bluuebunny/crossref_metadata_2025 huggingface dataset:
Economic evaluation of a clinical protocol for diagnosing emergency patients with suspected pulmonary embolism
Authors: Gospodarevskaya Elena V , Goergen Stacy K , Harris Anthony H , Chan Thomas , de Campo John F , Wolfe Rory , Gan Eng T , Wheeler Michael B , McKay John
Published: August 2006

Background

The objective of this paper is to estimate the amount of cost-savings to the Australian health care system from implementing an evidence-based clinical protocol for diagnosing emergency patients with suspected pulmonary embolism (PE) at the Emergency department of a Victorian public hospital with 50,000 presentations in 2001–2002.

Methods

A cost-minimisation study used the data collected in a controlled clinical trial of a clinical protocol for diagnosing patients with suspected PE. Thenumber and type of diagnostic tests in a historic cohort of 185 randomly selected patients, who presented to the emergency department with suspectedPE during an eight month period prior to the clinical trial (January 2002 -August 2002) were compared with the number and type of diagnostic tests in745 patients, who presented to the emergency department with suspected PE from November 2002 to August 2003. Current Medicare fees per test were usedas unit costs to calculate the mean aggregated cost of diagnostic investigation per patient in both study groups. A t-test was used to estimate the statistical significance of the difference in the cost of resources used for diagnosing PE in the control and in the intervention group.

Results

The trial demonstrated that diagnosing PE using an evidence-based clinical protocol was as effective as the existing clinical practice. The clinical protocol offers the advantage of reducing the use of diagnostic imaging, resulting in an average cost savings of at least $59.30 per patient.

Conclusion

Extrapolating the observed cost-savings of $59.30 per patient to the wholeof Australia could potentially result in annual savings between $3.1 million to $3.7 million.
Preparing clinical-grade myeloid dendritic cells by electroporation-mediated transfection of in vitro amplified tumor-derived mRNA and safety testing in stage IV malignant melanoma
Authors: Markovic Svetomir N , Dietz Allan B , Greiner Carl W , Maas Mary L , Butler Greg W , Padley Douglas J , Bulur Peggy A , Allred Jacob B , Creagan Edward T , Ingle James N , Gastineau Dennis A , Vuk-Pavlovic Stanimir
Published: August 2006

Background

Dendritic cells (DCs) have been used as vaccines in clinical trials of immunotherapy of cancer and other diseases. Nonetheless, progress towards the use of DCs in the clinic has been slow due in part to the absence of standard methods for DC preparation and exposure to disease-associated antigens. Because different ex vivo exposure methods can affect DC phenotype and function differently, we studied whether electroporation-mediated transfection (electrotransfection) of myeloid DCs with in vitro expanded RNA isolated from tumor tissue might be feasible as a standard physical method in the preparation of clinical-grade DC vaccines.

Methods

We prepared immature DCs (IDCs) from CD14+ cells isolated from leukapheresis products and extracted total RNA from freshly resected melanoma tissue. We reversely transcribed the RNA while attaching a T7 promoter to the products that we subsequently amplified by PCR. We transcribed the amplified cDNA in vitro and introduced the expanded RNA into IDCs by electroporation followed by DC maturation and cryopreservation. Isolated and expanded mRNA was analyzed for the presence of melanoma-associated tumor antigens gp100, tyrosinase or MART1. To test product safety, we injected five million DCs subcutaneously at three-week intervals for up to four injections into six patients suffering from stage IV malignant melanoma.

Results

Three preparations contained all three transcripts, one isolate contained tyrosinase and gp100 and one contained none. Electrotransfection of DCs did not affect viability and phenotype of fresh mature DCs. However, post-thaw viability was lower (69 ± 12 percent) in comparison to non-electroporated cells (82 ± 12 percent; p = 0.001). No patient exhibited grade 3 or 4 toxicity upon DC injections.

Conclusion

Standardized preparation of viable clinical-grade DCs transfected with tumor-derived and in vitro amplified mRNA is feasible and their administration is safe.
Loss of Spinal Substance P Pain Transmission under the Condition of LPAI Receptor-Mediated Neuropathic Pain
Authors: Inoue Makoto , Yamaguchi Asuka , Kawakami Megumi , Chun Jerold , Ueda Hiroshi
Published: August 2006

Among various machineries occurring in the experimental neuropathic pain model, there exists the loss of pain transmission through C-fiber neurons as well as the hypersensitivity through A-fibers. The current study reveals that molecular machineries underlying the latter hypersensitivity are derived from the events through LPA1 receptor and its downstream RhoA-activation following peripheral nerve injury. The loss of C-fiber responses, which are mediated by spinal substance P (SP) pain transmission was observed with the nociceptive flexor responses by intraplantar injection of SP in nerve-injured mice. The immunohistochemistry revealed that SP signal in the dorsal horn was markedly reduced in such mice. All these changes were completely abolished in LPA1−/− mice or by the pretreatment with BoNT/C3, a RhoA inhibitor. In addition, the loss of C-fiber responses and the down-regulation of spinal SP signal induced by single intrathecal LPA injection were also abolished in such treatments. All these results suggest that the loss of pain transmission through polymodal C-fiber neurons is also mediated by the LPA1 activation following nerve injury.
Alexithymia and anxiety in female chronic pain patients
Authors: Celikel Feryal Cam , Saatcioglu Omer
Published: August 2006

Objectives

Alexithymia is highly prevalent among chronic pain patients. Pain is a remarkable cause for high levels of chronic anxiety. The purpose of this study was to investigate the prevalence of alexithymia and to determine anxiety levels among DSM-IV somatoform pain disorder (chronic pain) female patients and to examine the relationship between alexithymia and the self-reporting of pain.

Methods

Thirty adult females (mean age: 34,63 ± 10,62 years), who applied to the outpatient psychiatry clinic at a public hospital with the diagnosis of chronic pain disorder (DSM-IV), were included in the study. Thirty seven healthy females (mean age: 34,46 ± 7,43 years), who matched for sociodemographic features with the patient group, consisted the control group. A sociodemographic data form, 26-item Toronto Alexithymia Scale (TAS-26), Spielberger Trait Anxiety Inventory (STAI) were administered to each subject and information was obtained on several aspects of the patients' pain, including intensity (measured by VAS), and duration.

Results

Chronic pain patients were found significantly more alexithymic than controls. There was a positive correlation between TAS-26 scores and the duration of pain. The alexithymic and nonalexithymic group did not differ in their perception of pain. Neither positive correlation nor significant difference was found between alexithymia and trait anxiety in pain patients.

Discussion

Alexithymia may be important in addressing the diversity of subjective factors involved in pain. The conceptualization of alexithymia as a personality trait as well as a secondary state reaction is underlined by our data.
Nutrient Intake, Weight, and Leu7Pro Polymorphism in Prepro-Neuropeptide Y in Children
Authors: Karvonen Matti K. , Ruottinen Soile , Koulu Markku , Pesonen Ullamari , Niinikoski Harri , Rask-Nissilä Leena , Simell Olli , Rönnemaa Tapani
Published: August 2006

Context: The important role of neuropeptide Y (NPY) in the regulation of food intake and energy balance has been firmly documented in rodents, but human data are sparse. The recently identified functional Leu7Pro polymorphism in the signal peptide region of the prepro-NPY is a useful tool for the investigation of the role of NPY in men. Pro7 substitution has been associated with the following: plasma NPY concentration, the risk factors of cardiovascular disease, birth weight of children, serum triglyceride concentration, and the function of vascular endothelium.

Objective: The objective of this study was to analyze the connection between Leu7Pro polymorphism and relative weight, nutrient intakes, and serum lipids in early childhood. We closely followed 647 healthy Finnish children participating in the Special Turku Risk Factor Intervention Project through their first 9 yr of life.

Results: Leu7Pro polymorphism showed no relation to intakes of energy, macronutrients, or the relative weight in either gender. However, Pro7 substitution was associated with serum triglyceride concentration in boys at the ages of 5, 7, and 9 yr.

Conclusion: The functional Leu7Pro polymorphism is not likely to be involved in the regulation of adiposity or major nutrient preferences in childhood. In boys, the Pro7 variant may have impact on serum triglyceride concentration.
Midlife Plasma Insulin-Like Growth Factor I and Cognitive Function in Older Men
Authors: Okereke Olivia I. , Kang Jae H. , Ma Jing , Gaziano J. Michael , Grodstein Francine
Published: August 2006

Context: Emerging biological and epidemiological evidence suggests possible benefits of higher IGF-I levels in cognitive aging.

Objective: The objective of the study was to examine the relation of midlife plasma IGF-I levels to late-life cognition.

Design, Setting, and Participants: We conducted a secondary analysis from the Physicians’ Health Study II, a prospective cohort of U.S. male physicians. Participants provided blood samples from 1982 to 1984 (mean age 57 yr). Using stored samples, we measured free IGF-I in 376 men and total IGF-I and IGF binding protein-3 in 460 men. Starting in 2001, we administered telephone-based tests of general cognition [the Telephone Interview of Cognitive Status (TICS)], verbal memory, and category fluency. We estimated multivariable-adjusted mean differences in cognitive performance across levels of free IGF-I and IGF-I to IGF binding protein-3 molar ratio.

Main Outcome Measures: Global score (averaging performance across all individual cognitive tests), the TICS, and a verbal memory score were measured.

Results: Each sd increment in free IGF-I was associated with a multivariable-adjusted increase of 0.08 U (P = 0.02) on the global score. This mean difference was equivalent to that observed between men 2 yr apart in age: i.e. each sd increase in free IGF-I appeared cognitively equivalent to staying 2 yr younger. No significant mean differences in TICS scores were observed across free IGF-I levels. For verbal memory, each sd increment in free IGF-I was associated with an adjusted mean difference of 0.08 U (P = 0.03). Results appeared consistent for the molar ratio but were not statistically significant.

Conclusion: Higher midlife free IGF-I may be associated with better late-life cognition.
Paternal chromosome segregation during the first mitotic division determinesWolbachia-induced cytoplasmic incompatibility phenotype
Authors: Tram Uyen , Fredrick Kurt , Werren John H. , Sullivan William
Published: August 2006

The most common Wolbachia-induced phenotype in insects is cytoplasmic incompatibility (CI), which occurs when sperm from infected males fertilize eggs from uninfected females. CI produces distinct phenotypes in three closely related haplo-diploid species of the genus Nasonia: mortality in N. longicornis and N. giraulti, and conversion to male development in N. vitripennis. We demonstrate that the majority of CI-induced mortality occurs during embryogenesis and that the pattern of paternal chromosome segregation during the first mitosis is a good predictor of CI phenotype. In N. giraulti and N. longicornis, the paternal chromosomes mis-segregate, producing abnormal nuclei connected by chromatin bridges. Consequently, these embryos arrest development with very few and abnormal nuclei. In contrast, the paternal genome in N. vitripennis is either not segregated or mis-segregates to one of the two daughter nuclei. Consequently, these embryos continue development utilizing the maternally derived haploid nuclei, resulting in male offspring. The latter class is the first documented example of asymmetric mitotic segregation of abnormal chromosomes. We conclude that in haplo-diploids, CI-induced embryonic lethality occurs only when abnormal paternal genome segregation affects both products of the first mitotic division. This is the first study to associate differences in types of CI with specific cytological defects.
Ubiquitylation-independent ER-associated degradation of an AE1 mutant associated with dominant hereditary spherocytosis in cattle
Authors: Ito Daisuke , Koshino Ichiro , Arashiki Nobuto , Adachi Hirokazu , Tomihari Mizuki , Tamahara Satoshi , Kurogi Kazuhito , Amano Takashi , Ono Ken-ichiro , Inaba Mutsumi
Published: August 2006

Various mutations in the AE1 (anion exchanger 1, band 3) gene cause dominant hereditary spherocytosis, a common congenital hemolytic anemia associated with deficiencies of AE1 of different degrees and loss of mutant protein from red blood cell membranes. To determine the mechanisms underlying decreases in AE1 protein levels, we employed K562 and HEK293 cell lines and Xenopus oocytes together with bovine wild-type AE1 and an R664X nonsense mutant responsible for dominant hereditary spherocytosis to analyze protein expression, turnover, and intracellular localization. R664X-mutant protein underwent rapid degradation and caused specifically increased turnover and impaired trafficking to the plasma membrane of the wild-type protein through hetero-oligomer formation in K562 cells. Consistent with those observations, co-expression of mutant and wild-type AE1 reduced anion transport by the wild-type protein in oocytes. Transfection studies in K562 and HEK293 cells revealed that the major pathway mediating degradation of both R664X and wild-type AE1 employed endoplasmic reticulum (ER)-associated degradation through the proteasomal pathway. Proteasomal degradation of R664X protein appeared to be independent of both ubiquitylation and N-glycosylation, and aggresome formation was not observed following proteasome inhibition. These findings indicate that AE1 R664X protein, which is associated with dominant hereditary spherocytosis, has a dominant-negative effect on the expression of wild-type AE1.
Complexation of Inorganic Anions with Heptakis(6-butylamino-6-deoxy)-β-cyclodextrin and Its Analogs in Acidic Media
Authors: Matsui Yoshihisa , Tanemura Eiji , Nonomura Tohoru
Published: August 2006

Heptakis(6-butylamino-6-deoxy)-β-cyclodextrin (2) forms 1 : 1 complexes with several inorganic anions in 0.10 mol dm−3 HCl or DCl at 25 °C. The binding constant for a complex of 2 with the SO42− ion was remarkably larger than those for complexes of 2 with univalent anions and those for complexes of the α- (1) and γ-cyclodextrin (3) analogs with the SO42− ion. The circular arrangement of the protonated amino groups in 2 may be advantageous for electrostatic interactions with the bivalent anion.
Cadmium (53P1)-Photosensitized Luminescence of Some Compounds Containing Two Functional Groups
Authors: Ahmed Omar , Yamamoto Shunzo , Sueishi Yoshimi , Nishimura Norio
Published: August 2006

The cadmium (53P1)-sensitized luminescence of some aliphatic compounds which have two functional groups have been studied under the conditions of steady-state illumination at temperatures between 473 and 573 K. It was found that 1,2-dimethoxyethane (DMOE), 2-methoxyethylamine (2-MOEA), and 3-methoxypropylamine (3-MOPA) have two emission bands (wavelengths at the peaks of these bands are about 400 and 455 nm for DMOE and about 460 and 500 nm for 2-MOEA and 3-MOPA), while 2-aminoethanol (2-AEA) and 3-amino-1-propanol (3-APA) do not have any emission band. These two bands were assigned to two kinds of 1 : 1 exciplex (cyclic and acyclic ones) between an excited cadmium atom and a substrate molecule. From the temperature dependence of the emission intensity ratios of these bands, the enthalpy changes (ΔH°) of the equilibrium between two exciplexes were evaluated. The values of ΔH° are correlated to the energy differences between the wavelengths of two emission bands.
Ion-Molecule Reactions of CO2+ with Butane and Isobutane at Thermal Energy
Authors: Tsuji Masaharu , Matsumura Ken-ichi , Funatsu Tsuyoshi , Nishimura Yukio , Obase Hiroshi , Kagawa Shinji , Kanetaka Yasuhito
Published: August 2006

Rate constants and product ion distributions have been determined for thermal energy reactions of CO2+ with n-C4H10 and i-C4H10 by using an ion-beam apparatus. The total rate constants are (9.8 ± 2.0) × 10−10 and (1.0 ± 0.2) × 10−9 cm3 s−1 for n-C4H10 and i-C4H10, respectively. These values amount to about 75% of the collision rate constants estimated from the Langevin theory. C4H9+, C3Hn+ (n = 5—7), and C2Hn+ (n = 3—5) are produced from n-C4H10 with branching ratios of 6, 56, and 38%, while C4H9+ and C3Hn+ (n = 5—7) are formed from i-C4H10 with branching ratios of 7 and 93%, respectively. The lack of C2Hn+ fragments from i-C4H10 is attributed to a low probability of significant rearrangement of chemical bonds for the formation of the C2Hn+ fragments. The product ion distribution in the CO2+/n-C4H10 reaction is in good agreement with that predicted from the fragmentation pattern of n-C4H10+ at 13.78 eV, indicating that the CO2+/n-C4H10 reaction proceeds through a near-resonant charge transfer without momentum transfer.
Different Routes in the Forward and Backward Occurrences of the Hydrogen Electrode Reaction on Pt Single Crystal Electrodes in Acid Solution
Authors: Kita Hideaki , Gao Yunzhi , Ye Shen , Shimazu Katsuaki
Published: August 2006

The hydrogen evolution and ionization reactions were studied on Pt single crystal electrodes in N2 or H2 saturated, acidic solutions. The hydrogen evolution reaction was structure insensitive and the ionization reaction was structure dependent. The Tafel constants of the respective reactions, and , and the reaction orders, and , with respect to proton, did not satisfy the relationships, + = 2 and − = −2, deduced by the rate-determining step which is the same for the hydrogen evolution and ionization reactions; The results were, + ≈ 4 and − ≈ −4. These suggest that the rate-determining steps is different for the evolution and ionization reactions in acidic solutions. A tentative model for the reaction routes was proposed.
Kinetic Studies of the Reaction of Nitrous Acid with Iodide Ion in the Presence of Molecular Oxygen in an Acid Solution
Authors: Kimura Masaru , Sato Miyuki , Murase Tomoko , Tsukahara Keiichi
Published: August 2006

The kinetics of the reaction between nitrous acid and iodide ion were studied in the presence of molecular oxygen (O2) in an acid solution (pH 1.9—3.1); much larger amounts of the triiodide ion than expected from the amounts of nitrous acid were formed under conditions of the iodide ion in excess over nitrous acid. The initial rates for the formation of I2 and I3− increased proportionally with increasing both the O2 and nitrous acid contents, and increased greatly with decreasing the pH in the solution. The reaction rate was also decreased by bubbling either air or O2 through the reacting solution, depending on the bubbling velocity. A chain mechanism is proposed to account for the results obtained in the dark: 2HNO2 + 2I− + 2H+ → 2NO + I2 + 2H2O; 2NO + O2 → 2NO2; 2NO2   N2O4; N2O4 + 2I− + 2H+ → 2HNO2 + I2; I2 + I−   I3−. The rate-determining step was the reaction of NO with O2. The addition of trace amounts of copper(II) or iron(II) ion enhanced the formation of I2 and I3− due to the occurrence of reactions of I− with the metal ions. Such an acceleration effect by the metal ions, however, could be diminished by the addition of ethylenediaminetetraacetic acid. Although the rate of the reaction of HNO2 with I− was not greatly changed by the irradiation of visible light during the initial period of reaction, it was greatly accelerated after some formation of I2 and I3−, being dependent on not only the light intensity, but also on the concentrations of H+ and I− ions. The effects of the metal ions as well as visible light are also accounted for by the above-mentioned mechanism.
Studies on Fused Azoles: Synthesis of Several New Polyfunctionally Substituted Fused Pyrazoles
Authors: Sadek Kamal Usef , Selim Maghraby Ali , Elnagdi Mohamed Hilmy , Otto Hans Hartwig
Published: August 2006

The synthesis of several new polyfunctionally substituted fused pyrazoles via reaction of 5-amino-3-methylthio-1H-pyrazole-4-carbonitrile (1) with different reagents is described.
One-Pot Synthesis of Tetraazabis(tropocoronand)s and Podands from Benzo[b]cyclohept[e][1,4]oxazine and α,ω-Polymethylenediamines
Authors: Shindo Kimio , Wakabayashi Hidetsugu , Ishikawa Sumio , Nozoe Tetsuo
Published: August 2006

The reactions of benzo[b]cyclohept[e][1,4]oxazine (9) with a 1.2 equivalent of α,ω-alkanediamines (2, n = 4—12) in ethanol at 80 °C afforded tropocoronands (5, n,n′ = 4,4—12,12) in a one-pot procedure and in high yields, while the reaction of 9 with an excess of 2 mainly gave tropopodands 12 (n,n′ = 4,4—6,6). The reactions of 9 with short-chain diamines 2 (n = 2,3) yielded bicyclic pyrazino or diazepino compounds as the main products. The reaction of 9 with ω-amino alcohol afforded the corresponding dihydroxy podands 23. The predicted pathways of the reaction of 9 with 2 were experimentally confirmed.
Oxidation of Lipids Induced by Dioctadecyl Hyponitrite and Di-t-butyl Hyponitrite in Organic Solution and in Aqueous Dispersions. Effects of Reaction Medium and Size of Radicals on Efficiency of Chain Initiation
Authors: Kigoshi Makoto , Sato Keizo , Niki Etsuo
Published: August 2006

The dynamics of the chain initiation of the oxidations of lipids by hyponitrites were studied in organic homogeneous solution and in aqueous dispersions of micelles and liposomal membranes. Di-t-butyl and distearyl hyponitrites were used in order to examine the effect of bulkiness of the alkoxyl radicals in different reaction media. Both hyponitrites induced the free radical-mediated chain oxidations of methyl linoleate in homogeneous solution and in aqueous emulsions and also of soybean phosphatidylcholine liposomal membranes. In aqueous dispersions, these lipophilic hyponitrites generated free radicals in the lipid compartment and aqueous radical-scavenging antioxidants could not suppress the oxidations induced by these hyponitrites. The efficiency of chain initiation decreased in the order of homogeneous solution > micelles > liposomal membranes in accordance with increasing viscosity of the medium. It was also dependent on the size of alkoxyl radical and distearyl hyponitrites was less efficient than di-t-butyl hyponitrite in initiating the chain oxidation in all of the above reaction media.
Mechanistic Study of the Photooxidation of Squalene Sensitized with 2,2′ : 5′,2″-Terthiophene and 2,2′-Bithiophene
Authors: Fujita Hitoshi , Tokiwa Kiminori , Sayama Katsuhide , Mori Hiroyuki , Sasaki Masako
Published: August 2006

To understand the photochemical basis of photodermatitis caused by 2,2′ : 5′,2″-terthiophene, photooxidation of squalene sensitized with 2,2′ : 5′,2″-terthiophene was studied with respect to mediation by singlet molecular oxygen, the activation energy, and the apparent quantum yield. Squalene was peroxidized in ethanol solution by irradiation with UV-A light in the presence of 2,2′ : 5′,2″-terthiophene and the related compound 2,2′-bithiophene. Involvement of singlet oxygen in the peroxidation was suggested on the basis of the suppressive effect of sodium azide and the enhancing effects of organic solvents which elongate the lifetime of singlet oxygen. The activation energy obtained, 11.2 kJ mol−1, was a reasonable value for oxidation of olefins by singlet oxygen. The quantum yields of peroxidation were estimated to 12.6 × 10−2 and 8.3 × 10−2 for photosensitization with 2,2′ : 5′,2″-terthiophene and 2,2′-bithiophene, respectively.
Interaction between Side-Chain Pyridyl Groups of α-Helical Polypeptide and Guest Trp in the Ternary Cu2+ Ion Complex
Authors: Nagata Yoshitomo , Kanuka Satoru , Kinoshita Takatoshi , Takizawa Akira , Tsujita Yoshiharu , Yoshimizu Hiroaki
Published: August 2006

Interaction between the side-chain pyridyl ligands of an α-helical poly(Nω-2-pyridylmethyl-l-glutamine) (P2PG) and guest ligands such as tryptamine and d- and l-tryptophan (d- and l-Trp) within ternary Cu2+ complexes was investigated by absorption and circular dichroism (CD) spectroscopy in 2,2,2-trifluoroethanol solutions. The host complex species, Cu2+-one pyridyl-substituted side-chain (s-2PG) complexes (1 : 1 Cu2+-P2PG, [Cu2+]/[s–2PG] > 1.0) and Cu2+- two s-2PGs complexes (1 : 2 Cu2+-P2PG, [Cu2+]/[s–2PG] < 1.0), were prepared, using Cu2+ and P2PG depending on the Cu2+ ion concentration. All guest molecules could bind noncovalently to the 1 : 1 Cu2+-P2PG system, having the ligand sites of Cu2+ partly unfilled, to yield their ternary Cu2+ complexes. The respective ternary complexes had induced optical activities in the CD spectra and a charge-transfer band indicating ligand–ligand stacking interactions involving charge transfer between the coordinated s-2PG and the guest indole moieties around Cu2+. The CD spectral intensity was in the order tryptamine < d-Trp, l-Trp, which suggests that the coordination of both amino and carboxyl groups of Trp to Cu2+ is important for the regular arrangement of the ligands on the periphery of the α-helix backbone of P2PG. The differences in the CD spectra suggest that the indole rings of d- and l-Trp face in a direction opposite to that of the pyridyl ring of P2PG. d- and l-Trp could also bind the 1 : 2 Cu2+-P2PG host system, whose Cu2+ coordination sites are filled with s-2PGs, but the 1 : 2 Cu2+-P2PG did not yield the ternary complexes with tryptamine.
Footprint Catalysis VII. Reinvestigation of the Imprinting Procedures for Molecular Footprint Catalytic Cavities: The Effects of Imprinting Procedure Temperature on the Catalytic Characteristics
Authors: Morihara Kensaku , Doi Sakurako , Takiguchi Michie , Shimada Toyoshi
Published: August 2006

The authors’ imprinting procedures for “molecular footprint” catalytic cavities on a silica (alumina) gel surface were reinvestigated. The increases of temperature during the incorporation of aluminum ions into the silicate matrix and during the footprint-imprinting with a template remarkably affected the catalytic characteristics of the resulting cavities. A change from room temperature to 75—80 °C increased the catalytic specificities (kcat/Km) by a factor of nearly 50. The results also provided experimental proof for the speculated mechanism of footprint formation. That is, the imprinting comprises precedent Lewis acid site generation on a silicate surface and subsequent Lewis acid–template complexation. The resulting acid–template complexes give rise to the footprint cavities upon removal of the template.
Studies on 5-8 Fused Ring Compounds. VII. The Conformations of the Eight-Membered Rings in C6–C8–C5 Fused Ring Compounds
Authors: Umehara Misao , Honnami Hiromi , Hishida Shinzaburo , Kawata Takashi , Ohba Shigeru , Zen Shonosuke
Published: August 2006

The five cis/trans isomers of C6–C8–C5 fused ring compound, tricyclo[9.4.0.04,8]pentadecane-2,9-dione were synthesized by photocycloaddition of decalin-1,3-dione to cyclopentene. The conformational analyses were carried out by MM2 and the results were compared with X-ray analyses. The eight-membered rings take predominantly boat-chair forms although those in C5–C8–C5 fused ring compounds exist in various conformations.
Convenient Radical α-Monoallylations of Carbonyl Compounds
Authors: Watanabe Yoshihiko , Yoneda Tetsuo , Okumura Tatsuya , Ueno Yoshio , Toru Takeshi
Published: August 2006

Free radical allylations of α-seleno carbonyl compounds with tributyl-substituted 2,4-pentadienyltin, 2-methyl-2-propenyltin, 2-butenyltin, and 3-methyl-2-butenyltin, are described. Such successful C–C bond formations, in particular with the 2-butenyltin and the 3-methyl-2-butenyltin, are owing to the high reactivity of the α-carbon radical, generated from α-seleno carbonyl compounds, toward allylic tin compounds.
The Synthesis of Salvinolone, Saprorthoquinone, and 4-Hydroxysapriparaquinone from (+)-Dehydroabietic Acid
Authors: Matsumoto Takashi , Tanaka Yasutaka , Terao Hiromitsu , Takeda Yoshio , Wada Makoto
Published: August 2006

Salvinolone, saprorthoquinone, and 4-hydroxysapriparaquinone isolated from the roots of Salvia prionitis Hance. were synthesized starting from (+)-dehydroabietic acid via 11,12-dimethoxyabieta-8,11,13-trien-7-one and 12-methoxyabieta-8, 11,13-triene.
Energy Transfer in β-Turned Peptide-Bridged Porphyrin Dimers
Authors: Tamiaki Hitoshi , Nomura Kimiatsu , Maruyama Kazuhiro
Published: August 2006

β-Turned peptide-bridged diporphyrinyl compounds were prepared. Each isomeric monozinc complexes were easily available; metal-free porphyrin–peptide–zinc porphyrin and zinc porphyrin–peptide–metal-free porphyrin. In the isomers, the intramolecular energy transfer efficiencies from zinc porphyrin moiety to metal-free porphyrin moiety were the same from analysis of the steady-state fluorescence spectra, indicating that the efficiencies should be independent upon the linked peptide spacer and dependent upon the distance between the porphyrin moieties in the molecule. Singlet energy might migrate intramolecularly from zinc porphyrin moiety to metal-free one mainly by through-space mechanism.
Crystal and Molecular Structure of (1R,6S)-3,6,14,16-Tetrahydroxyspiro[1,5]grayanotoxin-5-one
Authors: Sato Mamoru , Katsube Yukiteru , Terai Tadamasa , Katakawa Jun’ichi , Tetsumi Tadahiro
Published: August 2006

The three-dimensional structure of a grayanotoxin II derivative, (1R,6S)-3,6,14,16-tetrahydroxyspiro[1,5]grayanotoxin-5-one, has been determined by X-ray diffraction at room temperature. The structure was solved by direct methods and refined by the full matrix least-squares method to a final R = 0.043 for 1436 independent reflections with Fo ≥ 3σ(Fo). The molecule is based on a tetracyclic structure and consists of two six-membered and two five-membered rings. The absolute configuration at C(1) atom (spiro atom) was determined as R on the basis of internal comparison with the absolute structure of grayanotoxin II.
Novel Biradical Cyclization via Remote-Hydrogen Transfer in Photochemistry of 2-Dialylaminoethyl 3-Benzoylacrylates
Authors: Hasegawa Tadashi , Yamazaki Yuko , Yoshioka Michikazu
Published: August 2006

Upon irradiation, 2-(N,N-dibenzylamino)ethyl and 2-(N-benzyl-N-methylamino)ethyl 3-benzoylacrylate underwent photocyclization via remote-proton transfer from their (Z)-forms competing with (E)–(Z) isomerization. The quantum yield for the cyclization under the conditions where both (E)- and (Z)-isomers absorb the irradiation light was estimated to be 0.05 by applying the steady-state approximation.
Electronic Structure of the 1-(Benzoyloxy)ethyl Radical
Authors: Uchida Nozomu , Shiomi Tomoo , Imai Kiyokazu , Tatewaki Hiroshi
Published: August 2006

In the polymerization of vinyl benzoate, the tacticity of the obtained polymer is changed toward less isotactic by UV irradiation. To explain this phenomenon, it was assumed that the growing terminal of the polymer was excited by UV irradiation and that the coplanarity of the vinyl benzoates was broken. It was thus naturally concluded that the existence of a twisted radical reduced the isotacticity. To examine the above assumption, the electronic structures of the ground and excited states of 1-(benzoyloxy)ethyl radical () were studied as a model of the growing terminal of the polymer by ab initio SCF and CI calculations. The present calculation, however, showed that the planer structure was stable in both the ground and excited states.
Optical Properties and Thermochromism of the Crystals of Chloranil-Hexamethyl Benzene and Fluoranil-Perylene Charge-Transfer Complexes
Authors: Tanaka Masashi
Published: August 2006

The reflection spectra of the crystal of chloranil-hexamethyl benzene and fluoranil-perylene charge-transfer complexes were measured, and the charge-transfer degrees in these complexes were estimated. Furthermore, the polarized IR absorption spectra of these crystals were measured and compared with those of the powders of the complexes and the component compounds in the KBr disks. The thermochromism of these CT complex crystals was studied by differential scanning calorimetry and the IR spectra.
Quasi-Action Variable for Chaos in Chemical Dynamics
Authors: Takatsuka Kazuo
Published: August 2006

Is proposed quasi-action variable as a means to analyze the onset of classical chaos in molecular vibrational systems. The basic idea rests on a symplectic area generated by a classical trajectory in phase space, from which the geometrical information of a torus and its breakdown in extracted. The Fourier spectrum of the time derivative of this symplectic area centers on the following definition and findings: (1) in an integrable system, the action variables can be simply calculated in terms of the above Fourier amplitudes, (2) the quasi-action variable is also defined in a similar way and is a good approximation to the corresponding action variable, but (3) the construction of the quasi-action variable does not depend on the integrability and hence it it defined as well even for a chaotic system, and (4) the characteristics of chaos can be analyzed in the continuous spectrum of the quasi-action variable. Some numerical examples of the quasi-action variable are presented for a system of what we call phase-space large amplitude motion. As a byproduct, a simple method has been devised to calculate very accurate frequencies and amplitudes from the so-called Fast-Fourier-Transform (FFT) spectra without resorting to the so-called window technique.
Theoretical Study of Metal NMR Chemical Shifts. Selenium Compounds
Authors: Nakatsuji Hiroshi , Higashioji Takuji , Sugimoto Manabu
Published: August 2006

The 77Se chemical shifts of nine selenium compounds, SeRR′ (R, R′ = H, Me, Et, Ph, SiH3, GeH3), are theoretically investigated by ab initio Hartree–Fock/finite perturbation method. The calculated values agree well with the experimental values. The Se chemical shift is dominated by the Se valence 4p AO contribution to the paramagnetic term, and shows a parallelism with the 4p-hole population and the net charge of the central Se atom. The Se chemical shift moves downfield as an increase of the hole in the 4p orbitals, and therefore, as an increase in the electron-withdrawing ability of the ligands attached to the selenium atom.
Metallaboranes with Group 8 and 9 Transition Metals. Is Accurate ab initio Molecular Orbital Calculation of Structure, Stability, and NMR Chemical Shifts Possible?
Authors: Mebel Alexander M , Musaev Djamaladdin G , Koga Nobuaki , Morokuma Keiji
Published: August 2006

Ab initio MO study of structure, stability and rearrangements of nido-metallaboranes with Ir, Co, and Fe transition metals has been performed at HF and correlated MP2 levels. Reasonable agreement with experiment has been found for RHF optimized geometry of [(IrB5H8)(CO)(PH3)2] iridaborane, and the MP2 optimization improves the agreement to the maximum error of 0.035 Å. Two geometric isomers, 2- with basal Ir and 1- with apical Ir are close in energy for [(IrB5H8)(CO)(PH3)2]. NMR 11B and 1H chemical shifts calculated by the IGLO method qualitatively reproduce experimental spectra. Methods more sophisticated than MP2 would be necessary for accurate calculations of metallaboranes with first row transition metals.
The Random Graph Model of Hydrogen Bond Network
Authors: Sasai Masaki
Published: August 2006

A new lattice model of liquid water is developed. The hydrogen bond network is represented by the Ising variables with the method similar to the one used in combinatorial problems in random graph. Thermodynamic properties of the model are studies with the mean-field approximation. Phase diagram, density maximum, and anomalies of supercooled water are discussed. Dynamical properties are also investigated by using the coupled-map-dynamics method. Energy fluctuation is shown to have 1/f like long time correlation. The network structural rearrangement takes place collectively in localized regions.
Reinvestigation of the Electrochemical Reduction of KMnO4
Authors: Lin San-Chung , Wang Yung-Yun , Wan Chi-Chao , Chang J -Cheng
Published: August 2006

Investigating the electrochemical reduction behavior of MnO4−, we determined the consecutive reduction/oxidation potentials of MnO4− by the cyclic voltammetric method. We have also confirmed that MnO42− is reduced into MnO43−. We then investigated the cause of the generation of MnO2 on the electrode surface with the rotating ring-disk electrode method. The reversibility of the reduction of MnO4− depends on the concentration of KMnO4 and KOH. Reversibility increases when the concentration of KOH increases, but the reversibility decreases when the concentration of KMnO4 increases. The reaction rate of MnO4−/MnO42− follows the law:
Complexation Equilibria and Fluorescent Properties of Chelating Reagents Derived from Ethylene Glycol Bis(β-aminoethylether)-N,N,N′,N′-tetraacetic Acid
Authors: Yuchi Akio , Tanaka Atsushi , Hirai Manabu , Yasui Takashi , Wada Hiroko , Nakagawa Genkichi
Published: August 2006

The complexation equilibria of divalent and lanthanoid metal ions with 1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid (BAPTA) and 2-[(2-amino-5-methylphenoxy)methyl]-6-methoxy-8-aminoquinoline-N,N,N′,N′-tetraacetic acid (quin2) were studied by pH titration. In lanthanoids, BAPTA shows a maximum stability for Pr3+, whereas quin2 has higher affinities for heavier ones. These trends are discussed in terms of the rigidity and donor atoms of these ligands. Intense fluorescence was observed for quin2 complexes of Group-2 and -3 elements. Among the lanthanoids, only Sc, Y, La, Gd, and Lu enhance the fluorescence at around 380 nm.
Determination of Silicate by Ion-Exclusion Chromatography with Luminol Chemiluminescence Detection
Authors: Sakai Hiroyuki , Fujiwara Terufumi , Kumamaru Takahiro
Published: August 2006

An increased chemiluminescence (CL) emission was produced upon mixing an acidified solution of silicate with a basic solution of luminol and hydrogen peroxide. The new CL reaction was used to develop a simple and rapid post-column detection system for selective determination of silicate after separation by ion-exclusion chromatography (ICE). Separation of silicate from other anions like phosphate, nitrite, sulfide or carbonate ion was achieved using a low-capacity cation-exchange column and a dilute perchloric acid solution as an eluent. Also, the present method has an advantage of eliminating interferences from ionic metal species. The detection limit of 50 ng cm−3 and a linear calibration graph with a dynamic range from 100 ng cm−3 to 30 μg cm−3 was obtained for silicon(IV). The proposed ICE-CL method was applied to the determination of silicate in tap and river water samples.
Synthetic Studies of Venturicidins. Synthesis of the C1–C14 Segment of Venturicidins
Authors: Nakata Masaya , Ohashi Junji , Ohsawa Kunihiko , Nishimura Toru , Kinoshita Mitsuhiro , Tatsuta Kuniaki
Published: August 2006

The C1–C14 segment of venturicidins, (2R,6R)-3,6-dihydro-6-[(E)-7-(dimethoxyphosphinyl)-1-methyl-6-oxo-1-heptenyl]-2-methoxy-5-methyl-2H-pyran-2-acetic acid (1), has been synthesized. The C8–C13 segment of venturicidins, (E)-2-bromo-7-(4,4′-dimethoxytriphenylmethoxy)-2-heptene (2), was lithiated with t-butyllithium and the resulting vinyllithium compound was coupled with the C1–C7 segment, (2Z,7S)-7-(t-butyldimethylsilyloxy)-8-(t-butyldiphenylsilyloxy)-2-methyl-5,5-(trimethylenedithio)-2-octenal (4), to afford the alcohol. A subsequent seven-step conversion of this alcohol furnished the synthesis of the C1–C13 segment, (2R,6R)-3,6-dihydro-6-[(E)-6-hydroxy-1-methyl-1-hexenyl]-2-methoxy-5-methyl-2H-pyran-2-acetate (9). Finally, the known four-step transformation led 9 to the target compound 1.
Preparation of New Nitrogen-Bridged Heterocycles. 35. Smooth Synthesis of 10aH-Pyrido[1,2-d][1,4]thiazepine Derivatives
Authors: Kakehi Akikazu , Ito Suketaka , Hakui Jun-ichi
Published: August 2006

Various 1-pyridinio(thiocarbonyl)methylides and 2-isoquinolinio(thiocarbonyl)methylides react smoothly with dimethyl acetylenedicarboxylate at room temperature or at the reflux temperature in chloroform to give new heterocycles, dimethyl 10aH-pyrido[1,2-d][1,4]thiazepine-1,2-dicarboxylate derivatives, in moderate yields. Similarly, the reactions of some 3-(1-pyridinio)thiophene-2-thiolates with the same reagent afforded the corresponding dimethyl 6aH-pyrido[1,2-d]thieno[2′,3′-b][1,4]thiazepine-5,6-dicarboxylates. The structures of these 1,4-thiazepine derivatives were mainly assigned based on physical and spectral inspections, and were finally confirmed by X-ray analyses of three compounds.
The Addition Effect of Hydrogen Bromide on Methane Ignition behind Reflected Shock Waves
Authors: Takahashi Kazuo , Inomata Tadaaki , Jinno Hiroshi
Published: August 2006

Ignition delay times were measured in a CH4–O2–HBr–Ar mixture behind reflected shock waves. Hydrogen bromide retarded methane ignition, though methyl bromide accelerated it. Model calculations showed that two different chain cycles, promotion and inhibition cycles, were formed for bromine-containing species. The inhibition cycle was predominant in the HBr addition.
Determination of Trace Impurities in Corrosive Gases by Gas-Phase FTIR
Authors: Miyazaki Keiji , Kimura Takako
Published: August 2006

Trace moisture and other potential impurities (CO2, CH4, C2H6, and alkyl halides) in HCl and in HBr gases were analyzed by gas-phase FTIR spectroscopic technique. The detection limit was estimated to be 100 ppb with 2 cm−1 spectral resolution for 5-min measurement time at 1.2 kg cm−2 pressure, using an MCT detector and an 8-m-pathlength gas cell with BaF2 windows.
The Structure of Nickel Oxide Clusters inside the Supercage in Y-Zeolite by XAFS
Authors: Sano Mitsuru , Suzuki Minoru , Niwa Miki
Published: August 2006

XAFS has been measured for the nickel oxide cluster in the Y-zeolite. The atomic distances in the cluster are close to those in the crystallite NiO. However, the weak intensity of Ni-fourth neighbor Ni and the coordination numbers give a model of the cluster in the supercage.
Solvent Extraction of Scandium(III) with Hexafluoroacetylacetone into Chloroform in the Absence and Presence of Tetrabutylammonium Ions or Trioctylphosphine Oxide
Authors: Noro Junji , Sekine Tatsuya
Published: August 2006

The anionic chelate of scandium(III) with hexafluoroacetylacetone (Hhfa) was extracted into chloroform in the presence of the tetrabutylammonium ion (tba+), though such an anionic chelate was not extracted when the chelating extractant was 2-thenoyltrifluoroacetone (Htta). The extraction was also studied in the same systems in the presence of trioctylphosphine oxide (TOPO); the extraction of the anionic complex, Sc(hfa)4−tba+, was compared with that of the adducts with TOPO, Sc(hfa)3(TOPO)n.
Synthesis of cis-Olefins via Palladium-Catalyzed Coupling of Organic Halides, Norbornadiene, and Organotin Compounds
Authors: Kosugi Masanori , Kimura Tomoyuki , Oda Hiroshi , Migita Toshihiko
Published: August 2006

Palladium-catalyzed cross-coupling of organic halides with organotin compounds in the presence of norbornadiene gave 5,6-disubstituted norbornene, which was treated by a retro Diels–Alder reaction yielding cis-ethene and cyclopentadiene.
Effect of the Molecular Orientation on the Stability of Hydrogen-Bonded Benzoic Acid Dimers. Infrared Study of Liquid-Crystalline 4-Alkylbenzoic Acids
Authors: Kato Takashi , Jin Chihiro , Kaneuchi Fumiko , Uryu Toshiyuki
Published: August 2006

Liquid-crystalline benzoic acid derivatives, 4-pentylbenzoic acid and 4-hexylbenzoic acid, have been examined by infrared spectroscopy. These benzoic acids show nematic phases. In the crystalline state, only the dimeric form is observed. However, the monomeric non-hydrogen-bonded benzoic acid appears once the temperature reaches the crystal-nematic transition (melting) point. The fraction of the monomeric moiety increases upon heating and an abrupt increase is observed at the isotropization temperature. These results suggest that the stability of the hydrogen bonds is not simply a function of the temperature, but greatly depends on the molecular orientation.
Diamagnetic Susceptibilities of Ionic Functional Groups
Authors: Takahashi Fujio , Sakai Yasuzo , Tsuchida Satoru
Published: August 2006

The diamagnetic susceptibilities of various series of organic compounds containing one or two ionic functional groups were measured by Guoy’s method. The diamagnetic susceptibilities of ionic functional groups in organic compounds were determined by calculations according to an additive property of the magnetic susceptibility in a combination of Pascal’s method with the diamagnetic susceptibilities of Na+, K+, Cl−, and Br−, which are given by Pascal. The results showed that the diamagnetic susceptibilities of ·COO−, ·SO3−, ·NH3+, and ·N(CH3)3+ are −12.3 × 10−6, −29.2 × 10−6, −13.0 × 10−6, and −39.8 × 10−6 cm3 mol−1, respectively. It became possible to estimate the diamagnetic susceptibilities of organic compounds containing ionic bonds consisting of the above-mentioned ionic functional groups.
Revision of the Dual Scaling Method for Successive Categories Data and Its Application to Quantitative Structure–Activity Relationships (QSAR)
Authors: Takagi Tatsuya , Tange Koichi , Jikihara Takahiro , Onozawa Norihisa , Sakashita Kazumi , Fujiwara Hideaki , Sasaki Yoshio
Published: August 2006

Nishisato’s Dual Scaling Method for successive categories data has been revised in order to apply it to quantitative structure–activity relationships. The revised version can give category values of successive categories, even though the original one can give only boundary values between two adjacent successive categories. The new version can be applied to an analysis of the antimicrobial activities of polymethylene bi(pyridineamine) derivatives, which are potential agents for controlling and/or preventing the formation of dental plaque. The results show that the proper molecular length of the agents leads to the maximum antimicrobial activity.
X-Ray Crystallographic Studies on the Molecular Structures of Some Salts of Titanium(III) Complexes with Ethylenediamine-N,N,N′,N′-tetraacetate, Ba[Ti(edta)(H2O)]Cl·6H2O, Na2[Ti(edta)(H2O)]2·NaCl·7H2O, and K[Ti(edta)(H2O)]·2.5H2O
Authors: Mizuta Tsutomu , Wang Jun , Miyoshi Katsuhiko
Published: August 2006

The crystal and molecular structures of three TiIII-edta complex salts (edta = ethylenediamine-N,N,N′,N′-tetraacetate), violet Ba[Ti(edta)(H2O)]Cl·6H2O (I), reddish violet Na2[Ti(edta)(H2O)]2·NaCl·7H2O (II), and purple K[Ti(edta)(H2O)]·2.5H2O (III), were determined by a single crystal X-ray diffraction method. The crystal data are as follows: I: Monoclinic, P21/a, a = 14.480(2), b = 19.760(3), c = 7.517(1) Å, β = 94.21(1)°, Z = 4; II: Monoclinic, P21, a = 18.176(3), b = 12.688(3), c = 8.045(2) Å, β = 93.05(2)°, Z = 2; III: Orthorhombic, Fdd2, a = 15.453(3), b = 60.247(8), c = 7.237(2) Å, Z = 16. It was found that all of these complexes have seven-coordinate and distorted mono-capped trigonal-prismatic (C2v-CTP) structures, in contrast to the corresponding dark-blue sodium salt, Na[Ti(edta)(H2O)]·2H2O, which was previously confirmed to be also seven-coordinated, but to have an approximately pentagonal-bipyramidal(PB) structure. The delicate color changes of the TiIII-edta complex salts observed in the solid state when the counterion is varied are due to an accompanying subtle modification in the coordination geometry around the TiIII ion. The kinetic lability and acid-base behavior of the TiIII-edta complex in solution reported earlier are accounted for by the presence of a labile water molecule in the first coordination sphere.