Self Assemble Of Novel Discotic Nano Molecules Based On Polyhedraloligomericsilsesquioxanes

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Self-assemble of Novel Discotic Nano-molecules Based on Polyhedraloligomericsilsesquioxanes

Author : Mingxuan Li
Publisher :
ISBN 13 :
Total Pages : 44 pages
Book Rating : 4.:/5 (883 download)

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Book Synopsis Self-assemble of Novel Discotic Nano-molecules Based on Polyhedraloligomericsilsesquioxanes by : Mingxuan Li

Download or read book Self-assemble of Novel Discotic Nano-molecules Based on Polyhedraloligomericsilsesquioxanes written by Mingxuan Li and published by . This book was released on 2014 with total page 44 pages. Available in PDF, EPUB and Kindle. Book excerpt: Self-assembly is a process that components automatically form order patterns without any human intervention.1 The molecular self-assemble, including especially so called crystal engineering, has provided numerous of novel hierarchical structures with exceptional properties.2 However, due to their relatively small size, the intermolecular interactions play the vital role in the assemble process while the geometry effect is usually neglected. Recent studies of colloidal particles with size between tens of nanometers to several micrometers proved the significance of shape in the self arrangement of the molecules. Herein, we seek to engineer the self-assemble utilizing giant molecules which have precise chemical structure, symmetric discotic shape, and specially several nanometer size filling the gap between small molecules and colloidal particles. In this work, two novel discotic nano-molecules or so call giant molecules were successfully synthesized by connecting three POSS and six POSS to Truxene and Triphenylenecore respectively utilizing "Huisgen Cyclo addition" click reaction. Crystal structure of the giant molecule having three POSS attached to Truxene core was carefully investigated through X-ray diffraction and transmission electron microscope (TEM) diffraction. While for the giant molecule with six POSS cages attached to Triphenylene core, surprisingly it could show distinct self-assembly behavior in which A15 phase structure was found when POSS was not crystallized. This work could not only provide the detailed analysis of crystal structure and unusual A15 phase structure, but more importantly, deepen our understanding of intermolecular interaction and shape effect on hierarchical structures based on such simple discotic giant molecules.

Novel Three Dimensional C3v Symmetric Nano-molecules Based on Polyhedral Oligomeric Silsesquioxanes (POSS) Nano-atoms

Author : Shan Mei
Publisher :
ISBN 13 :
Total Pages : 59 pages
Book Rating : 4.:/5 (913 download)

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Book Synopsis Novel Three Dimensional C3v Symmetric Nano-molecules Based on Polyhedral Oligomeric Silsesquioxanes (POSS) Nano-atoms by : Shan Mei

Download or read book Novel Three Dimensional C3v Symmetric Nano-molecules Based on Polyhedral Oligomeric Silsesquioxanes (POSS) Nano-atoms written by Shan Mei and published by . This book was released on 2013 with total page 59 pages. Available in PDF, EPUB and Kindle. Book excerpt: The self-assembly of individual building blocks with different shapes into close packed ordered structures is prevalent in nature and has drawn much attention of human for long. The close packing of some simple shapes such as sphere and rods has been widely learned and established while the assembly of polyhedral structures is still unsolved and being studied with numerous efforts, of which tetrahedron is one with special interest. However, many previous researches only study the assembly of the building blocks with sizes either too big (tens or hundreds of nanometers) or too small (around one nanometer). Thus, we seek to obtain a size in between by using the newly emerged nano building blocks with precisely defined structures, persistent shapes and outstanding properties, e.g. Polyhedral Oligomeric Silsesquioxane (POSS). We can predict there to be distinctive difference in the self-assembly behavior and structure between the nano-sized molecules and the traditional ones. In this work, two novel claw-like C3v symmetric nano-molecules with different linkages were successfully synthesized by connecting 3 POSS nano-atoms to 1,3,5-Triphenyladmantane. The nano-molecules were carefully designed to ensure they possess enough shape persistent ability and 3-5 nm size, which fills the size gap between traditional small molecules and large colloidal particles. The crystals of the molecules were obtained via solvent evaporation method and the crystal structures would be explored. This work can not only provide us a new way of designing crystals with Nano-sized units but also help us to deepen our understanding of the relationship between molecular structure and crystal structure.

Giant Molecules Based on Perylene Dimides: Synthesis, Characterization and Self-assembly Behaviors

Author : Yuyang Ji
Publisher :
ISBN 13 :
Total Pages : 60 pages
Book Rating : 4.:/5 (17 download)

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Book Synopsis Giant Molecules Based on Perylene Dimides: Synthesis, Characterization and Self-assembly Behaviors by : Yuyang Ji

Download or read book Giant Molecules Based on Perylene Dimides: Synthesis, Characterization and Self-assembly Behaviors written by Yuyang Ji and published by . This book was released on 2017 with total page 60 pages. Available in PDF, EPUB and Kindle. Book excerpt: Designing giant molecules is a rapidly developing research area nowadays. Giant molecules could be connected by different kinds of nanoparticles and thus their chemical structures are well-defined. Common giant molecules, such as giant polyhedral, giant surfactants and giant Janus particles, are able to self-assemble into novel nanostructures with molecular weights as controllable as traditional polymers but much more specific. Organic nanoparticles, such as fullerenes, polyhedral oligomeric silsesquioxanes (POSS), polyoxometalates, perylene diimides (PDI) are widely used in building giant molecules. This work focuses on synthesizing giant molecules based on organic nanoparticles and detecting their self-assembly behaviors in bulk. Four giant molecules have been designed and synthesized: the giant molecule PS2.9K-PDI-DPOSS, the 2PS2.9K-PDI-DPOSS, the PS2.6K-PDI-Hex-ol and the 2PS8K-PDI-Hex-ol. These giant molecules built with PS tails and hydrophilic groups, are able to self-assembled into various nanostructures at different temperature. Characterization was accomplished by 1H NMR and GPC spectra. Self-assembly behaviors in bulk were studied by Small Angle X-ray Scattering (SAXS).

Design, Synthesis and Self-assembly of Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane-polymer Conjugates

Author : Kan Yue
Publisher :
ISBN 13 :
Total Pages : 225 pages
Book Rating : 4.:/5 (129 download)

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Book Synopsis Design, Synthesis and Self-assembly of Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane-polymer Conjugates by : Kan Yue

Download or read book Design, Synthesis and Self-assembly of Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane-polymer Conjugates written by Kan Yue and published by . This book was released on 2013 with total page 225 pages. Available in PDF, EPUB and Kindle. Book excerpt: Hierarchally ordered supramolecular structures generated by self-assembly of various nano-materials have attracted great amount of interests due to their potentials in advanced material designs and applications via the "bottom-up" approach. In the field of polymer science, studies on block copolymers and their well-documented micro-phase separation behaviors have been one of the central themes during the past a few decades. The consequentially proposed block copolymer lithography based on these studies is considered as one of alternative solutions to complement the traditional photolithography and further reduce the feature sizes of microelectronic fabrications. However, it is still a grand challenge to achieve micro-phase separated ordered structures with sub-20 nm feature sizes in common block copolymer systems, as well as to obtain unconventional self-assembled ordered phases. It replies on the development of novel materials to resolve these problems. "Shape amphiphiles", constructed by the chemical integration of molecular nano-building blocks with distinct shapes and competing interactions, emerge as a novel class of nano-materials. In this dissertation, the molecular design and synthesis of a library of shape amphiphiles with precisely defined structures based on conjugates of functionalized polyhedral oligomeric silsesquioxanes (POSS) and polystyrene (PS) are presented. These POSS-PS conjugates capture the structural features of small molecule surfactants but represent their size-amplified analogues and are thus, also referred as "giant surfactants". The development of a "sequential click approach" and the utilization of a series of "click adaptor molecules" facilitated the modular and efficient precision synthesis and the feasible structural diversification of molecular architectures for a systematic investigation. It was subsequently revealed that in the bulk state, driven by the nano-phase separation between the functionalized POSS cages and the polymer chains, POSS-based shape amphiphiles can self-assemble into various kinds of ordered supramolecular phases depending on the relative volume fraction of the two components and the molecular topology. The unique structural features of POSS-based shape amphiphiles, such as the shape persistence of the POSS cages and the high x value due to the clustering of functional groups, resulted in an asymmetric phase diagram of ordered structures with sub-10 nm feature sizes. Moreover, self-assembly of these shape amphiphiles exhibited a remarkable sensitivity on the molecular architectures, which resembles the properties of small molecule surfactants rather than the block copolymers. By tuning the molecular architectures, some exceptional phases could be observed, such as an inversed honeycomb phase and a highly asymmetric lamellar phase, as observed in the multi-headed giant surfactant system. Therefore, it is concluded that POSS-based shape amphiphiles provide a versatile platform for advancing our understanding about the self-assembled diverse equilibrium phase structures with sub-20 nm feature sizes.

Synthesis and Self-assembly of Star-shape Giant Molecules Based on Hydrophilic Polyhedral Oligomeric Silsesquioxane (POSS)

Author : Gaoyan Mu
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (17 download)

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Book Synopsis Synthesis and Self-assembly of Star-shape Giant Molecules Based on Hydrophilic Polyhedral Oligomeric Silsesquioxane (POSS) by : Gaoyan Mu

Download or read book Synthesis and Self-assembly of Star-shape Giant Molecules Based on Hydrophilic Polyhedral Oligomeric Silsesquioxane (POSS) written by Gaoyan Mu and published by . This book was released on 2018 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The chemical and physical properties of materials are determined not only by composition but also hierarchical structures. Hierarchical structures are formed by "bottom up" method, self-assembly of nano-scale building blocks into supramolecular assemblies via secondary interactions.1 In recent years, a series of functionalized POSS were utilized as "nanoatoms" to synthesize well-defined giant molecules. As a kind of giant molecules, giant surfactants are focused in my work. To investigate the fundamental principles of self-assembly, the giant surfactants with precise molecular structures have been synthesized by clicking "nanoatoms" to flexible polymer tails with controlled molecular weight. Because the self-assemblies of giant surfactants are sensitive to topological structures, a series of "giant surfactant" with multi-heads or multi-tails have been synthesized.2 In my work, the APOSS based star-shape giant molecules with or without polystyrene (PS) tails were precisely synthesized via "living" radical polymerization and "click chemistry". The chemical structure of the product was confirmed by 1H NMR spectrum, 13C NMR spectrum, GPC spectra, FT-IR spectra and MALDI-TOF mass spectra. After the self-assembly of samples in solution, the structures formed were investigated by transmission electron microscopy (TEM), static light scattering (SLS) and dynamic light scattering (DLS).

Design, Synthesis and Self-assembly of Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Materials

Author : Ni Bo
Publisher :
ISBN 13 :
Total Pages : 139 pages
Book Rating : 4.:/5 (13 download)

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Book Synopsis Design, Synthesis and Self-assembly of Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Materials by : Ni Bo

Download or read book Design, Synthesis and Self-assembly of Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Materials written by Ni Bo and published by . This book was released on 2018 with total page 139 pages. Available in PDF, EPUB and Kindle. Book excerpt: The giant molecules systems exhibit very interesting behaviors in the supramolecular assemblies over the past several years compared to other macromolecular systems. As an old Chinese saying goes "good tools are prerequisites for a successful execution of a job". This dissertation focuses on the synthetic possibilities based on the previous work and try to explore some progress in the first part. The second part of the dissertation encapsulates the self-assembly behaviors of the synthesized giant molecular systems. A pre-functionalization method was developed to achieve giant molecular families with more abundant functionalities. Fluorinated polyhedral oligomeric silsesquioxane (FPOSS), long alkyl chain functionalized POSS (C8POSS), and protected carboxylic acid group functionalized POSS (tAPOSS) were designed and prepared. These kinds of molecules are viewed as molecular nanoparticles (MNPs). The reactivities of the modules was proved by combining them with polymer systems like polystyrene via "click" chemistry. These precisely defined functionalized POSS-containing hybrids could serve as model molecules to investigate the self-assembly behaviors of giant molecules.The solution self-assembly of a giant surfactant consisting of a polystyrene-block-poly (ethylene oxide) (PS-b-PEO) diblock copolymer tail tethered onto a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) cage in 1,4-dioxane/water was investigated. Abundant unconventional micellar structures including toroids, two-dimensional hexagonally patterned colloidal nanosheets, and laterally structured vesicles were observed.2 This study not only exhibits various unique morphologies, but also promotes the fundamental understanding on the pathways of the transformations between different morphologies in the solution self-assembly behavior of giant surfactants.In the MNPs and polymer hybrid systems, the MNPs were with precise molecular weights and chemical compositions. But the polymers used still have a molecular weight distribution which originates from the nature of the polymerization methods applied. To eliminate the polydispersity effect from the system, it is crucial to have molecular systems with precise molecular weights and chemical structures from the physical point of view. Upon this anticipation, we have designed a series of dendrons which are compositionally identical, but their linkers are in different chemical connection geometries. These sets of macromolecules are composed of hydroxyl group functionalized POSS (DPOSS) and isobutyl functionalized POSS (BPOSS). The final dendron structure consists of three parts, one DPOSS at the apex, four BPOSSs at the periphery and the flexible linkers. Note that this series of dendrons is topological isomers. Self-assembled structures of four dendron topological isomers were studied using SAXS and TEM. The results help us to understand the role of linkers in a amphiphiles system and give us some guidance on how to design a molecular system in the future.

Manipulation of Self-assembled Nanostructures from Molecular Janus Particles Based on Polyoxometalates, Polyhedral Oligomeric Silsesquioxanes and [60]fullerene

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Author : Hao Liu
Publisher :
ISBN 13 :
Total Pages : 183 pages
Book Rating : 4.:/5 (17 download)

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Book Synopsis Manipulation of Self-assembled Nanostructures from Molecular Janus Particles Based on Polyoxometalates, Polyhedral Oligomeric Silsesquioxanes and [60]fullerene by : Hao Liu

Download or read book Manipulation of Self-assembled Nanostructures from Molecular Janus Particles Based on Polyoxometalates, Polyhedral Oligomeric Silsesquioxanes and [60]fullerene written by Hao Liu and published by . This book was released on 2015 with total page 183 pages. Available in PDF, EPUB and Kindle. Book excerpt: The ability to manipulate self-assembly behaviors of molecular building blocks is the key to precise "bottom-up" fabrication of desired nanostructures. In this dissertation, we focus on the rational design, facile synthesis, and self-assembly of a series of molecular Janus particles (MJPs) constructed by chemically linking a-Keggin-type polyoxometalate (POM), Lindqvist-type POM, polyhedral oligomeric silsesquioxane (POSS) derivatives and [60]fullerene (C60) derivatives. This dissertation contains two sub topics. The first one describes a rational strategy to obtain self-assembled two-dimensional (2D) nanocrystals of MJPs with definite and uniform thickness. Three different types of MNPs, namely POSS derivative, C60 derivative, and Lindqvist-type POM, are used as building blocks to construct several amphiphilic molecular Janus particles by covalently connecting hydrophobic crystalline BPOSS with a charged hydrophilic MNP. The formation of 2D nanocrystals with an exact thickness of double layers of molecules is driven by directional crystallization of the BPOSS MNP and controlled by various factors such as solvent polarity, number of counter ions, and sizes of the MNPs. Strong solvating interactions of the ionic MNPs in polar solvents (e.g., acetonitrile and dimethylformamide) are crucial to provide repulsive interactions between the charged outlying ionic MNPs and suppress further aggregation along the layer normal direction. The number of counter ions per molecule plays a major role in determining the self-assembled morphologies. Size matching of the hydrophobic and ionic MNPs is another critical factor in the formation of 2D nanocrystals. Self-assembly of rationally designed molecular Janus particles provides a unique "bottom-up" strategy to engineer 2D nanostructures.In the second sub topic, the facile synthesis and solution self-assembly behaviors of another series of MJPs are discussed. a-Keggin type POM nanoclusters and isobutyl-substituted BPOSS cages are covalently connected at 1:1, 1:2 and 1:4 ratios to construct Keggin-BPOSS, Keggin-2BPOSS, and Keggin-4BPOSS in high yields. Self-assembled nanostructures of these precisely-defined MJPs are resulted from the competing crystallization processes of the POM and the BPOSS building blocks. Since the Keggin-type POM nanocluster is slightly larger than BPOSS in the cross-section areas perpendicular to the long axis of the MJPs, crystallization of Keggin-BPOSS in the acetonitrile/water mixture was mainly directed by the POM building block, leading to an interesting "micellar-crystal" transition towards one-dimensional (1D) nanobelts. Directional crystallization of the BPOSS cages, however, dominated the self-assembly of Keggin-2BPOSS and Keggin-4BPOSS in their methanol/chloroform mixtures where the cross-section area of the Keggin POM nanocluster is smaller than those of 2BPOSS and 4BPOSS perpendicular to the long axis of the MJPs, and resulted in the formation of 2D nanosheets with exactly two layers of MJPs constructed in a head-to-head structure along the thickness normal. The distinct results manifest that the self-assembly of these MJPs could be controlled by the directional crystallization of the dominating building blocks. A rational strategy may thus be possible: we can purposely control and tune diverse unconventional nanostructures via design and synthesis of those giant molecules which follow defined chemical and physical principles of self-assemblies.

Synthesis and Self-assembly of Planar Giant Molecules Based on Polyhedral Oligomeric Silsesquioxanes(POSS)

Author : Lun Jin
Publisher :
ISBN 13 :
Total Pages : 52 pages
Book Rating : 4.:/5 (111 download)

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Book Synopsis Synthesis and Self-assembly of Planar Giant Molecules Based on Polyhedral Oligomeric Silsesquioxanes(POSS) by : Lun Jin

Download or read book Synthesis and Self-assembly of Planar Giant Molecules Based on Polyhedral Oligomeric Silsesquioxanes(POSS) written by Lun Jin and published by . This book was released on 2017 with total page 52 pages. Available in PDF, EPUB and Kindle. Book excerpt: The giant molecule is a kind of macromolecule with high molecular weight and precisely defined chemical structure. The self-assembly behavior of giant molecule can be influenced by intermolecular interactions, such as hydrogen bonding, hydrophobic force, metal coordination, van der Waals forces, pi- pi interactions and electrostatic effects. Besides the chemical interaction, the geometrical factor will also influence the final structure. POSS is a rigid conformation and fixed volume cage molecule with silicon-oxygen backbone. The precisely definable of the functional groups of POSS corresponding to the vertex number makes them fascinating building blocks. In the previous work, it was reported that POSS based three dimensional giant polyhedrons could self-assembly into Frank-Kasper A15 phase. [1] In this thesis, two dimensional planar giant molecules were designed and synthesized to explore novel self-assembly behaviors. Gallic acid derivatives C12 and BPOSS were linked to a simple planar C3 symmetric core, utilizing Sonogashira coupling reaction. By controlling the number of isobutyl-POSS, a series of giant molecules, 3C12-TEB, 2C12-TEB-1BPOSS and 1C12-TEB-2BPOSS were synthesized and studied. This series of target giant molecules were characterized by 1H NMR, 13C NMR, GPC and MALDI-TOF mass spectra. Their physical properties were studied by DSC and temperature-resolved SAXS. Two giant molecules, 2C12-TEB-1BPOSS and 1C12-TEB-2BPOSS, were discovered of hexagonal phase in bulk state.

Applications of Polyhedral Oligomeric Silsesquioxanes

Author : Claire Hartmann-Thompson
Publisher : Springer Science & Business Media
ISBN 13 : 904813787X
Total Pages : 440 pages
Book Rating : 4.0/5 (481 download)

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Book Synopsis Applications of Polyhedral Oligomeric Silsesquioxanes by : Claire Hartmann-Thompson

Download or read book Applications of Polyhedral Oligomeric Silsesquioxanes written by Claire Hartmann-Thompson and published by Springer Science & Business Media. This book was released on 2011-01-03 with total page 440 pages. Available in PDF, EPUB and Kindle. Book excerpt: The commercial availability and decreasing cost of polyhedral oligomeric silsesquioxanes in recent years has opened up the field to everybody who wishes to apply these unique properties in their own technologies. This is the first book to provide a comprehensive overview of these applications, and covers the synthesis, characterization and history of polyhedral oligomeric silsesquioxanes, their use as metallasilsesquioxane catalysts, their effect upon polymer properties and plastics performance, and their use in superhydrophobic nanocomposites, and electronics, energy, space and biomedical applications. "Applications of Polyhedral Oligomeric Silsesquioxanes" is a valuable reference for those working across a range of disciplines, including chemists, materials scientists, polymer physicists, plastics engineers, surface scientists, and anybody with a commercial or academic interest in plastics, composite materials, space materials, dental materials, tissue engineering, drug delivery, lithography, fuel cells, batteries, lubricants, or liquid crystal, LED, sensor, photovoltaic or biomedical devices.

Design, Synthesis, and Self-assembly of Nano-sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides

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Author : Jiahao Huang
Publisher :
ISBN 13 :
Total Pages : 248 pages
Book Rating : 4.:/5 (124 download)

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Book Synopsis Design, Synthesis, and Self-assembly of Nano-sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides by : Jiahao Huang

Download or read book Design, Synthesis, and Self-assembly of Nano-sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides written by Jiahao Huang and published by . This book was released on 2020 with total page 248 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Design, Synthesis, and Self-assembly of Well-defined Hybrid Materials Including Polymer Amphiphiles and Giant Tetrahedra Molecules Based on POSS Nanoparticles

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Author : Mingjun Huang
Publisher :
ISBN 13 :
Total Pages : 220 pages
Book Rating : 4.:/5 (14 download)

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Book Synopsis Design, Synthesis, and Self-assembly of Well-defined Hybrid Materials Including Polymer Amphiphiles and Giant Tetrahedra Molecules Based on POSS Nanoparticles by : Mingjun Huang

Download or read book Design, Synthesis, and Self-assembly of Well-defined Hybrid Materials Including Polymer Amphiphiles and Giant Tetrahedra Molecules Based on POSS Nanoparticles written by Mingjun Huang and published by . This book was released on 2015 with total page 220 pages. Available in PDF, EPUB and Kindle. Book excerpt: "Bottom-up" techniques-based self-assembly are always attracting people's interests since this technology provides relatively low economic cost and fast route to construct organized structures at different scales. Considering unprecedented benefits from polymer materials, self-assemblies utilizing polymer building blocks have been extensively studied to achieve diverse hierarchical structures and various attractive properties. However, precise controls of chemical primary structures and compositions and exact constructions of hierarchal ordered structures in synthetic polymers are far from being fully appreciated. In this dissertation, a novel approach has been utilized to construct diverse well-defined nano-building blocks, giant molecules, via conjugating different, and functionalized molecular nanoparticles (MNPs) which are shape- and volume-persistent nano-objects with precise molecular structure and specific symmetry. The representative examples of the three basic categories of giant molecules, "giant polyhedra", "giant surfactants", and "giant shape amphiphiles" were discussed in details. First, a class of precisely defined, nanosized giant tetrahedra was constructed by placing different polyhedral oligomeric silsesquioxane (POSS) molecular nanoparticles at the vertices of a rigid tetrahedral framework. Designed symmetry breaking of these giant tetrahedra introduces accurate positional interactions and results in diverse selectively assembled, highly ordered supramolecular lattices including a Frank-Kasper (FK) A15 phase. The FK and quasicrystal phases are originally identified in metal alloys and only sporadically observed in soft matters. It remains unclear how to correlate their stability with the chemical composition and molecular topology in the self-assembling systems. We then for this purpose designed and studied the self-assembly phase transition sequences of four series of hybrid giant surfactants based on hydrophilic POSS cages tethered with one to four polystyrene (PS) tails. With increasing the number of tails, molecular topological variations not only affect phase boundaries in terms of the PS volume fraction, but also open a window to stabilize supramolecular FK and quasicrystal phases in the spherical phase region, demonstrating the critical role of molecular topology in dictating the formation of unconventional supramolecular lattices of "soft" spherical motifs. The FK A15 phase was even surprisingly observed in the giant shape amphiphile molecule, triphenylene-6BPOSS, which has a disk-like flat triphenylene core connected with six hydrophobic POSS cages by sides. Without conical molecular shape, triphenylene-6BPOSS self-assembled and stabilized into supramolecular sphere via p-p interactions through a completely different mechanism with precious two cases. These studies indicate that "bottom-up" self-assemble based on well-defined giant molecules approach can be rather powerful to fabricate usually complicated hierarchical structures and open up a wide field of supramolecular self-assembly with unexpected structure and properties.

Self-Assembly

Author : Ramanathan Nagarajan
Publisher : John Wiley & Sons
ISBN 13 : 1119001366
Total Pages : 364 pages
Book Rating : 4.1/5 (19 download)

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Book Synopsis Self-Assembly by : Ramanathan Nagarajan

Download or read book Self-Assembly written by Ramanathan Nagarajan and published by John Wiley & Sons. This book was released on 2019-01-07 with total page 364 pages. Available in PDF, EPUB and Kindle. Book excerpt: An introduction to the state-of-the-art of the diverse self-assembly systems Self-Assembly: From Surfactants to Nanoparticles provides an effective entry for new researchers into this exciting field while also giving the state of the art assessment of the diverse self-assembling systems for those already engaged in this research. Over the last twenty years, self-assembly has emerged as a distinct science/technology field, going well beyond the classical surfactant and block copolymer molecules, and encompassing much larger and complex molecular, biomolecular and nanoparticle systems. Within its ten chapters, each contributed by pioneers of the respective research topics, the book: Discusses the fundamental physical chemical principles that govern the formation and properties of self-assembled systems Describes important experimental techniques to characterize the properties of self-assembled systems, particularly the nature of molecular organization and structure at the nano, meso or micro scales. Provides the first exhaustive accounting of self-assembly derived from various kinds of biomolecules including peptides, DNA and proteins. Outlines methods of synthesis and functionalization of self-assembled nanoparticles and the further self-assembly of the nanoparticles into one, two or three dimensional materials. Explores numerous potential applications of self-assembled structures including nanomedicine applications of drug delivery, imaging, molecular diagnostics and theranostics, and design of materials to specification such as smart responsive materials and self-healing materials. Highlights the unifying as well as contrasting features of self-assembly, as we move from surfactant molecules to nanoparticles. Written for students and academic and industrial scientists and engineers, by pioneers of the research field, Self-Assembly: From Surfactants to Nanoparticles is a comprehensive resource on diverse self-assembly systems, that is simultaneously introductory as well as the state of the art.

Giant Molecular Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes: Molecular Design, "click" Synthesis and Self-assembly

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Author : Yiwen Li (Chemist)
Publisher :
ISBN 13 :
Total Pages : 0 pages
Book Rating : 4.:/5 (134 download)

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Book Synopsis Giant Molecular Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes: Molecular Design, "click" Synthesis and Self-assembly by : Yiwen Li (Chemist)

Download or read book Giant Molecular Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes: Molecular Design, "click" Synthesis and Self-assembly written by Yiwen Li (Chemist) and published by . This book was released on 2013 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The emergence of giant molecular shape amphiphiles as important building blocks for "bottom-up" nanofabrication has sparked substantial interest because conformation rigidity and shape anisotropy provide additional factors in directing self-assembly into various hierarchical structures. It has been found that giant molecular shape amphiphiles are able to self-assemble into diverse hierarchical supramolecular structures, similar to those observed in small molecular amphiphiles and block copolymers; yet this class of amphiphiles possesses distinct differences with various molecular shape, symmetries, and topologies. The purpose of this research is to develop several kinds of Polyhedral Oligomeric Silsesquioxanes (POSS)-based giant molecular shape amphiphiles with precisely defined molecular structures and functionalities by using thiol-ene "click" chemistry and other precise transformations. To achieve this, a library of monofunctional vinyl POSS building blocks with C3V symmetry was firstly prepared in good yields, which could serve as important precursors for further design and synthesis of various POSS-based giant molecular shape amphiphiles. The supramolecualr structures of these assemblies along with the resulting ordered structures are also fully investigated to determine their structure-property relationships. Functionalized POSS cages with different surface chemistry and size were employed to construct dumbbell- and snowman-like molecular Janus particles with various symmetry breakings. The self-assembly of dumbbell-like Janus particles leads to the formation of hierarchically ordered supramolecular structures in bulk. While the ordered packing of POSS within each layer is lost upon heating via undergoing through a first order transition, the bi-layered structure persists up to the decomposition temperature. The driving force of the hierarchical structure formation was attributed to the free energy minimization via the pathway guided by the symmetry breaking in both geometrical sense and chemical sense. Another illustrating example is a series of novel functional POSS heads tethered polymer tails-based giant molecular shape amphiphiles including giant surfactants, lipids, gemini surfactants and miktoarm shape amphiphiles. Diverse architectures of this class of materials have been constructed using sequential "click" chemistry and their self-assembly processes in solution have also been fully discussed. This set of research results not only opens a new pathway for achieving supramolecular self-assemblies of POSS-based giant molecular shape amphiphiles, but also creates unique materials for developing advanced technologies by combining the properties of those hybrid materials.

Molecular Self-Assembly

Author : Alex Li Dequan
Publisher : CRC Press
ISBN 13 : 9814364312
Total Pages : 464 pages
Book Rating : 4.8/5 (143 download)

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Book Synopsis Molecular Self-Assembly by : Alex Li Dequan

Download or read book Molecular Self-Assembly written by Alex Li Dequan and published by CRC Press. This book was released on 2012-12-20 with total page 464 pages. Available in PDF, EPUB and Kindle. Book excerpt: In the past several decades, molecular self-assembly has emerged as one of the main themes in chemistry, biology, and materials science. This book compiles and details cutting-edge research in molecular assemblies ranging from self-organized peptide nanostructures and DNA-chromophore foldamers to supramolecular systems and metal-directed assemblies

Directed Self-assembly of Block Co-polymers for Nano-manufacturing

Author : Roel Gronheid
Publisher : Woodhead Publishing
ISBN 13 : 0081002610
Total Pages : 328 pages
Book Rating : 4.0/5 (81 download)

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Book Synopsis Directed Self-assembly of Block Co-polymers for Nano-manufacturing by : Roel Gronheid

Download or read book Directed Self-assembly of Block Co-polymers for Nano-manufacturing written by Roel Gronheid and published by Woodhead Publishing. This book was released on 2015-07-17 with total page 328 pages. Available in PDF, EPUB and Kindle. Book excerpt: The directed self-assembly (DSA) method of patterning for microelectronics uses polymer phase-separation to generate features of less than 20nm, with the positions of self-assembling materials externally guided into the desired pattern. Directed self-assembly of Block Co-polymers for Nano-manufacturing reviews the design, production, applications and future developments needed to facilitate the widescale adoption of this promising technology. Beginning with a solid overview of the physics and chemistry of block copolymer (BCP) materials, Part 1 covers the synthesis of new materials and new processing methods for DSA. Part 2 then goes on to outline the key modelling and characterization principles of DSA, reviewing templates and patterning using topographical and chemically modified surfaces, line edge roughness and dimensional control, x-ray scattering for characterization, and nanoscale driven assembly. Finally, Part 3 discusses application areas and related issues for DSA in nano-manufacturing, including for basic logic circuit design, the inverse DSA problem, design decomposition and the modelling and analysis of large scale, template self-assembly manufacturing techniques. Authoritative outlining of theoretical principles and modeling techniques to give a thorough introdution to the topic Discusses a broad range of practical applications for directed self-assembly in nano-manufacturing Highlights the importance of this technology to both the present and future of nano-manufacturing by exploring its potential use in a range of fields

Design, Synthesis and Self-assembly of Giant Molecules with Precisely Controlled Heterogeneities, Including Composition, Functionality, Topology and Sequence

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Author : Wei Zhang
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (981 download)

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Book Synopsis Design, Synthesis and Self-assembly of Giant Molecules with Precisely Controlled Heterogeneities, Including Composition, Functionality, Topology and Sequence by : Wei Zhang

Download or read book Design, Synthesis and Self-assembly of Giant Molecules with Precisely Controlled Heterogeneities, Including Composition, Functionality, Topology and Sequence written by Wei Zhang and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: In biological systems, it is well-known that the activity and function of biomacromolecules are dictated not only by their primary chemical structures, but also by their secondary, tertiary and quaternary hierarchical structures. Achieving similar levels of control in synthetic macromolecules has yet to be demonstrated. In 1960, Feynman raised a fundamental question: "What would the properties of materials be if we could really arrange the atoms the way we want them?" It is difficult to answer this question at truly atomic level. However, by taking the advantage of the unique giant molecular system recently developed by our group, we are trying to answer it at the "nanoatom" length scale in this dissertation. We started with design, syntheses and crystal structure analyses of three series dyads of sphere-plate giant shape amphiphiles with distinct shapes and precise chemical linkages based on C60-triphenylene (sphere-triangle), C60-perylene diimide (sphere-rectangle) and C60-Porphyrin (sphere-square). We then developed a novel synthetic methodology using orthogonal "click" chemistries, strain-promoted azide-alkyne cycloaddition (SPAAC), oxime ligation and thiol-ene click coupling (TECC), for preparing a library of polystyrene (PS)-polyhedral oligomeric silsesquioxane (POSS) giant surfactants with precisely arranged nano-building blocks. The heterogeneity of primary chemical structure can be precisely controlled and is reflected in the self-assembled supramolecular structures in bulk or in solution. The composition (the volume fraction of hydrophilic "nanoatoms") and functionality are the crucial to determine the assembled structures, illustrated by a series of linear configured PSm-(XPOSS)n. The functionality and topology are also found to affect the assembled structures when the volume fractions are identical, demonstrated by several linear and branched PSm-(XPOSS)n giant surfactants. Furthermore, the sequence effect is explored by comparing the self-assembly behaviors of a pair of sequence isomers. In order to step further answering Feynman's inquire, we extend the synthetic method to prepare truly precise "nanoatom" chains or dendrimers with polydispersity Đ equal to 1, which also form varies order supramolecular structures as we tune their primary chemical structures. Our work offers a promising opportunities to manipulate the hierarchical heterogeneities of giant molecules via precise and modular assemblies of various nano-building blocks, and provides a platform for making precise nanostructures that are not only scientific intriguing but also technologically relevant.

Construction of the Novel Core/interfacial Crosslinked Inorganic/organic Hybrid Micelle Based on Functionalized Polyhedral Oligomeric Silsesquioxane (POSS) Via Thiol-ene "click" Chemistry

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Author : Ziran Chen
Publisher :
ISBN 13 :
Total Pages : 50 pages
Book Rating : 4.:/5 (913 download)

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Book Synopsis Construction of the Novel Core/interfacial Crosslinked Inorganic/organic Hybrid Micelle Based on Functionalized Polyhedral Oligomeric Silsesquioxane (POSS) Via Thiol-ene "click" Chemistry by : Ziran Chen

Download or read book Construction of the Novel Core/interfacial Crosslinked Inorganic/organic Hybrid Micelle Based on Functionalized Polyhedral Oligomeric Silsesquioxane (POSS) Via Thiol-ene "click" Chemistry written by Ziran Chen and published by . This book was released on 2013 with total page 50 pages. Available in PDF, EPUB and Kindle. Book excerpt: Supramolecular structures formed by the spontaneous self-assembly of block copolymers in selective solvents have been the focus of academic interest over the last decade. The recent development of "living radical polymerization" synthesis methods has expanded the range of functional block polymers and improve the controllability of block length,6−10 which lead spherical polymer micelles and nanoparticles into significant potential in application. However, the spontaneous dissociation of micelles under their critical micelle concentration (CMC) always limits further applications.18,19,22 Later, the emergence of cross-linked micelle solved this problem.21 By cross-linking the core or shell of micelle, it leads to the formation of robust nanoparticles, which prevent the dissociation below CMC.21,22 In this work, to explore new and efficient crosslink strategy, stable spherical inorganic-organic hybrid micelles were prepared by covalent crosslinking of micellar core/interface, via thiol-ene click chemistry. Amphiphilic block copolymer, poly(ethylene oxide)-block-polystyrene with vinyl-funcitonalized polyhedral oligomeric silsesquioxanes (VPOSS) randomly distributed on the PS block (PEO-b-PS/VPOSS), was designed to form the core-crosslinked micelles by self assembly in a mixture of dimethylformamide (DMF) and water with PS/VPOSS as core and PEO as corona. Meanwhile, another polymer, PEO-b-PS with a VPOSS precisely located at the junction point of two blocks was synthesized to form the interfacial crosslinked micelles with VPOSS nanoparticles distributed on the interface between micellar core and shell in DMF/water solution. The stability of the micelles were greatly enhanced by crosslinking of vinyl groups on VPOSS moieties under UV irradiation with pentaerythritol tetrakis(3-mercaptobutylate) as crosslinking agent. The process is fast, efficient, and environmental tolerant. The crosslinked micelles can sustain their spherical morphology in organic solvent. The self assembly and crosslinking process were fully studied by Dynamic Light Scattering (DLS), and Transmission Electron Microscopy (TEM).