Self-assembling systems

Introductory text with an emphasis on self-assembly systems and emulsions... 

For technological applications it is highly desirable to be able to design self-assembling systems to have particular physico-chemical properties under a given set of experimental conditions. Using computer simulation, it is possible to construct an atomistic model of tapes, ribbons and fibrils to study all of the interatomic interactions within the system in a quantitative manner. Figure 13 shows atomistic... 

Self-assembling systems made of proteins provide many biological systems with essential structural elements, including viral envelopes, bacterial S-layers, microtubules, collagens, and keratins (see Ref. 6 for a review). Detailed studies on in vitro self-assembly optimization were carried out for several systems as a part of an ongoing effort to elucidate the in vivo mechanism. Data reported from such studies may provide an optional basis for the design and in vitro fabrication of nanostructures made of natural proteins (Fig. 1). 

DD can be monitored by a variety of experimental techniques. They involve thermodynamic, dilatometric, and spectroscopic procedures. Molecular dynamics (MD) simulations also become applicable to self-assembled systems to some extent see the review in Ref. 2. Spectroscopic methods provide us with molecular parameters, as compared with thermodynamic ones on the macroscopic level. The fluorescence probing method is very sensitive (pM to nM M = moldm ) and informs us of the molecular environment around the probes. However, fluorescent molecules are a kind of drug and the membrane... 

A four-component self-assembling system was described by Kuroda (46). Two rhodium porphyrins are coordinated by the terminal pyridine groups of an extended ligand constructed from a tartrate derivative. 

Many opportunities conversely are supported by reversible reactions of QM despite the noted complications. One example includes the synthesis and chiral resolution of binaphthol derivatives by two cycles of QM formation and alkylation.77 The reversibility of QM reaction may also be integrated in future design of self-assembling systems to provide covalent strength to the ultimate thermodynamic product. To date, QMs have already demonstrated great success in supporting the opposite process, spontaneous disassembly of dendrimers (Chapter 5). 

The first example of a donor-acceptor molecular complex was noted in 1949 by Bensei and Hildebrand [137] in their studies involving charge transfer complexes between benzene and molecular iodine. Subsequently such complexes were studied by Mulliken [138] and now more recently have been used by Stoddart et al. [16,139] in designing novel self-assembling systems. 

Recently, biodegradable polymers have been used to fabricate macro- and nanometer scale self-assembled systems such as microspheres (MSs), nanospheres (NSs), polymer micelles, nanogels, and polymersomes (Fig. 1). These have attracted growing interest because of their potential utility for drug delivery systems (DDS), tissue engineering, and other applications. To construct these self-assembled systems... 

Joralemon MJ, McRae S, Emrick T (2010) PEGylated polymers for medicine from conjugation to self-assembled systems. Chem Commun (Camb) 46 1377-1393... 

Imposing the shear on self-assembling systems may induce ordered morphologies that are not observable in equilibrium [102]. For example, the lamellar... 

Although the self-assembly process is easy and convenient to operate, success in obtaining the expected object is still a challenge for chemists. The aims of this article are to summarize the coordination chemistry of amino acids, to review our recent work on 3d-4f heterometallic clusters bearing amino acid ligands, and to expound the effects of several factors of influence on self-assembly, such as presence of a secondary ligand, lanthanides, crystallization conditions, the ratio of Cu2+ to amino acids, and transition metal ions. We hope that our systematic researches on the 3d-4f amino acid clusters can provide a useful framework of reference for the study of other self-assembly systems. 

Order and polydispersity are key parameters that characterize many self-assembled systems. However, accurate measurement of particle sizes in concentrated solution-phase systems, and determination of crystallinity for thin-film systems, remain problematic. While inverse methods such as scattering and diffraction provide measures of these properties, often the physical information derived from such data is ambiguous and model dependent. Hence development of improved theory and data analysis methods for extracting real-space information from inverse methods is a priority. 

Yu M, Bovet N, Satterly CJ, Bengio S, Lovelock KRJ, Milligan PK, Jones RG, Woodruff DP, Dhanak V (2006) True nature of an archetypical self-assembly system mobile Au-thiolate species on Au(lll). Phys Rev Lett 97 166102... 

Monolayer blown-film extrusion, VDC copolymers in, 25 725, 728-729 Monolayers, self-assembled, 77 57 Monolayer self-assembled systems, 16 800 Monolignols, 27 10—11, 13, 14 Monolithic drug delivery systems, 9 11 Monomagnesium phosphate, 78 839 Monomer addition, in PVC polymerization, 25 665-666... 

Tomalia, D. A. in Walsh, B. (ed.), Non-Viral Genetic Therapeutics Advances, Chal-langes and Applications for Self-Assembling Systems, IBC USA Conferences, Inc., Westborough, MA, 1996, pp. 1.2-1.2.36. 

Baker, J. R. Jr. in Heller, M. J., Lehn, P. and Behr, P. (eds), Conference Proceedings Series. Artificial Self-Assembling Systems for Gene Delivery, American Chemical Society, Washington DC, 1996, pp. 129-145. 

The Netherlands Present address DAF Trucks N.V. Advanced Engineering Engines Hugo van der Goeslaan 1 P.O. Box 90065 5600 PT Eindhoven The Netherlands Herman van Bekkum Delft University of Technology DelftChem Tech Self Assembling Systems Julianalaan 136 2628 BL Delft The Netherlands... 

During the course of the article, we will present evidence that the histones constitute part of a self-assembly system (Section IV). In the absence of DNA they retain the information to interact with each other to form a hierarchy of structures with dimensions, periodicities, and intermolecular contacts, compatible with what is known about the protein core of chromatin. This strongly suggests that histone-histone interactions have a fundamental role in chromatin structure. 

The energetics of peptide-porphyrin interactions and peptide ligand-metal binding have also been observed in another self-assembly system constructed by Huffman et al. (125). Using monomeric helices binding to iron(III) coproporphyrin I, a fourfold symmetric tetracarboxylate porphyrin, these authors demonstrate a correlation between the hydropho-bicity of the peptide and the affinity for heme as well as the reduction potential of the encapsulated ferric ion, as shown in Fig. 12. These data clearly demonstrate that heme macrocycle-peptide hydrophobic interactions are important for both the stability of ferric heme proteins and the resultant electrochemistry. 

Mihara and co-workers (120, 123) have shown in a self-assembly system composed of a helix-disulfide-helix and an iron(III) mesoporphyrin... 

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