Templated synthesis, polymeric

According to Ref. [12], template for synthesis of nanomaterials is defined as a central structure within which a network forms in such a way that removal of this template creates a filled cavity with morphological or stereochemical features related to those of the template. The template synthesis was applied for preparation of various nanostructures inside different three-dimensional nanoporous structures. Chemically, these materials are presented by polymers, metals, oxides, carbides and other substances. Synthetic methods include electrochemical deposition, electroless deposition, chemical polymerization, sol-gel deposition and chemical vapor deposition. These works were reviewed in Refs. [12,20]. An essential feature of this... 

Porous polymer materials, especially in particulate form, are of interest in a diverse range of applications, including controlled drug delivery, enzyme immobilization, molecular separation technology, and as hosts for chemical synthesis [101-104]. MS materials have been used as hosts for the template synthesis of nanoporous polymer replicas through in situ polymerization of monomers in the mesopores [105-108]. 

Production of materials in which the daughter polymer and the template together form a final product seems to be the most promising application of template polymerization because the template synthesis of polymers requiring further separation of the product from the template is not acceptable for industry at the present stage. Possible method of production of commonly known polymers by template polymerization can be based on a template covalently bonded to a support and used as a stationary phase in columns. Preparation of such columns with isotactic poly(methyl methacrylate) covalently bonded to the microparticulate silica was suggested by Schomaker. The template process can be applied in order to produce a set of new materials having ladder-type structure, properties of which are not yet well known. A similar method can be applied to synthesis of copolymers with unconventional structure. 

As discussed in Chapter 5, copolymers with unconventional distribution of units can be obtained by copolymerization in the presence of proper template. Synthesis of polymers with defined tacticity can be realized by template polymerization or copolymerization. In spite of the fact that many interesting potential applications seems to be possible neither template polymerization as a method of synthesis nor the products obtained in this process have been applied on an industrial scale until now. 

The inter-relationship between colloid and polymer chemistries is completed by colloidal polymer particles. The formation of 50-nm-diameter, 100- to 200-nm-long polyaniline fibrils in a poly(acrylic acid)-template-guided polymerization, similar in many ways to those produced from polymerized SUVs (see above), provides a recent example of polymer colloids [449], The use of poly(styenesulfonic acid) as a template yielded globular polyaniline particles which were found to be quite different morphologically from those observed in the regular chemical synthesis of polyaniline [449]. 

For the very low density varieties of the cases shown in Figure 2 and, more particularly, Figure 4 (curve 7), for which initiation is slow compared to both termination (release from end of template) and polymerization, a simpler treatment, in which the interference of one ribosome with another is totally neglected, should suffice. In this case an equation of the form of Eq. (1), herein only applied to the problem of DNA synthesis, should be valid, but Eqs. (2) and (3) should be modified to account for repetitive initiation at site 1 and continuing release from site K, respectively Eqs. (4) and (6) will not apply. In the even more restricted (but perhaps biochemically relevant) case in which, in addition to neglecting ribosome interference, one may also neglect the back reaction (kb x 0), one may solve this system of equations (Eq. (1), plus Eqs. (2) and (3) modified as described) very easily by taking Laplace transforms.13 This is the only case with repetitive initiation for which we have been able to find solutions for the transient, as well as steady state, behavior. 

A very important issue in the synthesis of MIPs is the study of the pre-organized complexes formed between the functional monomer(s) and the template. Preferably, this complex should be sufficiently stable to withstand polymerization conditions on the one hand and satisfactorily labile to allow both facile release of a template after polymerization and fully reversible rebinding of an analyte on the other. 

Polynucleotide polymerases, or nucleotidyl transferases, are enzymes that catalyze the template-instructed polymerization of deoxyribo- or ribonu-cleoside triphosphates into polymeric nucleic acid - DNA or RNA. Depending on their substrate specificity, polymerases are classed as RNA- or DNA-dependent polymerases which copy their templates into RNA or DNA (all combinations of substrates are possible). Polymerization, or nucleotidyl transfer, involves formation of a phosphodiester bond that results from nucleophilic attack of the 3 -OH of primer-template on the a-phosphate group of the incoming nucleoside triphosphate. Although substantial diversity of sequence and function is observed for natural polymerases, there is evidence that many employ the same mechanism for DNA or RNA synthesis. On the basis of the crystal structures of polymerase replication complexes, a two-metal-ion mechanism of nucleotide addition was proposed [1] during this two divalent metal ions stabilize the structure and charge of the expected pentacovalent transition state (Figure B.16.1). 

The molecular imprinting method can be used to synthesize enantioselective solid materials for asymmetric organic synthesis. The first attempt to use a metal complex with an attached chiral ligand as a template was attempted by Lemaire [52]. The Rh complex, ((15,25)-V,V -dimethyl-l,2-diphenylethane diamine)-[Rh(CgHj2)Cl]2 coordinated with optically pure l-(5)-phenylethoxide or phenylethoxide (Rh 1-phenylethanolate) (template) was polymerized in the presence of isocyanate, and the polyurea-supported Rh complex is reacted with isopropanol to extract the template from the polymer backbone. They reported the influence of molecular imprinting on catalytic performance (conversion and enantiomeric excess) for the asymmetric transfer hydrogenation (Table 22.2). The imprinted polymer exhibited higher enantioselectivity compared to a nonimprinted... 

The chemical methods for the preparation of nanomaterial could be categorized as either template-directed or template-free. The template synthesis methods commonly used for the production of one-dimensional nanostructured PANI are further subdivided into hard template (physical template) synthesis and soft template (chemical template) synthesis approach according to the solubility of the templates in the reaction media. Non-template routes for the synthesis of one-dimensional nanostructured PANI such as rapid-mixing reaction method, radiolytic synthesis, interfacial polymerization, and sonochemical synthesis have also been reported [56], Other approaches like combined soft and hard template synthesis are also known. An overview of hard-template, soft-template, and template-free procedures are presented in the following paragraphs. 

McKelvey, C.A., Kaler, E.W., Zasadzinski, J.A., Coldren, B. and Jung, H.T. (2000) Templating hollow polymeric spheres from catanionic equilibrium vesicles Synthesis and characterization. Langmuir, 16, 8285-8290. 

The most general definition of a template is as a structure-directing agent. In surfactant solutions the final templated polymers can be either discrete nanoparticles or mesostructured bulk materials as a consequence of polymerization, respectively, in the non-continuous or continuous domains of the template. Thermodynamically stable media, such as microemulsions, equilibrium vesicles, or lyotropic mesophases are especially useful as templates because of their structural definition and reproducible morphologies. The mesostructure of a thermodynamically stable template is defined by composition and temperature, but this same feature makes the structure unstable to changes in temperature, pH, or concentration. The aim of template synthesis is to transfer the self-organized template structure into a mechanically and chemically stable, durable, and processable material. 

Polymerization offers an approach to making vesicle formulations suitable for appUcations. The maj or benefits of polymerization include increasing the chemical-mechanical strength of the vesicle architecture, and the potential for performing subsequently a variety of reactions to create a highly functionalized surface. The most common approach to polymerization in vesicles is to use polymerizable surfactants (Fig. 2a). The use of polymerizable surfactants is best described as the polymerization of vesicles or fixation of vesicles, and so is a synergistic template synthesis. Typically, unsaturated biological surfactants have been specificaUy synthesized for these types of polymerizations, and there are a number of excellent reviews of this subject [3-6]. 

Liquid crystals combine properties of both liquids (fluidity) and crystals (long range order in one, two, or three dimensions). Examples of liquid crystalline templates formed by amphiphiles are lyotropic mesophases, block copolymer mesophases, and polyelectrolyte-suxfactant complexes. Their morphological complexity enables the template synthesis of particles as well as of bulk materials with isotropic or anisotropic morphologies, depending on whether the polymerization is performed in a continuous or a discontinuous phase. As the templating of thermotropic liquid crystals is already described in other reviews [47] the focus here is the template synthesis of organic materials in lyotropic mesophases. 

On the other hand, Kato et al. (52) reported the synthesis of 4 -thiopyrimidines (U and C) and their incorporation into transcripts by T7 RNA polymerase. The 4 -thio modification increased the stability of the transcripts 50-fold relative to the natural RNA transcripts. Using these libraries, Kato et al. (52) successfully performed a SELEX modification, and they were able to discover an aptamer to thrombin. Vaught et al. (56) showed that several UTPs substituted at the 5-position can be synthesized and subsequently transcribed using T7 RNA polymerase. Kuwahara et al. (59) have synthesized similar 5-modified dUTP compounds and have shown that a DNA polymerase efficiently catalyzed their template-dependent polymerization. Jaeger et al. 58) described a similar system for introducing a variety of modified bases into oligonucleotides using other DNA polymerases. 

This chapter aims to provide an update on the role of anions as templates. The review is divided in two main sections (a) anion-templated synthesis of assemblies linked together by irreversible bonds (or bonds that are inert under mild experimental conditions) (b) anion templates in systems where the bonds linking the components are reversible and lead to anion-controlled dynamic combinatorial libraries. Since some comprehensive reviews in the area of anion temptation have appeared over the past few years [5-7], this chapter will mainly focus on papers published recently and will aim to show the principles of anion temptation rather than being a comprehensive account of the literature. In addition, the scope of the chapter will be restricted to finite assemblies (molecular or supramolecular) and not polymeric (for a review on molecularly imprinted polymers using anions see Steinke s chapter in this volume). 

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