Solvent Action Research Articles

185. Studies in solvent action. Part III. Rotatory powers of l-menthyl methyl naphthalate in mixtures of alcohols with benzene or hexane

185. Studies in solvent action. Part III. Rotatory powers of l-menthyl methyl naphthalate in mixtures of alcohols with benzene or hexane

186. Studies in solvent action. Part IV. Optical rotation of l-menthyl hydrogen naphthalate in polar and in non-polar solvents

186. Studies in solvent action. Part IV. Optical rotation of l-menthyl hydrogen naphthalate in polar and in non-polar solvents

IV. The relationship of micro-organisms to the decay of stone

The first suggestion that bacteria might be agents in stone decay was probably that of Buchanan (1904) in a paper read before the Royal Philosophical Society of Glasgow in 1904. This paper contained evidence that bacteria, yeasts and moulds were associated with the decay of sandstones in the City of Glasgow, and included a brief sketch of the manner in which the autotrophic bacteria, sulphur bacteria, iron bacteria, and the nitrifying bacteria might play a part in sandstone decay. This paper was apparently unknown to later writers, Anderson (1910), Marsh (1923) and Fox and Harrison (1925), none of whom makes reference to it. In 1928 Buchanan published the results afresh with no important addition, but confirming his earlier work. Stutzer and Hartleb (1899) in an important paper, published five years before that of Buchanan, noted the solution of the lime of the cement on walls of reservoirs and dock sides. While the greater part of this solvent action was believed to be due to dissolved carbon dioxide in the water, part of it at least was attributed to the action of bacteria contained in a brown slime which covered the walls.

THE CONDITIONS OF RECOVERY OF TRANSMISSIVITY OF NEWLY REPASSIVATED IRON WIRES IN NITRIC ACID

1. Passive steel wires were activated in a bath (Bath A) containing 70 v. per cent HNO(3) (in which they undergo prompt repassivation), and immediately transferred to a second bath (Bath B) containing HNO(3) of a concentration varying in different experiments. After varying intervals in this bath they were transferred while still passive to a third bath (Bath C) containing strong HNO(3) (70 or 100 v. per cent) and there immediately activated. 2. During the immersion in Bath B the wires progressively recover their ability to transmit activation waves in strong HNO(3). The measure of this recovery is the distance travelled by the activation waves in Bath C after the varying times of exposure in Bath B. Transmissivity as thus measured is at first incomplete (decremental) and later becomes complete. The minimal exposures in Bath B required to render wires completely transmissive in the strong acid of Bath C were determined for concentrations of HNO(3) between 10 and 100 v. per cent. With 100 v. per cent HNO(3) in Bath C, these exposures range from 40 minutes or more in 15 v. per cent to 10 minutes in 100 v. per cent HNO(3) (temperature 19-20 degrees in all baths). 3. The time required for complete recovery varies inversely with the concentration of the acid in the recovery bath (Bath B), but increases rapidly with the concentration of the acid in the testing bath (Bath C). Hence at a time when a wire has recovered just sufficiently to transmit non-decrementally in a given strong acid (e.g., 70 v. per cent) it still transmits decrementally in a stronger acid. Complete recovery for transmission in 100 v. per cent HNO(3) requires about twice as long as for 70 v. per cent HNO(3). In HNO(3) of 50 v. per cent and less decremental transmission does not occur. 4. The indications are that recovery is an effect of the progressive solvent action of the external acid on the passivating oxide film, which at its first deposition appears to be relatively thick and hence resistant to electrochemical reduction. The final stage of recovery, when electrical sensitivity and speed of transmission are maximal, would on this hypothesis correspond to minimal thickness, possibly monomolecular. 5. The rate of recovery in Bath B is not far from proportional to the concentration of HNO(3) in the more dilute solutions, but in the higher, especially the strongly passivating, concentrations (70 to 100 v. per cent) the rate becomes appreciably slower than proportional, apparently because of the intense oxidizing action of these solutions, which reinforces the oxide sheet and retards the thinning process. 6. The bearing of these observations on the problem of the conditions of recovery in irritable living tissues (such as nerve) during the absolute and relative refractory periods is briefly discussed.

CCCLXX.—Studies in solvent action. Part II. Rotatory powers of d-β-octyl hydrogen phthalate and its methyl ester

The first page of this article is displayed as the abstract.

XCIII.—Studies in solvent action. Part I. Influence of polar solvents on the rotatory power of l-menthyl methyl naphthalate

The first page of this article is displayed as the abstract.

Isolation of the Film Responsible for the Passivity of an Iron Anode in Acid Solution

A RECENT paper (J. Chem. Soc., 1930, p. 478) showed that the direct solvent action of dilute sulphuric acid on ferric oxide films is very slow. The rapid, removal of a ferric oxide film from iron by acid is due to the formation of the local cell iron/acid/ferric oxide, which produces cathodic reduction of the ferric oxide to the rapidly soluble ferrous oxide. If the whole surface receives anodic treatment, this cathodic reduction is prevented, and hence an iron anode may remain passive in acid solution.

The growth of silver iodide films

It is now well established that a large class of important chemical reactions is controlled by the growth of obstructive films, but our knowledge of the mechanism of the growth of such films—especially at low temperatures—is still very imperfect. The present paper describes a detailed study of a particularly instructive case of film-growth, the action of iodine on silver; this reaction was chosen because silver iodide films—in contrast with oxide films—reach visible thickness rapidly at ordinary temperatures. The optical properties of these films have already been studied by Wernick, whilst much information regarding the velocity of film-growth has been obtained by Tammanm by Kohlschutter and Krahenbiihl, and by Hartung. Tammann used the interference colour as the means of arriving at the thickness of the film; this method has certain unique advantages, but the more recent work of Tammann and Bockow has indicated that—in the case of oxide-films at least—the particular form of the method employed gives values for the thickness differing widely from those obtained by the gravimetric method. Tammann expressed the relation between the thickness ( y ) and the time ( t ) by the parabolic equation y 2 = 2 pt , where p is a. constant. Kohlschütter and Krähenbiihl, and also Hartung, used microgravimetric methods to determine the amount of iodine taken up, and obtained curves connecting thickness and time ; these curves do not appear to follow the parabolic equation. All the experimenters mentioned used iodine vapour to attack the silver, but the concentration of iodine in the gas phase was not directly determined. In all cases the surfaces were prepared in air, and the possible effect of exposure to oxygen was not considered; yet in several of the reactions of copper and iron, pre-exposure to air or oxygen is known greatly to modify the result, owing to the fact that an oxide-film may become protective before reaching the thickness needed for interference colours. It may be mentioned that after exposure to vapour, the colour produced on metallic specimens is usually not uniform, but indicates a greater film-thickness near the edge. In the present research, it was decided to use a solution of iodine in an organic solvent; in this case, the concentration could be fixed or varied at will, and in general uniform colouration (indicating uniform thickness) could be obtained. Moreover, abrasion could be conducted, if required, below the surface of the solvent, instead of in air. Chloroform was .found to be a suitable liquid, since, whilst freely dissolving iodine, it had no appreciable solvent action on a silver iodide film.

Facilitating the Removal of the Spray Residue

A brief resume, concluded from practical and laboratory observations, is given of conditions that prevent the effective removal of spray residue by the chemical process. Of the factors that retard the solvent action, the settling of dust on the lead arsenate in the calyx and stem end of apples seems most difficult to overcome. In order to facilitate the removal of residue, numerous compounds were mixed with lead arsenate and applied to apples as a combination spray. The fruit sprayed with the various combinations were then treated in acid to learn what materials aided the solvent action of the acid.

CLXXVII.—The effect of gases on the colour of iodine vapour, and the solvent action of various vapours on solid iodine

CLXXVII.—The effect of gases on the colour of iodine vapour, and the solvent action of various vapours on solid iodine

THE EFFECT OF SOME OF THE CHEMICAL CONSTITUENTS OF TUBERCLE BACILLI ON THE PROTOPLASM OF AMOEBA DUBIA

1. Protein fractions derived from tubercle bacilli are toxic to the interior of Amoeba dubia but have no action on the plasmalemma. 2. Phosphatide fractions dissolve the plasmalemma but have no effect on the internal cytoplasm. 3. The fatty acid fraction has a marked solvent action on the plasmalemma when brought in contact with the surface of the cell. When injected it may slowly penetrate the cytoplasm to dissolve the contiguous plasmalemma. 4. The polysaccharide fraction has no effect upon the surface membrane or upon the internal cytoplasm of Amoeba dubia.

Postpartum eclampsia with death from cerebral hemorrhage and encephalomalacia limited to the left frontal lobe

Eclamptic patients are more liable to cerebral hemorrhage than we were wont to believe and if autopsy always included examination of the brain we would probably find more cases that clinically had gone unrecognized. Large hemorrhage may occur anywhere in the brain, most commonly in the parietal lobe, corpora striata and ventricles and least frequently in the pons, optic thalamus, and frontal lobe.Many small focal hemorrhages with surrounding areas of necrosis may form into one large hemorrhagic and necrotic area. This may be due to the solvent action of a circulating enzyme acting on the endothelial lining of the terminal blood vessels (Welch).4Hemorrhage in the frontal lobe may give no clinical evidence other than hysteria and is confusing with puerperal toxic psychosis.Blood transfusion, preceded by phlebotomy, given to eclamptic cases may arrest further extension of hemorrhage.I wish to thank Dr. S. A. Cosgrove, attending obstetrician to the Jersey City Hospital, for his courtesy in permitting me to follow up and report this case. My appreciation is extended to the pathologist, Dr. Brownstein, for his complete report.

An Outbreak of Plumbism in Horses, Due to the Solvent Action af a Soft Peaty Water on Lead Piping

An Outbreak of Plumbism in Horses, Due to the Solvent Action af a Soft Peaty Water on Lead Piping

CCCCVII.—Selective solvent action. Part VII. Solubilities in mixed solvents

The first page of this article is displayed as the abstract.

Bacterial proteins.—The presence of alcohol-soluble proteins

In the course of an investigation of the Gram-staining material in Strepto­cocci and Staphylococci, substances giving the general reactions of the alcohol-soluble proteins or gliadins have been isolated. Alcohol-soluble proteins, or prolamins (Osborne (1)), are especially characteristic of the seeds of cereals; among them gliadin of wheat and rye, hordein of barley, and zein of maize are typical examples. The present communication deals with the alcohol-soluble fraction of bacterial protein: the other soluble protein substances will form the subject of a later communication. The work was commenced in 1917 as part of the author’s study of war wounds, but had to be abandoned, and was not recommenced until the winter of 1923. Most investigations on bacterial proteins have been conducted by extracting the bacterial cells with alkaline solutions, with or without heating; such a pro­cedure is likely to modify certain of the proteins, and, as will be seen later, would entirely remove the alcohol-soluble fraction. Bacteria are especially resistant to the solvent action of the majority of biochemical solvents used for the extraction of proteins. The Gram-positive organisms, with the exception of Pneumococci, which are soluble in bile (Heidelberger and Avery (2) used this method in examining the protein of Pneumo­cocci) are especially refractory. Douglas and Fleming (3) extracted Staphylo­cocci with hot acetone and removed the Gram-reacting substance; Dreyer (4) used acetone and boiling formalin. All these processes are likely to alter the residual proteins. Liquid cultures are also unsatisfactory, are bulky to manipulate, and introduce disturbing factors.

The Resistance of Certain Metals and Metallic Alloys to Corrosion and Solution by Sea‐Water

Summary. A brief account is given of various tests relating to the corrosive and solvent action of sea‐water on metals and metallic alloys. Natural films of oxide or chemically‐induced protective coatings have been found in two cases to withstand fairly successfully the attack of sea‐water. The weakness of paints and varnishes as protective coatings lies in the formation of minute cracks and pinholes, which cause pitting when brought into contact with sea‐water. Semi‐immersion was found to be a more rigorous and exacting test than total immersion, and test samples should be submitted to both treatments before an opinion is expressed as to their corrosion‐resisting properties.

MICRURGICAL STUDIES IN CELL PHYSIOLOGY

I. Plasmalemma. 1. Of the salts used in these experiments the anions have only a modifying effect on the cations. The dispersive action of Na and, to a lesser extent, of K, predominates. Borate increases the toxicity of Na and acetate decreases it. 2. CO(2) and carbonates dissolve the plasmalemma readily. 3. Na lactate tends to dissolve the surface especially when brought into contact with it from the interior by injection. Lactate antagonizes the stimulating effect of Ca on the plasmalemma. II. The Internal Protoplasm. 4. Acid phosphate of Na and K, when injected, causes a membrane to form around the granular endoplasm within the ameba. 5. Na borate increases the toxicity of Na inside the cell. 6. Bubbles of CO(2), injected into the cell, cause an increase of fluidity of the internal protoplasm. These bubbles shrink and disappear from the cell more readily than air bubbles. 7. The anions modify the typical cation effect. Carbonates accentuate the liquefying and solvent action of Na. Phosphates prevent a complete rounding of the ameba caused by Na. Lactate inhibits the solidification and pinching off effect caused by Ca. III. Physiological Significance of Salts. 8. The buffer salts can be injected in high concentrations without toxic effects but amebae can be immersed in them only in very dilute solutions without injury. 9. The inhibiting action of lactate and the dispersive effect of CO(2), carbonates, and lactate on the plasma membrane, must be of importance in a consideration of the functions of the organism and perhaps in the production of pathological changes.

STUDIES IN THE PHYSICAL CHEMISTRY OF THE PROTEINS

1. The solvent action of a neutral salt upon a protein, oxyhemoglobin, has been found identical to the solvent action of a neutral salt upon a bi-bivalent or uni-quadrivalent compound. 2. The solubility of oxyhemoglobin in phosphate solutions of varying ionic strength has been defined by the equation: log See PDF for Equation in which micro is the ionic strength, and S(0) is the solubility in the absence of salt. 3. The values of S(0) have been calculated to be 12.2, 11.2, and 13.1 gm. per liter respectively at pH 6.4, 6.6, and 6.8. 4. The relatively great solubility of oxyhemoglobin in water has been ascribed to the strong affinity constants for acid and base of certain groups in oxyhemoglobin. 5. The small change in the solubility of oxyhemoglobin effected by neutral salts suggests that but few such groups are dissociated in oxyhemoglobin in the state in which it crystallizes near its isoelectric point. 6. Certain of the other properties of oxyhemoglobin, such as its low viscosity, are considered in the light of its molecular weight and its valence type.

CLXXXVII.—Selective solvent action. Part VI. The effect of temperature on the solubilities of semisolutes in aqueous alcohol

The first page of this article is displayed as the abstract.

An Outbreak of Plumbism in Horses, Due to the Solvent Action of a Soft Peaty Water on Lead Piping

An Outbreak of Plumbism in Horses, Due to the Solvent Action of a Soft Peaty Water on Lead Piping