Definitive support by transmission electron microscopy, electron diffraction, and electron density maps for the formation of a BCC lattice from poly[N-[3,4,5-tris(n-dodecan-1-yloxy)benzoyl]ethyleneimine].

Transmission electron microscopy (TEM), electron diffraction (ED), and electron density maps (EDM) experiments were carried out on a poly[N-[3,4,5-tris(n-dodecan-1-yloxy)benzoyl]ethyleneimine] [poly[(3,4,5)12G1-Oxz]] with a degree of polymerization (DP) of 20. All experiments confirmed the thermotropic body-centered cubic (BCC) Im3m lattice suggested previously by X-ray diffraction (XRD) experiments. The unit cell parameter determined by ED at 23 degrees C is a = 42.4 A, in good agreement with XRD results which show a = 42.6 A after quenching from 70 degrees C. EDM of the XRD results confirm that the supramolecular minidendrimer obtained from poly[(3,4,5)12G1-Oxz] adopts a spherical "inverse micellar-like" structure, with the polyethyleneimine backbone and the aromatic groups microsegregated and concentrated in the corners and in the center of the cubic unit cell. A space-filling continuum is realized by the n-alkyl groups that radiate out of the aromatic core of the spherical dendrimer. This manuscript is only the second example of complete structural analysis of a lattice generated from supramolecular objects and complements the previous example reported from our laboratory on the Pm3n lattice.

Poly(oxazoline)s with tapered minidendritic side groups as models for the design of synthetic macromolecules with tertiary structure. A demonstration of the limitations of living polymerization in the design of 3-D structures based on single polymer chains.

The synthesis and living cationic ring-opening polymerization of 2-[3,4-bis(n-alkan-1-yloxy)phenyl]-2-oxazolines with alkan being tetradecan and pentadecan, i.e., (3,4)nG1-Oxz with n = 14 and 15, is described. The structural analysis of the resulting polymers with well-defined molecular weights and narrow molecular weight distribution was carried out by a combination of techniques, including differential scanning calorimetry (DSC), thermal optical polarized microscopy (TOPM), and X-ray diffraction (XRD). At low molecular weights both polymers self-assemble into spherical supramolecules that self-organize into a Pm3n 3-D lattice while at high molecular weights they form cylindrical macromolecules that self-organize into a p6mm 2-D hexagonal columnar lattice. Both polymers exhibit a 3-D shape change as a function of their degree of polymerization as was reported for the first time in a previous publication from our laboratory (Percec, V.; Ahn, C.-H; Ungar, G.; Yeardley, D. J. P.; Möller, M.; Sheiko, S. S. Nature (London) 1998, 391, 161). Since these polymers can be obtained via a living polymerization, a detailed mechanistic investigation of the influence of the degree of polymerization and molecular weight distribution on the formation of a 3-D spherical macromolecule from a single polymer chain, i.e., a tertiary structure, was possible. The experimental results have demonstrated that the synthesis of nonbiological macromolecules exhibiting tertiary structure is possible in at most a few percent of all macromolecules via living polymerization. This is the case even when macromolecules with very narrow molecular weight distributions and well-defined molecular weights are used. Therefore, the design of synthetic macromolecules with tertiary structure requires not only chains with well-defined molecular weight but also, in particular, macromolecules with no distribution of their chain length.

Poly(oxazolines)s with tapered minidendritic side groups. The simplest cylindrical models to investigate the formation of two-dimensional and three-dimensional order by direct visualization.

The synthesis of 2-[3,4-bis(n-alkan-1-yloxy)phenyl]-2-oxazolines with alkan = octan, decan, dodecan, and tridecan is presented. Their living cationic ring opening polymerization produces cylindrical macromolecules that self-organize in a hexagonal columnar two-dimensional phase. The structural analysis of these polymers was carried out by a combination of techniques including differential scanning calorimetry, thermal optical polarized microscopy, X-ray diffraction, transmission electron microscopy, electron diffraction, scanning force microscopy, and atomic force microscopy (AFM). The diameter of these cylindrical macromolecules ranges from 33 to 44 A, and therefore they represent the simplest cylindrical macromolecules that can be directly visualized by AFM on a surface. Preliminary experiments have demonstrated the use of these cylindrical macromolecules as models to investigate the creation of two-dimensional and three-dimensional order via direct visualization and thus they represent the simplest nonbiological systems that mimic the role played by the complexes of nucleic acids with proteins in structural analysis by direct visualization.

Synthesis of functional aromatic multisulfonyl chlorides and their masked precursors.

The synthesis of functional aromatic bis(sulfonyl chlorides) containing an acetophenone and two sulfonyl chloride groups, i.e., 3,5-bis[4-(chlorosulfonyl)phenyl]-1-acetophenone (16), 3,5-bis(chlorosulfonyl)-1-acetophenone (17), and 3,5-bis(4-(chlorosulfonyl)phenyloxy)-1-acetophenone (18) via a sequence of reactions, involving in the last step the quantitative oxidative chlorination of S-(aryl)- N,N'-diethylthiocarbamate, alkyl- or benzyl thiophenyl groups as masked nonreactive precursors to sulfonyl chlorides is described. A related sequence of reactions was used for the synthesis of the aromatic trisulfonyl chloride 1,1,1-tris(4-chlorosulfonylphenyl)ethane (24). 4-(Chlorosulfonyl)phenoxyacetic acid, 2,2-bis[[[4-(chlorosulfonyl)phenoxyacetyl]oxy]methyl]-1,3-propanediyl ester (27), 5,11,17,23-tetrakis(chlorosulfonyl)-25,26,27,28-tetrakis(ethoxycarbonylmethoxy)calix[4]arene (38), 5,11,17,23,29,35-hexakis(chlorosulfonyl)-37,38,39,40,41,42-hexakis(ethoxycarbonylmethoxy)calix[6]arene (39), 5,11,17,23,29,35,41,47-octakis(chlorosulfonyl)-49,50,51,52,53,54,55,56-octakis(ethoxycarbonylmethoxy)calix[8]arene (40), 5,11,17,23-tetrakis(tert-butyl)-25,26,27,28-tetrakis(chlorosulfonyl phenoxyacetoxy)calix[4]arene (44), 5,11,17,23,29,35-hexakis(tert-butyl)-37,38,39,40,41,42-hexakis(chlorosulfonylphenoxyacetoxy)calix[6]arene (45), and 5,11,17,23,29,35,41,47-octakis(tert-butyl)-49,40,51,52,53,54,55,56-octakis(chlorosulfonylphenoxyacetoxy)calix[8]arene (46) were synthesized by two different multistep reaction procedures, the last step of both methods consisting of the chlorosulfonation of compounds containing suitable activated aromatic positions. 2,4,6-Tris(chlorosulfonyl)aniline (47) was obtained by the chlorosulfonation of aniline. The conformation of two series of multisulfonyl chlorides i.e., 38, 39, 40 and 44, 45, 46, was investigated by (1)H NMR spectroscopy. The masked nonreactive precursor states of the functional aromatic multisulfonyl chlorides and the aromatic multisulfonyl chlorides reported here represent the main starting building blocks required in a new synthetic strategy elaborated for the preparation of dendritic and other complex organic molecules.

Detecting the shape change of complex macromolecules during their synthesis with the aid of kinetics. A new lesson from biology.

The synthesis and living ring opening metathesis polymerization initiated with RuCl2(=CHPh)(PCy3)2 of three 7-oxanorbornene monomers containing two tapered 3a and respectively two conical 3b and 3c dendritic side groups is described. 3a and the corresponding polymer 4a self-assemble in a cylindrical shape, while 3b and 3c self-assemble in spherical shapes. The polymerization of 3a proceeds via a cylindrical growing chain and occurs with the same rate constant regardless of the initial monomer concentration and the initial ratio between 3a and the initiator. The polymers resulting from 3b and 3c exhibit, depending on the degree of polymerization, spherical and cylindrical shapes. The shape change of the propagating macromolecules that resulted from 3b and 3c were detected by the change in the rate constant of propagation. The implication of this kinetic method for the detection of shape change in the design of novel complex synthetic nanoscale functional macromolecules inspired from biology is discussed.