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Supramolecular Organization (supramolecular + organization)
Selected AbstractsTuning and Transcription of the Supramolecular Organization of a Fluorescent Silsesquioxane Precursor into Silica-Based Materials through Direct Photochemical Hydrolysis,Polycondensation and MicropatterningADVANCED FUNCTIONAL MATERIALS, Issue 3 2009Xavier Sallenave Abstract A new fluorescent silsequioxane precursor with tuned optical properties and controlled aggregation properties is designed. The two cyclohexyl moieties introduced in the molecular structure allow the formation of very good quality films. The J-aggregated structure is transcribed into the solid by photoacid-catalyzed hydrolysis,polycondensation. Aggregation of the chromophores is reduced and highly fluorescent materials are obtained. The photoacid generator lies on the surface of the homogeneous layer of the sol,gel precursor. This phase separation presents several advantages, including UV protection of the chromophore and easy removal of the PAG. The first example of chemical amplification in the photolithography of the conjugated silsesquioxane precursor is demonstrated. As hydrolysis,polycondensation could be achieved in a controlled way by UV exposure, chemically amplified photolithography is achieved by irradiating a composite film (,110,nm thick) on silicon wafer by using a copper TEM grid as shadow mask. The pattern is produced uniformly on a miscroscopic scale of 3,mm, the photopatterned pixels remaining highly fluorescent. The sizes of the photolithographed pixels correspond to the sizes of the rectangular holes of the 300,×,75 mesh grid (hole: 63,<$>,<$>m,×,204,<$>,<$>m). [source] Energy Collection, Transport, and Trapping by a Supramolecular Organization of Dyes in Hexagonal Zeolite Nanocrystals,ADVANCED FUNCTIONAL MATERIALS, Issue 2 2006C. Minkowski Abstract The incorporation of guest molecules into the cavities of molecular sieves leads to a large variety of highly interesting materials. Zeolite,L,an aluminosilicate with one-dimensional channels of open diameter 7.1,Å,is a very versatile material for building highly organized host,guest systems. We present materials where organic dye molecules have been incorporated into the channels of zeolite,L by means of diffusion, to build artificial photonic antenna systems. The channel entrance can be plugged by adding closure molecules that then connect the guest molecules inside with materials or molecules outside of the zeolite channels, since they can act as extensions of the interior of the zeolite crystal. The photophysical processes taking place in such dye-loaded zeolite,L antennae can be studied either on single-micrometer- or submicrometer-sized crystals or on crystals dispersed in a solvent or coated as thin layers on a support. The energy-transfer process occurring is of the Förster-type, and its transfer rate can be tuned by separating the donor dyes and the acceptor dyes locally by varying amounts of spacer molecules. The distribution of the dye molecules and empty sites within a zeolite crystal has been modeled by means of a Monte Carlo simulation. The Förster energy migration and transfer steps are described as a random walk. [source] Epoxidation of Polyunsaturated Fatty Acid Double Bonds by Dioxirane Reagent: Regioselectivity and Lipid Supramolecular OrganizationHELVETICA CHIMICA ACTA, Issue 10 2006Stanislav Abstract The use of dimethyldioxirane (DMD) as the epoxidizing agent for polyunsaturated fatty acids was investigated. With fatty acid methyl esters, this is a convenient method for avoiding acidic conditions, using different solvents, and simplifying the isolation procedures, with less contamination due to by-products. The reagent was also tested with free fatty acids in water. In this case, the supramolecular organization of fatty acids influenced the reaction outcome, and the epoxidation showed interesting regioselective features. The CC bonds closest to the aqueous-micelle interface is the most favored for the interaction with dimethyldioxirane. The preferential epoxidation of linoleic acid (=,(9Z,12Z)-octadeca-9,12-dienoic acid) to the 9,10-monoepoxy derivative was achieved, with a high yield and 65% regioselectivity. In case of arachidonic acid (=,(5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) micelles, the regioselective outcome with formation of the four possible monoepoxy isomers was studied under different conditions. It resulted to be a convenient synthesis of ,cis -5,6-epoxyeicosatrienoic acid' (=,3-[(2Z,5Z,8Z)-tetradeca-2,5,8-trienyl]oxiran-2-butanoic acid), whereas in reverse micelles, epoxidation mostly gave ,cis -14,15-epoxyeicosatrienoic acid (=,(5Z,8Z,11Z)-13-(3-pentyloxiran-2-yl)trideca-5,8,11-trienoic acid). [source] Blue-Gap Poly(p -phenylene vinylene)s with Fluorinated Double Bonds: Interplay Between Supramolecular Organization and Optical Properties in Thin FilmsADVANCED MATERIALS, Issue 10-11 2009Maria Losurdo Blue-light-emitting poly(p-phenylene vinylene)s with fluorinated vinylene units are presented. It is demonstrated that self-aggregation governs the strength and polarization of the absorption spectra of thin films of these polymers. This indicates that self-assembly of the polymer chains in the films provides a means of tuning the electronic and optical properties of the , -conjugated systems. [source] Supramolecular Organization of ssDNA-Templated ,-Conjugated Oligomers via Hydrogen BondingADVANCED MATERIALS, Issue 10-11 2009Mathieu Surin The templated self-assembly of water-soluble ,-conjugated molecules bearing a diaminotriazine moiety H-bonding to a single-strand oligothymine template leads to defined structures. We study these assemblies with molecular modeling, circular dichroism spectroscopy, and scanning probe microscopy, to get a better understanding of the factors governing the supramolecular organization and structural order. [source] Solid-State Supramolecular Organization of Polythiophene Chains Containing Thienothiophene UnitsADVANCED MATERIALS, Issue 10-11 2009Patrick Brocorens Abstract We use molecular modeling and the simulation of X-ray diffraction patterns to determine the molecular packing of a thiophene-based polymer showing exceptionally high field-effect mobilities (up to 1,cm2,V,1,s,1). We focus on the organization of the polymer chains in lamellae and the orientation of these crystalline domains with respect to the substrate in thin films. The analysis is supported by XRD and NEXAFS experiments and is complemented by calculating intermolecular transfer integrals, which govern the charge mobility. [source] ChemInform Abstract: Supramolecular Organization of Fullerenes by Quadruple Hydrogen Bonding.CHEMINFORM, Issue 18 2001Minze T. Rispens Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Epoxidation of Polyunsaturated Fatty Acid Double Bonds by Dioxirane Reagent: Regioselectivity and Lipid Supramolecular OrganizationHELVETICA CHIMICA ACTA, Issue 10 2006Stanislav Abstract The use of dimethyldioxirane (DMD) as the epoxidizing agent for polyunsaturated fatty acids was investigated. With fatty acid methyl esters, this is a convenient method for avoiding acidic conditions, using different solvents, and simplifying the isolation procedures, with less contamination due to by-products. The reagent was also tested with free fatty acids in water. In this case, the supramolecular organization of fatty acids influenced the reaction outcome, and the epoxidation showed interesting regioselective features. The CC bonds closest to the aqueous-micelle interface is the most favored for the interaction with dimethyldioxirane. The preferential epoxidation of linoleic acid (=,(9Z,12Z)-octadeca-9,12-dienoic acid) to the 9,10-monoepoxy derivative was achieved, with a high yield and 65% regioselectivity. In case of arachidonic acid (=,(5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) micelles, the regioselective outcome with formation of the four possible monoepoxy isomers was studied under different conditions. It resulted to be a convenient synthesis of ,cis -5,6-epoxyeicosatrienoic acid' (=,3-[(2Z,5Z,8Z)-tetradeca-2,5,8-trienyl]oxiran-2-butanoic acid), whereas in reverse micelles, epoxidation mostly gave ,cis -14,15-epoxyeicosatrienoic acid (=,(5Z,8Z,11Z)-13-(3-pentyloxiran-2-yl)trideca-5,8,11-trienoic acid). [source] Molecular pathology of NEU1 gene in sialidosis,HUMAN MUTATION, Issue 5 2003Volkan Seyrantepe Abstract Lysosomal sialidase (EC 3.2.1.18) has a dual physiological function; it participates in intralysosomal catabolism of sialylated glycoconjugates and is involved in cellular immune response. Mutations in the sialidase gene NEU1, located on chromosome 6p21.3, result in autosomal recessive disorder, sialidosis, which is characterized by the progressive lysosomal storage of sialylated glycopeptides and oligosaccharides. Sialidosis type I is a milder, late-onset, normosomatic form of the disorder. Type I patients develop visual defects, myoclonus syndrome, cherry-red macular spots, ataxia, hyperreflexia, and seizures. The severe early-onset form, sialidosis type II, is also associated with dysostosis multiplex, Hurler-like phenotype, mental retardation, and hepatosplenomegaly. We summarize information on the 34 unique mutations determined so far in the sialidase gene, including four novel missense and one novel nonsense mutations found in two Czech and two French sialidosis patients. The analysis of sialidase mutations in sialidosis revealed considerable molecular heterogeneity, reflecting the diversity of clinical phenotypes that make molecular diagnosis difficult. The majority of sialidosis patients have had missense mutations, many of which have been expressed; their effects on activity, stability, intracellular localization, and supramolecular organization of sialidase were studied. A structural model of sialidase allowed us to localize mutations in the sialidase molecule and to predict their impact on the tertiary structure and biochemical properties of the enzyme. Hum Mutat 22:343,352, 2003. © 2003 Wiley-Liss, Inc. [source] Atomic-Level Studies of Molecular Self-Assembly on Metallic SurfacesADVANCED MATERIALS, Issue 10-11 2009Giulia Tomba Abstract Shrinking devices to the nanoscale, while still maintaining accurate control on their structure and functionality is one of the major technological challenges of our era. The use of purposely directed self-assembly processes provides a smart alternative to the troublesome manipulation and positioning of nanometer-sized objects piece by piece. Here, we report on a series of recent works where the in-depth study of appropriately chosen model systems addresses the two key-points in self-assembly: building blocks selection and control of bonding. We focus in particular on hydrogen bonding because of the stability, precision and yet flexibility of nanostructures based on this interaction. Complementing experimental information with advanced atomistic modeling techniques based on quantum formalisms is a key feature of most investigations. We thus highlight the role of theoretical modeling while we follow the progression in the use of more and more complex molecular building blocks, or "tectons". In particular, we will see that the use of three-dimensional, flexible tectons promises to be a powerful way to achieve highly sophisticated functional nanostructures. However, the increasing complexity of the assembly units used makes it generally more difficult to control the supramolecular organization and predict the assembling mechanisms. This creates a case for developing novel analysis methods and ever more advanced modeling techniques. [source] Polyphenylene-Based Materials: Control of the Electronic Function by Molecular and Supramolecular ComplexityADVANCED MATERIALS, Issue 10-11 2009Bruno Schmaltz Abstract Organic electronics is one of the hottest and most exciting research topics today. However, its performance still lags behind that of inorganic-based electronics. This Progress Report demonstrates that by controlling the complexity of organic molecules at the molecular and at the supramolecular level as well as by choosing suitable processing techniques, the desired function for applications in electronics can be achieved. Our main focus is on polyphenylene-based nanomaterials, versatile organic molecules that allow access to novel intricate materials. We emphasize the molecular complexity as well as the supramolecular organization and the interfacing of novel organic materials as key guidelines. [source] Supramolecular Organization of ssDNA-Templated ,-Conjugated Oligomers via Hydrogen BondingADVANCED MATERIALS, Issue 10-11 2009Mathieu Surin The templated self-assembly of water-soluble ,-conjugated molecules bearing a diaminotriazine moiety H-bonding to a single-strand oligothymine template leads to defined structures. We study these assemblies with molecular modeling, circular dichroism spectroscopy, and scanning probe microscopy, to get a better understanding of the factors governing the supramolecular organization and structural order. [source] Single-Crystal Polythiophene Microwires Grown by Self-Assembly,ADVANCED MATERIALS, Issue 6 2006H. Kim Single-crystal polythiophene microwires with unprecedented electrical characteristics such as low resistance (0.5,M,), a channel current as high as 25,,A, and well-resolved gate modulation (see figure) have been obtained by specific control over the supramolecular organization of individual polymer chains, which show preferential well-ordered interchain stacking along the wire axis. This approach offers a promising protocol for new flexible electronics. [source] Fluorene-based materials and their supramolecular propertiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2009Robert Abbel Abstract Fluorene-based ,-conjugated polymers and oligomers combine several advantageous properties that make them well-suited candidates for applications in organic optoelectronic devices and chemical sensors. This review highlights strategies to synthesize these materials and to tune their absorption and emission colors. Furthermore, methods to control their supramolecular organization will be discussed. In many cases, a delicate interplay between the chemical structure and the processing conditions are found, resulting in a high sensitivity of both structural features and optical properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4215,4233, 2009 [source] Microbeam synchrotron imaging of hairs from Ancient Egyptian mummiesJOURNAL OF SYNCHROTRON RADIATION, Issue 5 2003L. Bertrand Developments in microfocus synchrotron techniques have led to new results regarding the long-term alteration of archaeological samples of biological origin. Here, ancient hair samples from two Egyptian mummies have been analyzed using a conjunction of structural and elemental synchrotron methods. In this favored context of conservation, structural analysis revealed a remarkable preservation of keratin supramolecular organization at any observed length scale. Bulk keratin structure has therefore not been modified significantly over 2000 years. However, infrared spectroscopy indicated a partial disorganization of keratins close to the hair surface through polypeptide bond breakage. Elemental mapping showed a strongly heterogeneous distribution which can be related to mummification and cosmetic treatments. [source] MicroCommentary: Subcellular localization of Escherichia coli osmosensory transporter ProP: focus on cardiolipin membrane domainsMOLECULAR MICROBIOLOGY, Issue 6 2007Eugenia Mileykovskaya Summary The role for specific lipids in the spatial distribution of the membrane proteins and formation of the lipid-protein membrane domains is an emerging theme in the studies of the supramolecular organization of the bacterial cell. A combination of the lipid and protein visualization techniques with manipulation of the cell lipid composition provides a useful tool for these studies. This MicroCommentary reviews the first experimental example demonstrating an involvement of the phospholipid cardiolipin in recruitment of a membrane protein (specifically H+ -osmoprotectant symporter ProP) to the Escherichia coli cell poles. The properties of cardiolipin domains employed in creating a specific environment for structural organization and function of membrane protein complexes are also discussed. [source] Effect of UVA or UVB Irradiation on Cutaneous Lipids in Films or in SolutionPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 3 2010Chloé Merle The barrier function of the skin is largely due to the stratum corneum which is essentially composed of lipids. Different external factors, such as UV irradiation, affect this skin layer and are responsible for a destabilization of the supramolecular organization of its constituted lipids. In this work, mass spectrometry and infrared spectroscopy are combined to study the correlation between the formation of oxidative compounds by UV irradiation and the lipid organization. Experiments were carried out on unsaturated lipids in film or solution form, exposed to UVA or UVB irradiation. UV exposure leads to the formation of oxygenated entities in the case of lipids with an unsaturated fatty acid moiety, resulting in a decrease in their packing which is greater when the lipids are in solution. The packing decrease is even greater following UVB irradiation. [source] Effect of organic additives on formation and structure of polyelectrolyte-oppositely charged surfactant complexes,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 11-12 2006J. A. Zakharova Abstract Effect of butanol and Triton X-100 on formation, supramolecular organization and local dynamics of poly(N -ethyl-4-vinylpyridinium)-dodecyl sulfate complexes have been studied by UV spectroscopy, high-speed sedimentation, laser light scattering and electron spin resonance (ESR) spectroscopy. It was found that solubilization of butanol promotes aggregation of the complex species in solution and results in contraction of the region in which water-soluble complexes are formed. On the contrary, highly aggregated complexes disaggregate up to molecularly dispersed state upon addition of Triton X-100. It was found that under the experimental conditions neither butanol (up to 3,wt%) nor Triton X-100 ([Triton X-100]/[sodium dodecylsulfate],,,1:1) cause destruction of the complexes. The results of ESR spin probe and spin label studies show that in both cases supramolecular realignments are accompanied by a slight increase of the local molecular mobility of surfactant ions in the complex micelles, segmental mobility of polyelectrolyte being unchanged. Copyright © 2006 John Wiley & Sons, Ltd. [source] Probing the shapes of chiral bis-(o -naphthalimidobenzoyl) systems using X-ray and circular dichroism methodsACTA CRYSTALLOGRAPHICA SECTION B, Issue 1 2009Urszula Rychlewska CD (circular dichroism) and X-ray investigations have been carried out in order to identify the prevalent conformations and define the forces that determine the molecular and supramolecular organization of the alkyl-bridged bichromophoric [NAB, ortho -(1,8-naphthalimido)benzoyl] units, each consisting of the benzoyl substituted in the ortho position with the 1,8-naphthalimide group. The results reveal that NAB bichromophores incorporated into the same molecule exist in a variety of conformation/helicity combinations. The molecular structures are largely stabilized by local 1,3-CH/CO dipole,dipole interactions, while the crystal packing besides dispersive H...H interactions is mostly governed by multiple C,H...O(=C) and C,H..., interactions. The relatively small contribution of ,..., interactions comes from a pairwise off-face stacking between naphthalimide rings or from pairwise carbonyl..., interactions. All these types of intermolecular interactions have been summarized quantitatively by means of a Hirshfeld surface analysis. [source] Benzene-1,4-diboronic acid,4,4,-bipyridine,water (1/2/2)ACTA CRYSTALLOGRAPHICA SECTION C, Issue 4 2010Araceli Vega In the presence of water, benzene-1,4-diboronic acid (1,4-bdba) and 4,4,-bipyridine (4,4,-bpy) form a cocrystal of composition (1,4-bdba)(4,4,-bpy)2(H2O)2, in which the molecular components are organized in two, so far unknown, cyclophane-type hydrogen-bonding patterns. The asymmetric unit of the title compound, C6H8B2O4·2C10H8N2·2H2O, contains two 4,4,-bpy, two water molecules and two halves of 1,4-bdba molecules arranged around crystallographic inversion centers. The occurrence of O,H...O and O,H...N hydrogen bonds involving the water molecules and all O atoms of boronic acid gives rise to a two-dimensional hydrogen-bonded layer structure that develops parallel to the (01) plane. This supramolecular organization is reinforced by ,,, interactions between symmetry-related 4,4,-bpy molecules. [source] Teaching the extracellular matrix and introducing online databases within a multidisciplinary course with i-cell-MATRIXBIOCHEMISTRY AND MOLECULAR BIOLOGY EDUCATION, Issue 2 2010A student-centered approach Abstract The biochemistry and molecular biology of the extracellular matrix (ECM) is difficult to convey to students in a classroom setting in ways that capture their interest. The understanding of the matrix's roles in physiological and pathological conditions study will presumably be hampered by insufficient knowledge of its molecular structure. Internet-available resources can bridge the division between the molecular details and ECM's biological properties and associated processes. This article presents an approach to teach the ECM developed for first year medical undergraduates who, working in teams: (i) Explore a specific molecular component of the matrix, (ii) identify a disease in which the component is implicated, (iii) investigate how the component's structure/function contributes to ECM' supramolecular organization in physiological and in pathological conditions, and (iv) share their findings with colleagues. The approach,designated i-cell-MATRIX,is focused on the contribution of individual components to the overall organization and biological functions of the ECM. i-cell-MATRIX is student centered and uses 5 hours of class time. Summary of results and take home message: A "1-minute paper" has been used to gather student feedback on the impact of i-cell-MATRIX. Qualitative analysis of student feedback gathered in three consecutive years revealed that students appreciate the approach's reliance on self-directed learning, the interactivity embedded and the demand for deeper insights on the ECM. Learning how to use internet biomedical resources is another positive outcome. Ninety percent of students recommend the activity for subsequent years. i-cell-MATRIX is adaptable by other medical schools which may be looking for an approach that achieves higher student engagement with the ECM. [source] Ionic Hydrogen Bonds Controlling Two-Dimensional Supramolecular Systems at a Metal SurfaceCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2007Dietmar Payer Abstract Hydrogen-bond formation between ionic adsorbates on an Ag(111) surface under ultrahigh vacuum was studied by scanning tunneling microscopy/spectroscopy (STM/STS), X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and molecular dynamics calculations. The adsorbate, 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA), self-assembles at low temperatures (250,300,K) into the known open honeycomb motif through neutral hydrogen bonds formed between carboxyl groups, whereas annealing at 420,K leads to a densely packed quartet structure consisting of flat-lying molecules with one deprotonated carboxyl group per molecule. The resulting charged carboxylate groups form intermolecular ionic hydrogen bonds with enhanced strength compared to the neutral hydrogen bonds; this represents an alternative supramolecular bonding motif in 2D supramolecular organization. [source] | ||||||||||||||||