of 22 with the lithium reagent prepared from butyllithium and 3-C-(benzyloxymethyl)-3,5,6-trideoxy-5-iodo-1,2-O-isopropylidene-α-d-ribo-5-hexenofuranose afforded only the “Cram” product 24 in a 61% yield. The homogeneous hydrogenation of 24 with [RhCl(Ph3P)3] gave 8-O-benzyl-3-C-(benzyloxymethyl)-3,5,7,9,12-pentadeoxy-1,2:5,6-di-O-isopropylidene-5,7,9-tri-C-methyl-d-erythro-d-altro-l-talo-dodecofuranose-(1,4) (25) and its C-5 epimer in 95 and 3.8% yields respectively. 6,8-Di-O-benzyl-3-C-(benzyloxymethyl)-3,5,7,9-tetradeoxy-1,2-O-isopropylidene-5,7,9-tri-C-methyl-d-altro-β-l-talo-decodialdofuranose-(1,4), derived from 25 in a 91% yield, was subjected to coupling with 3,3-diethoxy-2-lithio-1-propene to afford about 1.7:1 excess of the “Cram” product (30, 59% yield). The conversion of 30 into 3 was accomplished by the sequence of reactions involving homogeneous hydrogenation, debenzylation, and acetylation in a 75% yield. The 24-step synthesis of 3 from 8 was achieved in a 7% overall yield.
X-Ray Fluorescence Study of Manganese Compounds at Stoichiometric Compositions
Authors: Ghodsi M , Duvigneaud P H , Glade G
Published: July 2006

Manganese oxides and other inorganic compounds were studied by electron induced X-ray fluorescence. Mn Lα energy shifts were measured with respect to pure manganese Lα maximum. Those shifts were shown to be a smooth function of manganese partial charge if the latter is calculated from Sanderson’s electronegativity scale. The results are in good agreement with Yokokawa’s previous work on oxides.
Kinetics and Mechanism of the Interaction of Iminodiacetate with cis-Tetraamminediaquacobalt(III) Ion in Acidic Media
Authors: Bhattacharya Prabir , Banerjee Pradyot
Published: July 2006

Kinetics of the reaction of iminodiacetate (Hida−) with cis-tetraamminediaquacobalt(III) have been studied spectrophotometrically at pH 3.0–4.15, [iminodiacetate]T=0.03–0.4. mol dm−3, I=0.5 mol dm−3 (NaClO4), in the temperature range 30–50 °C. The reaction is governed by the rate law:

rate={k−1+k1[iminodiacetate]T}[complex],

where k−1 and k1 denote the reverse aquation and anation rate constants respectively. At 40 °C the k−1 values increase with pH and show a limiting tendency at pH≈4. The pH-anation rate profile indicates no reaction at pH<1.5 and in the range 3.5–3.9, k1 remains constant. The pH dependence on rate is expressed as k1=kAKAH/([H+]+KAH), where kA is the anation rate arising from the aqua complex ion and Hida− species and KAH, the dissociation constant for the iminodiacetic acid. The value of kA at 40 °C=(5±0.02)×10−5 mol−1 dm3 s−1. The activation parameters, ΔH\eweq and ΔS\eweq for the anation step are 170±2 kJ mol−1 and 239±3 JK−1mol−1. The reaction is believed to operate through the initial complexation at the carboxylate end followed by a fast intramolecular proton transfer with simultaneous ring closure to form a chelated product. The complexation probably takes place through a dissociative interchange (Id) mechanism.
Kinetics and Mechanism of Ce(IV) Oxidation of Free and Coordinated Glyoxylic Acid
Authors: Mohanty Nirod Kumar , Nanda Rabindra Kumar
Published: July 2006

The kinetics and mechanism of Ce(IV) oxidation of glyoxylic acid and pentaammineglyoxylatocobalt(III) perchlorate have been investigated in acidic sulfate media in the temperature range 35 to 50 °C and at ionic strength 0.95 M. The rate of decrease of [Ce(IV)] was found to be first order in [substrate] and [Ce(IV)]. The observed second order rate constant, kobsd for the disappearance of [Ce(IV)] is satisfactorily given by,

k obsd=\frack1+k2K3[HSO4−]⁄[H+]1+K3[HSO4−]⁄[H+] (for glyoxylato complex)

and

k obsd=\frack11+K3[HSO4−]⁄H+] (for glyoxylic acid)

Both Ce(SO4)2 and [Ce(SO4)3]2− appear to be the oxidant species for coordinated glyoxylate while for free glyoxylic acid Ce(SO4)2 seems to be the only oxidant species. The values of k1 and k2 and the associated activation parameters have been computed. A suitable mechanism has been suggested for the reaction.
Aromatic Stabilization of the Dewar-Chatt-Duncanson Bonding Model
Authors: Aihara Jun-ichi
Published: July 2006

Metal–olefin complexes can be considered as aromatics if their conjugated systems are described well by the Dewar-Chatt-Duncanson bonding model.
Substituent Effects on Cation-extraction and Transport Properties of a Series of 4′-Substituted Benzo-15-Crown-5 Derivatives
Authors: Tsukube Hiroshi , Takagi Kentaro , Higashiyama Tatsuo , Iwachido Tadashi , Hayama Naomi
Published: July 2006

The substituent effects on chemical functions of benzo-15-crown-5 derivatives were found to be considerably large and often comparable to the ring-size effects. For example, 4′-aminobenzo-15-crown-5 transported K+ ion 14-times faster than 4′-nitrobenzo-15-crown-5, while 4′-nitrobenzo-18-crown-6 showed 12-times higher transport rate than 4′-nitrobenzo-15-crown-5.
Effect of the Electron Correlational Screening upon the Calculated Transition Energies of Aromatic Hydrocarbons
Authors: Hirano Koichi
Published: July 2006

A new formalism for two-center repulsion Γμν, including a correlational screening factor, is presented. As a criterion of the screening strength, a parameter ρ (defined by Eq. 13) was introduced. Using Γμν and ρ, transition energy calculations were performed for aromatic hydrocarbons based on the P.P.P scheme. Calculated transition energies decreases as ρ increases. Adjusting ρ, we can obtain correct values of the transition energies. That optimal ρ values extend over the region 0.3–0.5 indicates the extent of that electron correlation is intermediate. The screening caused by the Ohono–Klopman and Nishimoto-Mataga formulae is very close to that by Γμν’s whose ρ values are 0.2 and 0.6. A linear relationship was found between ρ and n, the number-density of π electrons. Making use of it, a trial calculation of the anthracece transition energies was made and obtained results were quite acceptable.
ESR and Mass-Spectrometric Studies of Methanol Combustion. I. The Correlation between Labile and Stable Chemical Entities in Free-Burning Methanol–Air Flames under Atmospheric Pressure
Authors: Taniguchi Masayuki , Yoshida Hiroshi
Published: July 2006

The concentration profiles of labile (H, O, and OH) and stable chemical entities (CH3OH, O2, CH2O, H2, H2O, and CO2) in premixed methanol–air flames under atmospheric pressure have been studied by the probesampling-ESR method combined with mass-spectrometric detection. The concentrations of the labile intermediates have been determined by correcting their destruction in the sampling probe caused by gas-phase reactions, wall reactions, and reactions at the pinhole of the probe. The observed profiles are in good agreement with the numerical model developed previously by Westbrook and Dryer, except that the concentration changes in all the entities are quicker than expected. The dependence of the maximum concentrations of the labile intermediates on the composition of the premixed gas is essentially the same as that observed for the methanol–air flames at low pressure.
The Crystal and Molecular Structures of 2,4,4,6-Tetraphenyl-1,4-dihydropyridine and 4-Benzyl-1-methyl-2,4,6-triphenyl-1,4-dihydropyridine
Authors: Iwasaki Fujiko , Watanabe Toshiya , Maeda Koko
Published: July 2006

The crystal structures of 2,4,4,6-Tetraphenyl-1,4-dihydropyridine (1) and 4-benzyl-1-methyl-2,4,6-triphenyl-1,4-dihydropyridine (2) have been determined by the X-ray method. The crystals of 1 are monoclinic, P21⁄a, a=12.883(1), b=12.953(1), c=12.575(1) Å, β=94.95(1)°, V=2090.7(2)Å3, Z=4, Dx=1.225 Mg m−3. 2 is triclinic P\bar1, a=7.786(1), b=14.324(1), c=10.759(1) Å, α=90.51(1), β=106.89(1), γ=92.02(1)°, V=1147.2(2)Å3, Z=2, Dx=1.196 Mg m−3. The final R values are 0.037 and 0.044 for 1 and 2, respectively. The 1,4-dihydropyridine ring of 1 is a flat twisted boat, while that of 2 has a boat conformation with the apexes at N(1) and C(4). For 1 the dihedral angles of the phenyl rings and the plane of four C atoms, C(2), C(3), C(5), and C(6), of the pyridine ring are 46.6, 106.4, 62.3, and 30.5° for 2-, 4-, 4-, and 6-phenyl rings, respectively. The corresponding angles of 2 are 30.4, 50.2, and 39.1° for 2-, 4-, and 6-phenyl rings. The phenyl ring of benzyl group covers to the pyridine ring making the dihedral angle between these planes of 133.7°. The bond between C(4) and the methylene carbon is 1.576 Å, which is longer than the normal Csp2–Csp3 length.
Construction of an Adiabatic High-Pressure Calorimeter Using Helium Gas for Pressurization
Authors: Yamamuro Osamu , Oguni Masaharu , Matsuo Takasuke , Suga Hiroshi
Published: July 2006

A novel adiabatic high-pressure calorimeter was constructed with using helium gas as a pressure transmitting medium. It works under a constant pressure up to 250 MPa in the temperature range from 12 to 370 K. Sample cell is made of Be–Cu alloy and has internal volume of 26 cm3. The pressure transmitting tube is connected to an external pressure-control system, which enables to keep automatically the inner pressure constant within ±1 kPa over the whole pressure and temperature ranges. Thus the thermodynamic path that any specimen follows during the heat capacity measurement can be described unambiguously. Heat capacities of the sample cells loaded without and with 158.9 MPa He gas were measured in the temperature range from 25 to 370 K. The imprecision of heat capacity data of the compressed He gas was within 0.3%. Thus the present calorimeter enables us to extend the low-temperature thermodynamic study on various kinds of materials to high pressures without a significant loss of the claimed precision.
Extraction Equilibria of Hydrochloric Acid by Trioctylamine in Low-Polar Organic Solvents
Authors: Kojima Takashi , Fukutomi Hiroshi
Published: July 2006

Two-phase emf titrations have been performed for the extraction of hydrochloric acid from aqueous solution containing 1 M NaCl (M=mol dm−3) by trioctylamine (TOA) dissolved in cyclohexane, toluene, benzene, chlorobenzene, nitrobenzene, cyclohexane–benzene mixtures, and benzene–nitrobenzene mixtures. It has been found that the extraction is accompanied with the formation of monomeric trioctylammonium chloride and its successive aggregation from dimer to micell (n-mer) in organic phase: ‾TOA+H++Cl−=‾TOAHCl, Kd; (‾TOAHCl)i−1+‾TOAHCl=(‾TOAHCl)i, \barKi(i=2,3,···,n), where the concentration quotients of successive aggregation, \barKi, satisfy the relation 2 \barK2=3\barK3⁄2=···=n\barKn⁄(n−1). The quotients Kd and \barK2 vary with the total volume fraction of TOA in organic phase, ΨR°, according to equations, In Kd=1nKd°+gΨR° and 1n \barK2=1n\barK2°+h\barΨR°. Diluent effect on the equilibrium constants Kd° and \barK2° are discussed in detail based on the theory of regular solution.
Simultaneous Determinations of Inorganic and Organic Acids by Ion Chromatography
Authors: Itoh Hisaaki , Shinbori Yoshio
Published: July 2006

The elution behavior of seven common inorganic anions (F−, Cl−, NO2−, Br−, NO3−, SO42−, and phosphate) and a large number of organic acids in an AS-5 separator column using a weak carbonate eluent was examined and the possibility of simultaneous determinations of the inorganic and organic acids in a single injection was investigated. For pharmaceutical samples, such as a Ringer’s solution which contains some inorganic anions and a single organic anion as anion contents, each anion could be simultaneously analyzed with a relative standard deviation of below 0.6%. Furthermore, it was found that even in a sample such as the liquor of canned goods having a complex matrix, both inorganic and dicarboxylic acid contents could be simultaneously analyzed without any tedious pretreatment, except for a simple dilution with distilled and deionized water. For the liquor samples, the relative standard deviation for five measurments was less than 5.0%.
The Identification of Insoluble Adducts of Lewis Acids with Bases by Extension of the Continuous Variation Method to Solid-Liquid Reactions
Authors: Hihara Goro , Mitani Kazuhiro , Miyamae Hiroshi , Nagata Miharu
Published: July 2006

A method has been developed for identifying occurrence and composition of all the insoluble adducts formed in solid-liquid reactions by extension of the continuous variation method to the heterogeneous systems that were produced by the reactions of PbX2 (X=Cl, Br, and I) with ethylenediamine(=en) in ethanol solution. Four new adducts, PbX2·i(en) (i=1⁄2 and 1; X=Cl and Br), were found. The developed method was effective in identifying formation of the adducts such as PbCl2·1/2(en) and PbBr2·1/2(en) whose formation is liable to be overlooked in extending the mole ratio method to solid-liquid reactions.
Solid Phase Synthesis of Oligodeoxyribonucleotides Utilizing the Phenylthio Group as a Phosphate Protecting Group
Authors: Matsuzaki Jun-ichi , Kohno Kyoko , Tahara Shin-ichiro , Sekine Mitsuo , Hata Tsujiaki
Published: July 2006

Oligodeoxyribonucleotide synthesis utilizing the phenylthio group as a phosphate protecting group was applied to the solid phase method. The base residues of deoxyguanosine and deoxyadenosine were protected with bis(isobutyryloxy)ethylene (Bibe) and phthaloyl groups to avoid the base modification and depurination, respectively. A key synthetic intermediate of N2-isobutyryl-N1,N2-bis(isobutyryloxy)ethylenedeoxyguanosine was prepared in high yield by four-step reaction from deoxyguanosine and used for preparation of the building blocks of deoxyguanosine required for the polymer support synthesis. Two kinds of polymer supports, i.e., 1% cross-linked polystyrene and controlled pore glass were chosen. The latter was employed for the synthesis of dodecadeoxyribonucleotides by using an automated DNA synthesizer.
Synthesis of 2,2-Di-C-methyl-2-deoxy- and 4,4-Di-C-methyl-4-deoxypyranosides via Michael Addition of Conjugated Enopyranosiduloses
Authors: Kawauchi Nobuya , Sato Ken-ichi , Yoshimura Juji , Hashimoto Hironobu
Published: July 2006

Three hexopyranosides having gem-di-C-methyl group at 2- or 4-positions were synthesized by Michael addition to 2-enopyranosid-4-ulose and 3-enopyranosid-2-ulose derivatives, respectively, followed by hydroboration. A heptopyranosid-6-ulose having gem-di-C-methyl group at C–4 was also synthesized from 4-enopyranosid-6-ulose derivative in a similar way.
Selective 1,4-Chiral Induction in the Reaction of Enolates Generated from t-Butyl δ-Hydroxy Carboxylates
Authors: Narasaka Koichi , Ukaji Yutaka , Watanabe Kazutoshi
Published: July 2006

Lithium enolates generated from t-butyl esters of δ-hydroxy carboxylic acids with lithium dialkylamides in THF–HMPA were alkylated stereoselectively to give the corresponding syn-α-alkylated δ-hydroxy esters. The generation of the enolates was accelerated by the addition of lithium trifluoromethanesulfonate, and the successive aldol and hydroxylation reactions of the enolates also proceeded in a stereoselective manner.
Photo-Excitable Membranes. Effects of Nonactin as a Membrane Adtive on the Photoresponse of Poly(vinyl chloride)/Spirobenzopyran Membrane
Authors: Anzai Jun-ichi , Hasebe Yasushi , Ueno Akihiko , Osa Tetsuo
Published: July 2006

The magnitude of the photoinduced membrane potential across the poly(vinyl chloride)/spirobenzopyran/nonactin composite membrane depends considerably on the concentration of ammonium ion in the aqueous solution. The results are explained in terms of the charge density on the membrane surface.
Hexacarbonylmolybdenum(0)-Catalyzed Reaction of Allylic Carbonates with Arylsulfonyl-Stabilized Carbanions
Authors: Masuyama Yoshiro , Hirai Hidenori , Kurusu Yasuhiko , Segawa Koh-ichi
Published: July 2006

p-Tolylsulfonylacetonitrile reacted with allylic carbonates in the presence of a catalytic amount of hexacarbonylmolybdenum(0) to give monoallylated derivatives. Using sodium hydride as a base, methyl p-tolylsulfonylacetate reacted with those to give mixtures of mono- and di-allylated derivatives. No nucleophilic attack of bulky bis-(phenylsulfonyl)methane occurred, whether sodium hydride was present or absent.
Hexacarbonylmolybdenum(0)-Catalyzed Reductive Coupling of Allylic Acetates
Authors: Masuyama Yoshiro , Otake Kiyotaka , Kurusu Yasuhiko
Published: July 2006

The reaction of allylic acetates with zinc in the presence of a catalytic amount of hexacarbonylmolybdenum(0) led to reductive coupling for the formation of a 1,5-diene framework. Reductive coupling of nerolidyl acetate provided squalene and its isomers in high yield.
Synthesis on 1,4-Diaminocyclitol Antibiotics. III. Synthesis of 4-Hydroxypurpurosamine B Derivatives
Authors: Kanai Kazuaki , Sakamoto Itsuki , Ogawa Seiichiro , Suami Tetsuo
Published: July 2006

Methyl 2,6-di-N-acetyl-4-hydroxy-6-epi-α-purpurosaminide B and -4-hydroxy-α-purpurosaminide B have been prepared from d-glucosamine by sequence of reactions including stereoselective nitro aldol reaction.
Synthesis on 1,4-Diaminocyclitol Antibiotics. V. Synthesis of 3′-Enofortimicin D
Authors: Kanai Kazuaki , Yokoi Shigeki , Ogawa Seiichiro , Suami Tetsuo
Published: July 2006

3′-Enofortimicin D has been prepared by condensation of 1-O-acetyl-2,6-bis(2,4-dinitrophenylamino)-2,3,4,6-tetradeoxy-d-erythro-hex-3-enopyranose with 2,5-di-O-benzoyl-1,4-bis-N-(methoxycarbonyl)fortamine B, followed by deprotection.
Vertical Profiles of CCl3F, CCl2F2, and CH4 in the Stratosphere and Troposphere over Japan as Observed by Balloon Grab-Sampling and by Gas-Chromatographic Analysis
Authors: Makide Yoshihiro , Yokohata Akihito , Tominaga Takeshi , Honda Hideyuki , Kubo Haruya , Itoh Tomizo
Published: July 2006

Stratospheric and tropospheric air samples were collected by means of a balloon-borne grab-sampler launched from Sanriku (39°N, 142°E) in the late summers of 1981, 1983, and 1984. The mixing ratios of CCl3F and CCl2F2 were determined precisely by using gas chromatography with ECD, and that of CH4, by gas chromatography with FID. The vertical profiles of these compounds are presented and compared with the model calculations.
Generation and Reactions of Phosphorin 1-Sulfides
Authors: Tanaka Hideyuki , Motoki Shinichi
Published: July 2006

Phosphorin 1-sulfides generated by the thermolysis of 1-phospha-2-thiabicyclo[4.4.0]deca-3,7,9-triene 1-sulfides reacted with triphenylphosphine, dienophiles, or nucleophiles to give the corresponding phosphorins, 1-phosphabicyclo[2.2.0]octa-2,5-diene 1-sulfide, or 1,2-dihydrophosphorin 1-sulfide derivatives, respectively.
Homogeneous Isomerization of 1-Butene Catalyzed by [MX2(PR3)2]–NaBH4 Systems (M=Co, Ni, X=Halides, SCN, PR3=PPhnEt3−n)− Acceleration by Phosphine Addition and Stereoselectivity
Authors: Kanai Hiroyoshi , Sakaki Shigeyoshi , Sakatani Takenobu
Published: July 2006

The stoichiometric or a little excess amount of NaBH4 was treated with [MX2(PR3)2] (M=Co, Ni, X= halides, SCN, PR3=PPhnEt3−n) in THF–1,2-dimethoxyethane to form monohydride species which were active for isomerization of 1-butene. The reaction was accelerated by excess PPh3 in [CoX2(PPh3)2]–NaBH4 systems. Other catalytic systems have optimum ratios of excess phosphine to metal for getting maximum activities. Thiocyanate–metal complexes are the most active in each Co– and Ni–catalyst system. Cisselectivity depends on the cone angle of PR3, the size of anion ligands, and the congested structure of complexes.
Epitaxial Growth and Its Growth Mechanism in Physical Vapor Deposited Films of Alkyl Octadecanoates
Authors: Takamoto Michiko , Ogihara Seiji , Yase Kiyoshi , Okada Masakazu
Published: July 2006

Esters of octadecanoic acid and three primary alcohols such as methanol, ethanol, and propanol were deposited on substrates of potassium chloride (KCl), mica and amorphous carbon film under vacuum. The surface morphology of their films was observed by transmission electron microscope. They grew epitaxially to form the rectangular crystals with lateral molecular orientations on KCl substrate. On the other hand, ester molecules tend to arrange normal to the surface of mica and amorphous carbon film and construct the molecular layers like to Langmuir-Blodgett films. The crystal axis relationship between esters and KCl(001) surface was followed; c-axisester is parallel to 〈110〉KCl direction and 〈110〉ester direction inclines with an angle of about ±16° corresponding to 〈110〉KCl. These molecules had resemble crystal structures with trans configuration in the ester moiety. The optimum temperatures of substrates in the former epitaxial growth exist and the temperature decreases in proportion to the chain length of alcohol group with the discrepancy of about 10 to 30 °C.
Additivity Law for the Activity of a Counter Ion in Ion-Exchange Resin
Authors: Kimizuka Hideo , Waki Hirohiko , Matsubara Akira , Arimoto Y\={o}ichi
Published: July 2006

The ion-exchange resin–electrolyte solution equilibria were studied on the basis of thermodynamics. The experimental results showed that the external salt activity divided by the co-ion concentration in the ion-exchange resins was linear against the co-ion concentration in the resin. The equilibria were consistently explained by a partition coefficient of salt distribution with the additivity law for the counter ions in the ion-exchange resin. A thermodynamic expression for the ion-exchange reaction was also discussed.
129I Mössbauer Spectroscopic Study of 2:3 Molecular Complexes of Triphenylphosphine Sulfide–Iodine and Acridine–Iodine
Authors: Sakai Hiroshi , Maeda Yutaka
Published: July 2006

The 129I Mössbauer effect has been applied to investigate 2:3 molecular complexes of triphenylphosphine sulfide–iodine and acridine–iodine. The Mössbauer spectra indicate the presence of three unequivalent iodine sites (IA, IB, and IC), as expected from the crystallographic data of these complexes. The iodine atom (IA) coordinating to the sulfur or nitrogen atom of each donor molecule is more positively charged than that of the 1:1 molecular complex containing the same donor atom. This result can be interpreted in terms of the covalency of the S···IA or N···IA bond. The degrees of charge transfer in the 2:3 complexes are close to those in the 1:1 complexes, and the transferred charges are mainly localized on the terminal iodine atoms (IB). The iodine molecule (IC) cross-linked to two IB atoms has a slightly negative charge, consistent with the bond distance of the molecule. The iodine moieties of these complexes are very similar to the structure of I82− in Cs2I8.
Conductance Matrix of Amphoteric Ion-Exchange Membrane in Three Ion System
Authors: Yamauchi Akira , Shinohara Hitoshi , Shinoda Makoto , Date Masashi , Hirata Yutaka , Kimizuka Hideo
Published: July 2006

A conductance matrix describing the ion-transport phenomena in the membrane-three ion system has been determined. It was indicated there that six independent experiments were required in order to determine six independent elements of the conductance matrix. The NaCl–CaCl2–amphoteric membrane system was chosen as the three ion system, and three kinds of fluxes, two kinds of transport numbers, and the membrane conductance were measured. Nine elements were experimentally determined on the assumption of Onsager’s reciprocal relation. The results showed that the order of elements in conductance matrix was gCaCa>gClCl>gNaNa>gCaCl>gNaCl>gCaNa. In addition, it was pointed out that the interactions among ions can never be ignored when the ion-transport phenomena across membrane are studied.
Synthesis and Properties of 5,10,15,20-Tetrakis(3,5-di-t-butyl-2-nitrophenyl)porphyrin: Conformational Stabilities of the Respective Atropisomers and Oxygenation Capabilities of the Iron(III) and Manganese(III) Complexes
Authors: Miyamoto T Ken , Takagi Shigeru , Hasegawa Tai , Tsuzuki Seizi , Takahashi Eitaro , Okude Kojiro , Banno Itsuki , Sasaki Yukiyoshi
Published: July 2006

The synthesis and properties of new, bulky atropisomeric porphyrins are described. Four atropisomers of 5,10,15,20-tetrakis(3,5-di-t-butyl-2-nitrophenyl)porphyrins has been easily separated and purified by column chromatography. The isomers all have different thermal stabilities toward atropisomerization. Below 60 °C, however, they have rather high conformational stabilities, and an iron(III) or manganese(III) ion has been incorporated into each isomer, with a retention of the ligand conformation. By the use of these metal complexes, the catalytic oxygenation reactions, i.e., the epoxidation of olefins (styrene, α-methylstyrene, cyclohexene, and cyclooctene) and the hydroxylation of alkanes (cyclohexane and heptane), have been done in the presence of hypochlorite or iodosylbenzene as an oxidant. Products analyses by GLC show that these new complexes effectively catalyze the oxygenations in higher yields or in more selective ways, than the corresponding TPP complexes.
Calorimetric and Spectrophotometric Studies of Bromo Complexes of Copper(II) in N,N-Dimethylformamide
Authors: Ishiguro Shin-ichi , Ozutsumi Kazuhiko , Nagy László , Ohtaki Hitoshi
Published: July 2006

Complexation of copper(II) with Br− ions has been studied by calorimetry and spectrophotometry in N,N-dimethylformamide (DMF) containing 0.16 mol dm−3 (C2H5)4NClO4, 1 mol dm−3 LiClO4, and 1 mol dm−3 NH4ClO4 as constant ionic media at 25 °C. Calorimetric titration curves obtained in each solution were well explained in terms of formation of [CuBrn](2−n)+ (n=1–4) and their formation constants, enthalpies and entropies were determined. Electronic spectra of individual copper(II) bromo complexes were also determined in the (C2H5)4NClO4, LiClO4, and NH4ClO4 DMF solutions over the range 260–500 nm, the spectra of each complex being kept practically unchanged in these solutions. The complexation of copper(II) with Br− ions is considerably weaker in the LiClO4 solution than in the (C2H5)4NClO4 one and is even more weakened in the NH4ClO4 solution due to the formation of LiBr and NH4Br ion pairs in the relevant solutions. The variation of the stepwise enthalpy and entropy values suggests that the coordination structure around copper(II) ion changes from octahedral to tetrahedral at the formation of [CuBr3]−. The result for the complexation between copper(II) and bromide ions thus obtained was compared with that for the complexation between the metal and chloride ions.
Thermal Rearrangement of 2,5-Bis(allyloxy)tropone, Revisited. Formation of Four Thermolysates under the Claisen Rearrangement Conditions and Structure Revision of the Major Thermolysate
Authors: Takeshita Hitoshi , Mori Akira , Goto Yasutomo , Nagao Tomohiro
Published: July 2006

A reinvestigation of the Claisen rearrangement of 2,5-bis(allyloxy)tropone led to the isolation of three diallyl-5-hydroxytropolones along with an intermediary thermolysate, 3-allyl-5-allyloxytropolone. The structure of the formerly identified product was revised from 3,6-diallyl-5-hydroxytropolone to 4,6-diallyl-5-hydroxytropolone. The involvement of no cleavage-recombination process was established by cross-over deuterium labelling experiments. These derivatives were respectively converted to p-tropoquinones, one of which was further converted to a cyclohepta[b]pyranone derivative by an electrochemical reaction.
Convenient Methods for the Preparation of Vinylic and Allylic Sulfones from Alkenes, Haloalkanes, and Aldehydes. Stereochemistry of the Conversion of Vinylic Sulfones to the Corresponding Allylic Sulfones
Authors: Inomata Katsuhiko , Sasaoka Shin-ichi , Kobayashi Toshifumi , Tanaka Yuhji , Igarashi Susumu , Ohtani Takashi , Kinoshita Hideki , Kotake Hiroshi
Published: July 2006

1- or 2-p-Tolylsulfonyl(=tosyl)-1-alkenes, vinylic sulfones, were regioselectively prepared from 1-alkenes via iodosulfonization or sulfonylmercuration and also from 1-haloalkanes by the homologation or unhomologation methods. The vinylic sulfones thus prepared were further converted to the corresponding allylic sulfones under basic conditions. The stereochemistry of this conversion was discussed. One-carbon homologated allylic sulfones were directly obtained from aldehydes in good yields by the reaction with diethyl phenylsulfonylmethylphosphonate and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under mild conditions.
Redox-Photosensitized Reactions. XIV. Photochemistry of 4-Alkylated NADH Models, 1-Benzyl-4-(1-hydroxyalkyl)-1,4-dihydronicotinamides
Authors: Ishitani Osamu , Yanagida Shozo , Takamuku Setsuo , Pac Cyongjin
Published: July 2006

There were investigated photochemical behaviors of 4-alkylated 1-benzyl-1,4-dihydronicotinamides (1a–c) having R1R2C(OH) as the substituent (a: R1=Ph and R2=H; b: R1=Ph and R2=CF3; c: R1=p-NC–C6H4 and R2=H). The direct photolysis of 1a–c gave R1R2CO and the dimers of the dihydronicotinamide (BNA) fragment along with a minor amount of [C6H5CH(OH)]2, being thus interpreted in terms of the homolysis between the R1R2(OH) and BNA moieties. In the [Ru(bpy)3]2+-photosensitized reactions, it is suggested that 1a–c+· was generated as a key intermediate by electron transfer to excited [Ru(bpy)3]2+, undergoing a bond cleavage to give R1R2CO and the BNA. dimers. In the case of 1c, however, R1R2CH(OH) was formed, being attributed to a product from 1c−· that is formed by electron transfer from [Ru(bpy)3]+ to 1c.
Oxidation of 2,4-Alkadienoic Esters with Selenium Dioxide. A New Synthesis of Furans and Selenophenes
Authors: Tsuboi Sadao , Mimura Shigetoshi , Ono Shin-ichiro , Watanabe Kenji , Takeda Akira
Published: July 2006

Direct oxidation of 2,4-alkadienoic esters with selenium dioxide gave 5-alkyl-2-furancarboxylic esters along with 5-alkyl-2-selenophenecarboxylic esters. Ethyl 5-methylfurancarboxylate was converted to 5-hydroxymethyl-2-furancarbaldehyde, a component of honey, via ethyl 5-bromomethyl-2-furancarboxylate (5) in good yield. The compound 5 was converted to (5-ethoxycarbonyl-2-furyl)methyl dimethyldithiocarbamate possessing fungicidal activity. Reaction of triphenylphosphonium salt of 5 with nonanal gave ethyl 5-(1-decenyl)-2-furancarboxylate (E/Z=88:12) in 86% yield. Ethyl 5-methyl-2-selenophenecarboxylate was also converted to ethyl 5-(1-decenyl)-2-selenophenecarboxylate (E/Z=7:3) in 30% total yield.
Chemo- and Regioselective Reduction of Epoxides with Sodium Borohydride in Mixed Solvent Containing Methanol
Authors: Ookawa Atsuhiro , Hiratsuka Hiroshi , Soai Kenso
Published: July 2006

Mono- and gem-disubstituted epoxides were reduced to more substituted alcohols in good to high yields (73–100%) and in high regioselectivities (89–100:11–0) by sodium borohydride in a mixed solvent of t-butyl alcohol–methanol or 1,2-dimethoxyethane-methanol. The reaction of disubstituted epoxide depends on the steric hindrance and the position of the substituents. Trisubstituted epoxides were not reduced by the present reducing system. The reactivity order of epoxides by the present reducing system was mono->2,2-di->2,3-di->>trisubstituted epoxides. The chemoselectivity of the present reducing system is excellent. Thus, epoxides were selectively reduced in the presence of such reducible groups as carbamoyl, carboxyl, nitro, cyano, and bromo.
Photoresponsive Crown Ethers. 19. Photocontrol of Reversible Association-Dissociation Phenomena in “Tail(Ammonium)-Biting” Crown Ethers
Authors: Shinkai Seiji , Yoshida Tohru , Miyazaki Kiminori , Manabe Osamu
Published: July 2006

The aggregation properties of photoresponsive crown ethers (1) having a crown ring and an ammonioalkyl (H3N+–(CH2)n−, n=4, 6, 10) group attached to the two sides of an azobenzene have been evaluated through the measurements of average molecular weights and electric conductance. Osmometric determination of average molecular weights established that all trans-isomers (trans-1 (n=4, 6, 10)) form the pseudocyclic dimers due to intermolecular crown-ammonium complexation. Photoisomerized cis-1 (n=6) and cis-1 (n=10), which have been designed so that intramolecular “biting” of the ammonio group to the crown can occur upon photoisomerization, existed as the discrete monomers. On the other hand, cis-1 (n=4), which cannot form the intramolecular “tail-biting” complex because of the short tetramethylene spacer, existed as the pseudo-cyclic dimer. This difference was well reflected by electric conductance: in 1 (n=6) and 1 (n=10), the conductance increased synchronously with trans-to-cis photoisomerization and decreased with cis-to-trans photoisomerization. Such a photoresponsive conductance change was scarcely detected for 1 (n=4). Furthermore, the additives which enforce dissociation of the dimeric species to the monomeric species suppressed the magnitude of the photoinduced conductance change. This is a novel example that the light energy is transmitted to the conductance change.