Minimal technicolor on the lattice

We present results from a lattice study of SU(2) gauge theory with 2 flavors of Dirac fermions in adjoint representation. This is a candidate for a minimal (simplest) walking technicolor theory, and has been predicted to possess either an IR fixed point (where the physics becomes conformal) or a coupling which evolves very slowly, so-called walking coupling. In this initial part of the study we investigate the lattice phase diagram and the excitation spectrum of the theory.     

The effect of the properties of porous media on light scattering

Numerical wave-optical methods for light scattering simulations are used to asses the effect of porosity on the optical properties of paper coating. Both constant porosity profile and media with porosity contrast between layers at different depths are considered. We can predict optimal paper coating structures for both brightness and gloss from the results.     

Solvent exchange in thermally stable resorcinarene nanotubes

The assembly of C-methyl resorcinarene into a tubular supramolecular solid-state structure, its thermal stability, and its hosting properties are reported. Careful control of the crystallisation conditions of C-methyl resorcinarene and 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane (1,4-dimethyl DABCO) dibromide leads to a formation of two crystallographically different, but structurally very similar, solid-state nanotube structures. These structures undergo a remarkable variety of supramolecular interactions, which lead to the formation of 0.5 nm diameter nonpolar tubes through the crystal lattice. The formation of these tubes is templated by suitably sized small alcohols, namely, n-propanol, 2-propanol, or n-butanol. The self-assembly involves close pi...pi interactions between the adjacent resorcinarenes, and C--H...pi and cation...pi interactions between the resorcinarenes and the guest 1,4-dimethyl DABCO dications. The crystals of these supramolecular tube structures are thermally very stable and the included solvent alcohol can be removed from the tubes without breaking the single-crystalline structure of the assembly. After removal of the solvent molecules the tubes can be filled with other small, less polar solvent molecules such as dichloromethane.     

Substituent cross-interaction effects on the electronic character of the C=N bridging group in substituted benzylidene anilines--models for molecular cores of mesogenic compounds. A 13C NMR study and comparison with theoretical results

13C NMR chemical shifts delta(C)(C=N) were measured in CDCl3 for a wide set of mesogenic molecule model compounds, viz. the substituted benzylidene anilines p-X-C6H4CH=NC6H4-p-Y (X = NO2, CN, CF3, F, Cl, H, Me, MeO, or NMe2; Y = NO2, CN, F, Cl, H, Me, MeO, or NMe2). The substituent dependence of delta(C)(C=N) was used as a tool to study electronic substituent effects on the azomethine unit. The benzylidene substituents X have a reverse effect on delta(C)(C=N): electron-withdrawing substituents cause shielding, while electron-donating ones behave oppositely, the inductive effects clearly predominating over the resonance effects. In contrast, the aniline substituents Y exert normal effects: electron-withdrawing substituents cause deshielding, while electron-donating ones cause shielding of the C=N carbon, the strengths of the inductive and resonance effects being closely similar. Additionally, the presence of a specific cross-interaction between X and Y could be verified. The electronic effects of the neighboring aromatic ring substituents systematically modify the sensitivity of the C=N group to the electronic effects of the benzylidene or aniline ring substituents. Electron-withdrawing substituents on the aniline ring decrease the sensitivity of delta(C)(C=N) to the substitution on the benzylidine ring, while electron-donating substituents have the opposite effect. In contrast, electron-withdrawing substituents on the benzylidene ring increase the sensitivity of delta(C)(C=N) to the substituent on the aniline ring, while electron-donating substituents act in the opposite way. These results can be rationalized in terms of the substituent-sensitive balance of the electron delocalization (mesomeric effects). The present NMR characteristics are discussed as regards the computational literature data. Valuable information has been obtained on the effects of the substituents on the molecular core of the mesogenic model compounds.     

Mononucleotide gas-phase proton affinities as determined by the kinetic method

The goal of this work is to determine the proton affinities of (deoxy)nucleoside 5'- and 3'-monophosphates (mononucleotides) using the kinetic method with fast atom bombardment mass spectrometry. The proton affinities of the (deoxy)nucleoside 5'- and 3'-monophosphates yielded the following trend: (deoxy)adenosine monophosphates > (deoxy)guanosine monophosphates > (deoxy)cytidine monophosphates > deoxythymidine/uridine monophosphates. In all cases the proton affinity decreases or remains the same with the addition of the phosphate group from those values reported for nucleosides. The proton affinity is dependent on the location of the phosphate backbone (5'-vs. 3'-phosphates): the 3'-monophosphates have lower proton affinities than the 5'-monophosphates except for the thymidine/uridine monophosphates where the trend is reversed. Molecular modeling was utilized to determine if multiple protonation sites and intramolecular hydrogen bond formation would influence the proton affinity measurements. Semiempirical calculations of the proton affinities at various locations on each mononucleotide were performed and compared to the experimental results. The possible influence of intramolecular hydrogen bonding between the nucleobases and the phosphate group on the measured and calculated proton affinities is discussed.     

One-pot synthesis of [2+2]-helicate-like macrocycle and 2+4-μ4-oxo tetranuclear open frame complexes: Chiroptical properties and asymmetric oxidative coupling of 2-naphthols

Synthesis of binuclear Cu(II) terminally closed [ 2+2 ]- double-stranded helicate-like macrocycles 1, 1′ , 1″ , 2 , 2′ , 2″ and 2+4- μ₄-oxo tetranuclear open frame complexes 3 , 3′ , 3″ , 4 , 4′ , 4″ are established. Adapting one-pot self-assembly technique from simple three components systems: 1,1′-binaphthyl-2,2′-diamine, 4-methyl-2,6-diformyl phenol and cupric salts, the helicate-like [ 2+2 ]- macrocyclic complexes 1–1″, 2–2″ and 2+4- μ₄-oxo tetranuclear complexes 3–3″ , 4–4″ were obtained by appropriately altering the reaction condition such as temperature and subcomponent ratio. Density Functional Theory (DFT) calculations were carried out for understanding the structural geometries, intermediates involved in the diverse formation of [ 2+2 ] and 2+4 frameworks. The single crystal X-ray structures obtained for 1′ , 2 and 3 confirms the self-assembly process in line with DFT. This detailed analysis tempted us to derive a plausible mechanism for this long standing challenge in the synthesis of such macrocycles using 1,1′-binaphthyl-2,2′-diamine (BNDA) and aromatic aldehyde. The chiroptical properties of enantiopure complexes and their catalytic applications in asymmetric oxidative coupling of 2-naphthol to chiral 1,1’-Bi-2-naphthol (BINOL) achieved in good yield and ee were discussed.     

Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution

The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The ¹H NMR dimerization constants for the monomer–dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls. Furthermore, trends within the different groups of compounds can be observed. For example, the dimer is destabilized by internal double or triple bonds due to π–π repulsion. A strong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerization constants within the series of n-alkyls, n-Ω-alkenyls or n-Ω-alkynyls. This corresponds to the interaction of the parent hydrocarbons, as documented by an even/odd melting point alternation.     

Iodine(I) and Silver(I) Complexes of Benzoimidazole and Pyridylcarbazole Derivatives

The synthesis of iodine(I) complexes with either benzoimidazole or carbazole-derived sp² N-containing Lewis bases is described, as well as their corresponding silver(I) complexes. The addition of elemental iodine to the linear two-coordinate Ag(I) complexes produces iodine(I) complexes with a three-center four-electron (3c–4e) [N−I−N]⁺ bond. The ¹H and ¹H-¹⁵N HMBC NMR studies unambiguously confirm the formation of the complexes in all cases via the [N−Ag−N]⁺→[N−I−N]⁺ cation exchange, with the ¹⁵N NMR chemical shift change between 94 to 111 ppm when compared to the free ligand. The single crystal X-ray crystallographic studies on eight I⁺ complexes revealed highly symmetrical [N−I−N]⁺ bonds with I−N bond distances of 2.21–2.26 Å and N−I−N angles of 177–180°, whilst some of the corresponding Ag⁺ complexes showed a clear deviation from linearity with N−Ag−N angles of ca. 150° and Ag−N bond distances of 2.09–2.18 Å.     

Iodine Clathrated: A Solid-State Analogue of the Iodine–Starch Complex

Co-crystallizing iodine with a simple dicationic salt (1,8-diammoniumoctane chloride) results in the clathration of the iodine (I₂) molecules inside trigonal and hexagonal helical channels of the crystal lattice with 72 wt % overall I₂ loading. The I₂ inside the bigger trigonal channel forms a I−I⋅⋅⋅I−I⋅⋅⋅I−I halogen-bonded infinite helical chain, while the I₂ in the smaller hexagonal channel is disordered. In both channels the I₂ interaction with the channel wall happens through I−I⋅⋅⋅Cl⁻ halogen bonds. The helical channels in the crystal lattice are constructed via the strong charge-assisted H₂N⁺H⋅⋅⋅Cl⁻ hydrogen bonds between the dications and the chloride anions. The structure shows a marked similarity with the well-known starch–I₂ system, and thus may provide insight for the yet unresolved structure of the I₂ in the helical starch channel.     

Model studies on a diastereoselective synthesis of the C(33)-C(37) fragment of Amphotericin B

A new, short and highly diastereoselective synthetic route aiming at the C(33)-C(37) fragment of Amphotericin B has been developed. Studies with a model aldehyde (benzaldehyde) have given very promising results: the desired stereochemistry of all four stereocenters of the target molecule has been achieved with high diastereoselection. The stereochemistry of three key intermediates and the target segment has been confirmed by X-ray crystallography.