Synthese von Metallkomplexen des Tetra-(2,3-anthra)-tetraazaporphins und Vergleich ihrer Elektronenabsorptionsspektren mit denen anderer anellierter Tetraazaporphinsysteme

Copper, nickel and aluminium derivatives of tetra-2,3-anthratetraazaporphin bearing different substituents in the anthracen part have been prepared. The absorption spectra of these substances in different solvents are given and compared with metal complexes of other linearly annellated tetraazaporphins. In the series of vanadyl complexes of tetraazaporphin (_max 597 nm), tetra-[1,2-(4-tert-butyl)-benzo]-tetraazaporphin (_max 698 nm), tetra-[2,3-(6-tert-butyl)-naphtho]-tetraazaporphin (_max 807 nm), tetra-2,3-(anthra)-tetraazaporphin (_max 932 nm), tetra-2,3-(tetraceno)-tetraazaporphin (_max 1055 nm), the absorption maxima of the Q-band are shifted per annellated benzene ring about 100 nm to longer wave lengths.

     

Substituent dependence of the d-d transition band in the electronic absorption spectra of arylferrocenes and the corresponding arylferricenium salts

The electronic absorption spectra of 22 arylferrocenes and their arylferricenium salts with pentacyanopropenide (PCNP) were recorded. The attemptedHammett correlation of _max of the d-d transition bands of arylferrocenes revealed that this band is substituent dependent only for strong electron-withdrawing substituents. Excellent correlation of _max of the d-d transition bands with ⁺ constants was found in the case of arylferricenium cations. Good correlations of _max was also found with theE _1/2 oxidation potentials measured by cyclic voltametry.

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Substituentenabhängigkeit des d-d-Überganges in den Elektronenabsorptions-Spektren von Arylferrocenen und entsprechenden Arylferricenium-Salzen

Zusammenfassung Elektronenabsorptions-Spektren von 22 Arylferrocenen und ihren Arylferricenium-Pentacyanopropenid-Salzen wurden gemessen. VersuchteHammett-Korrelationen des längstwelligen d-d-Überganges (_max) zeigten, daß diese Bande nur von stark elektronenanziehende Substituenten abhängig ist. Im Fall der Arylferricenium-Kationen wurde eine ausgezeichnete Korrelation zwischen _max der d-d-Bande und den ⁺-Konstanten festgestellt. Eine gute Korrelation der _max-Werte wurde auch mit denE _1/2 Oxidationspotentialen gefunden, die durch cyclische Voltametrie meßbar sind.

     

Luminescence of dimeric Tl(I)-complexes: Metal-metal interaction in the electronically excited state

Summary Dimeric diethyldithiocarbamatethallium(I) [Et ₂NCS₂Tl]₂ shows a red emission at _max=608 nm which undergoes a huge Stokes shift with regard to the excitation maximum at =246 nm. It is suggested that the emission originates from a sp excited state which is characterized by strong metal-metal bonding.

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Lumineszenz von dimeren Tl(I)-Komplexen: Metall-Metall-Wechselwirkung im elektronisch angeregten Zustand (Kurze Mitt.)

Zusammenfassung Dimeres Thallium(I)diethyldithiocarbamat [Et ₂NCS₂Tl]₂ zeigt eine rote Emission mit _max=608 nm und eine große Stokes'sche Verschiebung im Bezug auf das Anregungsmaximum von =246 nm. Die Emission wird einem sp angeregten Zustand zugeordnet, der durch eine starke Metall-Metall Wechselwirkung charakterisiert ist.

     

Four spectrophotometric methods for determination of nitrofurazone in pharmaceutical formulations

Four simple and sensitive visible spectrophotometric methods (A-D) for the determination of nitrofurazone in bulk samples and pharmaceutical formulations are described. They are based on the formation of colored species by treating either its reduction product with 3-methylbenzothiazolin-2-one hydrazone in the presence of ferric chloride (method A: _max 600 nm) or its hydrolysis product with thiobarbituric acid (method B: _max 520 nm, 440 nm) or barbituric acid (method C: _max 400 nm) or by oxidizing it with excess N-bromosuccinimide and determining the consumed NBS using metol-isonicotinic acid hydrazide (method D: _max 620 nm).     

Spectrophotometric methods for the determination of labetalol hydrochloride in pure and dosage forms

Simple and sensitive Spectrophotometric methods for the determination of labetalol hydrochloride are described. The first two are based on the oxidative coupling reaction of labetalol hydrochloride withp-N,N-dimethyl-phenylenediamine dihydrochloride (method A, _max 685 nm) and 3-methyl-2-benzothiazolinone hydrazone hydrochloride (method B, _max 545 nm) in the presence of sodium hypochlorite and eerie ammonium sulphate as oxidants, respectively. The third depends on the formation of an ion-association complex of labetalol hydrochloride with suprachen violet 3B at pH 1.3, which is extracted into chloroform (method C, _max 565 nm). The methods obey Beer's law and the precision and accuracy of the methods were checked against the B.P. reference method and the relative standard deviations were in the range 0.35–0.52%. These methods are applied to the determination of labetalol in dosage forms.     

Spectrophotometric estimation of ketotifen fumarate in pharmaceutical formulations

Four simple and sensitive spectrophotometric methods (A–D) for the determination of Ketotifen fumarate in bulk samples and pharmaceutical formulations are described. They are based on the formation of coloured species by the coupling of the diazotised sulphanilamide with the drug (method A, _max 520 nm) or by oxidizing it with excessN-bromo-succinimide and determining the consumed NBS with decrease in colour intensity of celestine blue (method B: _max 540 nm) or by the reduction of Folin-Ciocalteau reagent (method C: _max 720 nm) or by the formation of a chloroform-soluble, coloured ionassociation complex between the drug and Azocarmine G at pH 1.5 (method D: _max 540 nm). Regression analysis of Beer-Lambert plots showed good correlations in the concentration ranges 1–10, 2–12, 4–28 and 2.5–25 g/ml for methods A–D, respectively. The validity of the proposed methods was tested by analysing pharmaceutical formulations containing KTF: the relative standard deviations were within ±1.0%. Recoveries were 98.9–100.2%.     

Triethyl tetrathiolothionophosphate

Triethyl tetrathiolothionophosphate was prepared by the reactions of diethyl disulfide with P₄S₁₀, 2,4-bis(4-ethylthio)-2,4-dithioxo-1,3,2⁵,4⁵-dithiadiphosphetane, or with the mixture of red phosphorus and elemental sulfur. The reactions are facilitated by ultrasound.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1310–1311, July, 1993.     

Selective colorimetric determination of p-haloaniline in a mixture witho-haloaniline by the reaction with chloranil

Summary p-Haloanilines react with chloranil to develope an intense color (_max: 545 nm), whileo-haloanilines do not. This difference in reaction has been applied to the selective determination ofp-haloanilines in a mixture witho-haloaniline.

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Zusammenfassung p-Halogenaniline geben mit Chloranil eine intensive Farbreaktion (_max= =545 nm), während die entsprechenden o-Verbindungen dies nicht tun. Auf dieser Grundlage wurde eine selektive Bestimmungsmethode für p-halogenierte Aniline in Gemischen mit o-halogenierten Anilinen ausgearbeitet.

     

Thermal decomposition of the pyridinium salt of 1,3-bis(trimethylsilyl)-2,4-dimercapto-2,4-dithioxo-1,3-diaza-2λ5, 4λ5-diphosphetidine

It was found that the first step of thermal decomposition of the pyridinium salt of 1,3-bis(trimethylsilyl)-2, 4-dimercapto-2,4-dithioxo-1,3-diaza-2⁵,4⁵-diphosphetidine (I) most probably involves breakdown to the acid form HS(S)P(NHSiMe₃)₂P(S)SH (II). The latter is very unstable and decomposes further, the end-product being a polymer (PNS)_x. In this work, the mechanism of this process is investigated.

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Zusammenfassung Man fand, daß der erste Schritt der thermischen Zersetzung des Pyridiniumsalzes von 1,3-Bis(trimethylsilyl)-2,4-dimercapto-2,4-dithioxo-1,3-diaza-25,45-diphosphetidin (I) sehr wahrscheinlich einen Abbau zur Säureform HS(S)P(NHSiMe₃)₂P(S)SH (II) beinhaltet. Letztere ist sehr unbeständig und zersetzt sich, wobei als Endprodukt ein (PNS)_x-Polymer entsteht. In vorliegendem Manuskript wird der Mechanismus dieses Prozesses näher untersucht.

     

Spectrophotometric determination of clozapine in pharmaceuticals

New Spectrophotometric methods for the assay of clozapine (CZP) in pure and dosage forms are described. Method A is based on the oxidative coupling reaction of CZP with 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) in the presence of ceric ammonium sulphate to form a coloured species (_max 570 nm). Method B is also based on the oxidative coupling reaction of CZP withP-,N,N-dimethylpheny-lenediamine dihydrochloride (DMPD) in the presence of sodium hypochlorite to form a coloured species (_max 690 nm). Method C is based on the formation of coloured charge-transfer complex between CZP and chloranilic acid (_max 540 nm). Regression analysis of Beer-Lambert plots showed good correlation in the concentration ranges 2–25, 10–120 and 15–300 g/ml for methods A, B and C, respectively. The validity of the proposed methods was tested by analysing pharmaceutical dosage forms containing CZP and the relative standard deviation values were within 1.0%.     

Sensitive spectrophotometric methods for the determination of pindolol

Two simple, sensitive and reproducible visible spectrophotometric methods for the determination of Pindolol in amounts as low as 1 g are described. The first method is based on the oxidation of Pindolol by sodium nitrite under acidic conditions and the coupling of the oxidised intermediate withN-1-(naphthyl)ethylenediamine dihydrochloride (NED) to the colored product. The spectrum of the colored solution is strongly dependent on the length of the incubation period at room temperature during oxidation (3 min, _max 620 nm; 10 min or above _max 540 nm). Other couplers [diphenylamine (DPA) or 1-naphthylamine (-NA)] or indole derivatives (indole, tryptophan or isatin) when used instead of NED or Pindolol, respectively, also react to give a colored product with same maximum in each case irrespective of the length of the incubation period during oxidation. The second method is based on the coupling reaction involving Pindolol and 1,2-naphthaquinone-4-sulphonic acid sodium salt to form a coloured product (_max 660 nm). Both the methods have been employed to determine Pindolol content in bulk forms and pharmaceutical preparations.     

Preparation of self-assembled fluorinated molecular aggregates, fluorescein nanocomposites: an extremely enhanced light absorption in nanocomposites

Self-assembled fluorinated molecular aggregates formed by fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers, N,N-dimethylacrylamide oligomers, and acrylic acid oligomers in methanol could selectively recognize fluoresceins as guest molecules to form a new class of fluorinated aggregates-fluorescein nanocomposites. These fluorinated fluorescein nanocomposites that are obtained exhibit an extraordinarily enhanced light absorption (_max ca. 440 nm) compared to that (_maxs 452, 480 nm) of the parent fluorescein in the absence of fluorinated aggregates.     

Thin layer chromatographic studies of anils II. Separation,identification and determination

Thin layer chromatographic behaviour of ten anils was studied on silica gel adsorbent mixed with starch binder with ten solvent systems. Simultaneous separation, identification and determination of ternary mixtures of isomers was stressed. TheR _F increasing order was found to be dependent on the solvent and independent of the degree of saturation of the chamber. The correlations ofR _F with _max and (C=O) of isomers were established and used in their identification. Six anils were separated in methanol—benzene (11).     

Photometrische Wismutbestimmung mit Brenzcatechinviolett

Zusammenfassung Es wurden die Bedingungen der photometrischen Wismutbestimmung mit Brenzcatechinviolett bei der WellenlÄnge _max=580 nm ausgearbeitet und der Einflu\ der Fremdionen untersucht. Das Lambert-Beersche Gesetz gilt in den Konzentrationsgrenzen 0,0–6,2 g Bi/ml bei 1,6 cm Schichtdicke.

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Summary A method is given for the photometric determination of bismuth using pyrocatechol violet, at the wave-length of _max=580 nm. Interferences by foreign ions have been examined. Beer's law is obeyed from 0.0 to 6.2 g Bi/ml (1,6 cm cuvettes).

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Als erste Mitteilung dieser Reihe soll die Arbeit: Malát, M.: Naturwissenschaften 48, 569 (1961) betrachtet werden.     

Unicyclic Graphs with Minimal Energy

If G is a graph and ₁,₂,..., _n are its eigenvalues, then the energy of G is defined as E(G)=|₁|+|₂|++| _n |. Let S _n ³ be the graph obtained from the star graph with n vertices by adding an edge. In this paper we prove that S _n ³ is the unique minimal energy graph among all unicyclic graphs with n vertices (n6).     

Anisotropie der WÄrmeleitung in gedehnten Elastomeren

Zusammenfassung An einigen schwach vernetzten, gedehnten Elastomeren und an gedehntem Weich-PVC wurde die WÄrmeleitfÄhigkeit senkrecht zur Dehnungsrichtung in AbhÄngigkeit von der Temperatur zwischen –10 C und +45 C gemessen. Die Dehnung blieb wÄhrend einer Messung konstant. ist kleiner als die WÄrmeleitfÄhigkeit der ungedehnten (isotropen) Substanz und nimmt mit steigender Dehnung ab. Die Anisotropie der WÄrmeleitfÄhigkeit zeigt sich besonders deutlich ( / ₀0,8 bis 0,9 für=200%) — gleiche Dehnung vorausgesetzt — bei Polymeren, deren Kettenmolekeln polare Seitengruppen enthalten (z. B. Butadien — Acryl-nitril — Copolymer, Polychloropren, chlorsulfoniertes PolyÄthylen), wÄhrend sie bei solchen, deren Molekelketten nur unpolare Seitengruppen enthalten (z. B. Naturkautschuk, Polyisobutylen), kaum in Ersoheinung tritt. Bei Weich-PVC sinkt die Anisotropie bei gleicher Dehnung mit dem Weichmachergehalt und verschwindet fast ganz bei Weichmacherkonzentrationen über 60 Gew.%, d.h. der Quotient / ₀ geht gegen 1, und zwar um so schneller, je grö\er die Wirksamkeit des Weichmachers ist. Eine ZeitabhÄngigkeit der Anisotropie konnte nicht beobachtet werden.

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Summary Thermal conductivity of some crosslinked strained elastomers and plasticized polyvinylchloride was measured normal to the direction of strain as function of temperature between –10 C and +45 C. The strain was held constant during one measurement. is smaller than the thermal conductivity of the unstrained (isotropic) material and decreases with increasing strain. The anisotropy of thermal conductivity appears specially clear ( / ₀ about 0,8 to 0,9 for=200%) — the same strain presumed — with polymers the chain molecules of which contain polar sidegroups (e. g. butadiene — acrylonitrile — copolymer, polychloroprene, chlorsulfonated polyethylene), whereas it can hardly be observed with polymers the chain molecules of which contain only non-polar sidegroups (e. g. natural rubber, polyisobutylene). Concerning strained plasticized Polyvinylchloride the anisotropy decreases at constant strain with the content of plasticizer and nearly vanishes at weight fractions above 60% plasticizer, that means, the quotient / ₀ will become 1. The decrease is the more rapid the greater the plasticizing effectiveness is. A time dependence of the anisotropy has not been observed.

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Herrn Prof. Dr.K.-H. Hellwege und Herrn Dr.W. Knappe danke ich für eingehende Diskussion und Förderung dieser Arbeit.     

Beitrag zur mathematischen Beschreibung des Spannungs-Dehnungs-Verhaltens von Elastomeren

Zusammenfassung Ausgehend von der Hypothese vonValanis undLandel, nach der die DehnungsenergieW( _x , _y , _z ) als Summe dreier identischer Funktionenw( _i ) der Dehnungsverhältnisse _i (i=x,y,z) dargestellt werden kann, wird fürw( _i ) ein Ausdruck vorgeschlagen, der sich durch seine relative Einfachheit auszeichnet. Es wird gezeigt, daß die mit Hilfe dieses Ausdruckes abgeleiteten Formeln für das Spannungs-Dehnungs-Verhalten von Elastomeren in der Lage sind, Meßdaten anderer Autoren mit guter Genauigkeit wiederzugeben. Untersucht wurden die Beanspruchungsarten einaxialer Zug, biaxialer Zug und reine Scherung mit Dehnungen bis zu ca. 700%.

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Summary Based on the hypothesis ofValanis andLandel that the strain-energy functionW( _x , _y , _z ) could be represented as the sum of three identical functionsw( _i ) of the principal extension ratios _i (i=x,y,z), an expression forw( _i ) is suggested which is distinguished by its relative simplicity. The stress-strain relations developed from this expression are tested successfully by applying them to experimental results of other authors. The types of strain which were examined were simple extension, biaxial extension and pure shear; the elongations were to about 700%.

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Mit 4 Abbildungen     

Study of colour-developing factors in spectrophotometric determination of cyanide by the pyridine-barbituric acid method

Summary The decomposition of cyanide-pyridine-barbituric acid in the wavelength around _max=583 nm gives rise to formation of a new color species around _max=490nm. Both reactions are first-order reactions with the same K value of 0.066 hr^–1, but with opposite sign. The pH value, the nature and concentration of the buffer solution influence absorption to a considerable extent. A method for estimation of cyanide is suggested.

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Untersuchung der Farbbildungsfaktoren bei der spektrophotometrischen Bestimmung von Cyanid nach der Pyridin-Barbitursäure-Methode

Zusammenfassung Die Zersetzung von Cyanid-Pyridin-Barbitursäure bei der Bandbreite um _max=583 nm verursacht die Bildung einer neuen Farbspecies um _max=490 nm. Beide Reaktionen sind solche erster Ordnung mit dem selben K-Wert von 0,066 hr^–1, aber mit umgekehrtem Vorzeichen. pH-Wert, Art und Konzentration der Pufferlösung beeinflussen die Absorption in beträchtlichem Maß. Eine Methode zur Bestimmung von Cyanid wird vorgeschlagen.

     

Photoreactions of vinylferrocene with carbon tetrachloride and tetrachloroethylene in cyclohexane

Summary The photodecomposition of vinylferrocene in binary equimolar solvents such as carbon tetrachloride — cyclohexane and tetrachloroethene — cyclohexane exposed to monochromatic ( = 300 nm) and polychromatic ( 300 nm) radiation has been studied, and the quantum yields of the photoproducts and of vinylferrocene photodecrement determined. U.V. spectra of the systems suggest that intermolecular charge-transfer complexes are formed, in the first interaction stage between vinylferrocene and halogen derivatives; equilibrium constants, K, and molar extinction coefficients, (_c), have been determined for this process.