Phosphorus-based p-tert-butylcalix[5]arene ligands

New calix[5]arene trivalent phosphorus derivatives have been synthesized which should be excellent ligands with which to study and control the interaction of a ligand atom with a metal. The larger cavity of the calix[5]arene (compared to calix[4]arene) provides a good balance between constraint and flexibility. Treatment of p-tert-butylcalix[5]arene with 2 equiv of either tris(dimethylamino)phosphine or dichlorophenylphosphine inserts two RP moieties into the calix[5]arene framework to give calix[5](PR)2(OH) (1, R = Me2N; 2, R = Ph). Further treatment of 1 with 4 equiv of HCl gives calix[5](PCl)2(OH) (3). Heating a solution of the monophosphorus compound calix[5](PNMe2)(OH)3 (4) releases dimethylamine to yield both monomeric calix[5](P)(OH)2 (6) and dimeric [calix[5](P)(OH)2](2) (7), the latter having a tubelike geometry. X-ray crystallographic studies confirm the structures and show that 1 and 2 have approximate cone conformations while 3 has an approximate 1,2-alternate conformation. The orientations of the phosphorus lone pairs and oxygen atoms in all derivatives provide a framework for both soft and hard ligand interactions within the calix[5]arene.     

Atomic/molecular layer deposited thin-film alloys of Ti-4,4'-oxydianiline hybrid-TiO(2) with tunable properties

By combining atomic layer deposition (ALD) and molecular layer deposition (MLD) thin-film techniques, the latter being a variant of the former in which organic precursors are used, it is possible to deposit thin films containing precisely controlled portions of inorganic and organic constituents. This in turn enables the adjustment of material properties by changing the number of ALD and MLD cycles applied during the deposition. In this work, the properties of such thin-film "alloys" prepared by varying the portions of Ti-4,4'-oxydianiline (Ti-ODA) inorganic-organic hybrid and TiO(2) in the structure were investigated. The films were deposited at 280 °C using TiCl(4) and water as precursors for TiO(2), and TiCl(4) and ODA for the Ti-ODA hybrid. The results demonstrate excellent tunability of the film properties such as degree of crystallinity, roughness, refractive index, and hardness depending on the relative number of TiO(2) and Ti-ODA cycles employed.     

Head-group-influenced mixed micellization of sodium deoxycholate with conventional hydrocarbon surfactants of identical hydrocarbon tails

Conductivity, viscosity, turbidity, and NMR measurements were performed over most of the mole fraction range for sodium deoxycholate (SDC) with hexadecyltrimethylammonium bromide (HTAB), hexadecylpyridinium bromide (HPyBr), and hexadecylpyridinium chloride (HPyCl). All studies demonstrate that the mixed-micelle formation is more favorable in SDC plus HTAB rather than SDC plus HPyBr or SDC plus HPyCl mixtures. The results showed that the bulky pyridinium head groups of HPyBr or HPyCl create steric incompatibility with rigid SDC monomers in the mixed state.     

Structure of poly(propyl ether imine) dendrimer from fully atomistic molecular dynamics simulation and by small angle x-ray scattering

We study the structure of carboxylic acid terminated neutral poly(propyl ether imine) (PETIM) dendrimer from generations 1-6 (G1-G6) in a good solvent (water) by fully atomistic molecular dynamics (MD) simulations. We determine as a function of generation the structural properties such as radius of gyration, shape tensor, asphericity, fractal dimension, monomer density distribution, and end-group distribution functions. The sizes obtained from the MD simulations have been validated by small angle x-ray scattering experiment on dendrimer of generations 2-4 (G2-G4). A good agreement between the experimental and theoretical value of radius of gyration has been observed. We find a linear increase in radius of gyration with the generation. In contrast, Rg scales as approximately Nx with the number of monomers. We find two distinct exponents depending on the generations, x=0.47 for G1-G3 and x=0.28 for G3-G6, which reveal their nonspace filling nature. In comparison with the amine terminated poly(amidoamine) (PAMAM) dendrimer, we find that Rg of Gth generation PETIM dendrimer is nearly equal to that of (G+1)th generation of PAMAM dendrimer as observed by Maiti et al. [Macromolecules 38, 979 (2005)]. We find substantial back folding of the outer subgenerations into the interior of the dendrimer. Due to their highly flexible nature of the repeating branch units, the shape of the PETIM dendrimer deviates significantly from the spherical shape and the molecules become more and more spherical as the generation increases. The interior of the dendrimer is quite open with internal cavities available for accommodating guest molecules, suggesting the use of PETIM dendrimer for guest-host applications. We also give a quantitative measure of the number of water molecules present inside the dendrimer.     

Thermodynamics of water entry in hydrophobic channels of carbon nanotubes

Experiments and computer simulations demonstrate that water spontaneously fills the hydrophobic cavity of a carbon nanotube. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed two phase thermodynamics method to compute translational and rotational entropies of confined water molecules inside single-walled carbon nanotubes and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with that of bulk water shows significant shifts in the positions of the spectral peaks that are directly related to the tube radius.     

Anion recognition by bisimidazolium and bisbenzimidazolium cholapods

Bile acid-based acyclic receptors bearing two imidazole and benzimidazole moieties have been synthesized. Anion binding studies using ¹H NMR revealed that imidazolium receptor exhibits high selectivity for chloride ion while benzimidazolium receptor showed selectivity for Y-shaped acetate ion through hydrogen bond interactions involving imidazolium C-2 and acetyl methylene hydrogens.     

Quantitative in vitro demonstration of two-photon photodynamic therapy using photofrin and visudyne

Photodynamic therapy (PDT), the combined action of a photosensitizer and light to produce a cytotoxic effect, is an approved therapy for a number of diseases. At present, clinical PDT treatments involve one-photon excitation of the photosensitizer. A major limitation is that damage may be caused to healthy tissues that have absorbed the drug and lie in the beam path. Two-photon excitation may minimize this collateral damage, as the probability of absorption increases with the square of the light intensity, enabling spatial confinement of the photosensitizer activation. A potential application is the treatment of the wet-form of age-related macular degeneration, the foremost cause of central vision loss in the elderly. Herein, the commercial photosensitizers Visudyne and Photofrin are used to demonstrate quantitative in vitro two-photon PDT. A uniform layer of endothelial cells (YPEN-1) was irradiated with a Ti:sapphire laser (300 fs, 865 nm, 90 MHz) using a confocal scanning microscope. Quantification of the two-photon PDT effect was achieved using the permeability stain Hoechst 33258 and a SYTOX Orange viability stain. Visudyne was found to be around seven times more effective as a two-photon photosensitizer than Photofrin under the conditions used, consistent with its higher two-photon absorption cross-section. We also demonstrate for the first time the quadratic intensity dependence of cellular two-photon PDT. This simple in vitro method for quantifying the efficacy of photosensitizers for two-photon excited PDT will be valuable to test specifically designed two-photon photosensitizers before proceeding to in vivo studies in preclinical animal models.     

Highly efficient hydrazination of conjugated nitroalkenes via imidazole or DMAP mediated Morita-Baylis-Hillman reaction

Novel alpha-hydrazino-alpha,beta-unsaturated nitroalkenes, which exhibit dynamic phenomenon on the NMR time scale, were synthesized in excellent yields via imidazole or DMAP mediated Morita-Baylis-Hillman (MBH) type reaction of nitroalkenes with azodicarboxylates.     

Systematic investigation of hexadecapole collectivity in even-even nuclei

Energies of the first 2⁺, 3⁻ and 4⁺ states of even-even nuclei are plotted against proton and neutron number. Using this systematics, shell effects and the corresponding quadrupole and hexadecapole collectivity and deformation effects are compared and contrasted. Also, the correspondingB(E2),B(E3) andB(E4) values are plotted against neutron number and their very different systematics compared. Among the new results are the presence of hexadecapole collectivity at the 82 proton and neutron closed shells and the presence of the maximum values ofB(E4) at neutron numbers 10, 90–92 and 140–146. Finally, the systematics of the hexadecapole (K=4⁺) vibrations is compared with that of the quadrupole (K=2⁺) gamma vibrations in the quadrupole deformed rare earth region. This research has been supported by the National Sciences and Engineering Research Council of Canada at McMaster University and by the Department of Atomic Energy, Government of India, at Banaras Hindu University.