Chiral phase transition and Anderson localization in the instanton liquid model for QCD

We study the spectrum and eigenmodes of the QCD Dirac operator in a gauge background given by an instanton liquid model (ILM) at temperatures around the chiral phase transition. Generically we find the Dirac eigenvectors become more localized as the temperature is increased. At the chiral phase transition, both the low lying eigenmodes and the spectrum of the QCD Dirac operator undergo a transition to localization similar to the one observed in a disordered conductor. This suggests that Anderson localization is the fundamental mechanism driving the chiral phase transition. We also find an additional temperature dependent mobility edge (separating delocalized from localized eigenstates) in the bulk of the spectrum which moves toward lower eigenvalues as the temperature is increased. In both regions, the origin and the bulk, the transition to localization exhibits features of a 3D Anderson transition including multifractal eigenstates and spectral properties that are well described by critical statistics. Similar results are obtained in both the quenched and the unquenched case though the critical temperature in the unquenched case is lower. Finally we argue that our findings are not in principle restricted to the ILM approximation and may also be found in lattice simulations.     

The hydroazocine route to highly functionalized pyrrolizidines

Studies of the preparation of 1,8-dihydroazocines and transannular cyclization of hydroazocines to produce functionalized pyrrolizidines are described. Results are presented which demonstrate that unsymmetrically substituted acetylenes bearing at least one electron withdrawing groups undergo efficient cycloaddition to 1 - β - styryl - 1,2 - dihydropyridine producing in a regio-selective fashion 3,4 - disubstituted - 1,8 - dihydroazocines. The dihydroazocines generated in this manner can be converted to 1 - formyl - Δ^4,5 - epoxyazocines which undergo interesting rearrangement reactions to form pyrrolizidines when subjected to methoxide deformylation followed by acid treatment. In addition, 1,6,7,8 - tetrahydroazocines can be converted to pyrrolizidines under bromination conditions. The intriguing chemical process which occur under the conditions outlined above are described.     

New prodrugs derived from 6-aminodopamine and 4-aminophenol as candidates for melanocyte-directed enzyme prodrug therapy (MDEPT)

Two novel tyrosinase mediated drug delivery pathways have been investigated for the selective delivery of cytotoxic units to melanocytes from urea and thiourea prodrugs. The synthesis of these prodrugs is reported, as well as oximetry data that illustrate that the targets are substrates for tyrosinase. The stability of each of the prodrugs in (i) phosphate buffer and (ii) bovine serum is discussed, and the urea prodrugs are identified as lead candidates for further studies. Finally, HPLC studies and preliminary cytotoxicity studies in a melanotic and an amelanotic cell line, that illustrate the feasibility of the approach, are presented.     

Induction of decision trees using genetic programming for modelling ecotoxicity data: adaptive discretization of real-valued endpoints

Recent literature has demonstrated the applicability of genetic programming to induction of decision trees for modelling toxicity endpoints. Compared with other decision tree induction techniques that are based upon recursive partitioning employing greedy searches to choose the best splitting attribute and value at each node that will necessarily miss regions of the search space, the genetic programming based approach can overcome the problem. However, the method still requires the discretization of the often continuous-valued toxicity endpoints prior to the tree induction. A novel extension of this method, YAdapt, is introduced in this work which models the original continuous endpoint by adaptively finding suitable ranges to describe the endpoints during the tree induction process, removing the need for discretization prior to tree induction and allowing the ordinal nature of the endpoint to be taken into account in the models built.     

Reentrant orbital order and the true ground state of LaSr2Mn2O7

Contrary to conventional wisdom, our purified La 2-2x Sr 1+2x Mn2O7 crystals exhibit CE-type orbital and charge order as the low-temperature ground state for a hole doping level h=0.5. For small deviations from h=0.5, the high-temperature CE phase is replaced at low temperatures by an A-type antiferromagnet without coexistence. Larger deviations result in a lack of CE order at any temperature. Thus, small inhomogeneities in cation or oxygen composition could explain why others commonly see this reentrance with coexistence.     

Precise Control of Molecular Self-Diffusion in Isoreticular and Multivariate Metal-Organic Frameworks

Understanding the factors that affect self-diffusion in isoreticular and multivariate (MTV) MOFs is key to their application in drug delivery, separations, and heterogeneous catalysis. Here, we measure the apparent self-diffusion of solvents saturated within the pores of large single crystals of MOF-5, IRMOF-3 (amino-functionalized MOF-5), and 17 MTV-MOF-5/IRMOF-3 materials at various mole fractions. We find that the apparent self-diffusion coefficient of N,N-dimethylformamide (DMF) may be tuned linearly between the diffusion coefficients of MOF-5 and IRMOF-3 as a function of the linker mole fraction. We compare a series of solvents at saturation in MOF-5 and IRMOF-3 to elucidate the mechanism by which the linker amino groups tune molecular diffusion. The ratio of the self-diffusion coefficients for solvents in MOF-5 to those in IRMOF-3 is similar across all solvents tested, regardless of solvent polarity. We conclude that average pore aperture, not solvent-linker chemical interactions, is the primary factor responsible for the different diffusion dynamics upon introduction of an amino group to the linker.