Novel laser-induced luminescence resulting from benzophenone/O-propylated p-tert-butylcalix[4]arene complexes. A diffuse reflectance study

Laser-induced room temperature luminescence of air-equilibrated benzophenone/O-propylated p-tert-butylcalix[ 4] arene solid powdered samples revealed the existence of a novel emission, in contrast with benzophenone/p-tertbutylcalix[ 4] arene complexes, where only benzophenone emits. This novel emission was identified as phosphorescence of 1-phenyl-1,2-propanedione, which is formed as the result of an hydrogen atom abstraction reaction of the triplet excited benzophenone from the propoxy substituents of the calixarene. Room temperature phosphorescence was obtained in air-equilibrated samples in all propylated hosts. The decay times of the benzophenone emission vary greatly with the degree of propylation, the shortest lifetimes being obtained in the tri- and tetrapropylated calixarenes. Triplet - triplet absorption of benzophenone was detected in all cases, and is the predominant absorption in the p-tert-butylcalix[ 4] arene case, where an endo-calix complex is formed. Benzophenone ketyl radical formation occurs with the O-propylated p-tert-butylcalix[ 4] arenes hosts, suggesting a different type of host/guest molecular arrangement. Diffuse reflectance laser. ash photolysis and gas chromatography - mass spectrometry techniques provided complementary information, the former about transient species and the latter regarding the final products formed after light absorption. Product analysis and identification clearly show that the two main degradation photoproducts following laser excitation in the propylated substrates are 1-phenyl-1,2- propanedione and 2- hydroxybenzophenone, although several other minor photodegradation products were identified. A detailed mechanistic analysis is proposed. While the solution photochemistry of benzophenone is dominated by the hydrogen abstraction reaction from suitable hydrogen donors, in these solid powdered samples, the alpha-cleavage reaction also plays an important role. This finding occurs even with one single laser pulse which lasts only a few nanoseconds, and is apparently related to the fact that scattered radiation exists, due to multiple internal reflections possibly trapping light within non-absorbing microcrystals in the sample, and is detected until at least 20 mus after the laser pulse. This could explain how photoproducts thus formed could also be excited with only one laser pulse.

Special issue: Selected papers from the sixth IFIP 2.6 working conference on visual database systems: Guest editors' introduction

While multimedia data, image data in particular, is an integral part of most websites and web documents, our quest for information so far is still restricted to text based search. To explore the World Wide Web more effectively, especially its rich repository of truly multimedia information, we are facing a number of challenging problems. Firstly, we face the ambiguous and highly subjective nature of defining image semantics and similarity. Secondly, multimedia data could come from highly diversified sources, as a result of automatic image capturing and generation processes. Finally, multimedia information exists in decentralised sources over the Web, making it difficult to use conventional content-based image retrieval (CBIR) techniques for effective and efficient search. In this special issue, we present a collection of five papers on visual and multimedia information management and retrieval topics, addressing some aspects of these challenges. These papers have been selected from the conference proceedings (Kluwer Academic Publishers, ISBN: 1-4020- 7060-8) of the Sixth IFIP 2.6 Working Conference on Visual Database Systems (VDB6), held in Brisbane, Australia, on 29–31 May 2002.

A comparative study of the intercellular connections between parasite/host in two Gelidiocolax/Gelidium algal parasitic systems

Comparative ultrastructural study of the intercellular connections between parasite and host cells in two algal parasitic systems, Gelidiocolax christianae Feldmann and Feldmann/Ge/iV/ium spathulatum (Kutz.) Bornet and Gelidiocolax deformans Seoane Camba/Gelidium sesquipedale (Clem.) Thur, shows quantitative and structural differences. The number of free conjunctor cells (before fusión with the adjacent host cells) differs between the two parasitic systems and is inversely related to the number of complex pit connections. The fibrillar cell wall structure of the conjunctor cells and the lamellar structure of the complex pit plugs in the two systems are also different A hypothesis concerning the different activity of the conjuntor cell wall in the two parasitic systems, related with the different structural appearance, is proposed.

Nonlinear Optical Properties of Organic and Polymer Systems

Present thesis has discussed the design and synthesis of polymers suitable for nonlinear optics. Most of the molecules that were studied have shown good nonlinear optical activity. The second order nonlinear optical activity of the polymers was measured experimentally by Kurtz and Perry powder technique. The thesis comprises of eight chapters.The theory of NLO phenomenon and a review about the various nonlinear optical polymers has been discussed in chapter 1. The review has provided a survey of NLO active polymeric materials with a general introduction, which included the principles and the origin of nonlinear optics, and has given emphasis to polymeric materials for nonlinear optics, including guest-host systems, side chain polymers, main chain polymers, crosslinked polymers, chiral polymers etc.Chapter 2 has discussed the stability of the metal incorporated tetrapyrrole molecules, porphyrin, chlorin and bacteriochlorin.Chapter 3 has provided the NLO properties of certain organic molecules by computational tools. The chapter is divided into four parts. The first part has described the nonlinear optical properties of chromophore (D-n-A) and bichromophore (D-n-A-A-n-D) systems, which were separated by methylene spacer, by making use of DPT and semiempirical calculations.Chapter 4: A series of polyurethanes was prepared from cardanol, a renewable resource and a waste of the cashew industry by previously designed bifunctional and multifunctional polymers using quantum theoretical approach.Chapter 5: A series of chiral polyurethanes with main chain bis azo diol groups in the polymer backbone was designed and NLO activity was predicted by ZlNDO/ CV methods.In Chapter 7, polyurethanes were first designed by computational methods and the NLO properties were predicted by correction vector method. The designed bifunctional and multifunctional polyurethanes were synthesized by varying the chiral-achiral diol compositions

Incorporation of a sodium ion guest in the host of copper(II)-Schiff-base complexes: Structural characterization and magnetic study

Three copper(II) complexes, [CuL1], [CuL2] and [CuL3] where L-1, L-2 and L-3 are the tetradentate di-Schiff-base ligands prepared by the condensation of acetylacetone and appropriate diamines (e.g. 1,2-diaminoethane, 1,2-diaminopropane and 1,3-diaminopropane, respectively) in 2:1 ratios, have been prepared. These complexes act as host molecules and include a guest sodium ion by coordinating through the oxygen atoms to result in corresponding new trinuclear complexes, [(CuL1)(2)Na(ClO4)(H2O)][CuL1], [(CuL2)(2)Na(ClO4)(H2O)] (2) and [(CuL3)(2)Na(ClO4)(H2O)] (3) when crystallized from methanol solution containing sodium perchlorate. All three complexes have been characterized by single crystal X-ray crystallography. In all the complexes, the sodium cation has a six-coordinate distorted octahedral environment being bonded to four oxygen atoms from two Schiff-base complexes of Cu(II) in addition to a perchlorate anion and a water molecule. The copper atoms are four coordinate in a square planar environment being bonded to two oxygen atoms and two nitrogen atoms of the Schiff-base ligand. The variable temperature susceptibilities for complexes 1-3 were measured over the range 2-300 K. The isotropic Hamiltonian, H = g(1)beta HS1 + g(2)beta HS2 + J(12)S(1)S(2) + g(3)beta HS3 for complex 1 and H = g(1)beta HS1 + g2 beta HS2 +J(12)S(1)S(2) for complexes 2 and 3 has been used to interpret the magnetic data. The best fit parameters obtained are: g(1) = g(2) = 2.07(0), J = - 1.09(1) cm(-1) for complex 1, g(1) = g(2) = 2.06(0), J = -0.55(1) cm(-1) for complex 2 and g1 = g2 = 2.07(0).J = -0.80(1) cm(-1) for 3. Electrochemical studies displayed an irreversible Cu(II)/Cu(I) one-electron reduction process. (C) 2008 Elsevier Ltd. All rights reserved.

Top-down systems biology modeling of host metabotype-microbiome associations in obese rodents

Covariation in the structural composition of the gut microbiome and the spectroscopically derived metabolic phenotype (metabotype) of a rodent model for obesity were investigated using a range of multivariate statistical tools. Urine and plasma samples from three strains of 10-week-old male Zucker rats (obese (fa/fa, n = 8), lean (fal-, n = 8) and lean (-/-, n = 8)) were characterized via high-resolution H-1 NMR spectroscopy, and in parallel, the fecal microbial composition was investigated using fluorescence in situ hydridization (FISH) and denaturing gradient gel electrophoresis (DGGE) methods. All three Zucker strains had different relative abundances of the dominant members of their intestinal microbiota (FISH), with the novel observation of a Halomonas and a Sphingomonas species being present in the (fa/fa) obese strain on the basis of DGGE data. The two functionally and phenotypically normal Zucker strains (fal- and -/-) were readily distinguished from the (fa/fa) obese rats on the basis of their metabotypes with relatively lower urinary hippurate and creatinine, relatively higher levels of urinary isoleucine, leucine and acetate and higher plasma LDL and VLDL levels typifying the (fa/fa) obese strain. Collectively, these data suggest a conditional host genetic involvement in selection of the microbial species in each host strain, and that both lean and obese animals could have specific metabolic phenotypes that are linked to their individual microbiomes.

Study of the nonlinear optical properties of a crosslinkable chromophore for use in guest host polymer films

A guest/host material system in which the guest molecule is a functionalized, optically nonlinear, chromophore is described. A verification of the crosslinking process, an assessment of the nonlinear properties of the chromophore, using Solvatochromic methods, and an investigation of the electric field induced molecular orientation using second-harmonic generation are included.

Pressure Perturbation Calorimetry and Guest-Host Chemistry of NDMG and N-MAP with p-Sulfonatocalix[6]arene

The aim of this project is to provide an explanation for recently obtained binding constants for two similar guest molecules, NDMG and N-MAP, with a p-sulfonatocalix[6]arene host in ammonium acetate buffer. This work was done primarily using pressure perturbation calorimetry, which is a technique that determines the coefficient of thermal expansion, α, which is in turn related to the solute molecule's effect on the order of the surrounding water molecules. A series of experiments were designed to test the effects of suspected confounding variables on the validity of PPC data. PPC was then used to study NDMG and N-MAP in ammonium acetate buffer. NDMG exhibited a minimum in α as function of temperature, while N-MAP did not. This difference was theorized to be due to the formation of an intramolecular hydrogen bond in monocationic NDMG that would lower the heat capacity of the molecule and better distribute the molecule's charge. Computational work and nuclear magnetic resonance spectroscopy confirmed that monocationic, ring-closed NDMG has less concentrated charge and more constrained motion than monocationic, ring-open NDMG. This evidence supports the theory that monocationic NDMG forms an intramolecular hydrogen bond and that this may be responsible for the minimum in α. This difference may explain the differences in binding constants between NDMG and N-MAP.

Determination of photoinduced and intrinsic birefringences in PMMA/DR13 guest-host film

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation of 3D cell culture systems for host-pathogen interaction studies

Traditional cell culture models have limitations in extrapolating functional mechanisms that underlie strategies of microbial virulence. Indeed during the infection the pathogens adapt to different tissue-specific environmental factors. The development of in vitro models resembling human tissue physiology might allow the replacement of inaccurate or aberrant animal models. Three-dimensional (3D) cell culture systems are more reliable and more predictive models that can be used for the meaningful dissection of host–pathogen interactions. The lung and gut mucosae often represent the first site of exposure to pathogens and provide a physical barrier against their entry. Within this context, the tracheobronchial and small intestine tract were modelled by tissue engineering approach. The main work was focused on the development and the extensive characterization of a human organotypic airway model, based on a mechanically supported co-culture of normal primary cells. The regained morphological features, the retrieved environmental factors and the presence of specific epithelial subsets resembled the native tissue organization. In addition, the respiratory model enabled the modular insertion of interesting cell types, such as innate immune cells or multipotent stromal cells, showing a functional ability to release pertinent cytokines differentially. Furthermore this model responded imitating known events occurring during the infection by Non-typeable H. influenzae. Epithelial organoid models, mimicking the small intestine tract, were used for a different explorative analysis of tissue-toxicity. Further experiments led to detection of a cell population targeted by C. difficile Toxin A and suggested a role in the impairment of the epithelial homeostasis by the bacterial virulence machinery. The described cell-centered strategy can afford critical insights in the evaluation of the host defence and pathogenic mechanisms. The application of these two models may provide an informing step that more coherently defines relevant molecular interactions happening during the infection.

Effect of terbium(III) on the binding of aromatic guests with sodium taurocholate aggregates

The effect of binding Tb(3+) to sodium taurocholate aggregates containing polyaromatic hydrocarbon guests was examined using pyrene and 1-ethylnaphthalene as guests that bind to the primary aggregate, and 1-naphthyl-1-ethanol as a secondary aggregate guest. Time-resolved fluorescence quenching studies were used to study the binding site properties, while laser flash photolysis quenching studies provided information on the dynamics of the guest-aggregate system. Both the primary and secondary aggregate binding sites became more compact in the presence of bound Tb(3+), while only the primary aggregate became more accessible to anionic molecules. The binding dynamics for the guest-primary aggregate system became faster when Tb(3+) was bound to the aggregate. In contrast, for the guest-secondary aggregate the presence of Tb(3+) resulted in a small decrease in the dissociation rate constant. The influence of bound Tb(3+) on the primary and secondary bile salt aggregates is significantly different, which affects how these aggregates can be used as supramolecular host systems to modify guest reactivity.