Investigation by infrared absorption of the by-products of the cyanoethylation of cotton cellulose

The soluble cyanoethyl ether of cellulose, prepared by reaction in the presence of NaOH catalyst to high degrees of substitution (DS = 2.95), can be precipitated by various organic media and contains more nitrogen than can be accounted for by simple addition of acrylonitrile at each cellulose hydroxyl group. Infrared absorption spectra of such samples and of the reacted residues show various types of vibrational absorption bands, characteristic of amino groups. At advanced stages of the reaction the characteristic broad unresolved band of cellulose extending from 1200–950 cm.^?1 largely disappears, leaving only a few weaker bands which likely overlap those due to C–N stretching. Comparison is made of the spectra of the partially cyanoethylated cellulose and the polyacrylonitrile which forms in the stock acrylonitrile, to characterize the products. It is inferred that the highly cyanoethylated cellulose, partly dissolved in the acrylonitrile, further degrades and changes under a complex mechanism to various forms of amines. The yellow to orange color of the samples is assumed to be due to these by-products. The thermogravimetric analysis reveals that these products are more heat-resistant than the cyanoethylated cellulose.     

Mass spectrometry in structural and stereochemical problems—CLXXXVII A study of skeletal rearrangements in chromans by combined 13C and deuterium labeling

Chroman (I), 2,2-dimethylchroman (II), flavan (III) and 2,2-diphenylchroman (IV) were labeled with ¹³C or deuterium at every position of importance. The mass spectra of these labeled compounds make possible a detailed interpretation of some very complex carbon skeleton rearrangements. The combination of deuterium and ¹³C-labeling revealed that loss of CH₃, C₂H₅ and C₇H₇ fragments from chroman (I), 2,2-dimethylchroman (II) and 2,2-diphenylchroman (IV) respectively, occurs by multiple pathways involving aryl or alkyl migrations with little hydrogen randomization prior to fragmentation. Although ejection of C₇H₇ from flavan (III) occurs to a small extent by a route similar to those mentioned above, its [M ? C₇H₇] fragment can also be formed by a pathway involving no phenyl migration but extensive hydrogen scrambling. The validity of the schemes proposed on the basis of the ¹³C labeling data was checked by using them to predict the spectra of the deuterium labeled compounds.     

Inaccessible hydroxyl groups on silica are accessible in supercritical CO2

The three main types of hydroxyl groups on a silica surface are classified as isolated, hydrogen bonded, and inaccessible. The isolated and hydrogen bonded groups are the most important as these readily exchange with D(2)O and thus are exposed to reactant molecules. However, it has generally been accepted that the inaccessible groups do not participate in surface reactions as only a small fraction of these groups exchange with D(2)O. It is shown that the inaccessible hydroxyl groups on nonporous fumed silica and mesoporous MCM-48 silica powders and films fully exchange with D(2)O and are reactive with octadecylydimethylchlorosilane when supercritical CO(2) is used as the solvent. Furthermore, it is found that the CO(2) penetrating the regions containing the inaccessible groups is not removed by simple evacuation but rather slowly diffuses from the silica over periods of months.     

Rare earth niobate systems and the phosphor GdNbO4:Bi

An investigation to determine the compounds present in the Ln₂O₃Nb₂O₅ systems (Ln = La, Gd, and Y) and attempts to activate such compounds with Ti, In, Sb, Bi, Eu, and Tb revealed that only the orthoniobate (LnNbO₄) compound was a suitable host lattice and LnNbO₄:Bi under 2537 Å excitation produced the best phosphors. GdNbO₄:Bi is a brighter phosphor than the La and Y analogs, emitting at slightly higher energies. The position of the GdNbO₄:Bi peak emission at 4500 Å is independent of the activator concentration whereas peak emissions for LaNbO₄:Bi and YNbO₄:Bi move to lower energies with increasing Bi concentration.     

Pentalene complexes of group 7 metal carbonyls: an organometallic mixed-valence system with very large metal-metal electronic coupling

The bimetallic complexes [M(CO)(3)](2)(mu:eta(5):eta(5)-Pn) (Pn = pentalene, C(8)H(6); M = Mn, Re) have been synthesized and characterized crystallographically; the Mn compound was isolated as solely the anti-isomer, while the Re analogue was formed as a mixture of anti- and syn-isomers. [Mn(CO)(3)](2)(mu:eta(5):eta(5)-Pn) may be reduced chemically to its mono- and dianions; the mixed-valence Mn(I)/Mn(0) monoanion is shown by ESR, vibrational, and electronic spectroscopies to be a Robin-Day class III system with an exceptionally large electronic coupling between the metal centers.     

Magnetic coupling and intermetallic electron transfer in the heterodinuclear bioctahedral complexes MW(III)Cl(9)(n-) (M = V(II), Cr(III), Mn(IV)): tweaking the balance between ferromagnetism and antiferromagnetism

Density functional theory (DFT) calculations have been used to investigate the effect of intermetallic electron transfer on the mode of magnetic coupling in the face-shared bimetallic complexes MWCl(9)(n-) (M = V, Cr, Mn; all with a nominal d(3) valence electronic configuration on each metal atom). These calculations illustrate a simple rule: when the oxidation state of M is lower than that of W, antiferromagnetic coupling is preferred, while ferromagnetism (via crossed exchange pathways) is favored when M has the higher oxidation state. This underlying trend in intermetallic interactions is seen to depend on the interplay among ligand field splitting, spin polarization splitting of alpha- and beta-spin orbitals, and the relative energies of the M and W valence d orbitals, and is mirrored in the results seen in a wider survey of mixed-metal, face-shared complexes.     

Vergleich der Me?genauigkeit der Szintillations-Z?hlung 3H- und/oder 14C-markierter Proben durch externe bzw. interne Standardisierung und Anwendung auf die Sauerstoff-Kolben-Verbrennung

Zusammenfassung Nach Verbrennung im Sauerstoffkolben zeigen die Szintillationsproben häufig über Stunden eine ansteigende Zählrate. Auch danach unterscheiden sich identisch präparierte Proben noch statistisch signifikant stärker, als aufgrund von Wäge- und Pipettierfehlern zu erwarten ist. Die zeitliche Inkonstanz und die Unterschiede von Probe zu Probe lassen sich durch Löschkorrekturkurven (Abhängigkeit der Zählausbeute und des externen Standardkanalverhältnisses von der Sauerstoffkonzentration) weitgehend eliminieren. Die so erhaltenen dpm-Werte haben geringere Standardabweichungen als die durch interne Standardisierung erhaltenen. Das Verfahren der externen Standardisierung wird einer Fehleranalyse für einzel- und doppelmarkierte Proben unterworfen. Ein Toluol/Methanol/Phenäthylamin-System absorbiert Kohlendioxid und Wasser quantitativ. Für einzelmarkierte Proben können mit diesem Gemisch für ³H 25% und für ¹⁴C 85% Zählausbeute erhalten werden. Bei ³H/¹⁴C-Markierung werden bei einer Kanaloptimierung nach Klein und Eisler noch 15% Zählausbeute für ³H neben 10% für ¹⁴C erhalten.

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Comparison of errors in liquid scintillation counting after quench correction by external or internal standardisation applied for oxygen flask combustion of ³H- and/or ¹⁴C-labelled samples

After oxygen flask combustion scintillation samples often show an increase in counting rates for several hours. Even after such a time identically prepared samples are statistically significantly more different as one should expect by weighing and pipetting errors. The inconstant cpm values during the first hours and the differences between the samples can mostly be eliminated by quench correction curves (dependence of counting efficiency and external channel ratio upon oxygen concentration). The dpm values achieved according to this method show smaller standard deviations than by internal standardisation. The procedure of the external standardisation was examined for error propagation. A system of toluene/methanol/phenethylamine absorbs carbon dioxide and water quantitatively. With this mixture the following counting efficiencies are achieved: 25% for ³H, 85% for ¹⁴C and for samples containing ³H and ¹⁴C 15% for ³H and 10% for ¹⁴C if the ³H channel is adjusted according to Klein and Eisler.

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Symbole und Abkürzungen ESKV Externes Standard-Kanal-Verhältnis - ESKV-ESKV₀ - ESKV₀ Beginn der Gültigkeit der Löschfunktion, stärkst gelöschte Probe - ZA auf 1,0 bezogene Zählausbeute - S Standardabweichung - cpm Impulsrate (min^–1) - dpm Zerfallsrate (min^–1) - A bzw. B nieder- bzw. höherenergetisches Nuklid - (A) Meßkanal A - k,l,m,n Eichfaktoren     

Influence of cysteine to cysteic acid oxidation on the collision-activated decomposition of protonated peptides: Evidence for intraionic interactions

Oxidation of cysteine residues to cysteic acids in C-terminal arginine-eontaining peptides (such as those derived by tryptic digestion of proteins) strongly promotes the formation of multiple members of the Y? series of fragment ions following low energy collision-activated decomposition (CAD) of the protonated peptides, Removal of the arginine residue abolishes the effect, which is also attenuated by conversion of the arginine to dimethylpyrim-idylornithine. The data indicate the importance of an intraionic interaction between the cysteic acid and arginine side-chains. Low energy CAD of peptides which include cysteic acid and histidine residues, also provides evidence for intraionic interactions. It is proposed that these findings are consistent with the general hypothesis that an increased heterogeneity (with respect to location of charge) of the protonated peptide precursor ion population is beneficial to the generation of a high yield of product ions via several charge-directed, low energy fragmentation pathways. Furthermore, these data emphasize the significance of gas-phase conformations of protonated peptides in determining fragmentation pathways.     

Characterizations of the Kerr metric

For stationary, asymptotically flat solutions of Einstein's equations, covariant functionals of the metric variables are defined which characterize the Kerr metric uniquely. For instance, we obtain a generalization of the Bach tensor to stationary metrics, which vanishes if and only if the solution is Kerr. We also give a new interpretation of the Schwarzschild-to-Kerr-transformation. Our results might be applicable to simplify the proof of the uniqueness theorem for stationary black holes.