Selective delignification of wood by white-rot fungi

The white-rot fungi,Cerrena unicolor, Ganoderma applanatum, G. tsugae,Ischnoderma resinosum, andPerenniporia medullapanis, caused two distinct types of decay. Large areas of decayed wood were selectively delignified and a typical white-rot causing a simultaneous removal of all cell wall components was present. Preferential lignin degradation was intermittently dispersed throughout the decayed wood. Scanning and transmission electron microscopy were used to identify the micromorphological and ultrastructural changes that occurred in the cells during degradation. In delignified areas the compound middle lamella was extensively degraded without substantial alteration of the secondary wall. The S₂ layer of the secondary wall was least affected. The loss of middle lamellae resulted in extensive defibration of the cells. Sulfuric acid lignin determinations indicated that 95–98% of the lignin was removed. Wood sugar analyses using high pressure liquid chromatography demonstrated that hemicelluloses were removed in preference to cellulose when lignin was degraded. The results suggest that a highly diffusible ligninolytic system was responsible for the selective degradation of the wood. In simultaneously white-rotted wood, all cell wall layers were progressively removed from the cell lumen toward the middle lamella, causing erosion troughs or holes to form. Large voids filled with fungal mycelia resulted from a coalition of degraded areas. Chemical analyses of white-rotted wood indicated lignin, cellulose, and hemicellulose were removed in approximately the same amounts. Degradation was confined to areas around fungal hyphae.     

A study of the reaction kinetics of electrogenerated superoxide ion with benzylbromide

The reaction kinetics between O₂^? and C₆H₅CH₂Br has been investigated in N,N′-dimethylformamide by electroanalytical techniques. A mechanism is proposed in which two molecules of the primary electrode product regenerate, via a following chemical reaction, one molecule of the original electroactive species. Furthermore, evidence for a S_N2 reaction mechanism between O₂^? and C₆H₅CH₂Br has been obtained. Second order rate constants resulted to be 11000 M^?1s^?1 and 3000 M^?1s^?1at room temperature and 0°C, respectively. The main products of the reaction were found to be benzylalcohol, benzaldehyde, benzene and biphenyl.     

The phase diagram for the binary system K2CrO4CaCrO4

The phase diagram for the binary system K₂CrO₄CaCrO₄ has been determined for CaCrO₄ concentrations up to 60 mole%, using the techniques of differential thermal analysis, X-ray diffraction, and drop calorimetry. Essential features of the phase diagram are: the solid-solid phase transition for pure K₂CrO₄ at 670°C, β-K₂CrO₄ ? α-K₂CrO₄; a eutectoid reaction at 14 mole% CaCrO₄ and 548°C, β-K₂CrO₄ ? α-K₂CrO₄ + K₂CrO₄ · CaCrO₄; a peritectoid event at 50 mole% CaCrO₄ and 640°C, β-K₂CrO₄ + CaCrO₄ ? K₂CrO₄ · CaCrO₄; and a eutectic reaction at 51 mole% CaCrO₄ and 678°C, L ? β-K₂CrO₄ + CaCrO₄. X-ray diffraction studies lead to the determination of the unit cell dimensions for the K₂CrO₄ · CaCrO₄ double salt, a C-centered monoclinic form with a₀ = 7.615(6) Å, b₀ = 22.797(15) Å, c₀ = 9.777(9) Å, β = 115.45(5)°.     

An optically active vinyl sulfoxide copolymer and the configuration of sulfoxide adjacent to radical or anionic sites

Optically active vinyl p-tolyl sulfoxide was synthesized and copolymerized with styrene to produce an optically active copolymer. The question of the configuration of sulfur in a sulfoxide when adjacent to a radical site is discussed. The configuration of sulfur in a sulfoxide is proven to be nonplanar when adjacent to an anionic site.     

Synthesis and reactions of β-(5-halo-3-uracyl) propionic acids

The reaction of elementary bromine and iodine with -(3-uracyl)-propionic acid has given the corresponding -(5-bromo-3-uracyl) and -(5-iodo-3-uracyl)propionic acids. The methyl esters and amides of the acids have also been synthesized for the first time.     

Ligand exchange reactions of ferrocene with phenanthrene or 9,10-dimethylphenanthrene in the presence of aluminum chloride and aluminum

Ligand exchange reactions between phenanthrene or 9,10-dimethylphenanthrene with ferrocene effected in the presence of AlCl₃-Al were carried out under a variety of conditions. With phenanthrene (I), hydrogenation at the C-9 and C-10 positions could take place during the reaction and the cationic products obtained were the η⁶-phenanthrene-η⁵-cyclopentadienyliron and η⁶-9,10-dihydro-phenanthrene-η⁵-cyclopentadienyliron moncations (II and III), and the η⁶-phenanthrene-$\text{trans}$-$\text{bis}$-η⁵-cyclopentadienyliron and η⁶-9,10-dihydrophenanthrene-$\text{trans}$-$\text{bis}$-η⁵-cyclopentadienyliron dications (IV and V). With 9,10-dimethylphenanthrene (VI), reactions carried out in refluxing cyclohexane gave the non-hydrogenated η⁶-9,10-dimethylphenanthrene-η⁵-cyclopentadienyliron monocation (VII) and η⁶-9,10-dimethylphenanthrene-$\text{trans}$-$\text{bis}$-η⁵-cyclopentadienyliron dication (VIII). When higher temperatures were used in an attempt to promote hydrogenation, decomposition predominated and no cationic product could be obtained. These finding are discussed and contrasted with previous results obtained from similar reactions using anthracene or 9,10-dimethylanthracene.     

Polyélectrolytes amphipathiques en milieu organique I. Propriétés thermodynamiques et structurales des échangeurs d'ions liquides

Resume Un polyélectrolyte dérivé de la poly (4 vinylpyridine) a été utilisé comme échangeur d'ions liquide pour des anions mono-et-divalents entre une phase aqueuse et l'octanol normal. Le polysavon sous forme sel de pyridinium est soluble dans l'octanol et la solution organique en contact avec une phase aqueuse contenant un mélange d'électrolytes possède des propriétés échangeuses d'ions. La sélectivité de l'échangeur vis à vis d'anions de nature différente est interprétée en fonction de la polarisabilité des anions. On a déterminé l'indice viscosimétrique des solutions organiques en fonction de la composition ionique du polymère et on a établi un parallèle entre les dimensions du polymère et l'affinité des ions pour les sites pyridinium compte-tenu de la faible constante diélectrique du milieu. Les variations de la viscosité en fonction de la composition sont interprétées à partir de la théorie de Flory transposée aux copolymères statistiques.

---

Summary A polymer obtained by quaternizing poly (4-vinylpyridine) with N-octadecyl bromide was used in developing liquid ion-exchange of mono- and divalent anions between water and 1-octanol phases. The polymer has a high solubility in 1-octanol and the organic polymeric solution in contact with aqueous phase containing a mixture of simple electrolytes behave similary to an anion exchange resin with selective properties. The mechanism by which selective association of anions on the polymeric pyridinium sites occurs is discussed from the data concerning the polarisability of anions. The conformational properties of the polymeric chain was determined from viscosity measurements. It is shown that the trend in chain dimensions parallels the affinity of the anions to bind on polymeric pyridinium sites in the low dielectric medium. The chain dimensions as a function of the ionic composition are discussed on the basis of a simple theoretical model in analogy with the behaviour of statistical copolymers.

---

Zusammenfassung Eine Lösung von Poly(-4-vinylpyridinium)salz in Octanol wurde als flüssiger Anionenaustauscher zwischen einer wässerigen Lösung und Octanol gebraucht. Diese organische Lösung in Berührung mit einer wässerigen Electrolytmischung behält die Eigenschaften der Ionenaustauscher. Die Selektivität des Austauschers für verschiedene Anionen wird durch die Polarisabilität der Ionen erklärt. Die Konformation der Polymeren wurde durch Viskositätsmessungen bestimmt und mit der verschiedenen Ionenaffinität in Vergleich gestellt. Die Dimensionsveränderungen der Polymeren während des Ionenaustausches wurden durch ein einfaches Modell erklärt, analog dem der statistischen Copolymeren.

     

N-dealkylation of 2-(tert-butyl)-3-hydroxy-3-(4-chlorophenyl)isoindolinone and n-(tert-alkyl)-2-aroylbenzamides in concentrated sulfuric acid

It has been established that 2-(tert-butyl)-3-hydroxy-3-(4-chlorophenyl)isoindolinone and N-(tert-Alkyl)-2-aroylbenzamides are dealkylated in concentrated sulfuric acid to give 3-hydroxy-3-arylisoindolinones. The reaction is realizable. only when there is a tert-alkyl group attached to the nitrogen atom. The reaction mechanism is discussed on the basis of data on the change with time in the electronic spectra of the investigated compounds in concentrated sulfuric acid and a comparison with the spectra of model structures.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 763–765, June, 1977.     

Lifetimes of Hg(3P0) complexes with methanol,ammonia, and water

Lifetimes of Hg(³P₀) complexes were determined by simultaneous observation of Hg(³P₀) optical absorption and complex emission, using a modulation technique and phase sensitive detection. The lifetimes of the mercury complexes with methanol, (1.4 ± 0.7) × 10^-8 s, and water, ? 8 × 10^-8 s, were found to be much shorter than reported in earlier work. For the ammonia complex, however a lifetime was measured which is in good agreement with previous determinations. Reasons for the large errors in earlier work where the methanol and water complex lifetimes were determined from complex emission data alone are discussed, and these data are reinterpreted. In the reaction rate of Hg(³P₀) with methanol no detectable contribution from the termolecular process Hg(³P₀) + 2CH₃OH → (Hg·CH₃OH)^* + CH₃OH could be observed.     

Phenolic resins for solid-phase peptide synthesis: Copolymerization of styrene and p-acetoxystyrene

Details are given of the synthesis and purification of p-acetoxystyrene and its solution and suspension copolymerization with styrene. Reactivity ratios, evaluated by the Tidwell-Mortimer method, were r₁ (p-acetoxystyrene) = 1.18, and r₂ (styrene) = 0.88 for (bulk) solution copolymerization. Corresponding values of the reactivity ratios for suspension copolymerization were, within experimental error, indistinguishable from unity. Thus the copolymer composition is governed simply by the monomer feed composition. Use of a specially designed reactor vessel permits convenient suspension copolymerization of styrene, p-acetoxystyrene, and divinylbenzene to give crosslinked resins having comparatively narrow particle size distributions. Acetoxy groups in the crosslinked resin are cleaved by hydrazine hydrate under very mild conditions to give crosslinked polystyrenes having phenolic groups which, in turn, provide a useful alternative to the more usual chloromethylated polystyrene resins for solid-phase peptide synthesis.