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Author : Meng Zhang
Publisher :
Page : 378 pages
File Size : 16,86 MB
Release : 2013
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Author : Sheng Zhong
Publisher :
Page : pages
File Size : 36,94 MB
Release : 2010
Category : Block copolymers
ISBN : 9781124241562
There is always an interest to understand how molecules behave under different conditions. One application of this knowledge is to self-assemble molecules into increasingly complex structures in a simple fashion. Self-assembly of amphiphilic block copolymer in solution has produced a large variety of nanostructures through the manipulation in polymer chemistry, assembly environment, and additives. Moreover, some reports suggest the formation of many polymeric assemblies is driven by kinetic process. The goal of this dissertation is to study the influence of kinetics on the assembly of block copolymer. The study shows kinetic control can be a very effective way to make novel polymeric nanostructures. Two examples discussed here are helical cylindrical micelles and patchy nanoparticles. Helical cylindrical micelles are made from the co-assembly of amphiphilic triblock copolymer poly(acrylic acid)- block -poly(methyl acrylate)- block -polystyrene and organoamine molecules in a mixture of tetrahydrofuran (THF) and water (H 2 O). This system has already shown promise of achieving many assembled structures. The unique aspects about this system are the use of amine molecules to complex with acid groups and the existence of cosolvent system. Application of amine molecules offers a convenient control over assembled morphology and the introduction of PMA-PS selective solvent, THF, promotes the mobility of the polymer chains. In this study, multivalent organoamine molecules, such as diethylenetriamine and triethylenetetramine, are used to interact with block copolymer in THF/water mixture. As expected, the assembled morphologies are dependent on the polymer architecture, selection and quantity of the organoamine molecules, and solution composition. Under the right conditions, unprecedented, multimicrometer-long, supramolecular helical cylindrical micelles are formed. Both single-stranded and double-stranded helices are found in the same system. These helical structures share uniform structural parameters, including the width of the micelles, width of the helix, and the pitch distance. There is no preference to the handedness, and both handednesses are observed, which is understandable since there are no chiral molecules or specific binding effects applied during the assembly. The helical structure is a product of kinetic process. Cryogenic transmission electron microscopy has been employed to monitor the morphological transformation. The study indicates there are two complicated but reproducible kinetic pathways to form the helices. One pathway involves the stacks of bended cylinders at early stages and the subsequent interconnection of these bended cylinders. Spherical micelles bud off of the interconnected nanostructure as the final step towards a defect-free helix. Another kinetic pathway shows very short helices are formed at first and aligned via head-to-tail style in the solution, and the subsequent sequential addition of these short helices results in prolonged mature helices. By using a ninhydrin-staining technique, amine molecules within the micellar corona are visualized and confirmed to preferentially locate in the inner side of the helical turns. The aggregation of amine molecules provides a strong attraction force due to electrostatic association between oppositely charged amine and acid groups and accumulation of hydrogen bonding among amine molecules to coil the cylindrical micelles into helical twisting features which are stabilized by the repulsion forces due to the chain packing frustration within the hydrophobic core, steric hindrance of amine molecules as well as the Coulomb repulsion of the excess charged amine groups. The formation mechanism of the helix offers the feasibility to manipulate the helical pitch distance and formation kinetics. The helical pitch distance can be enlarged or shrunk by varying the type and amount of amine molecules used in assembly, introducing inorganic salts, and changing pH. Luckily, the helical structure can be preserved permanently by inducing the amide reaction between amine and carboxylic acid groups. The kinetics of the helix is also subject to many factors, including used amine molecules, inorganic salts and preparation procedure. The aging time for the helix can be either reduced or prolonged. Furthermore, even though the helical formation is pathway-dependent, helical formation can still be triggered from extended cylindrical micelles or stacks of disklike micelles as long as a right condition is applied. Another strategy for kinetic assembly of block copolymer is presented as well. A novel patchy nanoparticle has been produced following this strategy. The patches are formed on the surface of polymeric colloids due to the phase separation of two chemically unlike segments. Certain level of mobility of the polymer chains is required for the blocks to segregate into patches. More importantly, the number and distribution geometry of the patches are related to the particle size. Future efforts are needed to control the particle size in order to manufacture uniform nanoparticles with desired patch patterns for the applications in nanotechnology, drug delivery and nanodevices.
Author :
Publisher :
Page : pages
File Size : 11,82 MB
Release : 2015
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Executive Summary Our work was devoted to understanding the structure and properties of a class of thin film polymer nanocomposites (PNCs). PNCs are composed of polymer hosts into which nanoparticles (metallic nanoparticles, quantum dots, nanorods, C60, nanotubes) are incorporated. PNCs exhibit a diverse range of functional properties (optical, electronic, mechanical, biomedical, structural), determined in part by the chemical composition of the polymer host and the type of nanoparticle. The properties PNCs rely not only on specific functional, size-dependent, behavior of the nanoparticles, but also on the dispersion, and organizational order in some cases, inter-nanoparticle separation distances, and on relative interactions between the nanoparticles and the host. Therefore the scientific challenges associated with understanding the interrelations between the structure and function/properties of PNCs are far more complex than may be understood based only on the knowledge of the compositions of the constituents. The challenges of understanding the structure-function behavior of PNCs are further compounded by the fact that control of the dispersion of the nanoparticles within the polymer hosts is difficult; one must learn how to disperse inorganic particles within an organic host. The goal of this proposal was to develop an understanding of the connection between the structure and the thermal (glass transition), mechanical and optical properties of a specific class of PNCs. Specifically PNCs composed of polymer chain grafted gold nanoparticles within polymer hosts. A major objective was to understand how to develop basic principles that enable the fabrication of functional materials possessing optimized morphologies and combinations of materials properties. Accomplishments: We developed: (1) fundamental principles that enabled the creation of thin film PNCs possessing more complex morphologies of homopolymers and block copolymer micellar systems [1-6]; (2) a new understanding of physical phenomena associated with the structure of PNC systems and the glass transition and dynamics [7-11], including surface dynamics [12, 13]; designed PNCs to understand the connection between structure and specific optical responses of the material [14, 15]; electrorheological phenomena [16-18]; coarsening/aggregation phenomena [19, 20]; directed assembly [21] and elastic mechanical properties of thin supported films [22]. We established procedures to design and control the spatial distribution of gold nanoparticles (Au-NP), onto which polystyrene (PS) chains were end-grafted, within thin film PS hosts.[1-3] We explained how enthalpic and entropic interactions between the grafted layers and the polymer host chains, the nanoparticle (NP) sizes and shapes determine the spatial distribution of NPs within the host (i.e.: the morphology). In brief, the chemistries of the grafted chains and the polymer hosts, the degrees of polymerization of grafted and host chains (N and P, respectively), and the surface grafting densities [Sigma] influence the thermodynamic interactions. Thin films are unique: the external interfaces (substrate and free surface) profoundly influence the spatial distribution of NPs within the PNC. For example, thin films are thermodynamically less stable than their bulk analogs due to the preferential attraction between the brush-coated nanoparticles and the external interfaces (i.e.: the free surface/polymer interface and the polymer/substrate interface). We investigated the organization of the brush-coated nanoparticles within a host composed on block copolymer micelles in a homopolymer [4, 5]. Block copolymers, composed of a polymer of type A that is bonded covalently to another polymer of type B (A-b-B) are known to form micelles within homopolymers A or B.A micelle is composed of an inner core of the A component of the copolymer and an outer corona of the B-component, that resides within homopolymer B, which serves as the host. If t ...
Author : Andrew Craig Miller
Publisher :
Page : 310 pages
File Size : 23,59 MB
Release : 2008
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ISBN :
(cont.) Following cavitation, the nanopatterned regions of exposed PAA are available for conjugation chemistry, demonstrated here through selective linking of a fluorescently labeled protein. Cavitation was also observed in polystyrene-block-poly(2vinyl pyridine) (PS-b-P2VP) spherical and cylindrical micelles. Biocompatible oils are used in a variety of medical applications ranging from vaccine adjuvants to vehicles for oral drug delivery. To enable such nonpolar organic phases to serve as reservoirs for delivery of hydrophilic compounds, we explored the ability of block copolymer micelles in organic solvents to sequester proteins for sustained release across an oil-water interface. Self-assembly of the block copolymer, poly (ecaprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP), was investigated in toluene and oleic acid, a biocompatible naturally- occurring fatty acid. Micelle formation in toluene was characterized by dynamic light scattering (DLS) and atomic force microscopy (AFM) imaging of micelles cast onto silicon substrates. Cryogenic transmission electron microscopy confirmed a spherical morphology in oleic acid. Studies of homopolymer solubility implied that micelles in oleic acid consist of a P2VP corona and a PCL core, while P2VP formed the core of micelles assembled in toluene. The loading of two model proteins (ovalbumin (ova) and bovine serum albumin (BSA)) into micelles was demonstrated with loadings as high as 7.8 % wt of protein per wt of P2VP in oleic acid. Characterization of block copolymer morphology in the two solvents after protein loading revealed spherical particles with similar size distributions to the asassembled micelles. Release of ova from micelles in oleic acid was sustained for 30 hours upon placing the oil phase in contact with an aqueous bath. Unique to the situation of micelle assembly in an oily phase, the data suggest protein is sequestered in the P2VP corona block of PCL-b-P2VP micelles in oleic acid. More conventionally, protein loading occurs in the P2VP core of micelles assembled in toluene.
Author : Ian W. Hamley
Publisher : John Wiley & Sons
Page : 300 pages
File Size : 31,75 MB
Release : 2005-12-13
Category : Technology & Engineering
ISBN : 0470016973
This unique text discusses the solution self-assembly of block copolymers and covers all aspects from basic physical chemistry to applications in soft nanotechnology. Recent advances have enabled the preparation of new materials with novel self-assembling structures, functionality and responsiveness and there have also been concomitant advances in theory and modelling. The present text covers the principles of self-assembly in both dilute and concentrated solution, for example micellization and mesophase formation, etc., in chapters 2 and 3 respectively. Chapter 4 covers polyelectrolyte block copolymers - these materials are attracting significant attention from researchers and a solid basis for understanding their physical chemistry is emerging, and this is discussed. The next chapter discusses adsorption of block copolymers from solution at liquid and solid interfaces. The concluding chapter presents a discussion of selected applications, focussing on several important new concepts. The book is aimed at researchers in polymer science as well as industrial scientists involved in the polymer and coatings industries. It will also be of interest to scientists working in soft matter self-assembly and self-organizing polymers.
Author : Redouane Borsali
Publisher : Springer Science & Business Media
Page : 1490 pages
File Size : 39,32 MB
Release : 2008-07-28
Category : Science
ISBN : 140204464X
This 2-volume set includes extensive discussions of scattering techniques (light, neutron and X-ray) and related fluctuation and grating techniques that are at the forefront of this field. Most of the scattering techniques are Fourier space techniques. Recent advances have seen the development of powerful direct imaging methods such as atomic force microscopy and scanning probe microscopy. In addition, techniques that can be used to manipulate soft matter on the nanometer scale are also in rapid development. These include the scanning probe microscopy technique mentioned above as well as optical and magnetic tweezers.
Author : Ashok Kakkar
Publisher : Royal Society of Chemistry
Page : 241 pages
File Size : 40,28 MB
Release : 2017-04-13
Category : Technology & Engineering
ISBN : 1788010426
The term ‘miktoarm polymers’ refers to asymmetric branched macromolecules, a relatively new entry to the macromolecular field. Recent advances in their synthesis and intriguing supramolecular chemistry in a desired medium has seen a fast expansion of their applications. The composition of miktoarm polymers can be tailored and even pre-defined to allow a desired combination of functions, meaning polymer chemists can have complete control of the overall architecture of these macromolecules. By carefully selecting the composition, they can create supramolecular structures with intriguing properties, particularly for applications in biology. Miktoarm Star Polymers features chapters from experts actively working in this field, and provides the reader with a unique introduction to the fundamental principles of this exciting macromolecular system. Topics covered include the design, synthesis, characterization, self-assembly and applications of miktoarm polymers. The book is an excellent overview and up to date guide to those working in research in polymer chemistry, materials science, and polymers for medical applications.
Author : Shin-ichi Yusa
Publisher : MDPI
Page : 229 pages
File Size : 28,57 MB
Release : 2018-04-20
Category : Science
ISBN : 3038428078
This book is a printed edition of the Special Issue "Polymer Micelles" that was published in Polymers
Author : Anbanandam Parthiban
Publisher : John Wiley & Sons
Page : 408 pages
File Size : 34,87 MB
Release : 2014-06-23
Category : Technology & Engineering
ISBN : 1118860489
Understanding the reactivity of monomers is crucial in creating copolymers and determining the outcome of copolymerization. Covering the fundamental aspects of polymerization, Synthesis and Applications of Copolymers explores the reactivity of monomers and reaction conditions that ensure that the newly formed polymeric materials exhibit desired properties. Referencing a wide-range of disciplines, the book provides researchers, students, and scientists with the preparation of a diverse variety of copolymers and their recent developments, with a particular focus on copolymerization, crystallization, and techniques like nanoimprinting and micropatterning.
Author : Anil Mahapatro
Publisher : American Chemical Society
Page : 442 pages
File Size : 36,85 MB
Release : 2008-04-17
Category : Medical
ISBN :
Research on applications of polymers for biomedical applications has increased dramatically to find improved medical plastics for this rapidly evolving field. This book brings together various aspects of recent research and developments within academia and industry related to polymers for biomedical applications.