Linear-poly architecture

In a similar fashion, the cationic polymerization of 2-oxazolines has been extensively studied and was found to provide the first verified entry to linear-poly(alkyleneimine) architectures. These acylated polymers were first recognized as precursors to linear poly(ethyleneimines) in the early 1960s [25]. Hydrolysis experiments demonstrated that deacylation of these products to linear PEI was possible. The original polymerization mechanism proposed by Tomalia et al. 

An alternative polymerization mechanism and polymer architecture has been proposed by Kirchhoff [1, 2, 3], Tan and Arnold [77], By this mechanism, polybenzocyclobutenes which do not contain reactive sites of unsaturation are proposed to polymerize by the 1,4 addition of the o-quinodimethane intermediates to give a substantially linear poly(o-xylylene) structure. Since the monomers all contain at least two benzocyclobutene units the net result of this reaction will to a first approximation be a ladder type polymer as shown in Fig. 17. The formation of a true ladder polymer however would require that all... 

Scheme 29. Unreported macromolecular architectures containing defined topological bonds polycatenane 9, linear poly[3]catenane 74, poly[2]catenane network 75, multicatenane network 76, rigid polymeric catenane 77, polymeric trefoil knot 78, and polyknot 79.

Gallot and coworkers studied the effect of macromolecular architecture on the lamellar structure of the poly(ethylene oxide) crystallizable block in linear poly-(4 - f er f-butylsty ren e-h - ethylene oxide) diblocks and PtBS (PEO)2 miktoarm stars by comparing results from SAXS and DSC [348]. At the same total molecular weight and composition, the melting temperature, the degree of crystallinity, and the number of folds of PEO chains are lower for the branched samples. 

Kuo, C. M. Clarson, S. J. Semiyen, J. A., Studies of Cyclic and Linear Poly(dimethylsiloxanes) 31. Effect of Molecular Architecture/Topology on Blends of Poly(methylphenylsiloxane) and Poly(dimethylsiloxane). Polymer 1994, 35,4623-4626. 

Figure 26 Frechet-type monodendrons (generations 1, 2, and 3) possessing various reactive groups at the focal point. Rod-shaped, dendritic-linear architectural copolymers obtained by coupling respective dendrons to linear poly(para-phenylene) (PPP) backbone. (Courtesy J. Am. Chem. Soc. 119 3297, 1997. Copyright 1997 American Chemical Society.)...

Simply stated, once a ligand has attached itself to a cell at one site, it suffers a smaller entropy loss by binding at neighboring sites. Mimicry of these biological adhesion parameters can be exquisitely modeled and tested with dendrimeric systems. Although a substantial number of linear, poly (valence) polymeric architectures (e.g., poly [acrylamides], etc.) have been tested with some success, [233-236] efforts toward the use of dendrimer technology to create multivalent ligands for these purposes are in their infancy. 

Kuo, C.M., Clarson, S.J., and Semiyen, J.A. (1994) Studies of cyclic and linear poly(dimethylsiloxane)s 31. Effect of molecular architecture/topology on blends of poly(methylphenylsiloxane) and polyfdimethylsiloxane). Polymer, 35,4623 26. 

Osano et al. [162] reported the synthesis of hybrid linear-dendritic ABA -type architectures, where A and B were hb poly(ether ketone)s and linear poly(ether sulfone)s, respectively. They prepared an AB2 monomer [3,5-bis(4 -fluorobenzoyl) phenol] to construct the hb segments, in an attempt to provide better control of the resultant hb structures than by utilizing the A2 + B3 approach. The monomer combination of linear block and AB2 monomer for the formation of ABA-type architecture are shown in Table 4, entry 4. Unreacted terminal groups of the ABA polymers were capped by teri-butylphenol and sodium 4-hydroxybenzene sulfonate. Such a flexible approach could allow different functional groups on the polymer chain ends simply by replacing the functional group on the phenol in the last part of the synthesis. 

For example, the parameters g = 0.77, h = 0.94, p = 1.4, and C = 0.158 measured for a polymer sample and compared with the plots in Figures 7.11 through 7.13 were most consistent with athree-arm star monodisperse polymer a poly disperse three-arm star would have g= 1.12,/ = 1.05,p= 1.6, and C close to 0.2. °° The second example was poly(vinyl acetate) (PVAc) prepared by emulsion polymerization. Since no data for linear equivalent were available, g and h were not calculated. At lower conversion/MW p= 1.84 was found, only slightly higher than the theoretically expected p = 1.73 for a randomly branched architecture, p slightly decreased with increasing M, indicating... 

That dendrimers are unique when compared with other architectures is confirmed by an investigation on porphyrin core dendrimers and their isomeric linear analogues [63]. The isomers displayed dramatically different hydrodynamic properties, crystallinity, and solubility characteristics when compared to those of their dendritic analogues, and photophysical studies showed that energy transfer from the poly(benzylether) backbone to the core was more efficient in the dendrimer because of the shorter distance between the donor units and the acceptor core. 

Dendrimers, or arborols, or cascade, or cauliflower, or starburst polymers, were first synthesized in the early 1980s [3,4]. In 1985 Tomalia et al. [5] and Newkome et al. [6] presented the first papers dealing with dendrimers. A multitude of dendrimers have been presented in the literature ranging from polyami-doamine [7,8],poly(propylene imine) [9,10], aromatic polyethers [11-13] and polyesters [14, 15], aUphatic polyethers [16] and polyesters [17], polyalkane [18-19], polyphenylene [20], polysilane [21] to phosphorus [22] dendrimers. Combinations of different monomers as well as architectural modifications have also been presented. For example, chirality has been incorporated in dendrimers [23,24]. Copolymers of linear blocks with dendrimer segments (dendrons) [25-27] and block-copolymers of different dendrons have been described [28]. 

In this section the unprecedented oligocatenanes, i.e. the [5]- and [7]catenanes 30 and 31 and the scarce experimental approaches to high molecular-weight linear polycatenane 9 have been presented. No synthetic Olympic network 32 has been reported to date, although their DNA analogs are known. The next section is dedicated to a new type of macromolecular architecture, structurally related to polycatenane 9, i.e. poly[2]catenanes. 

The mechanical and thermal properties of a range of poly(ethylene)/ poly(ethylene-propylene) (PE/PEP) copolymers have been examined by Mohajer et al. (1982). They studied the effect of variation of composition and copolymer architecture on the polymer properties by synthesizing a range of PE-PEP-PE and PEP-PE-PEP triblocks and PE-PF.P diblocks with high molecular weights (M > 200 kg mol (.The crystallinity, density and melting enthalpy for all copolymers were found to be linearly dependent on the PE content, indicating microphase separation of PE and rubbery PEP in the solid state. The... 

Thickness of the barrier layer, optimized at 220 nm [133], played a crucial role with respect to the chemosensor sensitivity, selectivity and LOD. So, eventually, the chemosensor architecture comprised a gold-film electrode, sputtered onto a 10-MHz resonator, coated with the poly(bithiophene) barrier layer, which was then overlaid with the MIP film. This architecture enabled selective determination of the amine at the nanomole concentration level. LOD for histamine was 5 nM and the determined stability constant of the MIP-histamine complex, XMn> = 57.0 M 1 [131], compared well with the values obtained with other methods [53, 136, 137]. Moreover, due to the adopted architecture, the dopamine chemosensor could determine this amine with the stability constant for the MIP-dopamine complex, XMip = (44.6 4.0) x 106 M-1 and LOD of 5 nM [133], which is as low as that reached by electroanalytical techniques [138]. The MIP-QCM chemosensor for adenine [132] also featured low, namely 5 nM, LOD and the stability constant determined for the MIP-adenine complex, XMIP = (18 2.4) x 104 M, was as high as that of the MIP-adenine complex prepared by thermo-induced co-polymer-ization [139]. The linear concentration range for determination of these amines extended to at least 100 mM. 

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