Spectral moments of polymer graphs

Summary It is shown that for anyk, thekth spectral moment of a polymer graph composed ofn monomer units is an exact linear function of the parametern. This linear relation holds for all values ofn, greater than a critical value ₀=₀(k).on leave from Faculty of Science, University of Kragujevac     

Preparation of micron-size monodisperse polymer microspheres having cationic groups

Micron-size monodisperse crosslinked polymer microspheres having chloromethyl groups were prepared by seeded copolymerization of styrene, divinylbenzene, and chloromethylstyrene in the presence of 2.1- monodisperse polystyrene seed particles produced by dispersion polymerization. The modification reaction of chloromethyl groups on the surfaces with polyamines such as triethylenetetramine and ethylenediamine was carried out. From the measurements of potential and the amount of chloride ion released, the introduction of a large number of cationic groups at the surfaces was confirmed.Part CXXXI of the series Studies on suspension and Emulsion.     

Comparison Between a Generalized Electronic Diabatic Approach and the Born–Oppenheimer Separation Scheme in Inertial Frames

We discuss a generalized electronic diabatic (GED) approach to diagonalize the exact Hamiltonian of an n-electron system which embeds an external background of positive charges. This Hamiltonian, denoted by _e(q,), is defined in an inertial frame, and it contains a quantum part (the electrons with coordinates q) and a classical part (the external charges in a three-dimensional configuration ). We derive a GED basis set { _k (q)} using an operator _e(q,⁰) for a single configuration ⁰, and then show that these are also eigenfunctions for any other _e(q,); only the ordering of eigenvalues may depend on (i.e., k=k()). The GED functions can also be used to represent the eigenstates of a fully quantum-mechanical system of electrons and nuclei. We discuss briefly the differences between the present procedure and the standard Born–Oppenheimer (BO) technique in the clamped-nuclei approximation. As illustration, we show how chemical changes emerge as transitions among diabatic states mediated by an electromagnetic field.     

Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphan/Azodicarbonsäurediethylester, 4. Mitt.: Transformationen an Mannose und Galaktose

Reaction of methyl -D-galactopyranoside (1) with two equivalents oft-butyldimethylchlorosilane yields methyl 2,6-bis-O-(tBDMSi)--D-galactopyranoside (1 b), methyl 3,6-bis-O-(tBDMSi)--D-galactopyranoside (1 c) and methyl 4,6-bis-O-(tBDMSi)--D-galactopyranoside (1 d). Likewise methyl -D-mannopyranoside (6) affords methyl 2,6-bis-O-(tBDMSi)--D-mannopyranoside (6 d) and methyl 3,6-bis-O-(tBDMSi)--D-mannopyranoside (6 b), which can be isomerised withTPP/DEAD to methyl 4,6-bis-O-(tBDMSi)--D-mannopyranoside (6 f). Methyl 6-O-(tBDMSi)--D-galactopyranoside (1 a) and methyl 6-O-(tBDMSi)--D-mannopyranoside (6 a) can be prepared from1 or6 with one equivalent oft-butyldimethylchlorosilane.Without an external nucleophile the sugar derivatives1 a and1 b react withTPP/DEAD to form the 3,4-carbonato--D-galactopyranosides1 h and1 i and the 3,4-carbonato-2-O-ethoxycarbonyl--D-galactoside (1 j). In contrast to the formation of the compound1 i by means ofTPP/DEAD the reaction of1 a withTPP and Di-t-butyl-azodicarboxylate (DTBAD) yields the 2,3-anhydro--D-taloside (4 b) and only a small amount of1 i. The epoxide4 b can be cleaved withp-nitrobenzoylchloride/pyridine to the 3-chloro-3-deoxy-2,6-di-O-p-nitrobenzoyl--D-idoside (5). Reaction of1 c and1 d withTPP/DEAD yields the 2,3-anhydro--D-gulopyranoside (2), which can be transformed with NaN₃/NH₄Cl to the 2-azido-2-deoxy--D-idopyranoside (3).Likewise6 a and6 d can be converted to the 3,4-anhydro--D-talosides (7 a and7 b). Reaction of7 b or6 d withTPP/DEAD/NH₃ leads to 3,4-anhydro-2-azido-2-deoxy--D-galactopyranoside (8) and 3-azido-3-deoxy--D-altropyranoside (10), resp.The epoxide7 b is opened with NaN₃/NH₄Cl to the 4-azido-4-deoxymannosides (11 a and11 c) and the 3-azido-3-deoxy--D-idopyranoside (12), while the epoxide8 affords the 2,4-di-azido-2,4-dideoxy--D-glucopyranoside (9).Structures were elucidated by¹H-NMR-analysis of the corresponding acetates.

H. H. Brandstetter undE. Zbiral, Helv., im Druck.     

Particle behaviour in shear and electric fields

Summary The interactions between two equal rigid conducting spheres in a Newtonian dielectric liquid in combined shear and electric fields are analyzed. The forces and torques, the translational and rotational velocities, and the resulting trajectories of the spheres are calculated for various ratios of the electric field strength to shear rate.The conditions under which the spheres can capture one another are deduced from which capture cross-sections, capture frequencies, and capture efficiencies are calculated, leading to a second order rate equation for capture at low particle concentrations.It is demonstrated that on capture the spheres should come into physical contact in a finite time. However, it is conjectured from previous experiments that dielectric breakdown is apt to occur in the interparticle gap because of the high electric field intensification; when this occurs, complications may be expected which are different in static and alternating electric fields.Closely related to the two sphere problem is the interaction of a rigid conducting sphere with a rigid conducting plane wall; this is discussed in the Addendum.

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Zusammenfassung Die Wechselwirkungen in gleichzeitig angelegten Scherströmungen und elektrischen Feldern zwischen zwei kleinen, gleiche, festen, leitenden, und in einer Newtonschen Flussigkeit schwebenden Kugeln sind untersucht werden. Die Krafte und Drehmomente, die Translations- und Rotationsgeschwindigkeiten, und die resultierenden Trajektionen der Kugeln werden für verschiedene Verhaltnisse der elektrischen Feldstärke und Schergeschwindigkeit berechnet. Entwickelt werden die Kugelanlagerungsbedingungen, wovon sich die Anlagerungsquerschnitte, die Anlagerungsgeschwindigkeiten, und die Anlagerungseffektivwerte ableiten lassen; dies führt zu einer Anlagerungsgleichung zweiter Ordnung bei geringer Teilchenkonzentration. Es wird gezeigt, daß die Kugeln sich physisch berühren sollten nach Ablauf einer bestimmten (endlichen) Anlagerungszeit. Jedoch, wie es sich aus vorhergehenden Experimenten ergab, dielektrischer Kurzschluß erfolgt im Kugelzwischenraum auf Grund der hohen elektrischen Feldverstarkung; folgendermaBen konnen Komplikationen erwartet werden, die sich für statische Felder und Wechselfelder verschieden ausarten mussen. Die Wechselwirkung zwischen einer kleinen, festen, leitenden Kugel und einer festen, leitenden, flachen Wand ist ein Sonderfall des Zwei-Kugel-Problems; dies wird im Addendum beschrieben.

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Nomenclature a, b ^*,c, d, e, f ^*,g, b hydrodynamic force and torque coefficients - a ^* b sinb - b sphere radius - B, C; B₀, C₀; C^E trajectory constants whenf=0 (B0,C0); when 0<f< and 2 (B ₀ 0,C ₀ 0) ; whenf= and 2. - C^* orbit constant of a touching doublet - e _i particle fixed unit vectors,i=1, 2, 3, (fig. 1) - E;E ₀ local electric field strength; uniform field applied to the particle-free medium. Normal type designates scalar quantities - E ₃ ^* E _DB E/E ₀; dielectric breakdown strength of medium - f electrohydrodynamic parameter defined in [28] - f _c;f _c ^E collision frequency per unit volume; capture frequency per unit volume - f _i ^E ;f _i ^r ;f _i ^S ;f _i ^t force coefficients of a sphere near a wall due toE ₀; to rotation; to shear; to translation - f(), h() trajectory functions for f=0 defined in [1] and [2] - F _i;F _i ⁰ electric force coefficients (i =1 to 10) defined in [12] and [13] when spheres have potential Vj; when Vj=0. - F ^E ,F ^r ,F ^S ,F ^t forces acting on a sphere near a plane wall - F _i ^E (j) electric force component alongx _i ^' on spherej =1, 2. - g _i ^r ,g _i ^S ,g _i ^t torque coefficients on a sphere near wall - G shear rate - k capture rate constant defined in [44] - K dielectric constant of medium - n integer (n 0) - n ₀;n ₂ number concentration ofsuspension of single spheres; of captured doublets - P _ij coefficients of electric induction - P(r _p ) orientation function of a rigid conducting prolate spheroid - q ₂,q ₃ defined in [66] - Q _j ;Q _j ^* net charges on spherej = 1, 2; charges induced on spherej =1, 2 if as earthed - r;r _p centre-to-centre distance between spheres; axis ratio of spheroid - S _m () functions defined in [48]m = 1,2 - S _ij pure shear (deformation) tensor components - T period of rotation of doublet about ₁ axis whenf < 1 - T ^E ;T ^E ;T ^*E contact time of two spheres; a sphere and a wall; = (2₀ KE ₀ ² / 3)T ^E - T ^r ,T ^S ,T ^t torques on a sphere near a wall - u undistrurbed flow velocity - U;U(j) particle velocity of sphere near wall; of spherej - V _j electric potential of spherej - w _j ;W ₁ ^* dimensionless electric potential of spherej; of sphere 1 whenQ ₁ =0 - x _i ;x _i ;x ₃ ^* space-fixed coordinates defined in figure 1; particle-fixed coordinates alonge 1; = (2₀ KE ₀ ² /3G) ₃ - cos²₂ - Y _n ;Z _n functions defined in [17d]; in [17e] Script symbols A(),B(),L(),D(),E() functions defined in [23] - (F); (F ^(E ); (F ^(s ) general force-torque vector; in an electric field; in shear - L _i () velocity coefficients of two spheres in an electric field,i=1 to 4     

The crystal structure of the molybdenum cementite Mo12Fe22C10 (ξ-phase)

The crystal structure of molybdenum cementite Mo₁₂Fe₂₂C₁₀ (-phase) has been determined by means of a single crystal x-ray diffraction study of crystal fragments. The lattice parameters were found to be:a=10.865 (3),b=7.767 (2),c=6.559 (2) Å and =120.13 (2)°, space group C2/m;Z=1. From the analysis ofPatterson maps and differenceFourier analysis the atomic parameters were derived, yielding a residual ofR=0.059. The crystal structure contains octahedral and triangular prismatic groups which accommodate the carbon atoms in their voids, as is usually found in interstitial compounds. The octahedral building group consists of four Mo- and two Fe-atoms, the triangular prism is built up by four Fe-and two Mo-atoms. The mode of filling of the metal polyhedra is discussed.

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Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase)

Zusammenfassung Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase) wird auf Grund von Einkristall-Beugungsaufnahmen unter Anwendung vonPatterson-and DifferentialFourier-Analysen bestimmt. In der monoklinen Elementarzelle (a=1.870;b=7.67;c=6.563 Å, =120.1°) Raumgruppe C 2/m befindet sich eine Formeleinheit Mo₁₂Fe₂₂C₁₀ (oderZ=2, Mo₆Fe₁₁C₅). DerR-Wert von 6% für 1200 Reflexe unterstreicht die Richtigkeit der Struktur, die aus oktaedrischen und trigonal prismatischen Gruppen aufgebaut ist. Die Oktaedergruppe besteht aus 4 Mo- und 2-Fe-Atomen, die trigonal prismatische Gruppe aus 4 Fe- und 2 Mo-Atomen. Die Kohlenstoffatome füllen die Lücken dieser Bauelemente, wie es für typische Einlagerungscarbide (Komplexcarbide) erwartet werden kann.

     

Cohesion of crystals and the temperature coefficient of their equilibrium surface pressure

Summary Surface tension _e of mercury in equilibrium with crystals (floating on its surface) of octacosane, 1-hexadecanol, 1-octadecanol, ethyl palmitate, benzophenone and azoxybenzene at 7° is almost equal to that at 23° (measured earlier); also the difference between the surface tension ( ₀) of uncontaminated mercury and _e (i. e., equilibrium surface pressure) is independent of temperature within the limits of the experimental error. This shows that the hypothesis making ₀- _e an analog of the vapor pressure of the solid is incorrect. The relation _e= (=cohesion of the crystal,=thickness of the surface layer of mercury) is in agreement with the negligible temperature coefficient of _e . The calculated is approximately 9 angstroems.

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Zusammenfassung Die Oberflächenspannung _e von Quecksilber im Gleichgewicht mit Kristallen (schwimmend auf der Oberfläche) von Octosane, 1-hexadecanol, 1-octodecanol, Äthylpalmitat, Benzophenon und Azoxylbenzol bei 7 °C ist nahezu gleich der bei23 °C gemessenen. Auch die Differenz der Oberflächenspannung von reinstem Quecksilber ( ₀) und ( _e), d. h. dem Gleichgewichtsobderflächendruck ist unabhängig von der Temperatur innerhalb der experimentellen Fehlergrenze. Dies zeigt, daß die Hypothese, nach der man ₀- _e in Analogie zum Dampfdruck des Festen betrachtet, unkorrekt ist. Die Beziehung _e= (=Kohäsion des Kristalls,=Dicke des Oberflächenfilms auf Quecksilber) ist in Übereinstimmung mit dem vernachlässigbaren Temperaturkoefifzienten von _e. Das berechnete beträgt ungefähr 9 Å.

     

Crystallization of filled Nylon 6 II. Isothermal crystallization

Summary Isothermal crystallization kinetics from the melt of nylon 6 containing various amounts of untreated glass beads and Aerosil (series GB and A) and aminosilane-treated glass beads (series GBA) was studied by DSC method. Treatment of experimental data in terms of Kolmogorov-Avrami equation has shown that time exponentn is relatively insensitive to presence of GBA filler, whereas it was found to decrease gradually with increasing filler content in samples of GB and A series to value as low as 0.5 for sample A–67. Nucleation free energy was the same in pure nylon 6 and filled samples of GBA series, but dropped suddenly in samples of GB series when mean interparticle separation x decreased below critical value _crit =(5–10) x 10^–6 m. Taking into account the concomitant drop of equilibrium melting temperature, it was concluded that these effects are a consequence of specific structural change in polymer phase accompanying transition into a boundary state. Temperature dependence of polyer crystallization rate in highly filled samples of A series at small supercoolings was found to obey them=4 law, which is characteristic of transformations in strained media. Experimental data seem to be consistent with the idea that the postulated strain energy might originate from negative capillary pressure between high-surface energy solid particles wette d by polymer melt. Quantitative analysis of overall crystallization rate dependence on interparticle distance x has shown that _crit may be identified with change of growth morphology from a three-dimensional to a two-dimensional one, while slowing down of growth rate at lower values of was attributed to increase of nucleation free energy due to increasing contribution from capillary forces.With 13 figures and 2 tables     

Determination de bases de gaussiennes optimales pour les molécules

Résumé Des bases comprenant n=1, 2, 3, 4, 5 fonctions gaussiennes, dont les exposants rendent minimale l'énergie SCF totale, ont été déterminées pour la molécule d'hydrogène. On montre qu'il suffit d'appliquer un facteur multiplicatif constant aux exposants donnés par Huzinaga pour l'atome libre. Pour n=1, le facteur d'échelle optimal est en accord avec la valeur de _s trouvée par Hirschfelder et Linnett dans un calcul en orbitales de Slater; la variation de ce facteur avec n obèit à la formule .

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Optimized Gaussian bases for moleculesI. Hydrogen

Bases of n=1, 2, 3, 4, 5 Gaussian functions, whose exponents minimize the SCF total energy, have been determined for the hydrogen molecule. It is shown that a convenient process is found by applying a scaling factor to the exponents given by Huzinaga for the free atom. This optimized scaling factor agrees for n=1 with the _s value reported by Hirschfelder and Linnett from a Slater-type orbital calculation; it varies with n according to the formula .

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Zusammenfassung Für das Wasserstoffmolekül sind für n=1, 2, 3, 4 und 5 Basissätze von Gaußfunktionen, deren Exponenten bezüglich der SCF-Gesamtenergie optimiert wurden, bestimmt worden. Es wird gezeigt, daß eine bequeme Methode gefunden werden kann, indem man die von Huzinaga für das freie Atom bestimmten Exponenten mit einem multiplikativen Faktor versieht. Dieser optimierte Multiplikationsfaktor stimmt für n=1 mit den _s -Werten überein, die Hirschfelder und Linnett mit einer Rechnung unter Zugrundelegung von STO-Funktionen erhielten; er verifiziert jedoch mit n gemäß der Formel .

     

The fitting of depth distributions of ion implanted analytes by split student-t functions: The physical basis and a recommended procedure

The non-standardized fitting of depth distributions of ion implanted analytes in solid matrices by arbitrarily chosen functions, as practiced at present, is unsatisfactory for the communication of results and is unacceptable for certification of ion implanted reference materials. Sampling theory applied to the nuclear slowing-down process of swift ions suggests that split Student-t functions should provide the mathematical representation sought. The exact shape and mathematical form of these functions are fully described and readily communicated by the use of five parameters (mode, two shape parameters and two scale parameters). A simple and fast fitting procedure is proposed.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Synthesis of some 5′-O-amino acid derivatives of uridine as potential inhibitors ofUDP-glucuronosyltransferase

Summary In an attempt to develop potential inhibitors ofUDP-glucuronosyltransferase, some 5-O-amino acid derivatives of uridine were synthesized. N-protectedL-amino acids were coupled at the 5-O-position of 2,3-O-isopropylideneuridine by esterification employing the method of symmetrical anhydrides in presence of 4-dimethylaminopyridine, 5-O-(N-benzyloxycarbonyl-O-tert.butyl-L-threonl)-23-O-isopropylideneuridine (1), 5-O-(N-tert.butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylideneuridine and (2), 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (3), and 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (4) were obtained in good yield after column chromatography on silica gel. The treatment of2 withTFA/CH₂Cl₂ (6:1) at room temperature for 30 min led to a selective removal of theBoc group without deblocking of the 2,3-O-isopropylidene group of uridine. Treatment of2 withTFA/H₂O (5:1) at room temperature for 1 h, however, released bothBoc and 2,3-isopropylidene groups. TheZ group of1 was deprotected by catalytic hydrogenolysis over 10% Pd/C/ammonium formate.

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Synthese von 5-O-Aminosäurederivaten des Uridins als potentielle Inhibitoren derUDP-Glukuronosyl-Transferase

Zusammenfassung In einem Versuch, potentielle Inhibitoren derUDP-Glukuronosyl-Transferase zu entwickeln, wurden einige 5-O-Aminosäurederivate des Uridins synthetisiert. N-GeschützteL-Aminosäuren wurden durch Veresterung mit der 5-O-Position des 2,3-isopropylidenuridins gekuppelt (Methode der symmetrischen Anhydride in der Gegenwart von 5-Dimethylaminopyridin). Solcherweise wurden 5-O-(N-Benzyloxycarbonyl-O-tert.butyl-L-threonly)-2,3-O-isopropylidenuridin (1), 5-O-(N-tert.Butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylidenuridin (2), 5-O-(N-tert.Butyloxycarbonyl-L-leucyl)-2,3-O-isopropylidenuridin (3) und 5-O-(N-tert.Butyloxycarbonyl-L-valyl)-2,3-O-isopropylidenuridine (4) nach Säulenchromatographie (Kieselgel) in guter Ausbeute hergestellt. Die Behandlung von2 mitTFA/CH₂Cl₂ (6:1) bei Zimmertemperatur (30 min) führte zu einer selektiven Abspaltung derBoc-Gruppe ohne Deblockierung der 2,3-O-Isopropylidengruppe des Uridins. Eine Behandlung von2 mitTFA/H₂O (5:1) bei Zimmertemperatur für 1 Stunde führte hingegen zur Abspaltung sowohl derBoc als auch der 2,3-O-Isopropylidengruppe. DieZ-Gruppe von1 wurde durch katalytische Hydrogenolyse auf 10% Pd/C/Ammoniumformiat abgespalten.

     

ξ-potential and surface dye-ability of poly(vinyl alcohol) fiber with different degree of formalization in a cationic dye solution

Summary The surface dyeability of the poly(vinyl alcohol) fiber with different degree of formalization was studied by measuring -potential of the fiber in alkaline aqueous solutions (pH 10) of a cationic dye Methylene Blue. With the increase in the dye concentration, the sign of the -potential of the fiber changed from negative to positive and thereafter the positive value approximated to saturated value, and the amount of dye adsorbed (expressed in mol/cm²-fiber) increased also. These results may possibly be attributed to the formation of the electrostatic bond between the fiber and the dye. The linear relations were found between and logC _d and its slope did not change with rise of temperature. The free energy of dyeing G (negative) calculated from the slope of the -logC _id curve, etc. increased with increasing the degree of formalization of the fiber. This fact corresponds to the increase in the surface dye adsorption with increasing the degree of formalization. With increasing the degree of formalization, the heat of dyeing H (negative) increased and the entropy of dyeing S (positive) decreased. The positive value of S for each fiber, suggests the formation of hydrophobic bond as a driving force to the dyeing of Methylene blue on the fiber surface in addition to the electrostatic bond.This paper is Part XXVII in a series on Studies on -potentials and Surface Dyeability of Natural and Synthetic Fibers in Dye Solution. Part XXVI: T. Suzawa andK. Kawakami, Nippon Kagaku Kaishi1975, No. 7,1134.     

Accommodation of an aliphatic guest molecule in hofmann-diaminooctane-type host. A model structure of a pillared intercalation compound

catena-[catena--(1,8-Diaminooctane)cadmium(II) tetra--cyanonickelate(II)]-(1-hexanol)(1/1) has been prepared as the first example of an aliphatic guest clathrate of the Hofmann-type and analogous metal complex hosts. The clathrate crystallizes in the monoclinic space groupP2/m,a=11.470(2),b=7.782(1), andc=6.945(1) Å, =105.29(1)°,Z=1;R=0.043 for 1865 reflections. The structure presents a model of pillared intercalation compounds formed between layers of metal complex sheets pillared by ,-ambidentaten-alkaneskeletal ligands andn-alkyl derivative guests. Supplementary Data relating to this article are deposited with the British Library as supplementary publication SUP 82069 (16 pages).     

Culcitosides C2 and C3 from the starfishCulcita novaeguineae

Two steroid glycosides not previously described have been isolated from the digestive system of the starfishCulcite novaeguiniae, and these have been called culcitosides C₂ and C₃. With the aid of chemical and spectral methods, the chemical structure of C₂ has been established as 24-methyl-5-cholestane-3,4,6,8,15,16,28-heptaol 28-O-[O-(2,4-di-O-methyl--D-xylopyranosyl)-(1 2)--L-arabinofuranoside, and that of C₃ as its 4-deoxy analogue.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center of the USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 592–596, September–October, 1986.     

Systematik des Adsorptionsverhaltens homologer aliphatischer Amine an der Grenzfläche Quecksilber/Elektrolyt

Zusammenfassung Dutch die wechselstrompolarographische Kapazitäts-Potential-und Kapazitäts-Zeit-Messungen (E _m = konstant) als Funktion der Aminkonzentration wurden die Adsorptionsisothermen homologer Amine und Amin-Hydrochloride beiT = 25 °C undT = 50 °C experimentell bestimmt.Die Ads orptionsisothermen wurden mittels dimensionsloser Adsorptionstherme nachFrumkin-Damaskin ausgewertet und in Form folgender Adsorptionsparameter diskutiert und verglichen: Attraktionskonstantea; Adsorptionskoeffizientb und freie StandardadsorptionsenthalpieG _A .Der Zuwachs in denG _A -Werten pro CH₂-Gruppe läßt sich zuG _A /CH₂0,3–0,5 kcal. Mol^–1 abschätzen. Bis auf wenige Ausnahmen sind die Adsorptionsparametera, b, undG _A Temperaturfunktionen

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Summary The adsorption isotherms of homologous amines and some of their hydrochlorides were obtained from capacity-potential- und capacity-time measurements atT = 25 °C andT = 50 °C.From the adsorption isotherms we computed the thermodynamic adsorption parameters according toFrumkin andDamaskin. On the basis of the adsorption parameters attraction constant (a), adsorption coefficient (b) and free standard energy of adsorptionG _A , the results have been discussed und compared.The increase ofG _A per CH₂-group is aboutG _A /CH₂ 0,3 to 0,5 Kcal Mol^–1. In most cases the adsorption parametersa, b andG _A are temperature functions.

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Mit 3 Abbildungen und 1 Tabelle     

Triterpene Glycosides and Their Genins from Astragalus. LXIX. Orbigenin, the First Lanostanoid from Astragalus Plants

The new lanostane methylsteroid orbigenin, the structure of which is 23,24-lanost-9(11)-en-3,7,16,19,23,24,25-heptaol, was isolated from Astragalus orbiculatus Ledeb. (Leguminosae). The structure of the new triterpenoid, the first lanostanoid from plants of the Astragalus genus, was determined using electron-impact mass spectrometry and PMR and ¹³C NMR spectroscopies interpreted using J-modulation, DEPT, and the 2D NMR methods: ¹H-¹H COSY, HSQC, and HMBC.     

Validity of energy distribution derived from heat of adsorption in an ammonia/cation-exchanged Y zeolite system

The validity of- functions (energy level functions) which were derived from experimentalq- functions (heat functions) was examined in an ammonia/cation-exchanged Y zeolite system. The- functions of Na-Y zeolite and Cs-Na-Y zeolite were respectively calculated from theirq- functions measured by ammonia adsorption at 373 K. The heat of adsorption of ammonia was also measured on a mixture of these two zeolites at a certain mixing ratio at 373 K. The- function of the mixture was likewise calculated on the basis of this measurement. The- function thus calculated was in good agreement with the synthesized- function derived by linearly combining two- functions of each zeolite mentioned above. The- function derived from experimental- function thus proved to be valid in an actual adsorption system.     

Steroid glycosides from the starfishSolaster dawsoni (Verrill)

Two novel glycosides from the starfishSolaster dawsoni (Verrill) have been isolated and characterized: 24-O-(-D-xylopyranosyl)-5-cholestane-3,6,15,24,26-pentaol (solasteroside S₁) and (24R)-29-O-[-D-galactofuranosyl-(16)--D-galactofuranosyl]-24-ethyl-5-cholestane-3, 6,8,15,16,29-hexaol (solasteroside S₂).Translated fromIzvestiya Akademu Nauk. Seriya Khimicheskaya, No. 5, pp. 980–982, May, 1993.     

Some remarks on the periodical change of the stability constants of the lanthanide complexes

The correlations between the values of the lgK (K = stability constant of the lanthanide complex) and the reciprocal of the ionic radius 1/r or the sum of the ionization potentials ₁ ³ I for the lanthanide ions were reviewed for different ligands. A straight-line relationship (lgK – lgK)/lgK vs. (1/r – 1/r)/(1/r) or vs. ( ₁ ³ I – ₁ ³ I)/ ₁ ³ I was found within the tetrads La-Nd, Gd-Ho, and Er-Lu.

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Bemerkungen zum periodischen Wechsel der Stabilitätskonstanten von Lanthaniden-Komplexen

Zusammenfassung Es wurde eine Übersicht der Korrelationen zwischen den Werten von logK (K = Stabilitätskonstante der Lanthanidenkomplexe) und den reziproken Ionenradien 1/r oder der Summe der Ionisierungspotentiale ₁ ³ I für die Lanthanidenionen für verschiedene Liganden gegeben. Dabei wurde eine lineare Korrelation für (lgK – lgK)/lgK gegen (1/r – 1/r)/(1/r) oder gegen ( ₁ ³ I – ₁ ³ I)/_1/3 I innerhalb der Tetraden La-Nd, Gd-Ho und Er-Lu aufgefunden.

     

Phytoecdysteroids of Rhaponticum carthamoides. II. Rhapisterone B

A new ecdysteroid (rhapisterone B) has been isolated from the seeds ofRhaponticum cathamoides (Willd.) Iljin. (familyCompositae). It has been shown that it is 2, 3, 11, 14, 20R, 24-hexahydroxy-5-cholest-7-en-6-one.Institute of the Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 806–808, November–December, 1991.