Synthesis of a biotinated amphiphile

The synthesis of a biotinated amphiphile assembled from d-(+)-biotin, ethylene diamine as spacer, galactaric acid and 1-dodecylamine was achieved in six steps. The key step was the synthesis of a bisacetonide protected galactaric ester, the structure of which was determined by X-ray analysis. Aminolysis, spacer attachment, coupling with biotin and deprotection led to the amphiphilic galactaramide.     

Integral approximations for molecular orbital theory

The electron repulsion integrals arising in LCAO-MO theory are approximated by replacement of the product of two orbitals on different centers by linear combinations of one-center products. The approximation differs from those previously proposed in that the coefficients of the various terms are determined by requiring agreement for certain integrals, and in the emphasis of the role of symmetry in selecting the one-center products. For two-center integrals, the new approximation is significantly better than older approximate methods. Reasons are given for expecting this improvement to extend also to multi-center integrals.

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Zusammenfassung Es wird ein Verfahren zur näherungsweisen Berechnung von Elektronenwechselwirkungsintegralen der LCAO-MO-Theorie beschrieben, bei welchem das Produkt zweier Zustandsfunktionen an verschiedenen Zentren durch eine Linearkombination von Produkten am gleichen Zentrum ersetzt wird. Der Unterschied zu ähnlichen Ansätzen liegt in der Justierung der Koeffizienten. Für Zweizentrenintegrale liefert die hier vorgeschlagene Methode bedeutend bessere Ergebnisse als das Mulliken-Verfahren.

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Résumé Les intégrales de répulsion électroniques intervenant dans la théorie LCAO MO sont calculées d'une manière approchée en remplaçant le produit de deux orbitales sur des centres différents par des combinaisons linéaires de produits à un centre. Cette approximation diffère de celles proposées auparavant par la détermination des coefficients des différents termes au moyen de l'ajustement de certaines intégrales et par l'importance du rôle de la symétrie dans le choix des produits monocentriques. Cette nouvelle approximation est bien meilleure que les anciennes en ce qui concerne les intégrales bi-centriques. Nous donnons des raisons d'espérer que cette amélioration s'étendra aux intégrales polycentriques.

     

Electrode processes in the oxidation of tetrahydroisoquinoline derivatives

The electrochemical oxidation of the alkaloid laudanosine (Ia) to O-methylflavinantine (II) has been studied in acetonitrile solvent. Using cyclic voltammetry, rotating disc voltammetry and preparative electrolyses on several alkaloids, simple aliphatic amines and aromatic compounds, some aspects of the mechanism of this coupling reaction are elucidated. The first anodic wave for laudanosine at platinum has E_p=0.55 V vs. Ag/Ag⁺. The electrode rapidly becomes partially passivated at potentials above 0.5 V. This is due to a film which “dissolves” below 0.5 V, at a rate independent of the potential. It is shown that the reaction (Ia)→(II) proceeds at 0.5 V by initial oxidation of the amine moiety. If acids such as sodium bicarbonate are added to the anolyte the amine is protonated causing the first wave to disappear. Oxidation at 1.1 V under these acidic conditions produces the same product, but more rapidly and in significantly higher yield because electrode filming and side reactions resulting from the amine oxidation are abrogated.     

A facile three-step synthesis of (±)-crispine A via an acyliminium ion cyclisation

A high yielding cyclisation of the readily available N-(4,4-diethoxybutyl)-2-(3,4-dimethoxyphenyl)acetamide to 8,9-bis(methyloxy)-2,3,6,10b-tetrahydropyrrolo[2,1-a]isoquinolin-5(1H)-one is described. The latter can be reduced with either AlH₃ or BH₃ to (±)-crispine A in an overall yield of 55%.     

Preferred dimerization of tetra-tolyl- and tetra-tosylurea derivatives of flexible and rigidified calix[4]arenes

The dimerization of tetratolyl- and tetratosyl-urea derivatives 1 and 2, derived from a tetrapentoxy calix[4]arene in the cone conformation and of the corresponding tetra-urea derivatives 3 and 4, in which the cone conformation is rigidified by the two crown-3 tethers, have been studied. All six possible equimolar mixtures were examined by 1H NMR using CDCl3 and CD2Cl2 as solvents. While no heterodimers are found for the combinations 1/3 and 2/4 in either solvent, all remaining combinations lead to the (exclusive) formation of heterodimers in CD2Cl2. In CDCl3 heterodimers are only observed for the combinations of 3 with 2 or 4. These results are discussed in terms of entropic and enthalpic contributions and compared with MD-simulations in a box of chloroform solvent molecules.     

Importance of the diamine reactant in the production of polyphosphonamides by the interfacial technique

The stirred interfacial polycondensation of phenylphosphonic dichloride and 1,6-hexanediamine has been studied as a function of several reaction variables. The reaction is rapid, being completed in less than 1 min. When organic solvent is varied and reactant molar ratio is varied with an excess of the acid chloride, yield is constant. When reactant molar ratio is varied polymer yield increases with increase in amine concentration. When reactant concentration is increased yield increases. With the addition of a soluble salt in the aqueous phase yield is increased. The above indicates that the diffusion of the amine to the reaction zone is of primary importance in determining polymerization rate and that the diffusion of the acid chloride is relatively unimportant. Polymer yield was found to be dependent on the pH of the amine in the aqueous phase. The observed trend is related to the apparent solubility of the amine in the aqueous phase such that the greater the apparent solubility of the amine, the less the polymer yield. Polymer molecular weight is found to be independent of reaction variables tested. Polymer was also formed from the condensation of phenylphosphonic dichloride with p-phenylenediamine, H₂N-D-NH₂ (where D is a 36-carbon hydrocarbon chain), 1,3-di-4-piperidylpropane, and 4-aminomethylpiperidine; phenyl phosphorodichloridate with 1,6-hexanediamine; chloromethyl phosphonic dichloride with 1,6-hexanediamine.     

Mössbauer and molecular orbital study of the myoglobin-CO complex

Experimental Mössbauer spectra of the Fe⁵⁷-enriched CO complex of sperm whale myoglobin (MbCO) at T= 4.2 K with and without applied magnetic field (H⊥γ) were measured to derive the sign of the electric field gradient (EFG), the quadrupole splitting ΔE _Q, and the isomer shift δ of the heme iron. We find a positive EFG, δE _Q = 0.363 mm/sec, and δ + 0.266 mm/sec. Molecular orbital calculations were carried out to obtain theoretical estimates of EFG and ΔE _Q for several steric arrangements of the CO ligand relative to the heme group. Our results are most consistent with the conclusion that the iron is situated in the heme plane, and that a bent geometry with a Fe-C-O angle of about 135 ° is more favorable than a more symmetric structure with a linear Fe-C-O geometry.     

Phenylated polyimides: Diels-Alder reaction of biscyclopentadienones with dimaleimides

A series of phenylated polydihydrophthalimides has been synthesized by the Diels-Alder reactions of 3,3′-(oxydi-p-phenylene)bis(2,4,5-triphenylcyclopentadienone) and 3,3′-(p-phenylene)bis(2,4,5-triphenylcyclopentadienone) with N,N′-o-, -m-, and -p-phenylenedimaleimide. The polydihydrophthalimides were soluble in dimethylformamide (DMF) and had intrinsic viscosities that ranged from 0.33 to 1.01, the polymers were dehydrogenated thermally and chemically to afford the corresponding phenylated polyphthalimides. The totally aromatic polyimides were also soluble in DMF but had intrinsic viscosities only as high as 0.41. The thermogravimetric analyses of the polyphthalimides showed breaks near 530°C in air and in nitrogen atmospheres.     

The nature of the C-defects in nickel and their rôle in the interpretation of radiation damage in metals

In previous Perturbed-Angular-Correlation (PAC) studies of the - emission of ¹¹¹In probe nuclei in cold-worked or particle-irradiated nickel, it has been found that thermal annealing in the temperature regime of recovery stage III leads to the formation of so-called C-defects (Cubic defects). This is indicated by the occurrence of a new frequency of about 80 Mrad/s, in addition to the frequency (200 Mrad/s) that is due to ¹¹¹In on substitutional sites. Obviously, the C-defects are complexes consisting of ¹¹¹In and the intrinsic point-defect species that migrates freely in recovery stage III. Therefore, they have played an important rôle in the long-standing controversy on whether the recovery-stage-III defects are vacancies (one-interstitial model) or self-interstitials (two-interstitial model). The present paper reports on a novel experimental effort to reveal the nature of the C-defects by combining PAC studies on nickel samples differently pretreated in a systematic way, investigations of the Extended X-ray Absorption Fine Structure (EXAFS) on In-doped nickel, and measurements of the decay rate of ¹¹¹In nuclei in the Electron-Capture-Induced Decay (ECID). On the basis of the results of these experiments it is concluded that the defects trapped by substitutional ¹¹¹In atoms (In_s) in recovery stage III are self-interstitials (I), as expected according to the two-interstitial model. Moreover, there is evidence that the C-defects are In interstitials on tetrahedral sites (In_i) that form exclusively in the vicinity of the specimen surface from In_s – I pairs via the reaction In_s+I In_i.     

Particle directionality and trapped proton fluences on LDEF

Directionality of incident space radiation is a significant factor in spacecraft shielding and astronaut dosimetry in low Earth orbit (LEO). Particle directionality of GCR and trapped protons were measured on LDEF with plastic nuclear track detectors (PNTD) from the P0006 west-side experiment. This experiment consisted of a thick detector stack and is described more fully in a companion article (Benton et al., 1996). The anisotropy of the trapped protons produced maximum intensity for protons arriving from the west. The fluences of the eastward directed trapped protons have been measured by selection of the particles on the basis of range in the PNTDs. The measured fluences are compared with the model calculations of Armstrong and Colborn (1993).