Rearrangement of Rare Earth Defects Under Domain Inversion in LiNbO3

Using high resolution excitation-emission spectroscopy we investigated the changes occurring in the optical transition of Er^3? ions in LiNbO₃ during inversion of the ferroelectric axis. In stoichiometric LiNbO₃ we find that a drastic reconfiguration among the different defect sites takes places favoring those centers which have already been dominant in the as-grown sample. The reconfiguration is attributed to changes in the arrangement of the local charge compensators. Furthermore, we find a small shift of the emission transition energy, which is consistent with an increase of the intrinsic electric field. These findings make the Er^3? ions very suitable probes for 3D imaging of domain structures and for in-situ studies of the dynamics of the domain inversion processes and the defect/domain wall interaction.     

Comparative Studies of Er3☎ Ions in LiNbO3 Waveguides Produced by Different Methods

We compare the optical properties of Er^3? in LiNbO₃ waveguides produced by different techniques and find by confocal luminescence microscopy characteristic differences in the excitation and emission transitions. Besides a small redistribution among the regular defect sites, essentially no direct Er^3?—Ti^4? interaction can be observed in Ti^4? diffused waveguides. However a significant shift in transition energies is found, which increases with Ti^4?concentration. Based on earlier results we associate this shift with a decrease in the intrinsic electric field. In addition to a similar shift, we find in Zn^2? diffused waveguides new defect types which suggest a change in direct environment. Finally, in annealed proton exchange waveguides we find no interaction effects at all.     

The scaling of the current voltage characteristics of the YBa2Cu3O7:Y2BaCuO5 composites

We have investigated features in the current voltage (I—V) characteristics of YBa₂Cu₃O₇:Y₂BaCuO₅ composite sinters which indicate the occurrence of a second-order phase transition. For each sinter composition similar families of characteristics are found for a wide range of magnetic fields. The relation between V and I is seen to be of the form V = f(I, ζ(B, T)) where a single parameter ξ contains all of the field and temperature dependence. The locus of points in the B, T plane for which ζ(B, T) is a constant have been examined, and a low field and a high field régime have been identified. Samples of different composition show families of I—V characteristics which scale onto one another in a simple way, hence we are led to suppose the V = f(I, ζ(B, T, p)) where p is the dilution fraction. Data taken at temperatures below the phase transition agrees well with a simple scaling picture of dissipation close to a second order phase transition, with exponents which are independent of magnetic field and composition. Above the transition, however, the behaviour is more complex.     

Comparison of chiral NMR solvating agents for the enantiodifferentiation of amines

Chiral, enantiomerically pure organic-soluble acids are often used as NMR chiral solvating agents (CSAs) for analyzing the enantiopurity of amines. However, the reports that describe CSAs for amines provide limited comparisons to other previously reported reagents. As such, it is difficult to know which among the many CSAs to pick when studying a new amine. We report a comparison of thirteen commercially available CSAs for the analysis of primary, secondary and tertiary amines in chloroform-d. (R)-α-methoxyphenylacetic acid, (R)-(-)-O-acetylmandelic acid, (R)-2-methoxy-2-(1-naphthyl)propionic acid and (R)-(-)-1,1′-binaphthyl-2,2′-diylhydrogenphosphate are identified as the best four to use as a starting point for the analysis of a new amine.     

Discrete-time stochastic modeling and simulation of biochemical networks

Since inherent randomness in chemically reacting systems is evident, stochastic modeling and simulation are exceedingly important for investigating complex biological networks. Within the most common stochastic approach a network is modeled by a continuous-time Markov chain governed by the chemical master equation. We show how the continuous-time Markov chain can be converted to a stochastically identical discrete-time Markov chain and obtain a discrete-time version of the chemical master equation. Simulating the discrete-time Markov chain is equivalent to the Gillespie algorithm but requires less effort in that it eliminates the generation of exponential random variables. Thus, exactness as possessed by the Gillespie algorithm is preserved while the simulation can be performed more efficiently.     

Substrate specificity of the acyl transferase domains of EpoC from the epothilone polyketide synthase

The production of epothilone mixtures is a direct consequence of the substrate tolerance of the module 3 acyltransferase (AT) domain of the epothilone polyketide synthase (PKS) which utilises both malonyl- and methylmalonyl-CoA extender units. Particular amino acid motifs in the active site of AT domains influence substrate selection for methylmalonyl-CoA (YASH) or malonyl-CoA (HAFH). This motif appears in hybrid form (HASH) in epoAT3 and may represent the molecular basis for the relaxed specificity of the domain. To investigate this possibility the AT domains from modules 2 and 3 of the epothilone PKS were examined in the heterologous DEBS1-TE model PKS. Substitution of AT1 of DEBS1-TE by epoAT2 and epoAT3 both resulted in functional PKSs, although lower yields of total products were observed when compared to DEBS1-TE (2% and 11.5% respectively). As expected, epoAT3 was significantly more promiscuous in keeping with its nature during epothilone biosynthesis. When the mixed motif (HASH) of epoAT3 within the hybrid PKS was mutated to HAFH (indicative of malonyl-CoA selection) it resulted in a non-productive PKS. When this mixed motif was converted to YASH (indicative of methylmalonyl-CoA selection) the selectivity of the hybrid PKS for methylmalonyl-CoA showed no statistically significant increase, and was associated with a loss of productivity.     

Annulation of internal alkynes through a hydroamination/aza-Heck reaction sequence for the regioselective synthesis of indoles

Highly regioselective annulation reactions of unsymmetrically substituted alkynes by primary 2-bromo or 2-chloroanilines are achieved with an efficient one-pot protocol, which relies on a regioselective TiCl₄-catalyzed intermolecular hydroamination and a subsequent palladium-catalyzed intramolecular aza-Heck reaction. The use of unsymmetrically substituted alkynes in this strategy enables the synthesis of diversely functionalized indoles, with a regioselectivity that is complementary to the one obtained when employing Larock's annulation reaction.     

DKxanthene biosynthesis--understanding the basis for diversity-oriented synthesis in myxobacterial secondary metabolism

The DKxanthenes are a family of yellow pigments which play a critical role in myxobacterial development. Thirteen unique structures from Myxococcus xanthus DK1622 differ in the length of their characteristic polyene functionality, as well as the extent of methyl branching. We aimed to understand the mechanistic basis for this "molecular promiscuity" by analyzing the gene cluster in DK1622, and comparing it to the DKxanthene biosynthetic locus in a second myxobacterium, Stigmatella aurantiaca DW4/3-1, which produces a more limited range of compounds. While the core biosynthetic machinery is highly conserved, M. xanthus contains a putative asparagine hydroxylase function which is not present in S. aurantiaca. This observation accounts, in part, for the significantly larger metabolite family in M. xanthus. Detailed analysis of the encoded hybrid polyketide synthase (PKS)-nonribosomal peptide synthetase (NRPS) assembly line provides direct evidence for the mechanism underlying the variable polyene length and the observed pattern of methyl functionalities.