bluuebunny/crossref_metadata_2025 huggingface dataset:
Photoreduction of Acridine in Deaerated and Aerated Ethanol Solutions
Authors: Kato Shunji , Minagawa Shigekazu , Koizumi Masao
Published: July 2006

1. The deaerated solution of acridine 1×10−4m in ethanol, when irradiated by 365 mμ produces acridane with a quantum yield of about 0.13. This reductive reaction can proceed even in the air-saturated solution with the rate about one third of that of the deaerated solution. For both cases the rate is simply proportional to the absorption of light.

2. When the concentration of dissolved oxygen is more than about twice that of acridine concentration, the rate of the reaction is approximately equal to that of the air-saturated solution independent of the oxygen concentration, and at the same time oxygen is consumed at the rate about twice as great as that of the reduction of acridine. Hence, when the existent oxygen is exhausted, the rate gains the value of the deaerated solution.

3. All the above results are almost entirely independent of temperature.

4. A possible scheme was proposed in which a certain type of intermediate is formed between semireduced acridine and oxygen and, from this intermediate acridine is partially recovered accompanied with the consumption of oxygen and, in competition with this, acridane is poduced, both by a bimolecular process.
A. C. Polarography of Thiamine Hydrochloride in Weakly Acidic Buffer Solutions
Authors: Okamoto Koichi
Published: July 2006

Although in ordinary D. C. polarography no well-defined polarographic reduction waves of thiamine in weakly acidic or in neutral buffer solutions have been reported, it was found that A. C. polarographic methods would be suitable for these studies.

A. C. polarographic waves of thiamine appeared at 1.27∼−1.35 V. in buffer solutions of pH 3.0∼4.75, and in the region of pH 4.75∼7.0 a new wave began to be observed at more positive potentials than −1.27∼1.35 V., while another wave was observed at −1.32∼−1.44 V. in the same pH region. The heights of two waves decreased with the increase of pH.

In basic buffer solutions the wave forms varied irregularly and the waves disappeared completely at pH 10.0.

According to the relation of is to temperature, mercury heights and concentrations, these two waves were both recognized as diffusion currents with a few tensammetric properties.

The nature of the first and second waves were attributed to the reductions of thiamine with Cl−, and with hydrochloric acid and Cl− to each dihydrothiamine, respectively.
The Photovoltaic Behavior in Organic Compounds
Authors: Inokuchi Hiroo , Maruyama Yusei , Akamatu Hideo
Published: July 2006

When a contact between a semiconductive material and a metal is made, it is expected that a potential barrier occurs at the boundary layer and the photovoltaic effect which is observed with illumination on this barrier. It has been found that this is the case for organic semiconductors. The photovoltaic cell was made with aromatic compounds sandwiched between two metal layers or metal and stannic oxide. One of them was a terminal electrode and the other, the junction electrode, was made with evaporated film of platinum, gold, silver, tin, lead or alkali metal. All observations of photovoltage were carried out in vacuo or in an atmosphere of insert gas.

With the illumination of white light from a tungsten lamp, the induced photovoltage varied from several millivolts to one volt, depending on the sorts of metals applied to the junctions. In most of these junctions, the organic solids acted as positive eletrodes with respected to the junction metal.

In the alkali metal-aromatics system, a fluctuation was frequently observed concerning the direction of electromotive force, but the value of photovoltage was generally much higher than in the case of the other metals; thus the spectral response of the voltage was measurable. This response was less dependent on the sorts of organic solids but dependent on the sorts of metals. On the other hand, the spectral response in the junction between organic solid and stannic oxide, was a curve which is in good coincidence with the optical absorption curve for solid organics.
Studies on Organophosphorus Compounds. II. On Phosphite Cuprous Halide Complex Compounds
Authors: Nishizawa Yoshihiko
Published: July 2006

Phosphites or phosphonites react with cuprous halides in one to one or two to one mole ratio to give phosphite, phosphonite, bis-phosphite or bis-phosphonite cuprous halides complex compounds. Their molecular weights in various organic solvents showed that these compounds formed polymer.

Phosphite cuprous halides react with pyridine, aniline or their derivatives and gave new complex compounds having phosphite, cuprous chloride and amine.
Polarography of Narcotine-N-oxide
Authors: Asahi Yutaka
Published: July 2006

Narcotine-N-oxide shows a catalytic hydrogen wave as narcotine and other alkaloids. The reduction waves of narcotine-N-oxide are ascribed to the 2-electron reduction of the N-oxide to narcotine. Their 1st step is an adsorption wave of the reductant. The adsorped film disturbs the further electrode reaction, an anomalous minimum wave is observed in higher concentration. The 2nd step in pH 1∼5 corresponds to the proton adduct of the N-oxide with lactone and the 3rd step in pH 5∼10 to the base of the N-oxide.

Narcotine and its N-oxide change reversibly to hydroxycarboxylate type in alkali, which gives more negative reduction potential of the N-oxide and an absorption maximum in shorter wavelength. The velocity constants of cleavage of the lactone and of the reverse reaction are proportional to [OH−] and [H+], respectively.
Studies on Lactone Formation in Vapor Phase. I. Synthesis of γ-Butyrolactone
Authors: Oka Shinzaburo
Published: July 2006

Vapor phase catalytic dehydrogenation of 1,4-butanediol to γ-butyrolactone with reduced copper supported on various carriers was studied. It was found that copper supported on zinc oxide or magnesium oxide was a superior catalyst. In the case of a catalyst consisting of 20% copper and 80% zinc oxide, the yield and space time yield of γ-butyrolactone were 95% and 0.28 at 230∼240°C, respectively.
Studies on Surface Heterogeneity in Adsorption of Carbon Dioxide on Nickel by Use of the Isotopic Desorption Method
Authors: Hirota Kozo , Kobayashi Yasushi , Kiji Jitsuo
Published: July 2006

By applying the isotopic desorption method of Roginsky under the experimental condition of least ambiguity, heterogeneity of nickel surface has been studied on the chemisorption of carbon dioxide by making heavy oxygen as the tracer. It has been shown that about one third of the surface can chemisorb carbon dioxide very strongly at −78, 0 and 19°C, and a part of carbon dioxide chemisorbed is not desorbed even by the evacuation at 300°C. Considering the isotopic balance of heavy oxygen, it can be said that the above effect is brought about by the primary heterogeneity of surface sites but not by the “induced heterogeneity” of adsorbate. However, it has been found difficult to make the detailed nature of such heterogeneity by the present data alone.
The Viscosity of Concentrated Aqueous Solutions of Strong Electrolytes
Authors: Satoh Takeshi , Hayashi Koreaki
Published: July 2006

The coefficients of the viscosity of concentrated aqueous solutions of 1–1 type electrolytes were measured at room temperature. Judging from the relationship between relative viscosity and concentration the electrolytes would be classified into two groups. One is normal and the other shows negative viscosity.It is the linear term that makes the most predominent contribution in the dilute range. We analyzed its factor by the use of Broersma’s concept of local viscosity. From the expression obtained, a condition of negative viscosity was derived as 6 in approximation. According to our interpretation, negative viscosity does not result from individual characters of ions of each electrolyte in question, but from delicate correlations between the local viscosities of neighboring hydration layers.
Thermo-magnetic Study of Mercury and Dilute Amalgams of Sodium and Potassium
Authors: Sriraman S , Shanmugasundaram V
Published: July 2006

The susceptibility of pure mercury was determined at different temperatures. Sodium and potassium amalgams were prepared in a pure state and the suscepribility of the amalgams of different concentrations at different temperatures was studied. The χ-values of amalgams were found to be practically constant in the range of temperature employed.
Reduction of Organic Compounds with Urushibara Catalysts under High Pressure. IX. Reduction of Some Carbonyl Compounds with Urushibara Catalysts by Various Modified Methods
Authors: Taira Shin-ichi
Published: July 2006

The catalytic reduction of deoxybenzoin, benzoin, benzil and furil with various Urushibara catalysts under high pressure were studied. It was found that benzil and furil was converted into the corresponding α-ketols by the partial reduction under proper condition.

Some modifications for the preparation of the Urushibara catalyst were attained. The newly developed precipitated nickel prepared by a very simple way proved to give a catalyst as active as the usual Urushibara nickel catalyst for practical use. Hydrochloric acid was found to be applicable for the digestion of the precipitated nickel in place of acetic acid.
Studies on the Composition and Properties of Less Familiar Metal Cyano Complexes. I. Composition of Nickel and Cobalt Octacyanomolybdates by Electrometric Methods
Authors: Malik Wahid U , Ali S Iftikhar
Published: July 2006

The composition of the freshly precipitated nickel and cobalt cyano molybdates was determined using conductometric, potentiometric and amperometric methods. The nickel compound is green in color and its composition may be represented as Ni2Mo(CN)8. The orange precipitate of the cobalt cyano molybdate has also got the composition Co2Mo(CN)8. Reverse conductometric titration (salt solution added to molybdocyanide) give evidence of the complexes K2NiMo(CN)8 and K2CoMo(CN)8. These titrations provide information of the adsorption of Mo(CN)84− ions by the freshly precipitated complex. Both the compounds show tendency to pass into the colloidal state when the salt solution is added to excess of potassium octacyano molybdate.
Infrared Absorption Spectra of Water of Crystallization in Ferrous Chloride Tetrahydrate Crystal
Authors: Gamo Itaru
Published: July 2006

The observed spectra of the water of crystallization were correlated with the crystal structure determined by X-rays. They were interpreted as affected by coördination and hydrogen bonding. The coördination was concluded to lower the bending frequency of water in general. Two remarkably sharp bending bands were found.
Energy Distribution of Secondary Electrons from Copper-Beryllium Alloy by Positive Ions of Inert Gases. I. Electro-polished Surface
Authors: Sugiura Toshio
Published: July 2006

The distribution curves of the kinetic energies of the secondary electrons from the electropolished copper-beryllium surface by inert gas ions were measured by the retarding potential method together with the yield of the secondary electron emission. The contact potential difference between the ion target (electro-polished copper-beryllium) and the electron collector (gold) was also measured by the retarding potential method for the thermal electrons from tungsten, and the correction of this contact potential difference was made for the kinetic energies of secondary electrons. The main results obtained are as follows.

(1) The contact potential difference between gold and electro-polished copper-beryllium(4%) is 0.95 eV. (gold, negative).

(2) The general features of the distribution curves of secondary electrons are similar to the distribution curves of the kinetic ejection measured by Waters.

(3) The present results of the energy distribution curves of secondary electrons by the inert gas ions indicate that the yield of secondary electrons is increased by increasing the kinetic energy of the primary ions, and that this increment in the yield is mainly contributed from the secondary electrons which have lower kinetic energies than that of the secondary electrons emitted by the incident ions of low kinetic energies. These phenomena are able to be postulated qualitatively by the idea of sternglass.

(4) The total number of emitted electrons is increased with the increase in the value of the ionization potential of incident ions, and the kinetic energies of emitted electrons become greater by increasing the potential energy of incident ions. These phenomena are difficult to explain by the mechanism of the kinetic ejection, therefore the electron emission from the electro-polished copper-beryllium surface by inert gas ions may occur according to the complicated mechanism in which the potential energies of incident ions contribute to the electron emission together with their kinetic energies.

(5) In contrast with the singly-charged ions, the doubly-charged ions give rise to the broadening of the energy distribution curves. This also suggests the occurrence of the comlicated ejection mechanisms.
Infrared Absorption Spectra of Quartz and Some other Silica Modification
Authors: Soda Reisuke
Published: July 2006

Some silica modification such as carplex and ground quartz particle, gives rise to the bands near 950 cm−1. This band has no relation with the skeletal structure of Si–O bond and can not be explained as overtone or combination tone. It is reasonable to assign this band to O–H deformation vibration of silanol group. The effect of particle size and grinding time on the spectrum of quartz was examined and it was concluded that the ground quartz particle was covered by some irregular structure on its surface, which was different from quartz structure. In this surface structure, the silanol group seems to be constructed.
The Study of Adsorption of Detergents at a Solution-Air Interface by Radiotracer Method. IV. The Valency and Concentration Effects of Added Electrolytes on the Adsorption of Alkyl Sulfate Ion
Authors: Matuura Ryohei , Kimizuka Hideo , Matsubara Akira
Published: July 2006

The adsorption of dodecyl sulfate ion in the presence of various inorganic electrolytes whose concentrations are all 10−4 mol./l. and the adsorption of alkyl sulfate ions in the presence of the excess salt were measured by using S-35 labeled alkyl sulfates.

In the presence of various electrolytes, both the rate of adsorption and the equilibrium adsorption of dodecyl sulfate ion increase with the cationic valency of added electrolyte, while they are almost independent of the anionic valency.

In the presence of the excess salt, both the rate and the equilibrium adsorption of the alkyl sulfate ions increase with the salt concentration. With increasing concentration of salt the rate of adsorption of the dodecyl sulfate ion approaches the rate of the simple diffusion theory, while that of tetradecyl- and hexadecyl sulfate ion exceeds the value predicted by the simple diffusion theory. It was pointed out that the higher rate of adsorption is attributed to the higher surface activity of solute.

The idea of surface activity was explicitly introduced in the explanation for the adsorption process and the discussions for the theories proposed earlier were given.
Thermodynamical Studies on Binary Systems Consisting of Polar and Non-polar Liquids. V. The Anomalies in the Binary Systems of Polar Liquid with Aromatic Non-polar Liquid
Authors: Amaya Kazuo
Published: July 2006

The anomalous stabilization energy for the systems containing polar and aromatic nonpolar liquids was evaluated on reasonable assumptions. The van Laar coefficient due to this stabilizing effect was found to be dependent on the concentration. The stabilization effect corresponding to the concentration dependent part of the van Laar coefficient was explained by the cooperative orientation of aromatic nonpolar molecules around the polar molecules.
Structure of Enteromycin. IV
Authors: Mizuno K\={o}mei
Published: July 2006

Catalytic reduction of enteromycin methyl ester afforded demethoxyenteromycin methyl ester. Since demethoxyenteromycin amide was presumed to be 3-amino-N-(hydroxyiminoacetyl)-β-alanine, while enteromycin amide was considered to be N-(hydroxyamidinocarbonyl)-3-aminoacrylic acid, the two presumptive formulas, I–i and I–ii, were proposed for enteromycin. As the amido compound prepared by amidation of synthetic ethyl O-methyl-aci-nitroacetate was assumed to have the structure of hydroxyamido carbonyl amide (oxamide monoxime) and as enteromycin was deme-thoxylated by heating under evolution of formaldehyde, the formula I–i was found to be preferential, considering together other properties of the compound, and therefore the plane structure of enteromycin was established to be N-(O-methyl-aci-nitroacetyl)-3-aminoacrylic acid. The steric configuration of the 3-amino acrylic acid seems to be trans and that of the O-methyl cis-nitroacetyl group (the configuration of the hydrogen attached to the α-carbon atom and of the coordinating oxygen) to be syn.
Synthesis of Several Tertiary Alcohols from Propanol-2 and Ethylene by Gamma-ray Irradiation
Authors: Hirota Kozo , Hatada Motoyoshi
Published: July 2006

Tertiary amyl and higher tertiary alcohols have been synthetized at 6∼60°C by irradiating gamma-rays on mixture of propanol-2 and ethylene enclosed in glass vessels. It has been found that as the irradiation temperature the G value of these telomers increases markedly, e.g. up to ca. 300 at 60°C. It has been concluded from the distribution of the telomers produced that this reaction proceeds by a chain mechanism, making isopropyl radical (CH3)2COH as the chain-carrying radical. It has been estimated that the characteristic of gamma-rays will be found in the step prior to the production of the isopropyl radical. If the rays can play some role in this reaction.
Photoreduction of Methylene Blue by the Visible Light in the Aqueous Solution Containing Certain Kinds of Inorganic Salts. III. Kinetic Treatment of the Reaction
Authors: Usui Yoshiharu , Koizumi Masao
Published: July 2006

Kinetic treatment was undertaken for the photobleaching of the aqueous solution of methylene blue containing various inorganic salts.

If a certain kind of inhibiting action due to some reaction product(s) is taken into consideration, the rate for borate buffer is satisfactorily reproduced as the first order of excited dye, while for phosphate buffer it is second order with regard to dye. It was further found from this analysis that the rate of the essential step (or steps) of the reaction for the case of borate is approximately proportional to the concentration of OH−, while for the case of phosphate it is almost independent of pH.

The quantity of irreversible decomposition of dye in case of borate buffer was estimated to be very small against that of the reversible bleaching, the former being a few tenths of the latter from the experimental results obtained when ferric chloride and o-phenanthroline were added to the borate buffer solution.

Judging from the results hitherto obtained,it is most plausible that the photoreduction of methylene blue in case of borate takes place through the decomposition of water. But in case of phosphate, there still remains some possibility that the reaction commences by the interaction of excited dye and ground state dye, electron transfer taking place between them.

The quantum yield of the bleaching reaction was measured and found to be (2∼3)×10−4 for borate buffer and (7∼9)×10−4 for phosphate buffer.
Studies on Phenolic Resins. IV. Physical and Chemical Properties of Coating Films of Japanese Lac (Urushi) (Rigidity Modulus-Temperature Relations Measured by Torsional Pendulum Method)
Authors: Kuwata Tsutomu , Kumanotani J\={u} , Kazama Seiji
Published: July 2006

As to Japanese lac some reports are found in literature concerning chemical identification of the lac component, or electrical insulation and resistance of the film to chemical reagents, but no physical and chemical properties related to internal polymer structure of the film had ever been investigated. In this paper the authors studied the physical and chemical properties of the film of Japanese lac by means of the torsional pendulum method.

As the results of the experiment, the following characteristics of the films prepared by various processes from Japanese lac were revealed:

1. The films do not show sharp glass transition phenomenon and are durable as a protective coating over a wide range of temperature.

2. The films from sugurome-processed Japanese lac have ample flexibility and considerable rigidity, ideally combined.

3. During exposure to air, the films are oxidized with formation of polar group in polymer molecules. But cross-linking does not take place except in air-dried film of raw Japanese lac.

The above mentioned physical and chemical properties of the film account for the characteristic, complicated three dimensional polymer structure caused by action of laccase and chemical structure of urushiol, and such excellent properties can not be found in any other films from synthetic resins. The results obtained are of practical use and they should be taken into consideration in the study of preparation of fillers or substitutes for Japanese lac.

Catechol derivatives synthesized by the authors were confirmed to be fairly good fillers.
Spectroscopic Studies on Molecular Configurations of Some Aliphatic Dinitriles. I. Infrared Spectra of Succinonitrile and Bis(succinonitrilo) copper(I) Nitrate
Authors: Matsubara Ikuo
Published: July 2006

The infrared spectrum of bis(succinonitrilo)- copper(I) nitrate, [Cu(NC–CH2–CH2–CN)2]NO3, has been studied in relation to the molecular configuration of the ligand succinonitrile, which is known from X-ray analysis to be the gauche form. The Spectral features of this complex are quite similar to those of free succinonitrile at −50°C in agreement with the conclusion of the previous workers that the gauche isomer of succinonitrile is stable at low temperatures. Thus all the main absorption bands of the complex were satisfactorily explained as due to the vibrations of the gauche isomer. Decomposition of the complex occurs as a result of interaction with alkali halides such as sodium chloride and potassium bromide, which causes the appearance of absorption bands corresponding to the vibrations of the trans isomer. Considering the frequency shifts of the nitrate vibrations the reaction of the complex with alkali halides should be ascribed largely to an ion interchange between the two phases. The increase of 26 cm−1 in the C≡N stretching frequency by complex formation may be understood from the linear structure of the Cu–N–C–CH2 group which suggest that the carbon-nitrogen bond is essentially of a triple-bond character, thr contributions of polar resonance structure such as –C+=N− being decreased. Assignment of the skeletal deformation frequencies has been made with the help of a normal coordinate treatment which also made possible discussion concerning the nature of these vibrations.
Polyaddition Reaction of Diphenylsilane to Diallyl Carboxylate
Authors: Kojima Kuniharu
Published: July 2006

The polyaddition reaction of diphenylsilane to diallyl phthalate was studied. The reaction was found to be of the second order at the initial stage. The over-all rate is proportional to the initial monomer and catalyst concentration. The over-all activation energy calculated for this reaction was found to be 12kcal./ mol. at 80∼120°C.

By a similar method following polyesters have been prepared from diphenylsilane and diallyl carboxylates: Polydiphenylsilylene 3, 3′-bis(trimethylene)oxalate, malonate, succinate, adipate, sebacate, phthalate, isophthalate and terephthalate. Their molecular weight and inherent viscosity were determined and properties have been described.
Liquid-Vapor Equilibrium of Isotope Mixture under Centrifugal Force
Authors: Amaya Kazuo
Published: July 2006

Expressions for the distribution of the isotope mixture in liquid-vapor phase system under centrifugal force were derived. By the use of these expressions, the efficiency of the isotope concentration was estimated for actual cases under accessible conditions. It was found that an efficient concentration of the isotope from their mixture was possible by the proper design of an apparatus for successive distillation.
The Surface Tension and the Critical Micelle Concentration in Aqueous Solution of β-d-Alkyl Glucosides and their Mixtures
Authors: Shinoda Kozo , Yamaguchi Tokio , Hori Ryohei
Published: July 2006

The surface tension in aqueous solutions of β-d-alkyl glucoside and their mixtures at 25°C has been measured. The CMC was determined from the inflexions of the curves; octyl glucoside, 0.025 mol./1., decyl glucoside 0.0022 mol./1., dodecyl glucoside, 0.00019 mol./1. The effect of hydrocarbon chain length was explained theoretically. The CMC of mixtures has been also explained by the extension of the theory of ionic agents. The effect of added sodium chloride, calcium chloride and sodium sulfate on the surface tension in aqueous solution of octyl glucoside has been measured. The effect of added salts on the CMC was determined from the inflexions of the surface tension vs. logarithm of concentration curves.
The Resonance Effect of Amide Group on the Polymerizability of Lactam Derivatives. II. The Basicity of Amide Group of Lactams
Authors: Ogata Naoya
Published: July 2006

The addition reaction of hydrogen chloride with several cyclic or chain amides has been investigated by the infrared absorption measurement in order to study the correlation between the polymerizability of lactams and the resonance in the amide group. The equilibrium constant K for the addition reaction with cyclic amide (cis form) is 150∼180 and it becomes greater with enlargement of the ring size, while K for N-methyl lactams is about 30∼40. The K value for secondary chain amide (trans form) is 60. The heat of the addition reaction of hydrogen chloride with lactams becomes lower with the enlargement of the lactam ring and also with the N-methyl substitution of the amide hydrogen.

The stronger basicity of the cis amide compared with the trans amide may be due to the decrease of resonance in the amide group, and the stabilization of the lactam ring by the N-methyl substituion may be ascribed to the increase in resonance by hyperconjugation of the methyl group.
Reduction of Organic Compounds with Urushibara Catalysts under High Pressure. VII. Feature of Various Urushibara Catalysts as Revealed in the Reduction of Benzophenone
Authors: Taira Shinichi
Published: July 2006

High pressure reduction of benzophenone was examined with various Urushibara catalysts under various conditions. The purity of benzophenone, the concentration and pH of a solution, reaction temperature and quantity of the catalyst exerted considerable effects on the rate of reduction. Effective Urushibara catalysts were prepared from the precipitated metals which were obtained from the metal chlorides and zinc dust at a low temperature.
Colloid Chemical Studies on Starching Materials. III. Dynamic Viscosity and Dynamic Rigidity of Starch Solutions
Authors: Nakagaki Masayuki , Muragishi Kazuko
Published: July 2006

The frequency dependences of dynamic viscosity and dynamic rigidity of (3 and) 5% starch pastes were measured by using a topdrive coaxial rheometer for potato starch, sweet potato starch and rice starch at 30°C. The results were compared with Maxwell’s four element model and Rouse’s model. Neither fit the experimental results. A structural change of the paste depending on the frequency was suggested.
Nuclear Magnetic Resonance Study of Hydrogen Bond in Salicylaldehyde
Authors: Yamaguchi Ichiro
Published: July 2006

The concentration dependent behavior of the proton resonance spectra of salicylaldehyde in several solution systems were measured. The behavior of the OH resonance line for the solution systems showed the evidence of the existence of considerably strong intramolecular hydrogen bond in the molecule. The behavior of the ring proton spectrum on dilution suggested the occurrence of the charge migration in the ring affected by the change in the hydrogen bonding situation.
On the Differences in Monolayer Properties of Poly-γ-benzyl-l-glutamate and Poly-β-benzyl-l-aspartate
Authors: Ikeda Shoichi , Isemura Toshizo
Published: July 2006

In view of the marked differences of PBLG and PBLA in crystals and in solutions, we have investigated their differences in monolayer states and further examined the monolayers of CP(BLG, BLA) and of the equimolar mixture of PBLG and PBLA. All these polymers were found to be of condensed type and their limiting areas to be about 22Å2. The surface compressibility at the region of rise of surface pressure was in the order: PBLA>CP(BLG, BLA)>PBLG. The surface moments of all these polymers were considerably higher than those of non-polar polypeptides. The surface moment of PBLA was 50 mD higher than that of PBLG, and that of CP(BLG, BLA) gave a value intermediate between them. PBLG and CP(BLG, BLA) exhibited high surface viscosities at a very low surface pressure region, but, in spite of the condensed nature of the monolayer, PBLA showed appreciable surface viscosity first at a high surface pressure region. The surface viscosities of PBLG and PBLA were higher at higher temperatures. From the data on surface pressure and surface moment, all these polymers were considered to have a configuration similar to the β-form in the spread state and possible configurations of side chains of PBLG and PBLA were deduced. It was found that the carbonyl group on the side chain of PBLG is far from the aqueous surface but that of PBLA is in contact with the surface and scarcely distinguishable from the carbonyl group on the main chain. Accordingly, PBLG can take a stable configuration like the β-form in monolayer, but the correspounding configuration of PBLA will be less stable owing to possible hydrogen bonding of the carbonyl group on the side chain with the imino group on the main chain and the resulting enhanced hydrophility of the side chain. This might be ascribed to the differences in surface compressibility and surface viscosity of PBLG and PBLA. The surface pressure behavior of the mixed monolayer of PBLG and PBLA was such as was expected, but its behavior in surface potential and viscosity was very anomalous.
Photochemical cis-trans Isomerizatin of Stilbene
Authors: Yamashita Shigeru
Published: July 2006

The photochemical isomerization of cis as well as trans-stilbene in n-hexane was studied kinetically in the temperature range 10∼30°C using the mercury lines of 313 and 334 mμ. Quantum yields were found to be 0.04 for the cis→trans, and 0.27 for the trans→cis conversion. Conversion rates for both directions obtained spectrophotometrically were found to be of the first order with respect to the substrate concentration, proportional to the light intensity, and nearly independent of temperature. Moreover in view of the difference in quantum yields and in optical properties of cis- and trans-stilbene, it seems probably that the reaction paths for the conversions in the two opposites directions are different from each other.
Oxidation of l-Dihydrocarveol and its Acetate with Selenium Dioxide
Authors: Sakuda Yoshitsugu
Published: July 2006

l-Dihydrocarveol and its acetate were oxidized with a solution of selenium dioxide dissolved in tert-butyl alcohol, in the range of 15∼50°C. In the case of l-dihydrocarveol, the active methyl group of C9 position outside the ring was oxidized mainly. As the reaction products, dihydrocarvone, 8(9)-p-menthene-2,10-diol and 8(9)-p-menthen-2-ol-10-al were obtained. In the case of l-dihydrocarvyl acetate, the active methylidyne group of C4 position in the ring was oxidized mainly.trans (8)9-p-Menthen-2,4-diol and its monoacetate, 8(9)-p-menthen-2-ol-10-al acetate and 3, 8(9)-p menthadien-2-ol were identified. Excepting dihydrocarvone, these products are new compounds.
Ultraviolet Spectra of N-Heterocyclic Systems. II. The Spectra of 5∼8-Hydroxyisoquinolines and Related Compounds
Authors: Nakanishi Koji , Ohashi Mamoru , Kumasaki Shoichiro , Koike Hisashi
Published: July 2006

The spectra of monohydroxymonoazanaphthalenes in which the hydroxyl group is neither α nor γ to the ring nitrogen atom have been compared under various conditions. Shifts of peaks accompanying changes in the species involved have been generalized and a distinction between the spectra of the α- and β-naphthol type hydroxyazanaphthalenes has been made.
Reactions of Quinaldil and its Related Compounds with Alkali. I. Quinaldil and Phenyl-2-quinolyl Diketone
Authors: Oda Daihei
Published: July 2006

In the reaction of quinaldil or phenyl-2-quinolyl diketone with alkali, the fission of C-C bond of dicarbonyl occurred and from the half part of diketone common to each, a red-orange compound and a small amount of hydroquinaldoin were obtained and the other half gave the corresponding acid. The colored compound was found to be consisting of quinaldic acid and 1,2,3,4-tetrahydroquinaldic acid. These results refuse to accept Hammick’s explanation about the reaction of quinaldil with alkali, in which there is a mistake fundamentally.
Reaction of Hydrogen Peroxide on Fatty Acid Esters under Pressure. III. Oxidation of Methyl 9,10-Dihydroxystearate
Authors: Kameoka Hiromu
Published: July 2006

Methyl 9,10-dihydroxystearate is oxidized with a 30% hydrogen peroxide solution, under such conditions as the mole ratio of methyl 9,10-dihydroxystearate to hydrogen peroxide is one to fifteen or more, the reaction time 2 hr., the temperature 138∼155°C, and the pressure 110∼145 kg./cm2. Also, it was recognized that 80% or more of methyl 9,10-dihydroxystearate was oxidized.

As the oxidation products, acetic, propionic, butyric, caproic, caprilic, pelargonic, caprinic and lauric acids were obtained as monobasic acids, and oxalic, malonic, succinic, adipic and azelaic acids were also produced as dibasic acids. Especially, succinic and adipic acids were obtained with good yield.
Bile Acids and Steroids. XXV. Studies on the Hog Bile Acids (Part 5). On the Oxidation of Epimeric 3,6-Dihydroxycholanoic Acids with N-Bromosuccinimide
Authors: Kawanami Jun’ichi
Published: July 2006

(1) The order of susceptibility of the hydroxyl groups in epimeric 3,6-dihydroxycholanoic acids to the oxidation with NBS was determined and the results were as follows:

6β(a)>3β(a)>3α(e)>6α(e) (A/B : cis)

6β(a)>3β(e)>6α(e) (A/B : trans)

(2) Reaction mechanism of the oxidation with NBS was discussed.
An Empirical Method for Estimating Normal Boiling Point and other Physical Properties of Alkene Hydrocarbons
Authors: Tamura Mikio , Kurata Michio , Nakanishi Koichiro , Nagata Isamu
Published: July 2006

A method of estimating the structural variation in the boiling point and other physical properties of alkenes is developed. By this method, all properties are expressed in terms of a structural constant called the “effective carbon number” which depends on the number and relative position of double bonds and those of side chains but not on external variables such as the temperature. An empirical equation is presented to correlate the effective carbon number with molecular structure. By combining the use with the previously presented nomogram, it is proved to be quite useful for rapid evaluation of various properties including the temperature-vapor pressure relationship and the critical constants.
Infrared Absorption Spectra of Water of Crystallization in Copper Sulfate Penta- and Monohydrate Crystals
Authors: Gamo Itaru
Published: July 2006

The observed spectra of water in the penta-and monohydrate crystals were interpreted by the effects of coordination copper-water and hydrogen bonding O-H…O. The whole difference in the spectra of the two crystals were explained in relation to the escape of the four ligand water molecules and the resulting rearrangement of atoms. The stretching, bending and rocking modes, which are single in the case of the pentahydrate, split into doublets in the monohydrate. This result was explained by a single assumption of strong coupling of two neighboring water molecules in the latter.
Neutron and γ-Irradiation of Propionamide
Authors: Tachikawa Enz\={o} , Tsuchihashi Gen-ichi
Published: July 2006

Two methylation reactions of propionamide by 14C-hot atom, and of methyl radical from 60Co γ-ray irradiation and methylation reaction of propionic acid by methyl radical from thermal decomposition of acetyl peroxide were carried out and the reactivities of these species were studied. The methyl radical produced by 60Co γ-ray irradiation of propionamide gave the 3:2 mixture of butyr- and isobutyramide. This ratio agrees with the activity distribution of butyr- and isobutyramide in the neutron irradiation of propionamide. On the other hand the methyl radical produced by the thermal decomposition of acetyl peroxide in propionic acid gave 1:2 mixture of butyric and isobutyric acid. From the above results the reactions in the γ-ray irradiation are considered to be high reaction of acetyl peroxide in propionic acid is considered to be a free radical reaction.
Fischer-Tropsch Synthesis with Tubular Reactor of 18.1 1. Catalyst Bed. I. Reactor with Constant Temperature Wall
Authors: Kuraishi Michio , Kurita Minoru , Hosoya Tadasuke , Ichinokawa Hideo , Ogawa Kiyoshi , Uchida Hiroshi
Published: July 2006

By the aid of the calculating procedure developed by us on the basis of experimental data available in the synthesis with the reactor of 21. catalyst bed, prediction of the temperature profile as regards the synthesis with the reactor of 18.1 1. catalyst bed has been made. The predicted temperature profile expresses the tendencies observed in the actual synthesis with the latter reactor, though a complete agreement has not yet been obtained because of a lower output than was expected.

The calculating procedure has been applied to draw the temperature profile on the basis of the present experimental concentration gradients along the reactor. The profile thus drawn agrees well with the measured one.
The Effects of pH on the Flocculation of Quartz Aqueous Suspensions
Authors: Ohyama Tadashi , Shimoiizaka Junzo , Usui Shinnosuke
Published: July 2006

The effects of pH on the flocculation of quartz aqueous suspensions containing Ba2+, Fe3+ or Cu2+, respectively, were investigated by means of electrokinetic measurements. The violent flocculation takes place in the characteristic range of pH with respective cation involved. The calculation of the potential energy between approaching quartz particles indicates that the violent flocculation is readily explained, not by the decrease of electrical repulsion, but by the consideration of an attractive force other than van der Waals attraction.
Electronic Spectra of Substituted Aromatic Hydrocarbons. II. Naphthols and Naphthylamines
Authors: Baba Hiroaki , Suzuki Satoshi
Published: July 2006

The ultraviolet absorption spectra of α-, β-naphthols and α-, β-naphthylamines have been newly measured down to 200 mμ. On the basis of a calculation which was carried out in the same manner as in the preceding paper, the effect of substitutions at α- and β-positions upon the spectrum of napthalene has been explained and the assignment of the observed absorption bands has been made. It is suggested that, upon substitution at the α-position, the Au→B3u+ band of naphthalene splits into two electronic bands because of the interaction of the B3u+ state with a B1g+ state. Molecular diagrams are given for naphthylamines and for aniline.
Theory on the Light Scattering of High Polymer Solutions Considering the Anisotropy of Segments
Authors: Nakagaki Masayuki
Published: July 2006

The anomaly of the angular dependency of the reduced scattering intensity in the Zimm plot for infinitely dilute solution was discussed for the solutions of high polymer molecules having anisotropical segments, and the theoretical relationship between Kc⁄Ru(θ) and θ was derived. The equation had the same form for both intrinsic anisotropy and form aniso-tropy. In the latter case, the axial ratio of the spheroid of excess polarizability was concluded to be not equal to the axial ratio of the segment. Moreover, the correction factor for the molecular weight was derived.

Applying these theoretical equations to the experimental data by Ehrlich and Doty on the solution of copolymer of methacrylic acid and 2-dirnethylaminoethyl methacrylate, it was shown that the anomalies of the Zimm plot could be explained by assuming that the segments have intrinsic anisotropy.

It was also suggested that the scattering ratio is a good criterion to see whether the anomaly is actually due to the anisotropy of segments or not.
The Mannich Base of Troponoid and its Application. V. On the Mannich Base of 3-Isopropyltropolone (α-Thujaplicin)
Authors: Ogura Kyozo
Published: July 2006

The Mannich reaction was applied to 3-isopropyltropolone and 3-isopropyl-5, 7-dimorpholinomethyl, and 3-isopropyl-5, 7-dipiperidinomethyltropolone were obtained. These substituents were easily substituted by diazonium salt or bromine. Some of the Mannich bases obtained were found to retain the zwitterion structure in the solid state.
Infrared Spectra and the Structure of Some Metal-oxamide Complexes
Authors: Kuroda Yoko , Kato Michinobu , Sone Kôzô
Published: July 2006

The infrared absorption spectra of potassium bis(oxamido)niccolate(II) and potassium bis-(oxamido)cuprate(II) were recorded in the wave number region from 700 to 4000 cm−1 and compared with those of pure oxamide. These spectra revealed that metal-nitrogen bonds are formed in these complexes. The observed frequencies were interpreted in terms of a planar structure having the symmetry D2h.
The Aconite Alkaloids. XXXV. On Lucidusculine. V
Authors: Amiya Takashi
Published: July 2006

Luciculine (II) was isomerized to a ketone base, isoluciculine (III), and this fact shows the presence of an allyl alcohol system in the structure of compound II. The previous report concerning bromoanhydrolucidusculine hydrobromide (IV) was in part revised.
Polarographic and Spectrophotometric Studies on Trimethylpyruvic Acid
Authors: Takagi Masanosuke
Published: July 2006

Polarographic and spectrophotometric behavior of trimethylpyruvic acid has been investigated.

The limiting current of trimethylpyruvic acid shows a minimum value in pH about 0.5. The absorption spectra show the absorption maximum at about 310 mμ in aqueous solutions, indicating the decrease of the optical density in strongly acid pH. These facts have been accounted for by the hydration of carbonyl group of undissociated acid.

pKa for apparent dissociation constant of trimethylpyruvic acid has been spectrophoto-metrically obtained to be 1.52 at 25°C.

Hydration constant of the undissociated acid (Kh=[AHaq]/[AH]) has been kinetically obtained to be 0.46 at 25°C. The rate constant of dehydration of hydrated trimethylpyruvate in buffer solution of pH about 5 was 2.8×10−2 sec−1 at 25°C. From the temperature dependence of the hydration constant, the heat of hydration of unhydrated acid has been found to be −8.2kcal.

A quantitative interpretation of the pH-dependence of the limiting current has been attempted by deriving the equation, involving the hydration and dissociation factors. The agreement of the theoretical curve with the experimental is good, except for the pH range below 0.5, where acid catalyzed dehydration of hydrated acid should be taken into consideration.

Rate constants of the dissociation and recombination of trimethylpyruvic acid have been found to be kd=6.0×105 sec−1 and kr=1.4×107 1. mol−1 sec−1, respectively.
A Simplified Model for the Structure of Water
Authors: Wada Goro
Published: July 2006

Various characteristic properties of liquid water can be explained fairly well by a simple structural model proposing that water consists of an equilibrating mixture between two states: the icy state which possesses ice structure and appears and disappears locally and temporarily, and the packed state in which water molecules are closely packed without hydrogen bondings. Only assuming that the fraction of the icy state at 100°C is 0.2, the fractions and the equilibrium constants at various temperatures are calculated, and therefrom the heat and the entropy of fusion of ice, the specific heat and the heat of vaporization of liquid water are derived, which are all in good agreement with the observed values. The radial distribution function of water obtained by X-rays reveals the packed state to have a structure similar to the closest packing, and the surface tension of water tells that the surface of water is more abundant in the icy state than the bulk water is, positively adsorbed as if it were a kind of surfactants. The heat of ionization and the activation energy of electric conduction are qualitatively described by the rotation mechanism of water molecules in the icy state. A reasonable explanation concerning the existence of the temperature of the maximum density and the effects of different substances upon it are also offered.
Iodine-photocatalyzed cis-trans Isomerization of Stilbene
Authors: Yamashita Shigeru
Published: July 2006

The rate of isomerization of cis- and trans-stilbene in n-hexane solution has been studied spectrophotometrically over the temperature range 10∼30°C in the presence of iodine under irradiation of light. The conversion rate of cis-stilbene has been found to be proportional to the square root of light intensity, to the concentration of cis-stilbene and to the square root of the iodine concentration in both wavelength ranges 360∼430 and 530∼600 mμ. The activation energies and quantum yields of conversion are however different in these ranges of wavelength. These results, combined with absorption curves of various components present in solution, show that the primary process in the range 530∼600 mμ is I2+hv→2I and that in the range 360∼430 mμ it is probably CI2+hv→CI2* followed by CI2*+C→2CI, where CI2 represents a molecular complex formed between iodine and cis-stilbene. Secondary reactions, suggested from the kinetics, are C+I\leftrightarrowsCI and CI→TI→T+I with one or more elimination steps for unstable species, T representing trans-stilbene. Rate of isomerization of trans-stilbene in the presence of iodine under irradiation of light in the range of wavelength 310∼400 mμ has been found to be identical with the rate observed in the absence of iodine under the same condition, excepting the absence of iodine. An explanation for this finding has been given.
Deuterium and Oxygen-18 Tracer Study of the Dehydration and the Hydration of Copper Sulfate
Authors: Okazaki Nobukazu , Okumura Akiko , Nakagawa Keiko
Published: July 2006

The deuterium and oxygen-18 exchange reaction of amorphous and crystalline copper sulfate monohydrate with water in the course of the hydration of the monohydrate with heavy water vapor and the subsequent dehydration of the product has been studied.

The exchange reaction of crystalline monohydrate is associated with the formation of hydrate. Amorphous monohydrate shows an increased degree of exchange over crystalline monohydrate. This increased exchangeability of amorphous monohydrate is due to the exchange reaction between surface molecules and adsorbed water. The similarity of the results of deuterium exchange reaction between oxalic acid and copper sulfate confirms the suggestion of the previous report that anhydrous oxalic acid prepared by dehydration in vacuo at low temperatures is amorphous and the degree of deuterium exchange reaction is related to the surface area of the dehydration product.

The results of the oxygen-18 exchange reaction of copper sulfate monohydrate with water vapor are almost identical in essentials with those of the deuterium exchange reaction. The fifth water molecule of copper sulfate is interchangeable with the other four in the process of dehydration of pentahydrate and the hydration of monohydrate.