bluuebunny/crossref_metadata_2025 huggingface dataset:
Overcoming Drug-Resistant Cancer by a Newly Developed Copper Chelate through Host-Protective Cytokine-Mediated Apoptosis
Authors: Mookerjee Ananda , Mookerjee Basu Jayati , Dutta Pranabananda , Majumder Surajit , Bhattacharyya Sankar , Biswas Jaydip , Pal Smarajit , Mukherjee Pratima , Raha Sanghamitra , Baral Rathindra N. , Das Tania , Efferth Thomas , Sa Gourisankar , Roy Shyamal , Choudhuri Soumitra K.
Published: July 2006

Purpose: Previously, we have synthesized and characterized a novel Cu(II) complex, copper N-(2-hydroxy acetophenone) glycinate (CuNG). Herein, we have determined the efficacy of CuNG in overcoming multidrug-resistant cancer using drug-resistant murine and human cancer cell lines.

Experimental Design: Action of CuNG following single i.m. administration (5 mg/kg body weight) was tested in vivo on doxorubicin-resistant Ehrlich ascites carcinoma (EAC/Dox)–bearing mice and doxorubicin-resistant sarcoma 180–bearing mice. Tumor size, ascitic load, and survival rates were monitored at regular intervals. Apoptosis of cancer cells was determined by cell cycle analysis, confocal microscopy, Annexin V binding, and terminal deoxynucleotidyl transferase–mediated dUTP nick end labeling assay ex vivo. IFN-γ and tumor necrosis factor-α were assayed in the culture supernatants of in vivo and in vitro CuNG-treated splenic mononuclear cells from EAC/Dox-bearing mice and their apoptogenic effect was determined. Source of IFN-γ and changes in number of T regulatory marker-bearing cells in the tumor site following CuNG treatment were investigated by flow cytometry. Supernatants of in vitro CuNG-treated cultures of peripheral blood mononuclear cells from different drug-insensitive cancer patients were tested for presence of the apoptogenic cytokine IFN-γ and its involvement in induction of apoptosis of doxorubicin-resistant CEM/ADR5000 cells.

Results: CuNG treatment could resolve drug-resistant cancers through induction of apoptogenic cytokines, such as IFN-γ and/or tumor necrosis factor-α, from splenic mononuclear cells or patient peripheral blood mononuclear cells and reduce the number of T regulatory marker-bearing cells while increase infiltration of IFN-γ-producing T cells in the ascetic tumor site.

Conclusion: Our results show the potential usefulness of CuNG in immunotherapy of drug-resistant cancers irrespective of multidrug resistance phenotype.
Strategies to Enhance Epidermal Growth Factor Inhibition: Targeting the Mevalonate Pathway
Authors: Dimitroulakos Jim , Lorimer Ian A. , Goss Glenwood
Published: July 2006

Mevalonate metabolites play an essential role in transducing epidermal growth factor (EGF) receptor (EGFR)–mediated signaling, as several of these metabolites are required for the function of this receptor and the components of its signaling cascades. Thus, the depletion of mevalonate metabolites may have a significant effect on EGFR function. Lovastatin is a specific and potent inhibitor of 3-hydroxy-3-methylglutaryl CoA reductase, the rate-limiting enzyme of the mevalonate pathway. Targeting 3-hydroxy-3-methylglutaryl CoA reductase using lovastatin induces a potent tumor-specific apoptotic response in a variety of tumor types at therapeutically achievable levels of this drug. The effects of lovastatin on EGFR function and the potential combination effects with EGFR tyrosine kinase inhibitors, such as gefitinib, were evaluated. Lovastatin treatment inhibited EGF-induced EGFR autophosphorylation and its downstream signaling cascades by 24 hours. Combining lovastatin and gefitinib showed enhanced inhibition and cooperative cytotoxicity in a variety of cell lines that included all eight squamous cell carcinomas, four non–small cell lung carcinoma, and four colon carcinoma cell lines tested. Isobologram analyses confirmed that this combination was synergistic, inducing a potent apoptotic response. A phase I study has shown the safety and potential clinical benefit of high-dose lovastatin in patients with recurrent squamous cell carcinoma. The use of lovastatin, which is metabolized by CYP3A4, is contraindicated with drugs, such as gefitinib and erlotinib, which are also metabolized by CYP3A4 due to greatly enhanced toxicity. Rosuvastatin, a relatively novel potent mevalonate pathway inhibitor that is not metabolized significantly by CYP3A4, is a more appropriate statin to combine with either erlotinib or gefitinib. The combination of erlotinib and rosuvastatin has been proposed for a phase I/II study in advanced non–small cell lung carcinoma.
“Oncogenic Shock”: Explaining Oncogene Addiction through Differential Signal Attenuation
Authors: Sharma Sreenath V. , Fischbach Michael A. , Haber Daniel A. , Settleman Jeffrey
Published: July 2006

“Oncogene addiction” describes the curious acquired dependence of tumor cells on an activated oncogene for their survival and/or proliferation, a phenomenon that has important implications for the success of targeted cancer therapies. However, the mechanisms explaining oncogene addiction remain elusive. We propose that “addiction” may be an illusion generated as a consequence of differential attenuation rates of prosurvival and proapoptotic signals emanating from an oncoprotein acutely following its inactivation. According to this model, which we call “oncogenic shock,” prosurvival signals dissipate quickly on oncoprotein inactivation whereas proapoptotic signals linger sufficiently long to commit the cell to an apoptotic death. This mechanism may contribute to the rapid and dramatic clinical responses observed in some cancer patients treated with selective tyrosine kinase inhibitors and could yield additional drug targets that determine the balance of signaling outputs from activated oncoproteins.
Inhibition of Growth and Metastasis of Mouse Mammary Carcinoma by Selective Inhibitor of Transforming Growth Factor-β Type I Receptor KinaseIn vivo
Authors: Ge Rongrong , Rajeev Vaishali , Ray Partha , Lattime Edmund , Rittling Susan , Medicherla Satya , Protter Andy , Murphy Alison , Chakravarty Jit , Dugar Sundeep , Schreiner George , Barnard Nicola , Reiss Michael
Published: July 2006

Purpose: Transforming growth factor-β (TGF-β) suppresses tumor development by inhibiting cellular proliferation, inducing differentiation and apoptosis, and maintaining genomic integrity. However, once tumor cells escape from the tumor-suppressive effects of TGF-β, they often constitutively overexpress and activate TGF-β, which may promote tumor progression by enhancing invasion, metastasis, and angiogenesis and by suppressing antitumor immunity. The purpose of this study was to test this hypothesis using TGF-β pathway antagonists.

Experimental Design: We examined the effects of selective TGF-β type I receptor kinase inhibitors, SD-093 and SD-208, on two murine mammary carcinoma cell lines (R3T and 4T1) in vitro and in vivo.

Results: Both agents blocked TGF-β-induced phosphorylation of the receptor-associated Smads, Smad2 and Smad3, in a dose-dependent manner, with IC50 between 20 and 80 nmol/L. TGF-β failed to inhibit growth of these cell lines but stimulated epithelial-to-mesenchymal transdifferentiation, migration, and invasiveness into Matrigel in vitro. These effects were inhibited by SD-093, indicating that these processes are partly driven by TGF-β. Treatment of syngeneic R3T or 4T1 tumor-bearing mice with orally given SD-208 inhibited primary tumor growth as well as the number and size of metastases. In contrast, SD-208 failed to inhibit R3T tumor growth or metastasis in athymic nude mice. Moreover, in vitro anti-4T1 cell cytotoxic T-cell responses of splenocytes from drug-treated animals were enhanced compared with cells from control animals. In addition, SD-208 treatment resulted in a decrease in tumor angiogenesis.

Conclusion: TGF-β type I receptor kinase inhibitors hold promise as novel therapeutic agents for metastatic breast cancer.
Effect of Epidermal Growth Factor Receptor Tyrosine Kinase Domain Mutations on the Outcome of Patients with Non–Small Cell Lung Cancer Treated with Epidermal Growth Factor Receptor Tyrosine Kinase Inhibitors
Authors: Jänne Pasi A. , Johnson Bruce E.
Published: July 2006

Somatic mutations in the epidermal growth factor receptor (EGFR) have been identified in patients with advanced non–small cell lung cancer who achieve dramatic clinical and radiographic response to the EGFR tyrosine kinase inhibitors (TKI) gefitinib and erlotinib. These mutations in EGFR are found more frequently in patients with adenocarcinomas, nonsmokers, patients of Asian ethnicity, and in females: the same populations that are the most likely to have a clinical response when treated with EGFR TKIs. Retrospective studies comparing the outcomes of patients with and without EGFR mutations treated with EGFR TKIs show a significant clinical benefit of EGFR TKIs in patients with EGFR mutations. These findings suggest that for patients with advanced non–small cell lung cancer bearing EGFR mutations, treatment with an EGFR TKI should be incorporated as at least part of their initial therapy. These approaches are being studied in ongoing clinical trials and will spur the development of additional technology for EGFR mutation detection.
The Limits of the Law of the Least Ambitious Program
Authors: Hovi Jon , Sprinz Detlef F.
Published: July 2006

Arild Underdal's work on the Law of the Least Ambitious Program (LLAP) is a significant contribution to our understanding of the logic of international collaboration. The LLAP, however, applies only under particular conditions. After comparing the law to the joint decision trap and the veto player concept, we discuss four observations that tend to limit the law's domain. First, while the LLAP is intended to apply to decision-making under unanimity, in a number of international bodies decisions are made by some kind of majority voting. Second, the LLAP assumes that the alternative to collective agreement is individual decision-making, yet in practice the relevant alternative (the “reversion rule”) is often the continuation of some pre-existing collaborative arrangement. Third, whereas the LLAP assumes that the unanimity rule invariably favors the least ambitious program, there are interesting cases where this assumption does not hold. Finally, the LLAP does not take into account that the outcome of international decision-making not only depends on the decision rule and the reversion rule, but also on the voting sequence.
Negotiating a New Design for a World Ocean Regime
Authors: Miles Edward L.
Published: July 2006

In a study assessing the effectiveness of international environmental regimes published in 2002 the authors chose to exclude the negotiations of the Third United Nations Conference on the Law of the Sea as a case study because it was not an environmental regime per se and because the conference was far too complex to be useful as a control case. The present essay applies the analytic structure of the environmental regime effectiveness study to the UNLCOS III negotiations to assess what value, if any, would now be added to a comprehensive analysis of those negotiations. The findings are that the approach of my previous research on UNCLOS III would have been considerably tightened by such an application and a much more nuanced and evolutionary analysis would have been possible on the variable of problem type in which malignancy first increased but later decreased.
Evaluation of a self-management programme for congestive heart failure patients: design of a randomised controlled trial
Authors: Smeulders Esther STF , van Haastregt Jolanda CM , van Hoef Elisabeth FM , van Eijk Jacques ThM , Kempen Gertrudis IJM
Published: July 2006

Background

Congestive heart failure (CHF) has a substantial impact on care utilisation and quality of life. It is crucial for patients to cope with CHF adequately, if they are to live an acceptable life. Self-management may play an important role in this regard. Previous studies have shown the effectiveness of the 'Chronic Disease Self-Management Program' (CDSMP), a group-based cognitive behavioural programme for patients with various chronic conditions. However, the programme's effectiveness has not yet been studied specifically among CHF patients. This paper presents the design of a randomised controlled trial to evaluate the effects of the CDSMP on psychosocial attributes, health behaviour, quality of life, and health care utilisation of CHF patients.

Methods/Design

The programme is being evaluated in a two-group randomised controlled trial. Patients were eligible if they had been diagnosed with CHF and experienced slight to marked limitation of physical activity. They were selected from the Heart Failure and/or Cardiology Outpatient Clinics of six hospitals. Eligible patients underwent a baseline assessment and were subsequently allocated to the intervention or control group. Patients allocated to the intervention group were invited to attend the self-management programme consisting of six weekly sessions, led by a CHF nurse specialist and a CHF patient. Those allocated to the control group received care as usual. Follow-up measurements are being carried out immediately after the intervention period, and six and twelve months after the start of the intervention.

An effect evaluation and a process evaluation are being conducted. The primary outcomes of the effect evaluation are self-efficacy expectancies, perceived control, and cognitive symptom management. The secondary outcome measures are smoking and drinking behaviour, Body Mass Index (BMI), physical activity level, self-care behaviour, health-related quality of life, perceived autonomy, symptoms of anxiety and depression, and health care utilisation. The programme's feasibility is assessed by measuring compliance with the protocol, patients' attendance and adherence, and the opinions about the programme.

Discussion

A total number of 318 patients were included in the trial. At present, follow-up data are being collected. The results of the trial become clear after completion of the data collection in January 2007.

Trial Registration

Trialregister (http://www.trialregister.nl/trialreg/admin/rctview.asp?TC=467) ISRCTN88363287.
Terminal mitoses require negative regulation of Fzr/Cdh1 by Cyclin A,preventing premature degradation of mitotic cyclins and String/Cdc25
Authors: Reber Achim , Lehner Christian F. , Jacobs Henning W.
Published: July 2006

Cyclin A expression is only required for particular cell divisions during Drosophila embryogenesis. In the epidermis, Cyclin Ais strictly required for progression through mitosis 16 in cells that become post-mitotic after this division. By contrast, Cyclin A is not absolutely required in epidermal cells that are developmentally programmed for continuation of cell cycle progression after mitosis 16. Our analyses suggest the following explanation for the special Cyclin A requirement during terminal division cycles. Cyclin E is known to be downregulated during terminal division cycles to allow a timely cell cycle exit after the final mitosis. Cyclin E is therefore no longer available before terminal mitoses to prevent premature Fizzy-related/Cdh1 activation. As a consequence,Cyclin A, which can also function as a negative regulator of Fizzy-related/Cdh1, becomes essential to provide this inhibition before terminal mitoses. In the absence of Cyclin A, premature Fizzy-related/Cdh1 activity results in the premature degradation of the Cdk1 activators Cyclin B and Cyclin B3, and apparently of String/Cdc25 phosphatase as well. Without these activators, entry into terminal mitoses is not possible. However, entry into terminal mitoses can be restored by the simultaneous expression of versions of Cyclin B and Cyclin B3 without destruction boxes, along with a Cdk1 mutant that escapes inhibitory phosphorylation on T14 and Y15. Moreover,terminal mitoses are also restored in Cyclin A mutants by either the elimination of Fizzy-related/Cdh1 function or Cyclin Eoverexpression.
Having the nerve to home: trigeminal magnetoreceptor versusolfactory mediation of homing in pigeons
Authors: Gagliardo A. , Ioalè P. , Savini M. , Wild J. M.
Published: July 2006

The ability of pigeons to find their way home from unfamiliar sites located up to hundreds of kilometers away is well known, but the mechanisms underlying this ability remain controversial. One proposed mechanism is based on the suggestion that pigeons are equipped with magnetoreceptors that can enable the detection of either the earth's magnetic field and/or magnetic field anomalies in the local terrain over which the pigeons fly. Recent reports have suggested that these magnetoreceptors are located in the upper beak where they are innervated by the ophthalmic branch of the trigeminal nerve. Moreover, this nerve has been shown to mediate pigeons' ability to discriminate the presence versus the absence of a magnetic field anomaly in a conditioning situation. In the present study, however, we show that an intact ophthalmic branch of the trigeminal nerve is neither necessary nor sufficient for good homing performance from unfamiliar locations, but that an intact olfactory nerve is necessary.
Diversification of gut morphology in caterpillars is associated with defensive behavior
Authors: Grant Jacqualine Bonnie
Published: July 2006

The relationship between insect gut structure and foraging strategy has been studied for several hundred years; however, we know little about how, or even if, other common insect behaviors are linked to gut morphology. For example, many insects defend themselves by regurgitation, a behavior which is expected to be closely connected to gut structure. Caterpillars belong to an insect taxon, the Lepidoptera, with a particularly well-studied digestive tract and a known predilection for defensive regurgitation. I have explored whether defensive regurgitation is associated with specific gut structure by examining the relationship between defensive behavior and gut morphology in the larvae of 36 butterfly and moth species. My analysis shows that predilection to defensively regurgitate is closely associated with fore- and midgut morphology. Species that primarily regurgitate in defense have enlarged foreguts and shortened midguts, whereas the opposite relationship is seen among those that do not readily regurgitate. These results reveal that: (i)defensive regurgitation is not the primary defense of all caterpillars, and(ii) gut morphology can be associated with other factors than the chemical and mechanical properties of ingested foods. These findings challenge long held beliefs concerning the ubiquity of defensive regurgitation in caterpillars and the causes of diversification of gut morphology, and further reinforce the gut's standing as a complex and sophisticated organ.
Neuromodulation of the locust frontal ganglion during the moult: a novel role for insect ecdysis peptides
Authors: Zilberstein Y. , Ewer J. , Ayali A.
Published: July 2006

In insects, continuous growth requires the periodic replacement of the exoskeleton during the moult. A moulting insect displays a stereotypical set of behaviours that culminate in the shedding of the old cuticle at ecdysis. Moulting is an intricate process requiring tightly regulated physiological changes and behaviours to allow integration of environmental cues and to ensure the proper timing and sequence of its components. This is under complex hormonal regulation, and is an important point of interaction between endocrine and neural control.

Here, we focus on the locust frontal ganglion (FG), an important player in moulting behaviour, as a previously unexplored target for ecdysis peptides. We show that application of 10-7 mol l-1 ecdysis-triggering hormone (ETH) or 10-7 mol l-1 and 10-6 mol l-1 Pre-ecdysis-triggering hormone (PETH) to an isolated FG preparation caused an increase in bursting frequency in the FG, whereas application of 10-6 mol l-1 eclosion hormone (EH) caused an instantaneous, though temporary, total inhibition of all FG rhythmic activity. Crustacean cardioactive peptide (CCAP), an important peptide believed to turn on ecdysis behaviour, caused a dose-dependent increase of FG burst frequency. Our results imply a novel role for this peptide in generating air-swallowing behaviour during the early stages of ecdysis. Furthermore, we show that the modulatory effects of CCAP on the FG motor circuits are dependent on behavioural state and physiological context. Thus, we report that pre-treatment with ETH caused CCAP-induced effects similar to those induced by CCAP alone during pre-ecdysis. Thus, the action of CCAP seems to depend on pre-exposure to ETH, which is thought to be released before CCAP in vivo.
Delayed Thermal Excimer Fluorescence of Acriflavine in a Stretched PVA Sheet
Authors: Sato Masao , Azumi Tohru , Azumi Hiroshi
Published: July 2006

A long-lived emission of acriflavine absorbed into a polyvinylalcohol sheet has been investigated. At higher concentrations, a new, previously-unobserved emission band has been observed. It has been shown that the newly-observed band can be interpreted by a mechanism in which the thermal excitation of the triplet state to the excimer state takes place, followed by an emission. The term “delayed thermal excimer fluorescence” has been given to specify the emission of this type.
A Study of the Surface Heterogeneity of Nickel Oxide Catalysts by the Flash Desorption Method
Authors: Kondo Junko , Uchijima Toshio , Yoneda Yukio
Published: July 2006

The flash desorption method was applied to the carbon dioxide - nickel oxide system in order to investigate the surface heterogeneity of nickel oxide catalysts. It was found that there were two peaks in flash desorption chromatograms. The Arrhenius plots for carbon monoxide oxidation on nickel oxide were found to be composed of two straight lines. It was shown that the inflection of the Arrhenius plots was due to the existence of two kinds of active sites which differ in activation energy for the oxidation reaction and in the strength of interaction with carbon dioxide. The numbers of active sites for carbon monoxide oxidation were determined by the measurement of the amounts of desorbed carbon dioxide.
Studies of the Photochemistry of Aromatic Diazo Compounds. II. The Electronic Structures of Some p-Substituted Benzenediazonium Cations
Authors: Sukigara Mitsunori , Kikuchi Shin-ichi
Published: July 2006

The electronic structures and electronic absorption spectra of p-fluoro-, p-chloro-, p-bromo-, p-iodo, p-methoxy-, and p-dimethylaminobenzenediazonium cations were studied by making molecular orbital calculations and by measuring the visible and near-ultraviolet absorption spectra. From the calculations it is understood that when an electron-donating group is introduced at the p-position of the benzenediazonium cation, the 1A1-1A1 transition shows a very large shift to longer wavelengths, while the 1A1-1B1 transition is not so much affected; at the same time, the N–N bond order in the ground state decreases. It is shown that there is a linear relationship between the N–N bond order and the wave number of the N–N stretching of the p-substituted benzenediazonium salt. It is concluded from the calculations that the electron affinity of the nonsubstituted benzenediazonium cation has a large value, such as 2.40 eV.
The Concentrations and the Reactivity of the Adsorbed Species during Surface Catalysis on a Ternary-component Methanol Synthesis Catalyst
Authors: Tsuchiya Susumu , Shiba Tadao
Published: July 2006

The relative reactivity of the adsorbed species during a catalytic methanol synthesis reaction on a ternary-component catalyst was investigated. Abrupt changes in the ambient pressure of a component in the gas phase, at a nearly equilibrium condition, were correlated with the corresponding changes in the amounts of the adsorption and in the total ambient pressure. The data collected from such dynamical treatments indicate that the species adsorbed on the catalyst surface, in a nearly equilibrated system of the simultaneous adsorption of hydrogen and carbon monoxide, is mostly the surface intermediate complex formed from both of them. Furthermore, the results obtained suggest an order for the reaction speed of each elementary step in the methanol synthesis reaction.
Internal Rotation of Propane from the Microwave Spectrum
Authors: Hirota Eizi , Matsumura Chi , Morino Yonezo
Published: July 2006

The microwave spectrum of propane was observed in the first-excited states of the CH3torsion. Each transition was split into a symmetric triplet; the splittings were 14–19% larger for the (−) state than for the (+) state. The top-top interaction and its effect on the rotational spectra were treated by the perturbation theory, and the results were applied to the analysis of the triplet splittings. The two barrier parameters, V3 and V3″, were thus determined to be 3325±20 and −170±30 cal/mol respectively.
Investigations of Solvent Effects on Paper Chromatography
Authors: Paul Agnes , Janardhan Pandarinath B
Published: July 2006

The mechanism of paper chromatography consists of three stages: i) adsorption; ii) desorption; iii) migration due to solvation. Solvation depends on the physical properties of the solvent. The present paper will attempt to correlate the Rf values of metal ions with such physical properties of the solvent as (a) surface tension, (b) viscosity, (c) solubilisation, and (d) the dielectric constant. Experiments have been conducted with pure and mixed solvents of the aliphatic alcohol series. As a result, it may be reported that the Rf values of cations (silver, copper, nickel and ferric ions) bear almost a linear relationship to the dielectric constant/viscosity quotient.
A Spectrophotometric Study on the Thorium Complex of o-Hydroxyphenyl-azo-chromotropic Acid
Authors: Toei Kyoji , Miyata Haruo , Nakashima Susumu , Kiguchi Sachiaki
Published: July 2006

o-Hydroxyphenyl-azo-chromotropic acid was used as a colorimetrie reagent for thorium. The acid dissociation constants of the reagent have been determined by the pH titration method. The pK1 (for the dissociation of the phenolic hydroxyl group) and pK2 (for that of the naphtholic hydroxyl group) were found to be 7.60 and 10.60 respectively at 25°C and μ=0.1. The reagent forms a violet 1 : 1 complex in an acidic solution, and its apparent stability constant is measured spectrophotometrically.
The Spectrophotometric Determination of Scandium(III) with Chromazurol S
Authors: Ishida Ryoei , Hasegawa Norio
Published: July 2006

Chromazurol S reacts with scandium(III) in a weakly acidic medium to form one of two kinds of complexes according to the pH value of the medium. Their compositions were confirmed; one had a 1 : 2 combining ratio of scandium (III) and chromazurol S at pH 5.2 or higher, and the other, a 1 : 1 ratio at pH below 4.0. The color development of the 1 : 2 complex is more sensitive than the other. Therefore, it was applied to the determination of scandium(III). Several conditions for the color development were investigated, a calibration curve was made under the optimum conditions, and the influences of coexisting ions were investigated. The maximum absorption wavelength of the complex is 550 mμ against the reagent blank. The optimum pH for the color development is about 5.6. By adding a reagent in an amount four times the scandium concentration, the maximum color intensity is given. The color intensity decreases gradually during the first 1.5 hr, and then it remains constant for several hours. A linear relationship between the absorbance and the scandium concentration is obtained in the concentration range from 4 to 27 μg per 10 ml. The value of the molar extinction coefficient of the complex at 550 mμ is 27000, and the sensitivity of the color reaction is 0.0017 μg/cm2 for log I0/I=0.001. The formation constant, K, of the complex is calculated to be 9.5×1011 under these conditions. Anions such as fluoride, phosphate, oxalate, tartrate, citrate, and EDTA interfere with the color development of the complex. Cations such as Al(III), Be(II), U(VI), Fe(II), Th(IV), Cu(II), Y(III), Fe(III), Zr(IV), and W(VI) interfere, too.
Isotopic Exchange Reaction between Bis(α-benzildioximato)nickel(II) and Nickel Ions in Pyridine and Pyridine-Water Solutions
Authors: Hirota Reiko , Saito Nobufusa
Published: July 2006

The rate of isotopic exchange reaction between bis(α-benzildioximato)nickel(II) and nickel ions in pyridine greatly increases in the presence of water. When the water content in pyridine is lower than 3 m, the reaction takes place according to the rate equation:

Rate=k1(complex)+k2(complex)(Ni2+)(H2O)

For the catalyzed step, a mechanism is proposed.
Copper(II) Complexes with Phthalic Acid
Authors: Shimizu Ichiro , Tsuchiya Ryokichi , Kyuno Eishin
Published: July 2006

Three copper(II) complexes with phthalic acid, [Cuph(H2O)] (I) (ph=C6H4(COO)2), [Cu(Hph)2(H2O)2] (II), and [Cuph]2 (III), were prepared. Compound I was prepared from an aqueous solution of copper sulfate and phthalic acid within the temperature range of 60–79°C. It was a light blue crystal forming a hexagonal unit, the parameters being a=13.07 Å and c=13.98 Å and with the chemical unit Z equalling 8. II was prepared at a temperature below 60°C. It was a blue crystal having a hexagonal unit of a=11.42 Å, c=13.68 Å, and Z=4. The magnetic moments of I and II were 1.87 B. M. and 1.96 B. M. (both 21.5°C) respectively, showing I and II to have a monomer structure with respect to the two copper atoms. III could be prepared at temperatures above 79°C. It was a bluish-green crystal containing a hexagonal unit of a=12.77 Å, c=13.02 Å, and Z=4. The magnetic moment of III was found to be 1.54 B. M. (18.4°C), suggesting that complex III consisted of a dimer structure with respect to the copper atoms. The appearance of a shoulder near 370 mμ. in the reflection spectra of the copper complex III in the powdered crystalline state confirmed the suggestion of a dimer structure.
Interaction of Excited Aromatic Hydrocarbons with Aromatic Amines
Authors: Mataga Noboru , Ezumi Kiyoshi
Published: July 2006

It has been established that many aromatic hydrocarbons in N,N-dimethyl aromatic amine solvents show their fluorescence spectra at much longer wavelengths than in such inactive solvents as n-hexane and toluene. Because the absorption spectra of the hydrocarbons in the amines do not show any essential change, it is confirmed that specific interaction between a hydrocarbon and an amine occurs only in the excited electronic state (the fluorescent state). It has been clearly demonstrated, from the relation between the frequencies of the long-wavelength fluorescence and the electron affinities of the excited aromatic hydrocarbons, the ionization potentials of the amines, etc., that this interaction can be ascribed to the charge transfer from the amine to the excited hydrocarbon, and that the long-wavelength fluorescence is a kind of charge-transfer fluorescence. At the temperature of liquid nitrogen, the interaction becomes much weaker because the rearrangement motions of molecules during the lifetime of the excited state, which are necessary for the charge-transfer complex formation, are more or less hindered in a rigid solvent at low temperatures. It has been confirmed that the interaction is still weaker in the phosphorescent state. This phenomenon has been explained by reference to the electronic processes in the complex.
The Autoxidation of Toluene Catalyzed by Metal Ions in Aqueous Solutions. I
Authors: Suzuki Nobutake , Hotta Hiroshi
Published: July 2006

The yield of benzaldehyde, which was the main product, depended on the kind of metal ions between 100°C and 200°C. The yield was high in a ferrous sulfate solution, even at lower temperatures, while it was extremely low in a ferric sulfate solution, even above 180°C. The yield in a cupric sulfate solution was appreciable at 180°C only with γ-radiation, while it was high near 200°C even without γ-radiation. All the yields were a little higher with γ-radiation than without γ-radiation. The rate-constant ratio of toluene to toluene-d8 was about 1.4 for the benzaldehyde and benzyl alcohol produced by using Fenton’s reagent at 70°C, respectively. It may be concluded from the experiments using the oxygen-18 enriched water that the oxygen of the benzaldehyde produced is transferred from the dissolved molecular oxygen, while that of benzyl alcohol is transferred partly from water. On the basis of these facts, a whole reaction scheme is proposed for the present system. The difference between toluene and benzene is also discussed in the present paper.
A New Spectrophotometric Method for the Determination of Micro Amounts of Sulfite
Authors: Okutani Tadao , Utsumi Satori
Published: July 2006

A new spectrophotometric method for the determination of a minute quantity of sulfite was studied. When a definite amount of aqueous solution of mercuric nitrate mixed with potassium bromide and an ethanol solution of diphenylcarbazone are added to the sample solution kept at pH 7.0, sulfite reacts with mercuric reagent and the excess of the mercuric reagent forms the reddish-violet complex with diphenylcarbazone which may be easily extracted by benzene. Sulfite is determined by measuring the absorbancy of the benzene phase which decreases upon an increase in the concentration of sulfite, at the wavelength of 562 mμ, The method which is applicable to the determination of both sulfite and sulfide has also been established, because sulfide as well as sulfite reacts with mercuric reagent. By this proposed method, sulfite (0.1—2.5 ppm) and sulfide (0.01—0.5 ppm) could be determined at the same time rapidly and accurately. The composition of the complex formed between mercury(II) and sulfite was also studied.
The Liquid Phase Oxidation of Acrolein. II. Solvent Effects in the Liquid Phase Oxidation of Acrolein and the Decomposition of Peracrylic Acid
Authors: Ohkatsu Yasukazu , Takeda Makoto , Hara Takao , Osa Tetsuo , Misono Akira
Published: July 2006

The liquid phase oxidation of acrolein and the decomposition of peracrylic acid with Co-(acac)3 in various solvents were investigated. The solvents of butyric and valeric acids gave the most desirable results with respect to the selective oxidation; for example, in butyric acid with 5×10−4mol/l of Co(acac)3 for 4 hr at 35°C, the conversion of acrolein and the selectivity of acrylic acid were 45.1% and 86.0%, respectively. The preferable solvent effects of C4 and C5 carboxylic acids were discussed in terms of the acidity and dielectric constant of the solvents, the oxygen solubility in the solvents and the interaction of the solvents with acrolein. Further more, from the comparison of solvent effects in the oxidation of acrolein with those in the decomposition of peracrylic acid, one of the rate determining steps in the oxidation was elucidated to be much concerned with the decomposition of peracrylic acid formed during the reaction.
An MO Interpretation of the Methylation of Olefins by the Methylsulfinyl Carbanion
Authors: Yamamoto Osamu , Kato Hiroshi , Yonezawa Teijiro
Published: July 2006

Recently the reaction of the methylsulfinyl carbanion with a number of olefins (quinoline, acridine, anthracene, butadiene, etc.) has been reported on by several authors. The superdelocalizability for the nucleophilic attack, Sr(N), is used as a theoretical index for discussing the intermolecular reactivity. It is pointed out that the calculated values of Sr(N) are useful in predicting the relative reactivity as well as the orientation in the nucleophilic aromatic methylation. In addition, the mechanism of the ring-opening reaction taking place with regard to benzofuran is discussed briefly.
Magnetic Properties of Aromatic Hydrocarbon-Alkali Metal Ion-Pair Salts. I
Authors: Nishiguchi Hiroaki
Published: July 2006

Measurements of magnetic susceptibility and electron paramagnetic resonance absorptions have been carried out on biphenyl (Bp)-potassium (K), -rubidium (Rb), and -cesium (Cs) ion-pair salts. These powder salts were prepared by the evaporation of the solvent from the corresponding anion radical solutions in vacuo. The magnetic susceptibility of the Bp-K system is paramagnetic and exhibits a maximum at 130±4°K. This susceptibility can be fitted approximately to the expression:

χM=\frac2Ng2β2kT·\frac13+eδ⁄kT,

which leads to a singlet-triplet dimer model consisting of a singlet ground state and a triplet state lying slightly above the ground state. The line width of the electron paramagnetic resonance (EPR) spectrum is also temperature-dependent and becomes broader as the temperature decreases. The Bp-Rb and Bp-Cs systems also exhibit susceptibilities which monotonously increase as the temperature decreases. These can be fitted to the higher temperature range (kT⁄δ>1) of the above equation rather than to the Curie-Weiss law. For these compounds single absorption lines have also been observed at g=2.002 in the EPR spectra at room temperature. The results suggest that these salts may be interpreted generally by means of the singlet-triplet dimer model proposed for the organic salts based on the anion radical of tetracyanoquinodimethane (TCNQ). However, one marked difference is that the singlet-triplet separations of these compounds are very small in comparison with those of the TCNQ radical salts.
Krafft Temperatures of Perfluoro-Octanoic Acid and of Its Salts
Authors: Nakayama Haruo
Published: July 2006

The Krafft temperatures of perfluoro-octanoic acid and of its alkali metal and ammonium salts have been determined from the solubility measurements. The heats of solution and of wetting of dry solid surfactants have also been measured. The solubility decreases in the order; Li-salt>Na-salt>K-salt, and then increases in the sequence; Rb-salt<Cs-salt. Ammonium salt is more soluble than sodium salt. Acid is least soluble. The heats of wetting depend markedly on the kind of counterions, but the heats of solution of hydrated solids, which are calculated from the temperature-dependence of single-dispersion solubility, are almost independent of the counterions. The order of Krafft temperatures for alkali metal salts is; Li<NaRb>Cs, just the reverse of that of the solubility. It is concluded that the Krafft temperature of each substance is mainly determined by the magnitude of the non-micellar solubility, and that the increasing order of the solubilities of salts can reasonably be estimated by comparing it with the solubility order of ordinary organic or inorganic salts which have the same chemical properties as the surfactants. This sequence of solubility is markedly determined by the strength of the acids from which the salts are derived.
The Structure of Mo7O246− Ion in the Crystal of Ammonium Heptamolybdate Tetrahydrate
Authors: Shimao Eikoh
Published: July 2006

The structure of a discrete polyanion, Mo7O246−, in the crystal of ammonium heptamolybdate tetrahydrate, previously determined by Lindqvist, has been redetermined and refined by a two-dimensional, single crystal X-ray diffraction study. The positional parameters of the oxygen atoms, which were left undetermined in the previous investigation, have been determined. Lindqvist’s description of the structure still applies. However, the distortion of the polyanion has been found to be more pronounced than was previously assumed. Comparisons with molybdenum oxides and oxyacids are discussed with regard to the structure, the Mo–Mo distances and Mo–O distances.
The Indirect Gas Ghromatographic Determination of Palladium in an Aqueous Solution
Authors: Hara Tadashi , Koga Tadashi , Takeda Hajime
Published: July 2006

An indirect method has been proposed for the gas-chromatographic determination of palladium in an aqueous solution. After a mixture of propylene and propane has come in contact with a palladium sample solution, the amount of propylene in the remaining gas is estimated, propane being used as an internal standard. An apparatus consisting of a gas sampler, a gas tank, etc. was devised. The reaction between propylene and palladium ions in less than 3.0 N perchloric acid goes to completion within 15 min. According to the present method, the calibration curve is straight for Pd up to 500 ppm and for Hg up to 1500 ppm. The following ions in concentrations less than that of Pd2+ are tolerable; Co2+, Mg2+, Mn2+, Li+, Sn4+, Ni2+, Cu2+, Cd2+, Zn2+, Pb2+, Al3+, ClO4−, Cl−, NO3−, CH3COO−, and SO42−, while Fe3+, Ag+, Hg2+, Pt2+ and Pt4+ interfere seriously. The interference of ferric, silver, and mercuric ions can be avoided by chloride or bromide precipitation, followed by passing the substances through a cation exchanger column. The behavior of the mercuric ion in the presence of the palladium ion, which is quite different from that of the mercuric ion alone, has also been discussed.
The Alkaline Hydrolyses of Chlorophenyl Phenyl Sulfoxides and Sulfones
Authors: Oae Shigeru , Khim Yong He
Published: July 2006

Both phenylsulfonyl and phenylsulfinyl group have been shown to activate the nucleophilic substitution of aromatic chloride from ortho- and para-positions, however, the effect of phenylsulfonyl group was substantially larger than that of phenylsulfinyl group. The activation by these sulfur groups is presumably due to the conjugative stabilization by the phenylsulfonyl or -sulfmyl groups through expansion of the sulfur valence shell. The addition complex is presumed to retain its configuration, since the stereo-integrity of the sulfoxide group has been shown to be maintained throughout the experiment.
Thermochemical Evidence of OH–π Type Intermolecular Hydrogen Bonds
Authors: Murakami Sachio , Fujishiro Ryoichi
Published: July 2006

A calorimeter for measuring the heat of mixing was constructed. Using the calorimeter, the heats of mixing were measured at 25.0±0.01°C for binary mixtures of benzyl alcohol with ethyl benzene or cyclohexane and ethyl benzene with cyclohexane, and at 35.0±0.01°C for binary mixtures of m-cresol with m-xylene or cyclohexane and m-xylene with cyclohexane. By plotting the values of the heats of mixing, ΔHx1M against the mole fraction of component 1, x1 and by extrapolating the curve to an infinite dilution (x1→0) for each system, the heats of mixing at an infinite dilution (\undersetx1→0limΔHx1M) were obtained graphically. By using the values of \undersetx1→0limΔHx1M obtained for these systems and by applying an enthalpy cycle, the OH–π type intermolecular hydrogen bond energies were estimated to be ΔH=−6.2 kJ for the benzyl alcohol-ethyl benzene - cyclohexane system and ΔH=−13.1 kJ for the m-cresol - m-xylene - cyclohexane system. The results obtained have been discussed from two points of view, that is, the proton-donating power of alcohols and the proton-accepting power of aromatic hydrocarbons.
Radiation Chemistry of Dicarboxylic Acids in the Solid State. II. C-13 Isotope Effects in the Radiation-induced Decarboxylation of Malonic and Several Aliphatic Dicarboxylic Acids
Authors: Hosaka Akio , Sugimori Akira , Tsuchihashi Gen-ichi
Published: July 2006

The C-13 isotope effects in the radiation-induced decarboxylation of several dicarboxylic acids were investigated. Malonic acid showed a C-13 isotope effect of about 2%; this is much greater than those of monocarboxylic acids. The greater isotope effect of malonic acid is attributed to the intramolecular competition of the C-carboxyl bond rupture. Succinic, adipic, and pimeric acid, in which the intramolecular interaction of two carboxyl groups can be expected, gave large isotope-effect values, whereas glutaric and sebatic acid, in which such an effect may be expected to be small, showed lower isotope effects. Analogously, maleic acid (cis isomer) showed a larger isotope effect than did fumaric acid (trans isomer).
Secondary Electrons in the Radiolysis of Cyclohexane
Authors: Sato Shin , Terao Terumi , Kono Michiyuki , Shida Shoji
Published: July 2006

Carbon dioxide and sulfur hexafluoride have been used as electron scavengers in the γ-radiolysis of cyclohexane. The dependence of G(H2) on the concentrations of additives can be interpreted satisfactorily in terms of diffusion-controlled reactions between electrons and the additives. A simple calculation was made using a function proportional to r2exp(−αr2) for the initial distribution of secondary electrons. The distribution constant α and the value of G(electrons) were adjusted to make the calculated curve of G(H2) vs- scanvenger concentration coincide with the observed one. The average initial separation of the secondary electron from the parent positive ion was found to be about 50 Å, and G(electrons) = 3.
Organic Catalysts. III. The Catalytic Action of Copper-Iron-Polyphthalocyanine on the Oxidation of Acetaldehyde Ethylene Acetal
Authors: Inoue Hiroo , Kida Yasuji , Imoto Eiji
Published: July 2006

Copper-iron-polyphthalocyanine shows catalytic activity on the oxidation of acetaldehyde ethylene acetal with oxygen at 30°C; this catalytic activity is remarkably dependent on the atomic ratio of copper to iron ions involved and on the activation energy of the electrical conductivity of copper-iron-polyphthalocyanine. The catalytic oxidation of acetaldehyde ethylene acetal with oxygen in the presence of copper-iron-polyphthalocyanine gives, selectively, ethylene glycol monoacetate as the main reaction product, together with small amounts of ethylene glycol diacetate, ethylene glycol, acetaldehyde, and acetic acid. This catalyst is also effective in the selective oxidation of cumene and benzaldehyde ethylene acetal.
Systematic Synthesis of Ammine Series of Chromium(III) Complexes
Authors: Kyuno Eishin , Kamada Minoru , Tanaka Nobuyuki
Published: July 2006

The systematic synthesis of ammine series of chromium (III) complexes has been developed by using aquopentamminechromium(III) nitrate as a starting material. The procedure for the preparation of aquopentamminechromium(III) nitrate was improved to increase the yield. Twenty five sorts of chromium(III) complexes were obtained by the systematic synthesis, of which the procedures for the preparation of eleven sorts of complexes including a new complex, dinitritotetramminechromium(III) bromide, are described. The visible and ultraviolet absorption spectra in aqueous solutions and infrared spectra in solid state of those complexes have been obtained and their structures are discussed.
A Spectrophotometric Study of the Thorium Complex of 2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-phenoxyacetic Acid
Authors: Miyata Haruo
Published: July 2006

2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-phcnoxyacetic acid has been synthesized. The acid dissociation constants of the reagent have been determined spectrophotometrically at 25 °C and at an ionic strength of 0.1. The reagent forms a violet 1 : 1 complex with thorium, showing an absorption maximum at 575 mμ in an acidic solution. The apparent stability constant of the thorium complex was measured over the pH range from 1 to 3.5.
The Preparation of Poly(Ethylene Carbamate)
Authors: Fujisawa Tamotsu , Koda Hajime , Mukaiyama Teruaki
Published: July 2006

Poly(ethylene N-chlorocarbamate) was obtained by the 1,4-addition-type ring-opening polymerization of ethylene N-chloroiminocarbonate with cationic catalysts, such as boron trifluoride etherate or sulfuric acid. Although it is an amorphous, tough elastomer, it is unstable in the air and decomposes to a brittle, pumiceous polymer. The reductions of polyethylene N-chlorocarbamate) by means of an aqueous solution of arsenic trioxide, butanol-zinc powder, t-butanol, and fluorene gave poly(ethylene carbamate), which is a new, stable, hydrogen-bonded polymer.
Kinetic Studies of Bimolecular Nucleophilic Substitution. VI. Rates of the Menschtkin Reaction of Methyl Iodide with Methylamines and Ammonia in Aqueous Solutions
Authors: Okamoto Kunio , Fukui Suguru , Shingu Haruo
Published: July 2006

The kinetics of the reactions of trimethylamine, dimethylamine, methylamine, and ammonia with methyl iodide in aqueous solutions have been investigated at temperatures ranging from 0 to 40°C. Kinetic analyses of the consecutive methylations of dimethylamine and methylamine have been conducted according to the method of French. In the case of ammonia a standard second-order kinetic treatment can be successfully used because of the relative sluggishness of the first stage as compared with the succeeding stages. The observed rates are in the sequence: Me3N>Me2NH>MeNH2>NH3. The factors which affect this rate sequence are discussed.