Absorption spectra of colored complex salts formed by ferrous ion with dimethylglyoxime, 8-hydroxyquinoline, α-nitroso-β-naphthol and nitroso-R salt were studied. The origin of a strong absorption band in the visible region in all of these complexes was attributed to the formation of unsaturated intramolecular five-membered rings. Determination of the composition of the complexes was made spectrophotometrically in the case of dimethylglyoxime, α-nitroso-β-naphthol and nitroso-R salt.
1. The molecular weight of the surface denatured serum albumin molecule is measured from the FA–F curve. The experiment has shown it to be about 70,000. 2. The surface area covered by one surfacedenatured serum albumin molecule is determined to be 9820 Å.2 from the compressibility measurement.
1. The relation between the friction ratio and the surface-diffusion constant has been derived. 2. The relation between the friction ratio and the ratio of two axes of an ellipse has been derived. 3. The relation between f/f0 and c⁄a has been shown in a curve which makes the estimation of c⁄a very simple.
1. The apparatus for measuring surface potential by the so-called ionization method has been described. 2. The relation between the surface potential and concentration of serum albumin and castor oil monolayers have been obtained. 3. The method for determining the shape of surface-denatured protein molecules has been described. This can be carried out on the grounds of the determination of surfacediffusion constant by the surface potential measurement. 4. The shape of horse serum albumin has been decided to be an elliptic disk having the value of a=20 Å., c=160 Å. and thickness of 10 Å.
A new thiazole, 2-amino-4-methyl-5-cyanothiazole (V) m. p. 164–166° was synthesized from thiourea and α-bromo-β-ketobutyronitrile (IV), b. p. 70–73°/4 mm., prepared by the action of bromine on β-iminobutyronitrile obtained from acetonitrile.
S-Alkyl-(I) and N-alkyl-derivatives (II) of 1-thiol-benzthiazole are prepared and tested as additions for silver chloride emulsions, and compared with previously reported S-alkylderivatives (III) of 2-thiol-benzimidazole. Properties of these substances as additions may differ according to alkyl radicals substituted, positions of substitution and their parent substances. (1) Most of these compounds (I, II and III) show blue-black developing property which can not be seen in parent substances. This effect is the weakest in (I) and the strongest in (II), and as a whole, being the substituent methyl, ethyl or allyl, its activity rises in turn. Benzyl derivatives of them are almost inactive and carboxymethyl derivatives of (I) and (III) are inactive. (2) As for the fog-preventing property, (II) and (III) have greater activity and increase activity as the number of carbon atoms in the substituent increases. (I) is not so active as (II) or (III) regardless of its substituents. (3) It is remrakable that (II) has somewhat sensitizing property added in emulsion, and accelerate the development when both (I) and (III) retard it. (4) The similarity of actions of (I) and (III) lies in parallel with the resemblance of their chemical constitution, but (I) is inferior to (III) in those properties which are supposed to be due to the imino group in the imidazole ring, as fog-preventing action. (5) The considerable difference between (I) and (II) which is the influence of the same substituent in different position of the molecule, is supposed to be attributable to the change of the constitution of the sulfur atom of thio-ether type to more reactive thio-keto type. The sensitizing, fog-preventing or development-accelerating action of the latter is supposed to be intimately related to the complex forming character of this thio-keto group with silver or silver salts.
The adsorption of barium, mercuric, cupric, aluminum, and thorium ions on the built-up films of stearic acid both transferred from water the surface of water, and converted from barium stearate multilayers, was studied. The adsorbed amount of barium ion increased with increasing pH, but the increase in thickness corresponding to the saturate adsorption for monolayer was constant for all pH. On the contrary, other ions studied showed the specific pH range for the optimum adsorption. A more or less complicated and large structure for these ions was concluded from the special nature of the adsorption hereby exhibited by these ions. Such a complex nature was most pronounced for aluminum and thorium ions.
Monolayer of siearic acid spread on water containing copper, aluminum, and thorium ions, has been transferred onto solid surface, and the apparent thickness of monolayer as well as its wettability towards water after the treatment with or without aqueous solution of salts were measured. Tentative explanations for these phenomena are given, taking into account of a macromolecular structure of aluminum soap.
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.
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.
Tests made with data in the recent literature show (1) that the Ishikawa formula is superior to the formulas of Macleod, Drucker-Kassel and Kendall which are often used as an ideal mixture law for viscosity, and (2) that the extraordinary values of K of his formula in PbCl2–PbBr2 and Na–K systems suggest the tendency of forming peritectic compounds of PbBr23PbCl2 and Na2K respectively.
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.
The visible and ultra-violet absorption spectra of Na[Co(NH3)4(SO3)2]·2H2O (brown salt) and Na[Co(NH3)4(SO3)2]·4H2O (yellow salt) have been measured. The results have proved that the SO3=-radical coördinates around the central cobalt (III) ion by the lone pair electrons of its sulfur atom, and that the brown salt has trans-configuration concerning the positions of the SO3=-radicals and the yellow salt cis-configuration. The absorption spectrum of NH4[Co(NH3)4(SO3)2]·3H2O (dark brown form) has also been studied and it has been assumed that the salt is trans-isomer contrary to several investigators’ assignmints of cis-strusture.
A survey of the absorption data of the tetrammine- or bisethylenediamine-Co(III) complexes available in previous literature as well as in the author’s measurements has shown that the frequency differences of the first bands (or second bands) of the cis- and trans-isomers are closely related to the spectrochemical series of the ligands which coördinated in cis- or trans-positions. This correlation has been interpreted as the result of a trans-influence of the ligands, i.e., a trans-substitution causes a greater shift of the first band (or second band) than corresponding cis- substitution. The visible and ultraviolet absorption spectra of two isomers of [Co(NH3)4NO2·NCS]+ have been measured and the steric configurations of both ions have been determined.
Evidence is presented to indicate that ethyl nitrate, nitromethane, and possibly also nitrourea are not able to accept hydrogen from nitrate reductase system of E. coli. p-Nitrobenzoic acid is reduced to p-aminobenzoic acid by the action of the dried cells of E. coli to a small extent. This reduction is, however, not achieved by nitrate reductase. Nitrite reductase contained in the organism is responsible for the reduction of aromatic nitro groups.
The authors studied on the new differential polarography; its instrumentation and result obtained were particularly reported in the present paper. Discussions for its quantitative analysis and for the electrode reactions and some utilities of current-alternator will be followed.
(1) Force-area curves were determined of monolayers of native ovalbumin and azo-ovalbumin with various number of diazonium groups. As a results it was found that the coupled diazonium groups do not contribute to the area of compressed protein film molecule, but tends to increase the thickness. (2) The mode of deposition, when the monolayers of azo-ovalbumins are deposited on metal slides covered with multilayers of barium stearate, was examined. Various types of deposited azo-ovalbumin films thus obtained were tested as to their antigenic activity. The results were discussed in relation to the structure of protein films.
The reaction of N-nitrosoacetanilide or benzenediazo hydroxide with bromobenzene gives all three isomerides of bromobiphenyls, the yields decreasing in the order ortho > meta > para. All the nuclear positions of bromobenzene are more reactive than benzene towards attack by the phenyl radicals.