巻号一覧
28 巻, 4-5 号
選択された号の論文の15件中1～15を表示しています
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小西 孝, 黒川 昌孝1972 年 28 巻 4-5 号 p. 83-90
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe aqueous solution of silk fibroin, prepared by the cupriethylenediamine method, was hydrolyzed by trypsin and chymotrypsin, then crystalline materials was deposited. The crystals from trypic proteolysis precipitate (FTP) and chymotrypic proteolysis precipitate (FCP) were found to be β-structure. The β-structure of FCP was changed to α-structure (FCPIX) in the recrystallization at room temperature in water. Crystals-blended materials of various composition were prerared by dissolving in 3/4 cupriethylenediamine and dialyzed. The blended white precipitates were obtained from the dialyzing tube and drops containing blended precipitates in suspension were dried by covering with thin film of cupper screen.
In this procedure, presence of β-structure was confirmed in their mixture if FTP (β-form) is contained more than 2% in the mixture of FTP and FCP1X. On the electron microscopic observations. α-form shows linear sheaf-like fibrillar crystals, but according to increase of FTP contents, crystals obtained from the mixture of FTP and FCP 1X are twisted and become short. Finally, the crystals approach at globular β-structure.
In the differential thermal analysis, when blends contain 5_??_10% FTP, the degradation of temperature were 324_??_326°C and thermal energy of degradation required to break down intermolecular bonds was greater than FTP and FCP 1X. Moreover, posture of crystals-blends of FTP and FCP 1X are discused briefly.抄録全体を表示PDF形式でダウンロード (4453K) -
石川 博, 塚田 益裕, 土井 詰功, 近田 淳雄, 平林 潔1972 年 28 巻 4-5 号 p. 91-98
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe following results were obtained from investigation of DSC thermograms of silk fibroin.
1. The decomposition temperature of the crystalline region of silk fibroin is estimated to be about 348°C from the DSC thermograms of the hydrolysis residue.
2. Silk fibroin is changed thermally into unoriented β-type by the treatment with CaCl2 solution in a free state, while the decomposition temperature of the samples treated at constant length becomes higher than the original samples.
3. The α-β transition of coagulated fibroin takes place at about 240_??_250°C, and the resulting β-type fibroin is decomposed at about 290_??_300°C. When the α-β transition is caused by swelling or heat-treatment, the coagulated fibroin is changed into β-type through the mixture of α and β type depending on the treating conditions.
4. α-type fibroin is easely changed into β-type by drawing in a swollen state. This β-type fibroin shows a characteristic double peak due to decomposition; the main peak observed at a higher temperature in the thermogram is shifted to higher temperature by drawing, while the other is unchanged.
5. DSC thermograms of fibroin powdered by grinding with a file have two endothermic peaks; one occurs at about 185°C and the other at abou 295°C. The former disappears and the latter shifts slightly to higher temperature by recrystalizing in the presence of water.
6. It is concluded that DSC thermograms of silk fibroin are divided into two components which are attributed to unoriented β-type component and oriented β′-type one, respectively.抄録全体を表示PDF形式でダウンロード (515K) -
石川 博, 黒田 静治, 近田 淳雄1972 年 28 巻 4-5 号 p. 99-105
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe wool fibers exhibited a negative dye dichroism with Congo Red when being set in boiling water for a few second or more. This phenomenon may be due to the alignment of the polymer chains in some part of matrix, perpendicular to the direction of stretch. The negative dichroism did not disappear even after the treatment giving rise to the super-contraction and restretching, probably on account of the formation of stable bonding in or arround the matrix having negative orientation. The samples dyed before setting showed smaller dichroic ratio than ones dyed after the setting. This fact indicates that the molecules of the dyestuff used in this experiment are difficult to penetrate into the oriented matrix regions. The appearance of the negative dye dichroism was independent of the growth of so-called cross-β structure.
The structral change of wool fibers in boiling water is discussed from the above and other observations in the relation to the Feughelman's series zone model.抄録全体を表示PDF形式でダウンロード (2384K) -
松川 三郎, 若林 義治, 鈴木 常代, 中村 良治, 大江 秀雄1972 年 28 巻 4-5 号 p. 106-111
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーFor the investigation of swelling wool the freeze-dry process used in histochemical fields was applied to various wool fibers. In our experiments, the swollen fibers were frozen in isopentan at -160°C and then dried at -60°C_??_-50°C for 2hrs. under the constant pressure at 1_??_5×10-2 mmHg. Such conditions prevented the deswelling of swollen fiber and kept the higher degree of swelling than that obtained with the usual drying method.
An attachment to embed the sample fiber by the vinyl polymerization method was deviced to prepare the cross-sections of the frozon-dried samples.
The results observed were as follows.
i) The cross-section of merino wool fiber deformed from the original elliptic shape to circular one by swelling-treatment.
ii) The more remarkable swelling of ortho-cortex was observed at the minor axis of crosssection.
iii) The indented perimetric irregularity on the ortho-cortex appeared but not on the paracortex.抄録全体を表示PDF形式でダウンロード (1709K) -
高橋 重三, 山崎 隆, 武内 民男, 相宅 省吾1972 年 28 巻 4-5 号 p. 112-119
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe polyglutamic acid (PGA) fibers were spun from concentrated poly-sodium-L-glutamate (PSLG) aqueous solution, using inorganic acids such as HCl, H2SO4 and H3PO4, as coagulant. The relations between the spinning conditions, such as drafting and drawing and the properties of the spun fibers, such as the molecular conformation the crystallinity and the mechanical properties were investigated.
The molecular chains of undrafted and undrawn fibers have the α-helix conformation regardless of acids used as coagulant, and the crystals were unoriented. On the other hand, the conformation of molecular chains of drafted and drawn fibers depended on acids as coagulant. The crystals comprised of molecular chains with β-structure were formed and the well-oriented fiber was obtained when H3PO4 was used as coagulant. The crystals of H2SO4-coagulated fiber were a mixture of α-helix and β-structure. However, with HCl-coagulant the α-helix conformation did not change and the crystals were oriented.
The mechanical properties and the stability of the fibers against hot water varied widely depending on the acids used as coagulant and the spinning conditions. The fiber spun with H3PO4 coagulant was more stable against water than those spun with other coagulants.抄録全体を表示PDF形式でダウンロード (2982K) -
羽賀 敏雄, 石橋 博1972 年 28 巻 4-5 号 p. 120-128
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーUndrawn and drawn poly-γ-methyl-L-glutamate (PMLG) fibers having different secondary structures were treated with 18N sulfuric acid, and the apparent weight loss was measured. From quantitative analysis by infrared spectra of the hydrolysis degree of side chain ester groups in insoluble residue, the apparent weight loss was devided into the weight loss due to hydrolysis of main chain and that of side chain. Besides, the density and intrinsic viscosity of insoluble residue were measured, and the accessibility of PMLG fibers to sulfuric acid is discussed in connection with secondary structures. The results were as follows;
(1) In both PMLG fibers, the weight loss due to hydrolysis of main chain proceeds at two stages, the early stage of higher rate and the later one of lower and constant rate. The former is considered to be due to the dissolution of more accessible amorphous region from the decreasing behavior of intrinsic viscosity of insoluble residue. The weight loss due to hydrolysis of main chain in the first stage is larger in undrawn fiber and therefore it is considered that undrawn fiber has larger accessibility than drawn fiber.
(2) Density of insoluble residue supports quantitative analysis of the hydrolysis degree of side chain by infrared spectra.
(3) The difference of accessibility to sulfuric acid between undrawn and drawn fibers was concluded to be caused by the following facts. Since random-coil structure is difficult to be recognized in both fibers, the region where α-helix dose not stand side by side but stand random situation in undrawn fiber decrease during the α→β transformation by drawing.抄録全体を表示PDF形式でダウンロード (1230K) -
青木 一三1972 年 28 巻 4-5 号 p. 129-136
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe interaction of metal ion with sericin was investigated by ultramicro-electrophoresis, X-ray diffraction, IR-spectra, DTA and pH titration.
The following results were obtained:
1) In the pH region lower than isoelectric point, both sericin bind with Sn2+ and Th4+ but not with Cd2+ and Al3+. Similar tendency was found with sericins prepared under the different condition. The binding amount of metal ion to sericin was less than that in alkaline region.
2) From the results of pH titration of metal salts and of electrophoresis of metal ion-negative AgI sol (pI 4), it is concluded that SnCl2 is hydrolyzed in the pH region lower than the isoelectric point of sericin and Al(NO3)3 is hydrolyzed in the higher pH region. It was found that free energies of binding to AgI sol for Sn2+ and Al3+ are as large as that of Th4+. These results are in good agreement with those in electro-phoresis for sericin bound with metal ions.
3) In sericin cocoon layers treated with Al(NO3)3 or Th(NO3)4 at pH 6.0, two endothermic peaks were observed at about 233°C and 270°C (dec. temp.), while that treated with Th (NO3)4 at pH 2.5 had a single endothermic peak and the decomposition temperature was lowered to 253°C.
4) The strong scattering was observed about the center (d>12.5A) in X-ray diffraction pattern of sericin cocoon layer treated with Th (NO3)4 at pH 2.5.
5) At both pH 2.5 and pH 6.0, poly-L-glutamic acid bound easily with Th4+, while poly-L-lysine almost did not bind with Th4+ at pH 2.5.抄録全体を表示PDF形式でダウンロード (1701K) -
柴田 勝喜, 小川 利彦, 高瀬 福巳1972 年 28 巻 4-5 号 p. 137-141
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe interaction between water-soluble proteins and acid dyes was investigated spectrophotometrically, where the crystalline bovine serum albumin (Ia) and egg albumin (Ib) were used. The acid dyes used were C. I. Acid Orange 7 (IIa), C. I. Mordant Violet 5 (IIb), C. I. Acid Red 178 (IIc), Acid Complex Violet 4R (IId) and C. I. Acid Blue 158 (IIe). The absorption spectra were measured with aqueous solutions of different concentrations of Ia and Ib. The absorption intensities of IIaand IIb at λmax, respectively, decreased in low concentration of albumin, reached the minimumat certain amount of I, and they began to increase with increase in I. In the case of IIc, however, the absorption intensity at the concentration of 4.3×10-5mol/l did not decrease until the added Ia reached 2.0×10-3g/l, and increased markedly from this point. The higher pH, the more quantity of I was required to reach the minimum absorption intensity of II. More quantity of Ib was required than Ia, since the charge Ib is lower than that of Ia. No significant change was observed in the spectrum of the aqueous solutions of IId and IIe upon addition of various amounts of I. The association equilibrium exists between monomer and dimer in the aqueous solutions of IIa, IIb and IIc. But IId and IIe could not be measured owing to little change.
In view of the observations on basic vinyl copolymer, it may be concluded that the bonding between I and II is ionic in character and changes in absorption intensity are attributable to the changes in aggregation of II on I.抄録全体を表示PDF形式でダウンロード (307K) -
藤原 康晴, 安田 武1972 年 28 巻 4-5 号 p. 142-146
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe wool fabrics were treated with reducing sugars (D-xylose, D-galactose, lactose) in aqueous solution under various conditions, i.e, treating time, temperature and concentration. The wool keratin reacted with reducing sugars to change the color from straw to deep dark brown.
When the free amino groups of wool keratin were substituted by acetyl groups, the browning rate was much reduced. With the progress of the reaction, the extent of weight loss of wool keratin in an aqueous urea solution became considerably smaller and the melting endothermic peak of wool keratin differential thermal analysis curve shifted to a higher temperature.
It is concluded from these results that the chromophore development in wool keratin treated with reduced sugars was due to the amino-carbonyl reaction which involved some interchain cross-linkings.抄録全体を表示PDF形式でダウンロード (376K) -
榎本 睦, 瀬戸山 幸一1972 年 28 巻 4-5 号 p. 147-153
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーIt was found that the formulae given by Norton-Nichols is the best among several formulae which express numerically the degrees of silk yellowing which correlates well with sensuous assessment.
There was a difference in wavelength dependence between yellowing and degradation, i.e., yellowing of silk occurred in the region of wavelength from 230mμ to 350mμ (max. 309_??_322mμ) and degradation of silk occurred in the region from 220mμ to 370mμ(max. 244_??_257mμ).
It appears that silk is, to some degree, bleached by visible light.
And yellowness index increased with increasing loss of tryptophan in silk fibroin, and yellowing by irradiation of Xenon lamp was greater than by that of carbon arc when compared under the same amount of the loss.
Finally, it was found that oxygen plays an important role in silk yellowing by irradiation of Xenon lamp.抄録全体を表示PDF形式でダウンロード (469K) -
中村 良治, 鎌田 健一, 田中 俊雄1972 年 28 巻 4-5 号 p. 154-159
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーAn apparatus for measuring the streaming potential of fibers was devised by improving the hydrodynamic apparatus for estimation of wettability of fiber assemblies previously reported by present authors.
Two silver-deposited lattice electrodes were installed respectively on the upper and lower sides of the sample chamber filled with the assembly and the dip-solution was passed at a constant hydrostatic pressure. Steel wires were used as the base material of electrodes, which could resist not only the force applied for the filling of fiber assembly but also the hydrostatic pressure during measurement. This hardness of wire was neccesary to have steady values of potential difference, namely the streaming potential.
On this apparatus, the measuring conditions were examined as follows: for experiments on the Merino wool fiber, reproducible value of potential difference between the electrodes were obtained when they were measured first at the flowing and then the static states. The difference of these two value is the streaming potential at corresponding pressure loss. The head of head tank was kept constant during the passage of dip-solution in the chamber. Thus, a continuous measurement of streaming potential was possible by repeating the above operation in optional interval. However, the time, during which the passing was stopped, had to be as short as possible. The influence of the porosity of fiber assembly on the streaming potential was also examined; when the fully pre-wetted sample was used at a high density, a linear relation was obtained between the streaming potential and pressure loss.抄録全体を表示PDF形式でダウンロード (506K) -
中村 良治, 鎌田 健一, 田中 俊雄1972 年 28 巻 4-5 号 p. 160-166
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーIn order to discuss wetting behaviors of wool fibers, three kinds of sample having different surface layers (the greased, degreased and descaled wool fibers) were prepared and the ζ-potentials were measured under various conditions. The results were as follows;
i) In preliminary dyeing experiments, a high affinity of the greased wool fiber to the basic dye and the increase in acid dye-sorption on this fiber with the addition of nonionic surfactant were shown. Then, these are discussed on the basis of the fact that the grease adherent on wool showed a negative ζ-potential. From this discussion and the streaming potential vs. pressure loss curves, it was found that even in the case of the greased wool, air bubbles absorbed on the fiber-surface could be removed by the forced streaming of dip-solution through the fiber assembly.
ii) Although the ζ-potential of the greased wool fiber was negative over the entire pH-region examined, ζ vs. pH curves of the degreased and descaled wool fibers cut the holizontal axis. In latter cases, the isoelectric points (pKI) were 3.5 and 4.3, respectively.
iii) From pKI value of cortex layer estimated from the dyeing method and from ζ vs. pH curves for the above three samples, it is concluded that the lower pKI value obtained on the degreased wool, whose surface is surrounded by intact scales, are due to the structure and properties of the surface layer. These considerations are quite in accord with the fact that the lower critical surface tension, i.e. 30dyne/cm, as compared with the values reported by other authors, for the intact degreased wool fiber.抄録全体を表示PDF形式でダウンロード (620K) -
Hiroshi Ishikawa, Kiyoshi Hirabayashi, Tomoko Muramatsu1972 年 28 巻 4-5 号 p. 167-169
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーPDF形式でダウンロード (871K) -
田川 高司, 森 淳一, 近土 隆1972 年 28 巻 4-5 号 p. 170-173
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーA specimen deformation apparatus for scanning electron microscope was devised and the surface structures of merino wool and mohair fibers were observed from relax to break down under stretching and twisting.
The specimens were prepared by coating gold on their surface. Electron microscopic observation of these specimens could be easily performed even in largely deformed state without charging.
The scanning electron micrographs reveals that the scales of mohair are thin and flat, and are piled more closely one upon another compared with those of merino wool. The shape of break ends of these fibers stretched or twisted slowly is characteristic, and it relates to their fine structure composed of A (para-) and B (ortho-) cortices. Since both cortices separate from each other in their boundaries during deformation, merino wool gives break ends of bilateral type, while mohair gives that of sheath and core.抄録全体を表示PDF形式でダウンロード (2916K) -
塩崎 英樹, 田中 芳雄1972 年 28 巻 4-5 号 p. 174-177
発行日: 1972/04/10
公開日: 2008/11/28
ジャーナル フリーThe addition reaction of phenyl glycidyl ether or epichlorohydrin to wool keratin containing water was investigated in different solvents at 75 or 68°C. The reaction rate varied with solvents used in the reactions and could be described by the solubility parameter of the solvents. The addons decreased with increasing solubility parameter of the solvents used to reach a minimum value at the parameter of about 10, that is, the solubility parameter of the epoxide, and then increased with the parameter. It is suggested that epoxides would react in an aqueous phase but not in an organic phase, as reported earlier for the epoxide-silk reactions in which the epoxide reacts mainly with tyrosine in the presence of a salt.抄録全体を表示PDF形式でダウンロード (265K)
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