bluuebunny/crossref_metadata_2025 huggingface dataset:
On the Electronic Structure of the Carbonyl and the Amide Groups
Authors: Nagakura Saburo
Published: July 2006

(1) Electronic structures of carbonyl and amide groups were investigated by the use of the molecular orbital method; calculated values of resonance energy and π-electron densities may be regarded as reasonable compared with these which were observed.

(2) Near ultraviolet absorption spectra were measured with acetone, acetylchloride, acetic acid, ethyl acetate and N-methylacetamide. As the result of these measurements, it becomes evident that the low intensity absorption band of acetone shifts to the side of shorter wave lengths when the methyl group of acetone is replaced Cl atom or OR and NR2 groups. These results can be explained by the present theoretical consideration if this absorption band is due to the n→π* transition.
On the Hydrazinolysis of Proteins and Peptides: A Method for the Characterization of Carboxyl-terminal Amino Acids in Proteins
Authors: Akabori Shiro , Ohno Ko , Narita Kozo
Published: July 2006

(1) A brief method for the characterization of carboxyl-terminal amino acids in peptides and proteins was investigated.

(2) Several new amino acid hydrazides were synthesized.

(3) Soveral di- and tri-peptides were hydrazinolyzed and identified their carboxylterminal amino acid.

(4) The method was applied to beef insulin and tyrocidin for the demonstration of its applicability.
The Electrical Conductivity of the Condensed Polynuclear Aza-aromatic Compounds
Authors: Inokuchi Hiroo
Published: July 2006

The electrical conductivity of the condensed polynuclear aza-aromatic compounds; (1) cyananthrone, (2) indanthrone black, (3) flavanthrone, (4) indanthrone, (5) indanthrazine, (6) 5, 6-(N)-pyridino-1, 9-benzanthrone and (7) 1,9,4,10-anthradipyrimidine,—has the character of a semi-conductor. The electrical resis tivity of these compounds can be expressed as ρ=ρ0exp(Δε⁄2kT) and the mechanism of the conduction is assumed to be that of the intrinsic semi-conductor as in the cases of the condensed polynuclear aromatic compounds The value of Δε and ρ at 15° were found as; (1) 0.20 e.V., 1.2×107Ω cm., (2) 0.56 e.V., 2.5×108Ω cm., (3) 0.70 e.V., 1.4×1011Ω cm., (4) 0.63 e.V., 7.5×1014Ω cm., (5) 0.66 e.V., 1.4×1015Ω cm., (6) 3.2 e.V., 8.5×1022Ω cm. and (7) 3.21 e.V., 8.8×1024Ω cm. The values of the electrical resistivity of this group are smaller than that of related condensed polynuclear aromatic compounds.
Concentration Polarization and the Polarographic Current-Time Curve. II. The Spherical Diffusion Current
Authors: Kambara Tomihito
Published: July 2006

Provided that the depolarizer and the electrode reaction product are water soluble, the spherical diffusion equations are integrated. The boundary condition is so chosen that the three elementary processes, i. e., the diffusion of depolarizer, the electrode reaction, and the diffusion of the product, proceed in an equal velocity at the electrode surface. The result thus obtained can explain the essential rôle of the curvature of the electrode in some problems concerning the electrode reaction.
On the Viscosity of Binary Mixture of Liquids
Authors: Tamura Mikio , Kurata Michio
Published: July 2006

A new semi-empirical equation for the viscosity coefficient of binary mixture of liquids, Eq. (11), has been derived and we have reached the conclusion that the assumption used in order to derive our equation corresponds to the Bethe-Fowler-Takagi approximation for regular assembly qualitatively. The equations for η and ε have been compared with the experimental values and satisfactory results have been obtained.
Mechanical Properties of Concentrated Hydrogels of Agar-agar. I. Modulus of Elasticity in Compression
Authors: Fujita Hiroshi , Ninomiya Kazuhiko , Homma Terutake
Published: July 2006

As the first step in a series of works on the mechanical behavior of a concentrated hydrogel of agar-agar, the experimental determination of its elastic behavior in compression was made. An apparatus which could record a compression stress-strain curve automatically was devised and used to obtain the results reported in this paper. Influences of tem-perature, concentration, and gelation time upon the modulus of elasticity (Young’s) were considered and plotted in Figures 4, 5 and 6.
Surface Chemistry of Synthetic Protein Analogues. I. Surface Pressure-Area Relation of Synthetic Polypeptides as the Model of Proteins
Authors: Isemura Toshizo , Hamaguchi Kozo
Published: July 2006

The surface pressure against area (F-A) curves of the monolayers of poly-Dl-α-aminocaproic, poly Dl-α-aminocaprylic, poly Dl-α-aminocapric, poly Dl-α-aminolauric acids, poly γ-methyl-l-glutamate and poly ε-aminocaproic acid (amilan) was measured. The results obtained were as follows:

(1) The F-A curve of poly Dl-α-aminocaproic acid having four carbon atoms in the side chain resembled in shape very closely to those given by natural proteins such as the egg albumin or pepsin. This fact is due to the resemblance of the carbon number in the side chains of both of the polypeptide and proteins.

(2) The plateau which is a region of very high compressibility appeared in the F-A curves of the polypeptides having more than six carbon atoms in the side chains. The curves of these polypeptides were entirely different from those of natural proteins.

(3) The area per amino acid which was found for every polypeptide to be in the closest packing of polypeptide backbone was all 14.7 Å.2 This value is in good agreement with the area calculated from x-ray data for an arrangement of β-keratin configuration.

(4) Poly γ-methyl-l-glutamate occupied the limiting area of 9.8 Å.2/amino acid residue on distilled water. This value can be sufficiently accounted for, if this polymer has a structure of α-configuration on water surface and the model of α-keratin configuration presented by Shimanouchi and Mizushima and by Ambrose et al. is accepted. On substrates containing hydrochloric, formic, or acetic acid, however, this polypeptide occupied the limiting area of 14.7 Å.2/residue, this value corresponding to the area of the other polypeptides which are arranged in close packed β-configuration. The α→β transformation of this polypeptide could be demonstrated by monolayer technique.

(5) The monolayer of the polymer of ε-aminocaproic acid is inadequate as a model of protein films.
On the Relation between Viscosity and Critical Micelle Concentration of Detergent Solutions
Authors: Sata Naoyasu , Tyûzyô Kiyoshi
Published: July 2006

(1) Several methods of determining CMC are compared and criticised.

(2) A new method of determining 1st CMC from viscosity is experimentally established.

(3) A new method of determining 2nd CMC from viscosity is established by transforming and viscosity in the new variables.

(4) Of each soap, characteristic constants [η1] and [η2] are discovered, and it is shown that a definite relation is concluded between these values and monomer molecular weight.

(5) The theoretical explanation of these newly found phenomena has not yet been made.
Electrostatic Lattice Energy of PbSO4, BaSO4, SrSO4 and CaSO4
Authors: Sakamoto Yosio
Published: July 2006

A plan for investigation of the physical chemistry of radical ions is stated with especial reference to the strict treatment of the lattice energy problem and the treatment of complex ionic crystals. First, the expressions suitable for the practical numerical calculation of Madelung’s coefficient of the general and the rectangular crystal lattice are derived from Ewald’s original general expressions. Next, they are verified in the two simple cases, NaCl and the rhombic CaCO3, by means of numerical application. Then, they are applied to the more complex cases, i. e., the rhombic crystals of PbSO4, BaSO4, SrSO4, and CaSO4, with SO4−− which is assumed to be a point charge. The degree of accuracy of the calculated values is further discussed; and, in connection with it, an attempt is made to estimate the extent of variability of Madelung’s “ coefficient” (or “constant,” as it is called). Finally, the electrostatic lattice energy is evaluated.
The Diamagnetic Sucseptibilities and Anisotropies of the Polynuclear Aromatic Compounds
Authors: Akamatu Hideo , Matsunaga Yoshio
Published: July 2006

The magnetic susceptibilities of condensed polynuclear aromatic compounds with higher molecular weights (ten hydrocarbons and twelve quinones) have been measured by the Gouy method, and the diamagnetic anisotropies have been approximately evaluated.

The diamagnetic anisotropy becomes progressively large as the number of rings increases, when the aromatic condensation takes place in the manner of the closely compact arrangement of rings; while, when it is not the case, it depends strikingly upon the molecular structure.

When the diamagnetic anisotropy has a smaller value, notwithstanding the molecule is made of a large number of rings, the localization of the π-electrons or some other excited states must be assumed. Such a case is found, when a molecule is not made of the aromatically conjugated system as a whole but separated into two predominant nuclei, as meso-naphthodianthrene and violanthrone, or when a molecule is made of a long shaped structure as pyranthrene or violanthrene.
Studies of Molecular Structures by Electron Diffraction. I. The Molecular Structure of Monofluoro- and Monobromobenzenes
Authors: Yuzawa Tooru , Yamaha Mashio
Published: July 2006

The molecular structures of monofluorobenzene and monobromobenzene have been investigated by the electron diffraction method. The C–F and C–Br distances in each molecule have been determined as 1.30±0.03 A and 1.86±0.02Å respectively. These distances are shorter than the case in which the bonds have the normal single bond characters. The double bond characters for these bonds have been calculated and obtained 16.9% for C–F and 13.3% for C–Br, in which we have considered the corrected single bond lengths in both cases.
Surface Chemistry of Synthetic Protein Analogues. II. Temperature Dependence of the Force-Area Relations of Some Polypeptides Monolayers and Thickness of the Monolayer
Authors: Isemura Toshizo , Hamaguchi Kozo
Published: July 2006

In the force-area curves of the monolayer of synthetic polypeptides of longer side chains, a plateau which is a region of very high compressibility appears. The appearance of the plateau can be attributed to the reorientation of the polymer molecule at the interface. The pressure at which the plateau appears, decreases with the rise of temperature. From the temperature dependence of this pressure, the heat of transformation was evaluated.

The polypeptides of shorter side chains of four carbon atoms or less in length scarcely need any energy for reorientation. Accordingly, no plateau was found with these polypeptides. The thickness of the monolayer of these polypeptides at the pressure above and under the transition pressure was determined optically by Langmuir-Blodgett technique. The thickness of the monolayer observed was compared with that calculated by using Stuart model (for the most part.) Our views on the reorientatoin of the film were ascertained.
Intermolecular Charge-Transfer Spectra. I. Halogen-Aromatic Complexes
Authors: Murakami Hideo
Published: July 2006

The intermolecular charge-transfer spectra of halogen-aromatic complexes have been studied theoretically. Especially, the dependence of absorption intensity on the structure of aromatic component has been investigated. To solve the discrepancies between experimental results and Mulliken’s theoretical predictions, we have introduced the statistical consideration for the relative configurations between two components. Using some reasonable assumptions, we have obtained the satisfactory agreement between theoretical predictions and experimental results, at least qualitatively.
Synthesis and Dielectric Polarization of 9-Anthranol
Authors: Nukada Kenkichi , Bansho Yoshié
Published: July 2006

1) The condition of synthesis to obtain pure 9-anthranol was established.

2) Times required for the complete disappearance of fluorescence of solution were measured and assumed to be measures of reaction velocities of tautomerism from 9-anthranol to anthrone. In ethanol, ether, dioxane and benzene the reaction velocities were small.

3) Dielectric constants of 9-anthranol in benzene, dioxane, benzene-dioxane mixtures and toluene solutions were measured. Reproduci-bility was satisfactory. In the said solvents 9-anthranol was relatively stable and ω∼ε12 curves were straight lines except in toluene.

4) The stability of 9-anthranol in solvent was supposed to be increased, by an interaction between π-electrons of solvent and proton of solute O–Hgroup in the case of benzene, or by O… H–O combination in the case of dioxane.
Spectrochemical Study of Microscopic Crystals. IV. The Dichroism of the Tetrahalogeno-Complex Type
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

(1) Dichroisms of K2PdI4, K2Pd(SCN)4 and K2Pt(SCN)4 have been quantitatively determined by the microscopic method, and it has been found that all of them belong to the group which exhibits the dichroism of the “tetrahalogeno-complex type.”

(2) For the tetrahalogeno-complexes, the following rules have been found : νCl>νBr>νI and kCl<KBRkI for the corresponding absorption band, and the oscillator strength of the second band is larger for || -absorption than for ⊥-absorption.

(3) For tetrahalogeno- and tetrathio-cyanato-complexes of platinum (II) and palladium (II), common regularities have been induced on the dichroisms of the tetrahalogeno-complex type.
Walden Inversion of Amino Acids. VII. The Formation of N-p-Toluenesulfonylproline from Nδ-p-Toluenesulfonylornithine
Authors: Izumiya Nobuo
Published: July 2006

(i) Kapfhammer and Eck’s report touching the synthesis of N-p-toluenesulfonyl-l-proline was corrected.

(ii) N-p-Toluenesulfonylproline was resulted by the amination and methylamination of [l]-δ-p-toluenesulfonylamino-α- bromovaleric acid. In this case, racemization took place in consequence of amination at 100°, and partial Walden inversions were caused by amination at 0° and methylamination at 0° and 100°.
Spectrochemical Study of Microscopic Crystals. III. The Dichroisms of μ-Peroxo-Dicobalt Compounds
Authors: Yamada Shoichiro , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

(1) The dichroisms of decammine-μ-peroxodicobalt (III) nitrate dihydrate, [(NH3)5Co-O2-Co(NH3)5](NO3)4·2H2O, and of decammine-μ-peroxocobalt (III)-cobalt (IV) nitrate, [(NH3)5Co-O2-Co(NH3)5](NO3)5, and the absorption spectrum of the latter in aqueous solution have been quantitatively measured.

(2) The empirical rules on the dichroisms of those crystals have been obtained.

(3) The considerations on the absorption spectra of the above compounds have led to the conclusions that there exists a kind of mutual interaction between metallic ions through a bridging peroxy-radical and that the interaction between Co (III) and Co (IV) is considerably larger than that between two Co (III) atoms. The interaction of the above type is supposed to be applicable to the explanation of unusually deep colors in the crystals containing the same atoms in different oxidation states.
An Equation of State in Analytical Form
Authors: Ishikawa Tetsuya
Published: July 2006

(1) An equation of state in analytical form is proposed:

(Remark: Graphics omitted.)

Values of (2–ε) keep constant over a wide range of pressures of each isotherm. Taking the mean of (2–ε) values at each isotherm, we obtain an equation of state which is more reasonable and accurate than the usual isothermal equation of algebraic form.

(2) Tests made with 66 kinds of substances having low dielectric constants prove that values of (2–ε) at critical points are universal to give 1.923±0.008.

(3) The following three formulae at the critical point are derived from the new equation in which Vc is expressed in cc./mol.

(Remark: Graphics omitted.)

The first formula is concordant with ±2.6% average divergence for 66 kinds of low dielectric substances and the two following are also equally concordant with the experimental data.
The Condensation of Furfural with Methyl Ethyl Ketone by Aqueous Sodium Hydroxide
Authors: Midorikawa Hiroshi
Published: July 2006

From the condensation product of furfural with methyl ethyl ketone by aqueous sodium hydroxide were isolated 4-(2-furyl)-3-methyl-3-buten-2-one (I) and 1-(2-furyl)-1-penten-3-one (II).

The former ketone (I) was oxidised by sodium hypochlorite to yield α-methyl-2-furanacrylic acid, (III) but gave no γ, ζ-dioxo-ε-methylcaprylic acid by refluxion with alcoholic hydrochloric acid.

The latter ketone (II) gave γ, ζ-dioxopelargonic acid (IV) by refluxion with alcoholic hydrochloric acid, but was no acted upon by sodium hypochlorite.

The semicarbazone of 1-(2-furyl)-1-penten-3-one (II) existed in two forms of the needle crystals melting at 183∼184° and the tabular crystals melting at 166∼167°.
Spectrochemical Study of Microscopic Crystals. V. Relation between Dichroism and Direct Interaction between Metal Atoms in the Crystals of Bis (Dimethylglyoximo)-Copper (II), Nickel (II) and Platinum (II)
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Dichroism of the crystals of bis (dimethyl-glyoximo)-copper (II), nickel (II) and platinum (II) has been quantitatively determined by the microscopic method in the region from 2400 to 7000 Å.

The crystal of the copper compound has been found to show dichroism of the normal type, indicating that no specific metal-metal interaction can be expected in this crystal.

The crystals of the nickel (II) and platinum (II) compounds exhibit anomalous dichroism. It has been concluded that in these crystals there should exist metal-metal interaction.

A hypothesis has been presented, in order to explain the tendency that the specific metal-metal interaction similar to that proposed above has been found mostly with Ni (II), Pd (II) and Pt (II) compounds.
Studies on the Organic Phosphorescence. I
Authors: Kato Shunji , Koizumi Masao
Published: July 2006

Assuming Lewis′ scheme, mathematical formulation was given for the decay of organic phosphorescence, which would help us to judge whether the quenching action of the added substance affects on singlet or triplet state. The decay curves of Trypaflavine-filter paper phosphor in various con-centrations, were accurately measured by and, oscillograph, and from the results obtained, it was tentatively concluded that the triplet state is not affected much in the concentration quenching.
The Syntheses from Levulinic Acid. A Possible Use of Some 2-Methyl-5-oxopyrrolidine-2-carboxylic Esters as Plasticizers
Authors: Takenishi Tadao , Simamura Osamu
Published: July 2006

The synthesis of 2-amino-2-methylglutaric acid from levulinic acid by Strecker’s method is reported. This acid gives 2-methyl-5-oxopyrrolidine-2-carboxylic acid on dehydration, and some of its esters were prepared and tested for plasticizer performance.
Some Observations on the Reactions of α,α′-Dimethylstilbene and Related Compounds
Authors: Simamura Osamu , Suzuki Hiroshi
Published: July 2006

Cis- and trans-α,α′-Dimethylstilbene, heated with a little sulfuric acid at 210°, were isomerized to an equilibrium mixture consisting of 55% of the trans and 45% of the cis isomers. Heated with iodine at 210°, they yielded meso-2,3-diphenylbutane. The action of bromine produced 1,4-dibromo-2,3-diphenyl-2-butene; under certain experimental conditions the concurrent cis-trans isomerization was observed. This fact, together with the isolation of a small smount of α–bromoacetophenone as a by-product, supports the view that the reaction proceeds by a mechanism involving bromine atoms. The action of bromine on some α,α′-disubstituted stilbenes was examined. The reactions observed were discussed in terms of the steric effect exerted by the bulky groups at the ethylenic linkage.
The Dipole Moments and Molecular Structures of Some Substituted Tropones
Authors: Kurita Yukio , Kubo Masaji
Published: July 2006

The dipole moments of Ortho-substituted tropones were measured in benzene solution at room temperature. The values obtained are as follows : 2-bromotropone, 4.94 D ; 2,7-dibromotropone, 5.27 D; 2-mercaptotropone, 4.36 D; 2-aminotropone, 3.78 D; 2-methylmercaptotropone, 4.64 D. These values together with those of tropolone and methoxytropone were compared with the calculated moments and the following conclusions were derived. The moments of the bromotropones are lower than those calculated by simple vector addition owing to ortho effect. In tropolone, mercaptotropone and aminotropone, the substituent groups take such configurations that these groups are conjugated with the cycloheptatriene ring in the highest degree and that an intramolecular hydrogen bond is formed between the carbonyl oxygen and the hydrogen atom of each of the substituent groups. In methoxytropone and methyl mercaptotropone, on the other hand, the conjugation is weak and each of the substituent groups lies in a plane nearly perpendicular to the ring.
Spectrochemical Study of Microscopic Crystals. VI. Light Absorption of Non-planar Quadri-co-ordinated Complexes
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Absorption spectra of crystals of dicesium tetrachlorocuproate, tricesium cobaltous pentachloride and potassium tetrathiocyanatocobaltoate tetrahydrate have been quantitatively determined in the visible and ultraviolet region by the microscopic method with polarized light.

In accordance with the flattened-tetrahedral configuration of tetrachlorocuproate anion, the crystal of CS2CuCl4 exhibits anisotropy of light absorption.

It has been found that crystals of Cs3CoCl5 are almost isotropic, supporting the regular-tetrahedral configuration of the CoCl4−− ion in this crystal.

It has also been found that K2Co(NCS)4·4H2O in the crystalline state shows a marked dichroism. It is concluded from this observation that Co(NCS)4−− ions in this crystal are distorted-tetrahedral, just like the CuCl4−− ions in the crystal of CS2CuCl4.

It has been found that Cs3CoCl5 in the crystalline state and K2Co(NCS)4·4H2O in alcoholic solution show their second absorption band with a series of sharp peaks, which have been shown to be correlated with electronic-vibrational transitions. This fact is in harmony with the idea on the origins of the absorption bands of metallic co-ordination compounds proposed by one of the authors.
The Nature of the Hydrogen-Bond. I. The Delocalization Energy in the Hydrogen-Bond as Calculated by the Atomic-orbital Method
Authors: Tsubomura Hiroshi
Published: July 2006

The delocalization energy for the hydrogen-bonded water molecules has been calculated non-empirically by use of the atomic orbital method, with a simplified model. The delocalization energy thus calculated amounts to about 8 kcal./mol. which is rather greater than the calculated electrostatic energy that has been usually considered to be the most important source of the binding force. The proton-accepting strengths of ether, acetone and acetonitrile have been discussed by use of this result.
Electron Diffraction Investigation on Tribromotropolone
Authors: Kubo Masaji , Kimura Masao , Kimura Katsumi
Published: July 2006

Tribromotropolone of melting point 126° was investigated in gaseous state by electron diffraction method. The two Br–Br distances equal to 5.40 Å and 6.77 Å respectively were found as distinct isolated peaks in the radial distribution curve. These distances together with the known configuration of tropolone ring already studied gave decisive evidence that in this molecule three bromine atoms are substituted for hydrogen atoms of tropolone at ortho, ortho′ and para positions. This conclusion is in good agreement with the prediction of molecular orbital treatment of tropolone and proves the adequacy of the assumption made in the structural determination by dipole moment data, i.e. that electrophilic atoms and groups substiute hydrogen atoms of tropolone at ortho, ortho′ and para positions but not those at meta and meta′ positions.
Two Uncommon Amino Acids obtained from Roseothricin
Authors: Nakanishi Koji , Ito Toshiko , Ohashi Mamoru , Morimoto Ichiro , Hirata Yoshimasa
Published: July 2006

Roseothricin has been hydrolysed to give two uncommon amino acids, viz., β,ε-diaminocapric acid (I, β-lysine), and 2-amino-4(or 5)-(1-carboxy-1-hydroxy-2-amino)-ethyl-2-imidazoline (II, roseonine) as the sole ninhydrin positive products.
Structural Change in Some Solutions Having Structural Viscosity
Authors: Nakagaki Masayuki , Sakata Shigeo
Published: July 2006

The structural viscosity of V2O5 sol is measured by Ostwald’s overflow viscometer. A linear relation is found between the relative viscosity (η/ηω) and the reciprocal of flow amount (1/Q). Viscosity of Newtonian flow ηn and yield value P0 are calculated from it. ηn and P0 is nearly linearly varied with concentration. A decisive conclusion however, cannot be obtained owing to the slip of liquid on the capillary wall.

Hg-SS (Hg-sulfosalicylate) sol also showed a linear relation between η/ηω and 1/Q. By the irradiation of ultrasonic wave, ηn and P0 decreases. ηn again increases after about 10 min., but the recovery of P0 took more time. A clear conclusion cannot be obtained due to the slip.

Electron micrographs showed that Hg-SS has a net-work structure, which is broken by shaking or by the irradiation of ultrasonic wave. When it is kept standing, the net-work is again constructed. V2O5 sol showed analogous structural changes.
The Structure of Trimethylacetic Acid in Condensed Phases as Revealed from Dielectric Studies
Authors: Kondo Sei-ichi , Oda Tsutomu
Published: July 2006

The authors have investigated the electric properties of trimethylacetic acid in the liquid and solid states. From the markedly small values of dielectric constant and conductivity, combined with the results of the X-ray investigation, it is proposed that the crystal of the room temperature phase is composed of nonpolar dimer units having disordered orienation.
Alkylalkoxypolysiloxanes. II. Ethylisopropoxypolysiloxanes
Authors: Okawara Rokuro , Ishimaru Iwao
Published: July 2006

(1) Ethylisopropoxychlorosilanes have been prepared and characterized.

(2) By the thermal reaction of partially isopropanolysis product of ethyltrichlorosilane, linear ethylisopropoxypolysiloxanes containing from 1 to 3 silicon atoms and cyclotrisiloxane have been prepared and characterized.

(3) Ethyldiisopropoxychlorosilane and isopropoxypolysiloxanes were refluxed and the two compounds of the series of linear ethylisopropoxypolysiloxanes in which one terminal group is the ethyl one have been synthesized and characterized.
Studies on the Oxy acid Phosphors. III. Aluminate Phosphors. (Part I)
Authors: Kotera Yoshihide , Sekine Tadao
Published: July 2006

Various aluminate phosphors were prepared and some of their emissions were measured. When activated by manganese, aluminate phosphors emit green, orange, or red light, while those activated by lead show blue or violet emission. Cerium acts as an activator only for calcium aluminate and emits violet light under ultraviolet excitation Strontium aluminate activated by manganese and lead shows a weak emission under short wavelength ultraviolet excitation. This may be caused by the double activation due to manganese and lead.
Dye-sensitized Photopolymerization of Vinyl Compounds. Polymerization of Styrene by Cyanine Dyes. II
Authors: Watanabe Ai , Koizumi Masao
Published: July 2006

Choosing pinacyanol iodide as a sensitizer, the authors studied the effects of temperature, concentration of dye and the wave lengths of incident light upon the photo-polymerization of styrene in a mixture of styrene and butanol (15:1). It was found that the number of initiation processes as for polymerization produced by one decomposed dye molecule is decidedly less than 1 at 40°C, while it is about 2 at 60°C, and, from this result and other facts, it was concluded that the initiation of polymerization and the photobleaching are not necessarily an identical process though the two processes are related quite closely. As for the probable scheme of the polymerization in light, it was proposed that the addition of dye and illumination only increases the initiation process without any effects upon the remaining processes in the polymerization.

It was further found that, in favorable conditions, the fragment of decomposed dye molecule is attached to the polymer, which can also initiate the polymerization photochemically.

A more detailed account of the experiments will be reported in Journ. Instit. of Polytech., Osaka City Univ.
Heats of Combustion and Formation of Some Methoxy polysilanes and -polysiloxanes: Si-O Bond Energy
Authors: Tanaka Toshio , Watase Takeo
Published: July 2006

1. The heats of combustion of the following four compounds have been measured at 20°C and at constant volume: Tetramethoxysilane, hexamethoxydisiloxane, octamethoxytrisiloxane and hexamethoxydisilane.

2. From these combustion results the corresponding heats of combustion and formation at constant pressure and Si-O bond energy have been calculated, and it has been found that the Si-O bond energy in methoxy-polysilanes and -polysiloxanes was slightly lower than that in amorphous silica.
Alkylalkoxypolysiloxanes. III. Lower Members of Ethylmethoxypolysiloxanes with One to Six Silicon Atoms
Authors: Okawara Rokuro
Published: July 2006

(1) Ethylmethoxypolysiloxanes have been prepared by the reaction of sodium bicarbonate with partially methanolyzed ethyltrichlorosilane.

(2) Distribution of the lower polymers was determined with regard to the composition of the partially methanolyzed product.

(3) Linear ethylmethoxypolysiloxanes containing from one to six silicon atoms have been prepared and characterized.

(4) Ethylmethoxycyclopolysiloxanes containing from three to six silicon atoms have been found, but they could not be accurately characterized.
Hyperconjugation. II. The Electronic Structures and Conjugation Energies of Alkylbenzenes
Authors: I’haya Yasumasa
Published: July 2006

The theory of hyperconjugation has been rescrutinized for a series of alkylbenzenes using the empirical LCAO MO method including overlap integrals for neighboring atoms. A detailed comparison of the theoretically computed and empirically determined conjugation energies of benzene gives a value of −70. 0 kcal. for β, the reasonance integral for benzene C-C. Using this value hyperconjugation energies for toluene, ethylbenzene and tert-butylbenzene are 1.45, 1.24 and 0.79 kcals. respectively. The third-order conjugation energies are found to be considerably less than any previous evaluations. Comparison of the predicted and observed dipole moments, absorption frequencies and oscillator strengths show fairly satisfactory agreements between them.
Rheology of Surface Films. IV. Viscoelastic Properties of 6-Nylon Films at Air/Water Interface
Authors: Inokuchi Kiyoshi
Published: July 2006

(1) Using a surface-rheometer, the straintime curves at constant shear stress, the stress-relaxation curves at constant strain, and the stress-strain curves at constant rate of strain were determined with the spread films of 6-nylon at air/water interface, and the rheological data were measured in relation to their dependence upon stress, temperature, and molecular weight of the sample under varying compressions, and were arrayed in the light of the mechanical models.

(2) It was found that the rheological characteristics of the film were classified into two types according to the degree of compression, i.e., a simple elastic type at large areas which involves a Hookean elasticity alone, and a viscoelastic type at considerably small areas, which is characterized by an instantaneous elasticity, the delayed. elasticity, and stationary flow under constant stress.

(3) The stress-strain curves at constant rate of strain revealed that the film, which was simply brittle at large areas transformed to tough as the compression proceeded, the mechanical properties resembling to that in bulk.

(4) It was also observed that the film strength, which was readily set up after compression, was considerably improved by the rhythmic strains applied to it, indicating the two-dimensional rheopexy.

(5) Instantaneous elastic modulus versus-area curve showed a conspicuous plateau at the areas from about 33 to 24 Å2/residue, which suggests that at least two different phases are experienced during the process of compression.

(6) Temperature dependence of the instantaneous elasticity suggests that the elasticity is mainly due to the energy effect rather than entropy effect.

(7) Molecular weight variations of the film elasticity and of the gelation area were examined together with their pH dependence of the substratum, and discussions were made in molecular terms.

(8) The stationary flow under constant stress behaved as a plastic flow, which is characterized by a yield stress above which flow practically begins to occur. Apparent activation energy of flow was estimated as about 6 kcal./mol.

(9) Overall forms of the strain-time curves and of the stress-relaxation ones were found to be well fitted by the mechanical models of six parameters.

(10) From the temperature dependence of the relaxation times, it was suggested that at least two different modes of relaxation mechanism do exist within the films of high compression.
Electron Transfer Spectra in the Crystals of Hexamminecobalt(III) Salts
Authors: Kondo Yukio
Published: July 2006

(1) The ultraviolet absorption spectra of the crystals of fourteen hexamminecobalt(III) salts were qualitatively measured using a reflecting microscope (magnification 100×), a quartz spectrograph and a recording microphotometer.

(2) All the crystals investigated showed, besides the weak absorption bands due to the complex ion, the strong absorption edges which were situated at longer wave lengths than those in aqueous solutions, and the positions of which were largely affected by anions. The most remarkable example was the iodide, the absorption edge of which extended to the visible region.

(3) It is concluded that, at least in the case of the halogenides, all the possible transitions within the complex ion and an anion are inadequate explanations and the electron transfer from an anion to the complex ion is most statisfactory for the origin of these strong absorption bands.

(4) The differences between the wave lengths of the absorption edges of hexamminecobalt(III) iodide, iodide selenate, iodide sulfate and the bromide sulfate were calculated by the energy cycle method and the results agreed fairly well with the experimental values, thus showing that these bands corresponded to the excition bands in ionic crystals.
Studies on Molecular Structure by the Measurement of the Dielectric Constants of Gases. III. The Dipole Moment and the Structure of Alkyl Nitrites
Authors: Chiba Takehiko
Published: July 2006

The dipole moment measurement was made at various temperatures on ethyl, i-propyl and t-butyl nitrites. Observed moments are 2.41D for ethyl, 2.57D for i-propyl, 2.70D for t-butyl nitrite at room temperature. The moment of the latter two compounds decrease slightly with temperature while ethyl compound remains constant. These esters are considered to consist of two isomers: the trans and the cis separated by a barrier of several kcal. due to a resonance effect. The energy difference ΔE between the two isomers is found to be zero in ethyl, <140 cal. in i-propyl, and <340 cal. in t-butyl nitrite; in the latter two the trans from being more stable.

This change in ΔE with replacing R is satisfactorily explained as due to the steric energy between R and the end oxygen atom.
Hydrogen Deformation Vibrations
Authors: Nakagawa Ichiro , Mizushima San-ichiro
Published: July 2006

The CH, CH2 and CH3 deformation frequencies in various organic compounds and the NH3 deformation frequencies in metal ammine complexes have been calculated based on the Urey-Bradley field. The fact that diagonal terms of G-matrices for these vibrations are much larger than the cross terms makes the approximate calculation quite easy. The frequency range of each of these vibrations has been tabulated and their specific features have been pointed out, which will aid in the assignment of the frequencies observed for many organic compounds and metal ammine complexes.
Studies on the Cooking Mechanism of Wood. XII. On the Nature of the weakly Acidic Group of Lignosulphonic Acid
Authors: Mikawa Hiroshi , Sato Koichiro , Takasaki Chizuko , Ebisawa Kiyo
Published: July 2006

α-Lignosulphonic acid has about one weak carboxyl group per 8–9 methoxyl, and about the same, or somewhat lesser amount of conductometrically titrable phenolic hydroxyl group, and both these groups correspond to the so-called weakly acidic group of lignosulphonic acid.
Semi- and Photo-conductivity of Molecular Single Crystals. Anthracene and Pyrene
Authors: Inokuchi Hiroo
Published: July 2006

The electrical resistivity and photoconductivity of single crystals—anthracene and pyrene—, which could be grown by slow evaporation of a solvent over a month in Solvesso, were measured. The temperature dependency of electrical resistivity (ρ) has been expressed by the next formula, ρ=ρ0 exp (Δε⁄2kT), and the values of resistivity (ρaT 15°) and thermal activation energy (Δε) are 1022Ω cm., for anthracene and 1020Ω cm., 2.4 eV. for pyrene. This activation energy and the longest wave edges of absorption spectra in the solid state coincided with each other, then this phenomenon will be due to the fact that molecular single crystals are intrinsic semi-conductors as in the case of powdered form.
Spectrochemical Study of Microscopic Crystals. X. The Absorption Spectra and Configuration of Bis(ethylenediamine)-copper(II) Complexes
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Polarized absorption spectra of bis (ethylenediamine)-copper(II) perchlorate, nitrate dihydrate and tetrathiocyanato-mercurate(II) in the crystalline state have been determined by Tsuchida-Kobayashi’s microscopic method in the region between 2400 and 7000Å. These compounds all show a band at about 50×1013/sec. (band A) and another absorption at a wave-length shorter than 90×1013/sec. (band B).

The band A of the latter two compounds suffers bathochromic effect, and the polarization property for the band B is reversed, as compared with the former. From these differences, it has been concluded that in the former two compounds, OH2 or NCS− causes a considerable effect upon the copper atom.

Using the results of the measurements, the nature of the absorption bands and absorption spectra of the complex ion in aqueous solution has been discussed.
Electronic States of the C2 Radical
Authors: Fueki Kenji , Higuchi Jiro
Published: July 2006

LCAO MO’s and ionization energies have been calculated for the 3Σ9−  KK′ (1σg)2(1σu)2(1πu)2(2σg)2 and 1Σg+KK′(1σg)2(1σu)2(1πu)4 state of the C2 radical at the internuclear distance of 1.33 Å using the LCAO-SCF method. The interactions of all the electrons have been taken into consideration, but the orthogonality relationship between the Is and the other orbitals was assumed. The LCAO MO’s obtained are in good agreement with those predicted by Mulliken. Using these LCAO MO’s, the lower electronic states have been investigated without configuration interaction. The calculated levels are generally in good agreement with the experimental. The ground state obtained is the 3Σg− state, while the observed is the 3IIu, but the result is not conclusive because of the ignorance of the inner-shell-outer-shell-mixing.
On the Base Strength of Some Nitrogen Heterocycles in the Excited State
Authors: Mataga Noboru , Kaifu Yozo , Koizumi Masao
Published: July 2006

1. The fluorescence and absorption spectra of aqueous solutions of quinoline, acridine and 2,8-diaminoacridine were observed at various pH values, and it became clear that the stabilization energy by proton addition is larger in the excited state than in the ground state.

2. The effects of hydrogen bonding and proton addition upon the spectra were confirmed to be the same in tendency.

3. On the basis of the fluorescence intensities in various organic solvents, some discussions were made about the contribution of non-bonding electron to the inner quenching of fluorescence.

4. The vapor spectrum of quinoline was-taken and line spectra were observed, which are most certainly attributable to n→π* transition.
Ultraviolet Spectrophotometric Determination of Nickel with α-Benzil dioxime.
Authors: Uzumasa Yasumitsu , Washizuka Shigenari
Published: July 2006

A new method described here involves the extraction of nickel (II)-benzildioxime with chloroform and the spectrophotometric measurements of the colored system in the same solvent. The wide pH range for the extraction eliminates the use of a buffer, and nickel is readily separated from ferric iron, aluminum, zinc, chromate, vanadate, and molybdate ions. By obviating the excessive benzildioxime with dilute alkali, the most sensitive absorbance readings are achieved, and the sensitivity at 275 mμ is 0.0013. Beer’s law holds up to 1 p. p. m. of nickel at 275 mμ, and up to 4 p. p. m. at 358 and 406 mμ. The nature and degree of interference of copper and cobalt on the color development are also discussed, and their allowable amounts are determined.
Studies on Crystals of Metallic Tris-ethylenediamine-complexes. I. The Crystal Structure of Dl-Tris-ethylenediamine-cobalt (III) Chloride Trihydrate, [Co en3]Cl3·3H2O
Authors: Nakatsu Kazumi , Saito Yoshihiko , Kuroya Hisao
Published: July 2006

The crystal structure of [Co en3]Cl3·3H2O has been determined by X-ray methods. It is trigonal D3d4–P\bar3c1 with four formula units in a cell of dimensions: a=11.50±0.02, c=15.52±0.04 Å. The configuration of the two stereoisomeric complex ions [Co en3]3+ is described. The three ethylenediamine molecules in a complex ion assume “ gauche ” forms; their nitrogen atoms form a slightly distorted octahedron around a central cobalt atom. It is shown that ionic bonds essentially link the complex ions in the structure. The watermolecules are weakly associated to chlorine it is found that a single crystal can be completely dehydrated by gently heating at 120°C, without bringing about any remarkable change in its appearance, except a loss. of transparency. A single crystal oscillation photograph was obtained even after complete dehydration.
Solvent Effects upon Fluorescence Spectra and the Dipolemoments of Excited Molecules
Authors: Mataga Noboru , Kaifu Yozo , Koizumi Masao
Published: July 2006

A general formula for the difference of solvent shifts of fluorescence and absorption spectra in the approximation of long range dipolar interaction was derived using Ooshika’s theory of light absorption in solution.

Measurements of fluorescence and absorption spectra of some naphthalene derivatives in various organic solvents were undertaken, and the data were analysed by the theoretical formula. The formula reproduces the experimental data satisfactorily, and from this fact it was concluded that the most predominant factor which determines the difference of solvent shifts of fluorescence and absorption spectra of these molecules is the interaction energy between solute and solvent molecules due to orientation polarization. The incremental values of dipolemoments in the excited state were estimated, and those for α-, β-naphthols and β-naphthyl methyl ether were interpreted as due to the increase of electron migration from the substituent in the excited state.
Studies on Serine Peptides. II Synthesis of Optically Active Serine Peptide Derivatives
Authors: Okawa Kenzi
Published: July 2006

The derivatives of optically active textscl-seryl peptides containing trifunctional amino acids have been synthesized by the Sheehan’s method in good yield.

In this method, the free hydroxyl group of the serine must have been substituted by a suitable protecting group, fx. benzyl rest, in order to obtain good results.
Rheology of Surface Films. V. Mechanical Behaviours and Structures of 6-Nylon at Air Water Interface
Authors: Inokuchi Kiyoshi
Published: July 2006

(1) Surface films of 6-nylon at air/water interface were investigated by means of electron microscopic observation together with the study of the surface pressure and potential.

(2) An unique structure involving the microfibrils of about 40 A thick were revealed which are formed from the monomolecular network at large areas, and are transformed to polyfibrillar layer during the compression process.

(3) Network structures of the film were divided into two types: a monomolecular network at large areas, and a network of the microfibrillar structure at small areas. Rheological characteristics of 6-nylon film were explained in terms of such structures.

(4) Many evidences were provided which support the view that the surface pressure measured with this film is not likely to have the osmotic pressure as commonly considered, but is intimately related to the surface elasticity of the film.

(5) It was observed that the compression process orients the microfibrils at right angles to the direction of compression. This phenomenon was explained by the anisotropy of surface pressure set up by the compression of the film.
Ionization Potentials of Some Organic Molecules. II. Aliphatic Compounds
Authors: Omura Itiro , Higasi Keniti , Baba Hiroaki
Published: July 2006

Ionization potentials of seven alcohols, three amines and nine other aliphatic compounds were determined by a mass spectrometer of Hagstrum type. In view of the fact that no reliable explanation of the ionization potentials of molecules has been given an examination of the possible interpretations of the results was presented. The relation of ionization potentials to the dipole moments, nonbonding electrons and the group orbital method are briefly discussed.
Ionization Potentials of Some Organic Molecules. III. Aromatic and Conjugated Compounds
Authors: Baba Hiroaki , Omura Itiro , Higasi Keniti
Published: July 2006

First ionization potentials of 18 aromatic and conjugated compounds were measured by the electron impact method. Seven out of these were newly determined in the present work. Discussion of the results was given with special reference to their relation to the ultraviolet data.

It was suggested that the ionization potential in benzene derivatives are primarily determined by π-electrons, while those in pyridine and picolines are largely by one of the non-bonding electrons belonging to the N atoms in the ring.
Internal Rotation in Amino Acids
Authors: Hayashi Michiro , Shimanouchi Takehiko , Mizushima San-ichiro
Published: July 2006

Equibrium angles of internal rotation about single bonds in amino acids have been calculated based on the data of the X-ray structure analysis. The result was similar to that obtained so far for many molecules containing similar bonds
Ultraviolet Absorption Spectra of 4-Chloro- and Bromo-pyridine N-Oxides
Authors: Hata Norisuke
Published: July 2006

The solution spectra of 4-chloro- and bromopyridine N-oxides were measured in various solvents, in each of which were observed two-absorption regions, one weak and the other strong.

The weak one was assigned to the transition involving the excitation of an oxygen non-bonding electron and the strong one to the transition involving the excitation of a π-electron.