bluuebunny/crossref_metadata_2025 huggingface dataset:
Tumor growth or regression: powered by inflammation
Authors: Nelson Delia , Ganss Ruth
Published: July 2006

Malignant cells thrive in a highly specialized, stromal environment, which harbors support cells, blood vessels, and diverse leukocyte populations. There is increasing evidence that “by default”, intratumoral inflammation fosters angiogenic and vasculogenic processes and simultaneously creates an immunosuppressive micromilieu. This self-amplifying loop of proangiogenic inflammation represents a serious obstacle for adaptive anticancer immune responses. However, angiogenesis is a highly dynamic process, which can be reversed in the “right” inflammatory context; this in turn facilitates immune effector cell entry and tumor rejection. Thus, we propose that a shift from proangiogenic to antiangiogenic inflammation creates a tumor environment permissive for immune destruction. This is a new concept, which integrates antiangiogenic and immune therapeutic treatment modalities.
Dual role of macrophages in tumor growth and angiogenesis
Authors: Lamagna Chrystelle , Aurrand-Lions Michel , Imhof Beat A
Published: July 2006

During the neoplastic progression, macrophages as well as dendritic and NK cells are attracted into the tumor site and initiate the immune response against transformed cells. They activate and present tumor antigens to T cells, which are then activated to kill tumor cells. However, tumor cells are often capable of escaping the immune machinery. As the immune surveillance is not sufficient anymore, tumor-associated macrophages contribute to tumor progression. It is notable that tumor-associated macrophages promote the proliferation of tumor cells directly by secreting growth factors. They also participate in tumor progression by acting on endothelial cells and thus promoting the neovascularization of the tumor. Tumor-associated macrophages are indeed key protagonists during angiogenesis and promote each step of the angiogenesis cascade.
Coastal Ecosystems and Tsunami Protection after the December 2004 Indian Ocean Tsunami
Authors: Chang Stephanie E. , Adams Beverley J. , Alder Jacqueline , Berke Philip R. , Chuenpagdee Ratana , Ghosh Shubharoop , Wabnitz Colette
Published: July 2006

An exploratory study was conducted on the role of coastal ecosystems in protecting communities from the December 2004 Indian Ocean tsunami, focusing on mangrove forests on the Andaman coast of Thailand and how well villages were undertaking environmental conservation. Remote sensing analysis identified predisaster mangrove change and postdisaster structural damage and landscape changes. Field data from five sites (20 villages), gathered via the VIEWS™ data collection system, validated and supplemented this analysis. Key informants at several of these villages were also interviewed. A preliminary comparison of villages that otherwise faced similar tsunami exposure suggests that the presence of healthy mangroves did afford substantial protection. Village performance in mangrove conservation and management efforts, and thus the presence of healthy forests, is influenced by both social capital and the design of external aid delivery programs.
Somalia Field Survey after the December 2004 Indian Ocean Tsunami
Authors: Fritz Hermann M. , Borrero Jose C.
Published: July 2006

The 26 December 2004 tsunami severely affected Somalia, with some 300 deaths at a distance of 5,000 km from the epicenter of the magnitude 9.0 earthquake. Somalia's physical characteristics allowed a detailed assessment of the far-field impact of a tsunami in the main propagation direction. The UNESCO mission surveyed five impacted towns south of the Horn of Africa along the Puntland coast in northern Somalia: Eyl, Bandarbeyla, Foar, Xaafuun, and Bargaal. The international team members visited Somalia during 2–10 March 2005. The team measured tsunami runup heights and local flow depths on the basis of the location of watermarks on buildings and eyewitness accounts. Maximum runup heights were typically on the order of 5–9 m. Each measurement was located by means of global positioning systems (GPS) and was photographed. Numerous eyewitness interviews were recorded on video.
Post-December 2004 Tsunami Reconstruction in Sri Lanka and Its Potential Impacts on Future Vulnerability
Authors: Khazai Bijan , Franco Guillermo , Ingram J. Carter , Rumbaitis del Rio Cristina , Dias Priyan , Dissanayake Ranjith , Chandratilake Ravihansa , Kanna S. Jothy
Published: July 2006

The 26 December 2004 tsunami displaced more than 500,000 people and killed an estimated 31,000 in Sri Lanka. Damage was not uniform, often reflecting distinct patterns of social, infrastructural, and ecological vulnerability. Severely affected populations tended to be poorer, to live in fragile structures, and to be more exposed to the tsunami as a result of prior environmental degradation in the coastal zone. The massive reconstruction effort may further decrease the resilience of rural communities by degrading the natural environment that sustains their livelihoods. A sustainable reconstruction approach must therefore consider long-term solutions that increase community resilience by fostering socioeconomic, infrastructural, and environmental progress. A reconnaissance team monitored the initial recovery stages and identified mechanisms in supporting research on reducing the long-term vulnerability of human settlements and ecosystems to future environmental hazards.
Smong: How an Oral History Saved Thousands on Indonesia's Simeulue Island during the December 2004 and March 2005 Tsunamis
Authors: McAdoo Brian G. , Dengler Lori , Prasetya Gegar , Titov Vasily
Published: July 2006

The tsunamis on 26 December 2004 and 28 March 2005 killed only 7 people on Simeulue Island in Indonesia's Aceh province. At Langi, on the north end of Simeulue, which is 40 km south of the December earthquake's epicenter, maximum wave heights exceeded 10 m less than 10 minutes after the shaking ceased. In the more populous south, wave heights averaged 3 m and caused significant structural damage, destroying entire villages. Oral histories recount a massive 1907 tsunami and advise running to the hills after “significant” shaking (∼1 minute). All the interviewed Simeulue survivors knew of this event and of the necessary action. However, Jantang, on the Aceh mainland, suffered far more casualties. Simeulue's oral history provided an extraordinarily powerful mitigation tool that saved countless lives where even a high-tech warning system with a 15-minute response time would have been of no help.
Response and Recovery in India after the December 2004 Great Sumatra Earthquake and Indian Ocean Tsunami
Authors: Murty C. V. R. , Jain Sudhir K. , Sheth Alpa R. , Jaiswal Arvind , Dash Suresh R.
Published: July 2006

The rescue and relief work undertaken in the Andaman and Nicobar islands and in mainland India after the 26 December 2004 Indian Ocean tsunami was massive. A number of new initiatives undertaken by the government and nongovernmental agencies were innovative and successful. Also, since the tsunami was not a typical disaster for India, it raised a number of new concerns related to reconstruction along the coast.
Myanmar Coastal Area Field Survey after the December 2004 Indian Ocean Tsunami
Authors: Swe Tint Lwin , Satake Kenji , Aung Than Tin , Sawai Yuki , Okamura Yukinobu , Win Kyaw Soe , Swe Win , Swe Chit , Tun Soe Thura , Soe Maung Maung , Oo Thantzin , Zaw Saw Htwe
Published: July 2006

A post-tsunami survey was conducted along the Myanmar coast two months after the 2004 Great Sumatra earthquake ( Mw=9.0) that occurred off the west coast of Sumatra and generated a devastating tsunami around the Indian Ocean. Visual observations, measurements, and a survey of local people's experiences with the tsunami indicated some reasons why less damage and fewer casualties occurred in Myanmar than in other countries around the Indian Ocean. The tide level at the measured sites was calibrated with reference to a real-time tsunami datum, and the tsunami tide level range was 2–3 m for 22 localities in Myanmar. The tsunami arrived three to four hours after the earthquake.
Investigation of Tsunami-Induced Damage and Fragility of Buildings in Thailand after the December 2004 Indian Ocean Tsunami
Authors: Ruangrassamee Anat , Yanagisawa Hideaki , Foytong Piyawat , Lukkunaprasit Panitan , Koshimura Shunichi , Imamura Fumihiko
Published: July 2006

The December 2004 Indian Ocean tsunami caused human loss and devastating damage to civil engineering structures along the west coast of southern Thailand. This damage was investigated to evaluate the vulnerability of structures. Criteria for post-tsunami investigation were developed, and a database system was established to manage and present the data. The database of reinforced concrete (RC) buildings was then analyzed to find the relationship between the damage level and (a) the distance from the shoreline or (b) the inundation height. A representative RC column's capacity to resist lateral forces was measured by a full-scale loading test to gain insight into the relationship between the observed damage and the actual structural performance.
Performance of Structures in Indonesia during the December 2004 Great Sumatra Earthquake and Indian Ocean Tsunami
Authors: Saatcioglu Murat , Ghobarah Ahmed , Nistor Ioan
Published: July 2006

A reconnaissance was conducted in Indonesia to investigate the effects of the 26 December 2004 earthquake and tsunami on buildings, bridges, and other physical infrastructure. The infrastructure in the coastal regions of Banda Aceh was completely devastated by both tsunami wave pressures and seismic ground excitations. The damaging effects of the tsunami were most pronounced in unreinforced masonry walls, nonengineered reinforced concrete buildings, and low-rise timber-framed buildings. Engineered structures survived the tsunami pressure, but many suffered extensive damage due to seismic forces. The majority of the seismic damage was attributed to poor design and detailing of nonductile buildings. Specific observations made during the reconnaissance indicate the engineering significance of the disaster.
Performance of Structures in Thailand during the December 2004 Great Sumatra Earthquake and Indian Ocean Tsunami
Authors: Saatcioglu Murat , Ghobarah Ahmed , Nistor Ion
Published: July 2006

A reconnaissance was conducted in Thailand to investigate the effects of the 26 December 2004 tsunami on buildings, bridges, and other physical infrastructure. It was observed that nonengineered reinforced concrete buildings, low-rise timber frames, and unreinforced masonry walls suffered extensive damage from hydrodynamic pressures generated by the tsunami. A large number of nonengineered reinforced concrete frame buildings experienced partial or total collapse, while well-designed engineered structures survived the tsunami with little or no damage. Specific observations made during the reconnaissance indicate the engineering significance of the disaster.
Andaman Seacoast of Thailand Field Survey after the December 2004 Indian Ocean Tsunami
Authors: Siripong Absornsuda
Published: July 2006

The post-tsunami runups on the damaged Andaman Sea coastline of Thailand from the tsunami of 26 December 2004 were surveyed by Thai and Korean teams for 99 transects from 23 January to 7 February 2005. The highest runup in Thailand was 15.68 m at Cape Coral, in Phang-nga province, and the longest inundation distance was 3 km at Bang Nieng, in Phang-nga province. The causes of the variation in runup were analyzed by using the method of splitting tsunami (MOST) model, tide gauges, satellite imagery, and field data with topographic charts. The distribution of runups reflects the effects of bathymetry, coastal topography, coastline configuration and slope, the pattern and density of land use, and the biological and geomorphological characteristics of offshore and near-shore areas.
Runup Measurements of the December 2004 Indian Ocean Tsunami
Authors: Synolakis Costas E. , Kong Laura
Published: July 2006

We summarize some of the findings and observations from the field surveys conducted in the aftermath of the horrific tsunami of 26 December 2004 and reported in this issue. All these field surveys represent an unprecedented scientific undertaking and involved both local and international scientists working side by side. The 26 December tsunami was the first with transoceanic impact, since comprehensive postevent hydrodynamic surveys began to be conducted in the early 1990s with modern measurement tools. The tsunami impacted at least 16 nations directly: Indonesia, Malaysia, Thailand, Myanmar, India, Sri Lanka, Oman, Somalia, Kenya, Tanzania, Madagascar, the Maldives, Rodrigues, Mauritius, Réunion, and the Seychelles. The death toll included citizens from many other countries in Asia, Europe, the South Pacific, and the Americas, giving this tsunami the grim distinction of being the first universal natural disaster of modern times.
Developmental and Tissue-Specific Involvement of Peroxisome Proliferator-Activated Receptor-α in the Control of Mouse Uncoupling Protein-3 Gene Expression
Authors: Pedraza Neus , Rosell Meritxell , Villarroya Joan , Iglesias Roser , Gonzalez Frank J. , Solanes Gemma , Villarroya Francesc
Published: July 2006

Uncoupling protein-3 (UCP3) is a member of the mitochondrial carrier family expressed preferentially in skeletal muscle and heart. It appears to be involved in metabolic handling of fatty acids in a way that minimizes excessive production of reactive oxygen species. Fatty acids are powerful regulators of UCP3 gene transcription. We have found that the role of peroxisome proliferator-activated receptor-α (PPARα) on the control of UCP3 gene expression depends on the tissue and developmental stage. In adults, UCP3 mRNA expression is unaltered in skeletal muscle from PPARα-null mice both in basal conditions and under the stimulus of starvation. In contrast, UCP3 mRNA is down-regulated in adult heart both in fed and fasted PPARα-null mice. This occurs despite the increased levels of free fatty acids caused by fasting in PPARα-null mice. In neonates, PPARα-null mice show impaired UCP3 mRNA expression in skeletal muscle in response to milk intake, and this is not a result of reduced free fatty acid levels. The murine UCP3 promoter is activated by fatty acids through either PPARα or PPARδ but not by PPARγ or retinoid X receptor alone. PPARδ-dependent activation could be a potential compensatory mechanism to ensure appropriate expression of UCP3 gene in adult skeletal muscle in the absence of PPARα. However, among transcripts from other PPARα and PPARδ target genes, only those acutely induced by milk intake in wild-type neonates were altered in muscle or heart from PPARα-null neonates. Thus, PPARα-dependent regulation is required for appropriate gene regulation of UCP3 as part of the subset of fatty-acid-responsive genes in neonatal muscle and heart.
The multiple personalities of Alix
Authors: Odorizzi Greg
Published: July 2006

Alix is a cytosolic protein in mammalian cells that was originally identified on the basis of its association with pro-apoptotic signaling. More recent evidence has established that Alix has a hand in regulating other cellular mechanisms, including endocytic membrane trafficking and cell adhesion. Although Alix appears to participate directly in these various activities, the role it plays in each process has largely been inferred from the functions of proteins with which it interacts. For example, recruitment of Alix to endosomes is mediated by its N-terminal Bro1 domain, the structure of which was recently solved for its yeast orthologue, Bro1. The diversity of Alix functions is due to its proline-rich C-terminus, which provides multiple protein-binding sites. With this blueprint in hand, we can now ask whether Alix acts simply as an adaptor that links different proteins into networks or, instead, contributes a specific function to distinct molecular machineries.
Self Aggregation of Cationic Porphyrin in Water
Authors: Kano Koji , Nakajima Takeshi , Takei Masao , Hashimoto Shizunobu
Published: July 2006

Self aggregation of 4,4′,4″,4'″-(21H,23H-porphine-5,10,15,20-tetrayl)tetrakis[1-methylpyridinium] cation (TMPyP4+) in water has been verified by means of fluorescence and 1H NMR spectroscopy. The novel fluorescence behavior of TMPyP such as extraordinarily red-shifted Q(0-0) fluorescence band, blue shift of this band upon dilution, effects of added sodium chloride and sodium dodecyl sulfate micelles, and short fluorescence lifetime strongly suggests the formation of a stacking-type dimer of TMPyP4+ at the TMPyP concentrations above 1×10−6 mol dm−3. The 1H NMR signal due to the porphyrin ring protons was observed as a broad singlet even though the concentration of TMPyP in D2O was 1×10−5 mol dm−3 while the signal in DMSO-d6 was a sharp singlet, suggesting the spontaneous association of TMPyP4+ to form the face-to-face dimer having a considerably loose structure. The π–π interaction has been assumed to be enhanced upon photoexcitation.
Nonstoichiometry and Electrical Resistivity in Two Mixed Metal Oxides, La2NiO4−x and LaSrNiO4−x
Authors: Ishikawa Kenji , Kondo Shin-ichi , Okano Hirofumi , Suzuki Shigenori , Suzuki Yasuo
Published: July 2006

Two mixed oxides, La2NiO4−x and LaSrNiO4−x, had the K2NiF4 structure in the oxygen-pressure range from 58000 down to 130 Pa at 1173 K. The oxygen-vacancy concentration, x, in both La2NiO4−x and in LaSrNiO4−x at 1173 K was determined by thermogravimetric analysis in the oxygen-pressure range from 58000 to 1.3 Pa. The vacancy concentration of LaSrNiO4−x was greater than that of La2NiO4−x at the same oxygen pressure at 1173 K. The electrical resistivities of La2NiO4−x and LaSrNiO4−x were measured at 473–1173 K under an oxygen atmosphere at 98–58000 Pa. The density of the state and the drift mobility of oxygen stoichiometric La2NiO4 and LaSrNiO4 were estimated from the resistivity data and from the results on the thermogravimetric analysis.
Effect of Sodium Dodecyl Sulfate on Spectral Properties of Five- and Six-Coordinate Nitrosyl(protoporphyrin IX dimethyl esterato)iron(II) Complexes
Authors: Yoshimura Tetsuhiko
Published: July 2006

EPR and electronic spectra of five- and six-coordinate nitrosyl(protoporphyrin IX dimethyl esterato)iron(II) (Fe(ppixdme)(NO)) complexes as model systems for nitrosylhemoproteins have been investigated in the absence and the presence of sodium dodecyl sulfate (SDS). Dimethyl sulfoxide, an O-donor ligand, is weakly coordinated to iron in an axial vacant position trans to a nitrosyl group in Fe(ppixdme)(NO). Upon addition of SDS to Fe(ppixdme)(NO) in dimethyl sulfoxide, EPR and electronic spectra were changed into five-coordinate type spectra. On the other hand, the addition of SDS to Fe(ppixdme)(NO)(NMeIm) in dimethyl sulfoxide resulted in EPR and electronic spectra arising from a mixture of five- and six-coordinate complexes. Accordingly, sodium dodecyl sulfate was found to hinder the interaction of dimethyl sulfoxide with the sixth axial vacant position of Fe(ppixdme)(NO), and to cleave only partly the iron to imidazole bond in Fe(ppixdme)(NO)(NMeIm) complex.
Mixed Ligand Complexes of Trivalent Metal Ions with an Amine-N-polycarboxylate and Fluoride
Authors: Yuchi Akio , Hotta Hitoshi , Wada Hiroko , Nakagawa Genkichi
Published: July 2006

The formation constants of the mixed ligand complexes MLF(M : Al3+, Ga3+, In3+, Fe3+, Sc3+, Y3+, La3+; L: nta3−, hedta3−, edta4−, cdta4−) were determined. Reactivity of a trivalent metal ion with fluoride generally decreases by the coordination of an amine-N-polycarboxylate. From the decrease the structures of the parent and mixed ligand complexes are discussed.
Syntheses and Properties of [1,1′-Bis(α-Aminoisobutyric Acid)]Gramicidin S and [1-α-Aminoisobutyric Acid]Semigramicidin S
Authors: Kondo Michio , Kimura Mikio , Sato Ken-ichi , Horimoto Hideaki
Published: July 2006

Analogs of gramicidin S, [1,1′-bis(α-aminoisobutyric acid)]gramicidin S (18) and [1-α-aminoisobutyric acid] semigramicidin S (11), have been synthesized by a conventional solution method. The cyclization reactions of a linear pentapeptide active ester and a linear decapeptide active ester yielded exclusively a protected cyclic pentapeptide and a protected cyclic decapeptide, respectively. After deprotection of these peptides, we obtained the final products (11 and 18). The mobility of 18 in paper electrophoresis was the same as that of gramicidin S, however, the CD spectrum of 18 in a methanol solution showed a markedly different pattern from that of gramicidin S. Both analogs (11 and 18) are inactive against the Gram-positive microorganisms tested. The results suggest that the positions of the valine residues in gramicidin S require a hydrophobic amino acid having l-configuration to show activity.
Autoxidation of Guaiazulene and 4,6,8-Trimethylazulene in Polar Aprotic Solvent: Structural Proof for Products
Authors: Matsubara Yoshiharu , Takekuma Shin-ichi , Yokoi Katsumi , Yamamoto Hiroshi , Nozoe Tetsuo
Published: July 2006

Autoxidation of guaiazulene and 4,6,8-trimethylazulene at 100–120°C in DMF (or HMPA) respectively yielded 25 and 17 separable products, including several known compounds. Most of these new compounds were derivatives of 1,5- and 1,7-azulenequinone, 1H-inden-1-one, naphthoquinone, and benzenoid, or dimeric and trimeric forms; structures of these products were established on the basis of spectroscopic (NMR, UV, IR, and MS) and half-wave potential (E1⁄2) data. 1H NMR (200-MHz) parameters of various azulene derivatives are given for comparative study. Possible reaction pathways are suggested for the formation of such a wide variety of interesting products.
Asymmetric Hydrogenation of N,N′-Dimethyl-5-alkylidene- and arylmethylenehydantoins Catalyzed by (Achiral Base)bis(dimethylglyoximato)cobalt(II)-Chiral Cocatalyst System
Authors: Takeuchi Seiji , Ohgo Yoshiaki
Published: July 2006

Asymmetric hydrogenation of N,N′-dimethyl-5-alkylidene- and arylmethylenehydantoins catalyzed by an achiral base coordinated bis(dimethylglyoximato)cobalt(II)-chiral 2-quinuclidinecarboxamide was examined. Attempts resulted in a maximum optical yield in this system (82.1% ee), strongly supporting a proposed asymmetric hydrogenation mechanism in which the chiral base acts as a proton donor, namely, a cocatalyst.
Carbonate Formation from Oxiranes and Carbon Dioxide Catalyzed by Organotin Halide-Tetraalkylphosphonium Halide Complexes
Authors: Baba Akio , Nozaki Takashi , Matsuda Haruo
Published: July 2006

Cycloaddition of carbon dioxide to oxiranes was excellently promoted by the complexes of organotin halides and tetraalkylonium halides, while either components of the complexes had no catalytic activity individually. Particularly, the complex composed of Bu3SnI–Bu4PI was the most favorable catalyst, yielding a variety of fivemembered cyclic carbonates under neutral and mild conditions.
Studies on the Lattice Dynamics in Ferrocene Derivatives by Means of Recoil-Free Fraction and Thermal Shift in Mössbauer Spectra
Authors: Iwai Kumiko , Katada Motomi , Motoyama Izumi , Sano Hirotoshi
Published: July 2006

Lattice dynamics in ferrocene derivatives, mono- and disubstituted acetyl-, carboxy-, and ethylferrocenes, tetrachloro(1,1′-diacetylferrocenato-O,O′)tin(IV) and tetrachlorobis(acetylferrocenato-O)tin(IV) have been studied by determining the temperature dependence of the recoil-free fraction and the thermal shift in the Mössbauer spectra. It was found that the lattice vibrations in acetyl- and carboxyferrocenes and adducts could be satisfactorily explained by assuming a harmonic oscillation model, while those of ethyl-substituted ferrocenes could not be interpreted by assuming harmonic vibrations.
Glycinoeclepins, Natural Hatching Stimuli for the Soybean Cyst Nematode, Heterodera Glycines. I. Isolation
Authors: Masamune Tadashi , Anetai Masaki , Fukuzawa Akio , Takasugi Mitsuo , Matsue Hideki , Kobayashi Kiroku , Ueno Shoji , Katsui Nobukatsu
Published: July 2006

Hatching stimuli, designated as glycinoeclepins, for the soybean cyst nematode (Heterodera glycines) have been isolated by repeated chromatography of the aqueous extracts of dried roots of kidney bean (Phaseolus vulgaris), one of the host plants of the nematode. One of these compounds, glycinoeclepin A, stimulates the hatching and emergence of larvae in vitro in highly diluted aqueous solutions.
Photoreduction of Anthraquinone by Triethylamine in Ethanol and Toluene Studied by Steady-State Photolysis and Laser Photolysis
Authors: Hamanoue Kumao , Nakayama Toshihiro , Yamamoto Yoshiaki , Sawada Kazuhide , Yuhara Yoshihito , Teranishi Hiroshi
Published: July 2006

Photoreduction of anthraquinone (AQ) by triethylamine (TEA) in toluene and ethanol was studied by means of steady-state photolysis and laser photolysis. In toluene, addition of TEA enhanced the quantum yield of photoreduction of AQ, and the reaction was found to originate via the formation of an exciplex between ground-state TEA and the lowest triplet state of AQ: This exciplex changed to a contact ion pair followed by proton transfer, generating anthrasemiquinone radical and triethylamine radical, and 9,10-anthracenediol was obtained as the final photoproduct. Although the mechanism of the photoreduction of AQ in ethanol/TEA was essentially the same as that in toluene/TEA and the final products in ethanol/TEA were 9,10-anthracenediol and its anion, the quantum yield of photoreduction decreased with increase in TEA concentration. It was proposed that the exciplex in ethanol was quenched by ground-state TEA via the formation of a triplex of a radical anion of AQ and a radical cation of TEA dimer bonded by the three σ-electrons on two nitrogen atoms, based on the suggestion made by Hub et al. (J. Am. Chem. Soc., 106, 701 (1984); 106, 708 (1984)).
Three-Component Coupling Synthesis of Prostaglandins: The Aldol Route
Authors: Suzuki Masaaki , Kawagishi Toshio , Yanagisawa Akira , Suzuki Takehiko , Okamura Noriaki , Noyori Ryoji
Published: July 2006

A one-pot, high yield construction of the whole prostaglandin (PG) skeleton is accomplishable by combination of the copper-mediated conjugate addition of an ω side-chain unit to a 4R-oxygenated 2-cyclopentenone derivative and aldol condensation of the in situ generated enolate with an α side-chain aldehyde. Subsequent removal of the 7-hydroxyl group from the adducts and deblocking of the protective groups give PGs of E series. PGE1 has been prepared in 56% overall yield through the five-step sequence. Selective transformation of the PGE to PGD structure can be realized simply by appropriate selection of the hydroxyl protective groups in the five-membered ring and ω side-chain units. The vicinal carba-condensation using methyl 6-formyl-5-hexynoate as the α side-chain aldehyde unit followed by deoxygenation from the aldol products gives the 5,6-didehydro-PGE2 derivatives which serve as key intermediates in the general synthesis of various natural PGs. An efficient method for resolution of 4-hydroxy-2-cyclopentenone is also described.
Copper(II)–Lanthanoid(III) Complexes of Binucleating Ligands Derived from 3-Formylsalicylic Acid and Diamines
Authors: Sakamoto Masatomi , Takagi Minoru , Ishimori Tomitaro , Okawa Hisashi
Published: July 2006

Heterometal binuclear complexes, [CuLn(fsaen)(H2O)n](NO3) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; n=4–5) and [CuLn(fsapn)(H2O)4](NO3) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, or Dy) have been synthesized and characterized, where H4fsaen and H4fsapn denote N,N′-bis(3-carboxysalicylidene)ethylenediamine and N,N′-bis(3-carboxysalicylidene)-1,2-propanediamine, respectively. The ligand field band due to the copper(II) ion bound to the N2O2-site is at 18.5×103–19.5×103 cm−1 for [CuLn(fsaen)(H2O)n](NO3) and 18.4×103–19.2×103 cm−1 for [CuLn(fsapn)(H2O)4](NO3), which are higher frequencies than those of the mononuclear complexes, [Cu(H2fsaen)](H2O)0.5 and [Cu(H2fsapn)](H2O)0.5 (18.3×103 and 18.4×103 cm−1, respectively). When the complexes are dissolved in pyridine (Py), dimethyl sulfoxide (DMSO), or N,N-dimethylformamide (DMF), the d–d band frequency decreases in the order of the solvent DMSO>DMF>Py for the binuclear complexes, whereas it decreases in the order of DMF>DMSO>Py for the mononuclear complexes. These trends were discussed in terms of the different affinities of solvent molecules for copper(II) and lanthanoid(III) ions. No significant magnetic spin-exchange interaction occurred between metal ions.
Syntheses and Reactions of Allylic and Homoallylic Pyrophosphate Tetraesters
Authors: Butsugan Yasuo , Nagai Kenji , Nagaya Fumitoshi , Tabuchi Hiroki , Yamada Katsuhisa , Araki Shuki
Published: July 2006

Pyrophosphate tetraesters possessing allylic and homoallylic side chains were synthesized. Reaction of alkyl allyl (and 3-methyl-3-butenyl) phosphorochloridates with sodium hydrogencarbonate gave P1,P2-dialkyl P1,P2-diallyl [and P1,P2-bis(3-methyl-3-butenyl)] pyrophosphates. Condensation of alkyl allyl (and 3-methyl-3-butenyl) phosphorochloridates with dialkyl phosphates gave trialkyl allyl (and 3-methyl-3-butenyl) pyrophosphates. Reactions of crotyl (2-butenyl) pyrophosphates with various nucleophiles such as phenolic ethers, aromatic amines, and nitrogen-containing heterocycles in the presence of boron trifluoride etherate gave good to moderate yields of crotylated products. The crotyl pyrophosphates were found to be much more reactive than the corresponding orthophosphate esters.
Regioselective Para Halogenation of Substituted Benzenes with Benzeneseleninyl Chloride and Aluminum Halide
Authors: Kamigata Nobumasa , Satoh Takeshi , Yoshida Masato , Matsuyama Haruo , Kameyama Masayuki
Published: July 2006

In the presence of aluminum halide, benzeneseleninyl chloride is an efficient regioselective halogenating reagent for activated aromatics such as toluene, phenol, anisole, phenetole, diphenyl ether, and N,N-dimethylaniline. Benzene and chlorobenzene are not halogenated under similar conditions.
Formation of 1,4,2,5-Dithiadiazines as a Heterocyclic System by Reaction of 1,4,2-Dithiazolium Salts with Sulfenamides
Authors: Yonemoto Katsumi , Shibuya Isao , Honda Kazumasa
Published: July 2006

The first example of application of sulfenamides for ring expansion on nitrogen atom has been reported to give 1,4,2,5-dithiadiazines (3) from 1,4,2-dithiazolium salts (1). The structure of 3 was confirmed by X-ray crystallographic analysis. The similar ring expansion reaction occurred on 1,3-dithiolium salts (5) to afford 1,4,2-dithiazines (6).
A Simple and Convenient Synthesis of Aryl-Substituted Push–Pull Butadienes from 1,1-Diaryl-2-Propyn-1-ols
Authors: Nakatsuji Shin’ichi , Nakashima Kenichiro , Iyoda Masahiko , Akiyama Shuzo
Published: July 2006

1,1-Diaryl-2-propyn-1-ol derivatives reacted with several nucleophiles to afford novel 1,1-diarylbutadiene systems. An efficient one-step synthesis of aryl-substituted push–pull butadiene systems was achieved by this reaction.
Structural Study of Lithium, Magnesium, and Barium Vanadate Glasses by Means of Mössbauer Spectroscopy
Authors: Nishida Tetsuaki , Saruwatari Setsuko , Takashima Yoshimasa
Published: July 2006

All the isomer shifts for Li2O–, MgO–, and BaO–V2O5 glasses containing 10 mol% Fe2O3 are in a range of 0.39–0.37 mm s−1, indicating that iron is present as tetrahedral Fe3+ ions. This suggests that all the Fe3+ ions are present at the substitutional sites of tetrahedral V5+ or V4+ ions constituting the skeleton of each glass matrix. Distinct decreases in the quadrupole splitting and the glass transition temperatures are observed when Li2O is incorporated into V2O5 matrix, suggesting a gradual change of the glass matrix from the layer structure originally composed of VO5 tetragonal pyramids to a chain structure composed of VO4 tetrahedra. This structural change is essentially the same as that of Na2O– and K2O–V2O5 glasses. On the other hand, simultaneous increases in the quadrupole splitting and the glass transition temperatures are observed with increasing MgO or BaO content in the case of MgO– and BaO–V2O5 glasses. This suggests a gradual change of the glass matrix from the original layer structure to a highly complicated three-dimensional network structure composed of VO4 tetrahedra, similarly to the case of P2O5–V2O5 glasses.
The Synthesis of Methyl (15S)-16-Hydroxydehydroabietate and Its (15R)-Epimer
Authors: Matsumoto Takashi , Imai Sachihiko , Hayashi Noriaki
Published: July 2006

In order to elucidate the absolute configuration of C-15 in natural 16-hydroxydehydroabietic acid, a metabolite of (+)-dehydroabietic acid in rabbits, methyl (+)-dehydroabietate was transformed into methyl (15S)-16-hydroxy-8,11,13-abietatrien-18-oate (3a) and its (15R)-epimer (3b). The synthetic 3a was identical with a methyl ester derived from the natural acid. Thus, the absolute configuration of C-15 in natural 16-hydroxydehydroabietic acid was conclusively assigned as an S-configuration.
Catalytic Properties of Perovskite-Type Mixed Oxides (ABO3) Consisting of Rare Earth and 3d Transition Metals. The Roles of the A- and B-Site Ions
Authors: Nitadori Taihei , Ichiki Tatsumi , Misono Makoto
Published: July 2006

The catalytic activities of perovskite-type mixed oxides (LnBO3 and Ln0.8Sr0.2CoO3, Ln=rare-earth (lanthanoid) elements, B=3d transition metals) for the oxidation of propane and methanol have been studied comparatively. It has been found that the catalytic activities of LnBO3 were principally determined by the B-site elements and were similar to those of the corresponding oxides of the B-site elements. The roles of the rare-earth ions of the A-site were secondary as long as they were trivalent. Upon the partial replacement of Ln3+ by Sr2+, the catalytic activities of LnCoO3 increased several times, the magnitude of the increase being similar among all the rare-earth ions. These results demonstrate that the kind and the valence of a B-site metal are of primary importance for the control of the catalytic activity for oxidation, almost regardless of the kind of trivalent rare-earth elements at the A-site.
The Volumes of Hydrated Glucose, Sucrose and Raffinose Molecules, and the Osmotic Pressures of These Aqueous Saccharide Solutions as Measured by the Freezing-Point-Depression Method
Authors: Kiyosawa Keitaro
Published: July 2006

The osmotic pressures of aqueous saccharide solutions were calculated from the data obtained by means of the freezing-point-depression method. Thus, the water activity and the osmotic pressure of d-glucose, sucrose, and raffinose solutions were measured by the freezing-point-depression method. For dilute aqueous saccharide solutions, the freezing-point depression was proportional to their molal concentrations. However, the higher the molal concentration, the larger the freezing-point depression observed became than those to be expected from the molal concentration dependent on the size of the saccharide molecules. The osmotic pressures calculated from the data of the freezing-point-depression method were compared with those measured with semi-permeable membranes by Morse and his colleagues. To obtain the apparent volumes of hydrated d-glucose, sucrose, and raffinose molecules, their partial molal volumes were measured, together with the partial molal volumes of the water of their solutions. The partial molal volumes of the water were verified to be equal to the molar volumes of pure water up to the highest concentrations examined. The apparent volumes of the hydrated d-glucose, sucrose, and raffinose molecules were calculated to be 0.1865, 0.3525, and 0.5105 nm3 respectively.
The Crystal and Molecular Structure of Aquachloro (meso-tetraphenylporphyrinato)cobalt(III)
Authors: Iimura Yasuhiro , Sakurai Tosio , Yamamoto Kiyoko
Published: July 2006

The crystal and molecular structure of the title compounds, [CoIIICl(tpp)(H2O)], has been determined by means of X-ray diffraction techniques. The compound crystallizes in the monoclinic system; space group P21⁄c. The unit cell has a=13.542(2), b=25.760(2), c=10.423(1) Å, β=99.33(2)°, and Z=4. The cobalt atom is coordinated by four porphyrinato nitrogen atoms, one chlorine atom, and one oxygen atom of water, and is displaced by 0.039(2) Å from the mean plane defined by the four porphyrinato nitrogen atoms towards the axial chlorine atom. The average Co–N(tpp) distance is 1.955(2) Å. The Co–Cl distance is 2.216(1), and the Co–O(water) distance, 1.979(3) Å. The porphyrinato core is significantly ruffled and has an approximate \bar4 symmetry. The [CoIIICl(tpp)(H2O)] molecules are stacked along the c axis by O–H···Cl hydrogen bonds.
The Reaction of Oxiranes with Carbon Disulfide under High Pressure
Authors: Taguchi Yoichi , Yanagiya Koshin , Shibuya Isao , Suhara Yasuo
Published: July 2006

The reaction of 2,2-dimetyloxirane with carbon disulfide in the presence of triethylamine was accelerated under high pressure to give 5,5-dimethyl-1,3-oxathiolane-2-thione in a high yield, while 2-hexyloxirane under the same reaction condition formeds 4-hexyl-1,3-dithiolane-2-thione (2b) as the main product and 5-hexyl-1,3-oxathiolane-2-thione (1b) as a minor product. A feasible mechanism for this formation is that 1b and 2-hexylthiirane (4b) are produced in the first stage of reaction, and that 2b is then formed by the reaction of 1b or 4b with carbon disulfide. In reactions of a variety of oxiranes with carbon disulfide, 1,3-dithiolane-2-thiones were obtained in high yields under 800 MPa at 100 °C within 20 h. Concerning the effect of substituents in oxiranes, the selectivity for product 2b is in the decreasing order; 2-phenyl->2-methyl->2-ethyl->2-hexyl->2,3-tetramethylene->2,2-dimethyl->2-(chloromethyl)-. Tertiary amines, such as N,N-dimethylethylamine, pyridine, and N-methylmorpholine, serve as good catalysts for the reaction.
The Liquid-Phase Oxidation of p-Methoxytoluene to p-Anisaldehyde with Co(OAc)2/Ce(OAc)3/Cr(OAc)3 Catalyst
Authors: Kitajima Nobumasa , Sunaga Shigeru , Moro-oka Yoshihiko , Yoshikuni Tadatsugu , Akada Mitsuo , Tomotaki Yoshihisa , Taniguchi Masatoshi
Published: July 2006

The liquid-phase oxidation of p-methoxy toluene to p-anisaldehyde in the presence of Co based catalysts has been studied. With Co(OAc)2 alone in acetic acid as a solvent, only a trace amount of p-anisaldehyde could be obtained; however, upon the addition of a second metal salt (e.g., Mn(OAc)2 or Ce(OAc)3) a considerable improvement in the yield (up to 60%) was observed. The synergism of Co and the second component as well as the optimization of the reaction conditions were investigated. Co(OAc)2–Ce(OAc)3–Cr(OAc)3 (3:1:2) was finally found to be the most effective catalytic system, which gave a 76% yield of p-anisaldehyde under 3 atm O2 at 110° for 3 h.
Metal Colloids Produced by Means of Gas Evaporation Technique. V. Colloidal Dispersion of Au Fine Particles to Hexane, Poor Dispersion Medium for Metal Sol
Authors: Satoh Naoki , Kimura Keisaku
Published: July 2006

Metal fine particles are not dispersed at all in pure solvents with a low dielectric constant, such as hexane. The gas flow-cold trap method combined with surfactants was found to be effective in stabilizing ultrafine metal particles in solvents with a low dielectric constant. Ultrafine gold particles can be stably dispersed in hexane in a colloidal state by this method. It was found that the stabilizability of the colloid depends on the ionic types of the surfactant. Thus, a cationic surfactant such as dimethyldioctadecylammonium chloride (DOAC) shows good dispersibility, whereas an anionic surfactant such as 1,2-bis(2-ethylhexyloxycarbonyl)ethanesulfonate (AOT) dose not. The optical spectra of colloid solutions suggest a difference in the local colloidal state between two types of surfactants. Colloidal solutions of a gold fine particle/DOAC/hexane system are so stable against heating or drying that the solvents are easily substituted.
Stereoselective Synthesis of Conjugated 2,4-Alkadienoates via the Palladium-Catalyzed Cross-Coupling of 1-Alkenylboronates with 3-Bromo-2-alkenoates
Authors: Yanagi Teiji , Oh-e Takayuki , Miyaura Norio , Suzuki Akira
Published: July 2006

(2E,4E)-, (2Z,4E)-, and (2E,4Z)-2,4-Alkadienoates can be synthesized in high yields by the cross-coupling of ethyl (E)-3-bromoacrylate, methyl (E)-3-bromo-2-methylpropenoate, ethyl (Z)-3-bromocrotonate,1-bromo-2-(ethoxycarbonyl)cyclohexene, and 4-bromocoumarin with 2-[(E)-1-alkenyl]-1,3,2-benzodioxaboroles or diisopropyl (Z)-1-hexenylboronate in the presence of 3 mol% of Pd(OAc)2, 6 mol% of PPh3, and 2 equivalents of Na2CO3 or K2CO3 in alcoholic solvents while retaining the original configuration of the double bonds in β-bromo esters and 1-alkenylboronates. Although the coupling reaction with 1-hexenylboronate with (Z)-3-bromoacrylate gave a mixture of ethyl (2Z,4E)- and (2E,4E)-nonadienoates in a ratio of 63 : 37, it was found that the use of bis(diphenylphosphino)ferrocene as a ligand of palladium brought about the stereoselective coupling under mild conditions.
DECOMPOSITION OF DITHIOCARBAMATES. IV. METHYLDITHIOCARBAMATE TO METHYLISOTHIOCYANATE IN ALKALINE SOLUTIONS
Authors: Takami Fumitaka , Wakahara Shigeru , Maeda Takashi
Published: July 2006

The title reaction was investigated over a range of pH 8 ∼ H− 18.2. The rate-pH profile fits with an equation kobs = k(H+)/(K + (H+)). The decomposition proceeds directly via IV but not via its conjugate base V. The rate dependence on the initial concentration of IV is also discussed.
REACTIONS OF CARBON DIOXIDE WITH TRANSITION METAL ALKOXIDES
Authors: Hidai Masanobu , Hikita Tomoji , Uchida Yasuzo
Published: July 2006

Alkoxides of transition metals, such as Fe, Ti, Nb, and Zr, were found to react with atmospheric carbon dioxide in benzene solution at 30°C. The measurement of CO2 volume absorbed and IR data suggest that transition metal alkoxides are partially carbonated.
LEUCOTHOL B AND C, FURTHER EXAMPLES OF ANTHRADITERPENOIDS FROM LEUCOTHOE GRAYANA MAX.
Authors: Hamanaka Nobuyuki , Miyakoshi Hidehiro , Furusaki Akio , Matsumoto Takeshi
Published: July 2006

The structure of leucothol B, a new diterpenoid from Leucothoe grayana Max., has been determined as 1 by X-ray crystallographic analysis. Leucothol C has been characterized as 2 by spectroscopic and chemical means.
A NOVEL SYNTHESIS OF N-CARBOXY-α-AMINO ACID ANHYDRIDE
Authors: Oya Masanao , Katakai Ryoichi , Nakai Hiroyuki , Iwakura Yoshio
Published: July 2006

N-Carboxy-α-amino acid anhydrides were prepared by the reaction of α-amino acids with trichloromethyl chloroformate. The yields were good to moderate, and the products obtained were as pure as those obtained by a conventional way using phosgene.
CRYSTAL STRUCTURE OF CYTIDINE-SALICYLIC ACID COMPLEX
Authors: Tamura Chihiro , Yoshikawa Masako , Sato Sadao , Hata Tadashi
Published: July 2006

Crystal and molecular structure of cytidine-salicylic acid complex has been determined by X-ray diffraction methods and refined by block diagonal least-squares technique to the R-index of 4.7%. Hydrogen bonds in the complex are formed between the imidine and carboxyl groups.
THE ENDOR SPECTRA OF t-BUTYLPHENYLNITROXIDE
Authors: Ishizu Kazuhiko , Nagai Hiroshi , Mukai Kazuo , Kohno Masahiro , Yamamoto Takamitsu
Published: July 2006

The ENDOR spectrum of t-butylphenylnitroxide were observed in either toluene or ethyl alcohol, and the solvent effects on the proton hyperfine coupling constants were investigated. Based on the Allendoerfer and Maki’s correction, the observed ENDOR intensities were compared with those calculated from the electron spin–spin relaxation time, T2.
GLASS FORMATION IN THE Ln–Al–O SYSTEM (Ln: LANTHANOID AND YTTRIUM ELEMENTS)
Authors: Yajima Seishi , Okamura Kiyohito , Shishido Toetsu
Published: July 2006

Oxide glasses in the Ln–Al–O system were prepared with the molar ratio of Ln2O3:Al2O3 of 10:1 to 1:10 for all the lanthanoids and yttrium by an impact quenching technique. Each quenched material was examined by polarizing microscope, X-ray diffraction and electron diffraction. The electron diffraction patterns show diffuse halos characteristic of an amorphous state.
THE STRUCTURE OF PTERIDINES FROM PHOTOBACTERIUM PHOSPHORIUM
Authors: Matsuura Sadao , Odaka Munehiko , Sugimoto Takashi , Goto Toshio
Published: July 2006

Three pteridines were isolated from the mycelium of Photobacterium phosphorium. One of them, photopterin-A, is a new compound and its structure was deduced as 6-(Dl-1,2-dihydroxyethyl)-8-d-ribityl-2,4,7-trioxopteridine. Other two pteridines were identified as 2 and 7 The configuration of the tetrahydroxypentyl group in those pteridines was confirmed unambiguously by comparison of their ORD spectra with those of all possible isomers synthesized.
REACTION OF BENZYNE GENERATED FROM 1-(2-CARBOXYPHENYL)-3,3-DIMETHYLTRIAZENE WITH BENZALDEHYDE AND SOME OTHER CARBONYL COMPOUNDS
Authors: Nakayama Jyuzo , Yoshida Masayuki , Simamura Osamu
Published: July 2006

1-(2-Carboxyphenyl)-3,3-dimethyltriazene, on being heated in benzaldehyde, affords 2-dimethylaminobenzhydrol and cis- and trans-2,4-diphenyl-1,3-benzodioxins; similar products were obtained with some other carbonyl compounds.
THE FORMATION OF ADSORBED ANION RADICAL OF DIPYRIDYL ON MAGNESIUM OXIDE AND THE ELECTRON TRANSFER TO OXYGEN MOLECULE FROM ADSORBED ANION RADICAL
Authors: Iizuka Tokio
Published: July 2006

The generation of 2,2′- and 4,4′-dipyridyl anion radicals by adsorption on magnesium oxide was confirmed by means of electron spin resonance and visible spectroscopies. When the adsorbed species were exposed to air, the dipyridyl anion radical faded away and the ESR spectrum which was attributed to the oxygen molecule anion radical was observed.
EFFECT OF 2-CHLOROETHANOL, DIOXANE, OR WATER ON THE CONFORMATION OF A GEL-FORMING β-1,3-d-GLUCAN IN DMSO
Authors: Ogawa Kozo , Miyagi Masanobu , Fukumoto Tsugio , Watanabe Takehiko
Published: July 2006

The change of viscosity, optical rotation, and flow birefringence of a gel-forming β-1,3-d-glucan in DMSO with the addition of 2-chloroethanol, dioxane, or water was studied. The results indicate a conformational transition of the glucan from a flexible disordered form to a rigid ordered structure with increasing mole fraction of these nonsolvents.
THE OXIDATION OF ACROLEIN CATALYZED BY A METAL POLYPHTHALOCYANINE
Authors: Hara Takao , Ohkatsu Yasukazu , Osa Tetsuo
Published: July 2006

Kinetic studies on the homogeneous liquid-phase oxidation of acrolein using a metal polyphthalocyanine as a catalyst revealed that the rate of chain initiation (Ri) can be expressed as Ri = k1(acrolein)(cat)(O2). The rate constant k1 is determined as (6.3±0.3)×10−2 M−2sec−1 at 40 °C in benzene. The result may indicate that a phthalocyanine–O2 complex abstracts the aldehyde hydrogen to initiate the oxidation.
ANTIFERROMAGNETIC RESONANCE OF ORGANIC FREE RADICAL POLYCRYSTALLINE 1,3-BISDIPHENYLENE-2-(p-CHLOROPHENYL)-ALLYL
Authors: Yamauchi Jun
Published: July 2006

The paramagnetic resonance of polycrystalline 1,3-bisdiphenylene-2-(p-chlorophenyl)-allyl can be observed in the temperature region above 3.25 K. Below the temperature the anomalous resonance absorptions, which may be the antiferromagnetic resonance, were observed. This may be the first experimental observation in organic free radicals.
ALKYL GROUP ISOMERIZATION IN THE REACTION OF σ-ARYL PALLADIUM COMPLEXES WITH ALKYLLITHIUM COMPOUNDS
Authors: Yamamura Masaaki , Moritani Ichiro , Murahashi Shun-Ichi
Published: July 2006

Reaction of di-μ-chlorobis[2-(N-phenylformimidoyl)-3-tolyl]dipalladium (1) with secondary alkylithium compounds provides evidence indicating that a secondary alkyl-palladium isomerizes to the primary via a hydrido-olefin intermediate.
THE MECHANISM OF THE OSCILLATORY DECOMPOSITION OF HYDROGEN PEROXIDE BY THE I2–IO3− COUPLE
Authors: Matsuzaki Isao , Nakajima Tsuyoshi , Liebhafsky Herman A
Published: July 2006

In addition to the second-order back-activatory autocatalytic process 2HIO2 + HIO + H2O2 → 3HIO2 + H2O, which was recently found to be an oscillation source for the oscillatory decomposition of H2O2, another similar autocatalytic process 2HIO + H+ + I− + H2O2 → 3HIO + H2O has been found capable of serving as an oscillation source.