Studies in chlorin chemistry. II. A versatile synthesis of dihydrodipyrrins

[reaction: see text] Dihydrodipyrrins are key building blocks for the synthesis of hydroporphyrins, many of which have important biological activity. The title compounds were prepared in stereo- and regioselective fashion by a three-step sequence consisting of (1) Pd(0)-catalyzed coupling-cyclization of 2-iodopyrroles with gamma-alkynoic acids to afford enelactones of the desired substitution pattern, (2) methylenation at the lactone carbonyl group employing the Petasis reagent, and (3) in situ enol-ether hydrolysis and amination of the resultant 1,4-diketone to close the pyrroline ring (nine examples). Yields for each step were generally high, although in substrates not blocked by geminal substitution aromatization to a dipyrromethane is a competing side reaction.     

An infrared renormalization group limit cycle in QCD

We use effective field theories to show that small increases in the up and down quark masses would move QCD very close to the critical renormalization group trajectory for an infrared limit cycle in the three-nucleon system. We conjecture that QCD can be tuned to the critical trajectory by adjusting the quark masses independently. At the critical values of the quark masses, the binding energies of the deuteron and its spin-singlet partner would be tuned to zero and the triton would have infinitely many excited states with an accumulation point at the 3-nucleon threshold. The ratio of the binding energies of successive states would approach a universal constant that is close to 515.     

Nonmonotonic behavior of resistance in a superconductor-Luttinger liquid junction

Transport through a superconductor-Luttinger liquid junction is considered. When the interaction in the Luttinger liquid is repulsive, the resistance of the junction with a sufficiently clean interface shows nonmonotonic temperature or voltage dependence due to the competition between the superconductivity and the repulsive interaction. The result is discussed in connection with recent experiments on single-wall carbon nanotubes in contact with superconducting leads.     

Beitrag zur Bestimmung von 2-Oxo-pyrrolidin-Derivaten aus biologischem Material

Zusammenfassung 2-Oxo-1-pyrrolidin-essigsäure-Derivate lassen sich weder UV-spektroskopisch, colorimetrisch noch fluorimetrisch bestimmen, GC-Bestimmungen sind nur bedingt anwendbar. Zur Bestimmung von 2-Oxo-1-pyrrolidin-essigsäure, deren Amid, Hydrazid sowie 1,2-Bis(2-oxo-pyrrolidin-1-essigsäure)-hydrazid bzw. ,-Bis(2-oxo-1-pyrrolidinacetamido)-alkanen in biologischem Material eignet sich die Extraktion der gefriergetrockneten Analysenproben mit Chloroform/Methanol-Gemischen, Dünnschicht-Chromatographie auf Kieselgel und Detektion mit verschiedenen Sprühreagentien. Durch Flächengrößenvergleich/Scannen sind Bestimmungen aus Vollblut, Plasma, Organhomogenaten und Urin möglich. Die Anwendbarkeit der Methode wird am Beispiel von Stabilitätsprüfungen in biologischem Material, Resorptionsnachweisen, Plasma- und Urinspiegeln bei Ratten, Hunden und Menschen demonstriert.

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Contribution to the determination of 2-oxo-pyrrolidine derivatives in biological material

Summary Determination of 2-oxo-1-pyrrolidine-acetic acid derivatives cannot be carried out either spectroscopically, colorimetrically or fluorimetrically, and GC determination is only conditionally suitable. For the determination of 2-oxo-1-pyrrolidine-acetic acid, its amide, hydrazide as well as 1,2-bis (2-oxo-pyrrolidine-1-acetic acid)-hydrazide and ,-bis(2-oxo-1-pyrrolidine-acetamido)-alkanes in biological material, a suitable method is the extraction of freeze-dried analytical samples with chloroform/methanol mixtures, TLC on silica gel and detection with various spray reagents. Determinations from whole blood, plasma, organ homogenates and urine are possible by spot area comparison or scanning. The practicability of the method is demonstrated with the example of stability tests in biological material, proof of absorption, and determination of plasma and urine levels in rats, dogs and in man.

     

Iodine etching of the GaAs(1̄1̄1̄)As surface studied by LEED,AES, and mass spectroscopy

The iodine interaction with the GaAs(1̄1̄1̄)As surface prepared by molecular beam epitaxy has been studied by LEED, LEED intensity measurements, Auger electron spectroscopy (AES) and computer controlled mass spectroscopic study of the whole desorption spectrum. It is shown that an iodine beam hitting the GaAs(1̄1̄1̄)As face at 300 K under UHV conditions etches the surface continuously. After this etching there remains an adsorbate of GaI_x where x is a number between 0 and 3. By thermal desorption of this GaI_x adsorbate an As stabilized GaAs(1̄1̄1̄)As surface showing a (2 × 2) structure can be prepared, which up to the present could be done only by molecular beam epitaxy.     

The well-tempered auxiliary-field Monte Carlo

The auxiliary-field Monte Carlo (AFMC) is a method for computing ground-state and excited-state energies and other properties of electrons in molecules. For a given basis set, AFMC is an approximation to full-configuration interaction and the accuracy is determined predominantly by an inverse temperature "beta" parameter. A considerable amount of the dynamical correlation energy is recovered even at small values of beta. Yet, nondynamical correlation energy is inefficiently treated by AFMC. This is because the statistical error grows with beta, warranting increasing amount of Monte Carlo sampling. A recently introduced multi-determinant variant of AFMC is studied, and the method can be tuned by balancing the sizes of the determinantal space and the beta-parameter with respect to a predefined target accuracy. The well-tempered AFMC is considerably more efficient than a naive AFMC. As a welcome "byproduct" low lying excitation energies of the molecule are supplied as well. We demonstrate the principles on dissociating hydrogen molecule and torsion of ethylene where we calculate the (unoptimized) torsional barrier and the vertical singlet-triplet splitting.