Mechanism for large first hyperpolarizabilities of phosphonic acid stilbene derivatives

This paper presents calculations of dipole moments (mu), static polarizabilities (alpha), and first hyperpolarizabilities (beta) of phosphonic acid stilbene derivatives calculated in the framework of density functional theory. These calculations were performed using a finite field approach implemented in the density functional program ALLCHEM and were of an all-electron type using local exchange-correlation functional and specially designed basis sets. The molecular structures have been fully optimized using the semiempirical program MSINDO. Some of the investigated stilbenes have been synthesized very recently while others are described for the first time. Donor and acceptor groups of these analogues have been modified and the influence of these changes on the first hyperpolarizabilities has been investigated. This work demonstrates that the nonlinear optical response beta of these compounds increases dramatically when the acceptor moiety is displaced by analogues containing alkali metal groups. A general mechanism for the design of novel nonlinear optical materials with large first hyperpolarizabilities is described.     

Isochorismate pyruvate lyase: a pericyclic reaction mechanism?

Isochorismate pyruvate lyase (IPL) catalyzes the cleavage of isochorismate to give salicylate and pyruvate, a key step in bacterial siderophore biosynthesis. We investigated the enzyme from Pseudomonas aeruginosa using isochorismate selectively deuterated at C2 as a substrate. Monitoring the reaction by 2H NMR spectroscopy revealed that the label is quantitatively transferred from C2 to C9, producing stoichiometric amounts of [3-2H]pyruvate as product. Moreover, the deuterium kinetic isotope effect of 2.34 +/- 0.08 on kcat indicates that C-H cleavage is significantly rate limiting. Consistent with these data, hybrid density functional theory (HDFT) calculations at the Becke3LYP/DZ+(2d,p) level of theory predict a concerted but highly asynchronous pericyclic transition structure, in which carbon-oxygen bond cleavage is more advanced than hydrogen atom transfer from C2 to C9; the calculated 2H isotope effect of 2.22 at C2 is in excellent accord with the experimental value. Together, these findings indicate that IPL should be added to the small set of proteins that are known to catalyze pericyclic reactions. They also raise the possibility that enzymes, such as chorismate pyruvate lyase, salicylate synthase, 4-amino-4-deoxychorismate lyase, and anthranilate synthase, which accelerate formally similar reaction steps, may also exploit pericyclic mechanisms.     

Dynamics and energetics of the self-assembly of a hydrophobically modified polyelectrolyte: Naphthalene-labeled poly(acrylic acid)

Steady-state and time-resolved fluorescence studies were performed on aqueous solutions of poly(acrylic acid) hydrophobically modified with two very different levels of naphthalene (Np). It is demonstrated that unique information on association phenomena involving hydrophobe-modifed polymers can be obtained from an extended fluorescence study by using data for a less-modified polymer as a reference. For the more highly modified polymer, the presence of excited-state (as well as ground-state) dimers in addition to monomer emission due to locally excited naphthalene gives evidence for hydrophobic association between naphthalene groups. This association becomes, as expected, much less important at higher pH due to the electrostatic repulsion between different chain segments. However, it is noted that even at high pH there is a significant self-association. The coexistence of static and dynamic quenching phenomena of the Np monomer label was also revealed in the time-resolved fluorescence data. The data are compatible with the existence of two types of monomers and one excimer and suggest that the essential contribution to the monomer emission comes from isolated chromophores, whereas excimer formation arises from both a dynamic route (excited Np chromophores able to produce a dynamic excimer) and a static route (excitation of ground-state Np dimers). At room temperature, the dissociative reaction, excimer-to-monomer, can be neglected, and thus the rate constant for excimer formation and decay could be obtained with and without considering the influence of preformed dimers. Temperature has shown to induce different behavior in the polymer photophysics. In the case of the less-labeled polymer, the decays were found to be single-exponential with the fluorescence lifetime decreasing with increasing temperature. From the temperature dependence of the steady-state fluorescence data, the activation energy for excimer formation and the binding energy of the excimer were evaluated at different pH values, through the Stevens-Ban-type plots of the excimer-to-monomer intensity ratio. With the time-resolved data, measured in the temperature range of 5-60 degrees C, it was possible to extract the intrinsic activation energies for excimer formation. The thermodynamic driving force for the intrapolymeric association was found to be dependent on a balance between hydrophobic and electrostatic interactions, which are dependent on the pH, temperature, and hydrophobic content of the polymer.     

Neue acetonylsubstituierte Azole I. 5-Acetonyl-1,2,4-oxadiazole

Aliphatic amidoximesR—C (NH₂)=NOH react with diketene to yield 5-acetonyl-3-alkyl-1,2,4-oxadiazoles, which are susceptible to a wide variety of reactions at the keto-group as well as at the methylene-group. Their transformations into 1-methyl-2-oxadiazolyl-vinylN,N-dimethylcarbamates, 2-chloro-1-oxadiazolylpropenes, 1-oxadiazolyl-2-(1,2,4-triazol-1-yl)propenes, 1,1-dichloro-1-oxadiazolylacetones and 3-hydroxy-2-oxadiazolyl-crotonic amides are described as well as their reactions with diazonium salts, with sodium nitrite and with carbon disulfide. Further products obtained are carbamates of of 1-oxadiazolyl-2-oxo-propane-1-oximes, 2-chloro-2-oxadiazolylvinyl phosphates and an oxadiazolyl pyrimidine.

Herrn Prof. Dr.Klaus Weissermel zu seinem 60. Geburtstag.     

Die Phase La2U2N5

In the system U–La–N a new phase of composition La₂U₂N₅ was observed. The differaction pattern of this phase can be indexed with a tetragonal unit cell:a=8.43 Å,c=8.50 Å andc/a=1.008. The pseudocubic sub-cell withaca/2 is closely related to the CsCl-type.

Auszug aus der von der Technisch-Naturwissenschaftlichen Fakuktät der TU Wien approbierten Diplomarbait des Herrn Dipl.-Ing.J. Waldhart.     

Some developments in reaction and solution microcalorimetry,with particular reference to its use in biochemistry and cellular biology

The field of isothermal microcalorimetry as applied to systems of interest for aqueous solution chemistry, biochemistry and in cellular biology is briefly reviewed. Some techniques recently developed in the author's laboratory are described.     

A fully automated mass spectrometer for the analysis of organic solids

Automation of a mass spectrometer—computer system makes it possible to process up to 30 samples without attention after sample loading. An automatic sample changer introduces the samples successively into the ion source by means of a direct inlet probe. A process control unit determines the operation sequence. Computer programs are available for the hardware support, system supervision and evaluation of the spectrometer signals. The most essential precondition for automation — automatic evaporation of the sample material by electronic control of the total ion current — is confirmed to be satisfactory. The system operates routinely overnight in an industrial laboratory, so that day work can be devoted to difficult analytical problems. The cost of routine analyses is halved.     

Measurement of Diffusion in Zeolites—A Never Ending Challenge?

A review is given on the main problems associated with the determination and interpretation of molecular diffusion in zeolites. It is shown that the diffusivities may most decisively depend on the relevant space and time scales of observation, as well as on the physical state under which the measurements are carried out. Special emphasis is given to the microscopic techniques and their most recent evidence on the existence of transport resistances distributed over the intracrystalline space.