Search results for "supramolecular chemistry"
showing 10 items of 721 documents
Synthesis and characterisation of novel chemical conjugates based on alpha, beta-polyaspartylhydrazide and beta-cyclodextrins
2006
A new family of supramolecular systems based on a synthetic polyaminoacid and cyclic oligosaccharides such as beta-cyclodextrins (beta-CDs) was synthesised. The pharmaceutical potential of these systems arises from the proper combination between the complexing properties of cyclodextrins and the particular pharmacokinetic profile that can be obtained by using macromolecular conjugates with a biocompatible backbone. Five supramolecular conjugates were synthesised by using alpha,beta-polyaspartylhydrazide (PAHy) as a polymeric component and various amounts of two P-CD derivatives. In particular, by reaction of PAHy with beta-CD monoaldehyde, samples named as A(1), A(2) and A(3), bearing, resp…
Cooperative structure formation by combination of covalent and association chain polymers: 4. Designing functional groups for supramolecular structur…
1991
Abstract A small number of polar functional groups are attached to polybutadiene by a polymer analogous reaction. Depending on their molecular structure, different degrees of supramolecular ordering result from the aggregation of these polar groups. In the case of phenylurazole units, which carry a single site for hydrogen-bond complexation, binary contacts are formed; whereas linear association chain structures are formed in the case of polybutadiene carrying phenylurazole units additionally substituted with a carboxy group in meta or para positions of the phenyl ring. In the latter case, association chains aggregate cooperatively to an ordered supramolecular structure. The different struc…
Automated Large-Scale Synthesis of Supramolecular Oligo(p-benzamide) Block Copolymers
2007
A fully automated large-scale synthesis procedure has been developed that allows the preparation of supramolecular rod−coil copolymers on a 100 g scale. The new reaction cycle allows the stepwise growth of oligo(p-benzamide)s onto the chain end of amine-terminated polymers. Amine-terminated poly(ethylene glycol) (PEG, Mn = 5000 g mol-1) and poly(styrene) (PS, Mn = 2950 g mol-1) were prepared, and an octa(p-benzamide) oligomer block was grown from the chain end in an automated computer-controlled reaction cycle. Plotting the apparent molecular weight of the PEG copolymer against the number of reaction cycles revealed a linear relationship, which emphasized the high level of control this meth…
Supramolecular Linear-g-Hyperbranched Graft Polymers: Topology and Binding Strength of Hyperbranched Side Chains
2013
Complex, reversible hyperbranched graft polymer topologies have been obtained by spontaneous self-assembly. Well-defined adamantyl- and β-cyclodextrin-functionalized polymers were employed to generate linear-g-(linear–hyperbranched) supramolecular graft terpolymers. For this purpose the synthesis of monoadamantyl-functionalized linear polyglycerols (Ada-linPG) and hyperbranched polyglycerols (Ada-hbPG) as well as poly(ethylene glycol)-block-linear polyglycerol (Ada-PEG-b-linPG) and poly(ethylene glycol)-block-hyperbranched poly(glycerol) (Ada-PEG-b-hbPG) block copolymers was established. Isothermal titration calorimetry (ITC) with β-cyclodextrin revealed a shielding effect of hyperbranched …
Halo and Pseudohalo Cu(I)-Pyridinato Double Chains with Tunable Physical Properties
2015
The properties recently reported on the Cu(I)-iodide pyrimidine nonporous 1D-coordination polymer [CuI(ANP)] (ANP = 2-amino-5-nitropyridine) showing reversible physically and chemically driven electrical response have prompted us to carry a comparative study with the series of [CuX(ANP)] (X = Cl (1), X = Br (2), X = CN (4), and X = SCN (5)) in order to understand the potential influence of the halide and pseudohalide bridging ligands on the physical properties and their electrical response to vapors of these materials. The structural characterization of the series shows a common feature, the presence of -X-Cu(ANP)-X- (X = Cl, Br, I, SCN) double chain structure. Complex [Cu(ANP)(CN)] (4) pre…
Local dynamics in supramolecular polymer networks probed by magnetic particle nanorheology
2019
Transient supramolecular polymer networks are promising candidates as soft self-healing or stimuli-sensitive materials. In this paper, we employ a novel nanorheological approach, magnetic particle nanorheology (MPN), in order to better understand the local dynamic properties of model supramolecular networks from a molecular point of view. Hence, the bond strength between four-arm star-shaped polyethylene glycol (PEG) functionalized at the four extremities with terpyridine ligands is tuned by implementing different metal ions with variable complexation affinities for the ligand. We show that MNP allows for the evaluation of the strength and connectivity of the polymer networks by the estimat…
Mechanical Properties of Single Molecules and Polymer Aggregates
2013
This chapter deals with the mechanical properties of single polymer chains, aggregates, and supramolecular complexes. The topics discussed cover a broad range from fundamental statistical mechanics of the equilibrium elastic properties of single polymer chains to details of the behavior of binding pockets in biomolecular assemblies as observed by force spectroscopy. The first section treats the equilibrium mechanical properties of single polymer chains in various environments, investigated via extensive simulations employing coarse-grained models that have proven extremely successful in many branches of polymer physics, namely the bond-fluctuation model and the self-avoiding walk model. Apa…
A Comparison of Shuttling Mechanisms in Two Constitutionally Isomeric Bistable Rotaxane-Based Sunlight-Powered Nanomotors
2006
To find out how best to optimize shuttling of the macrocycle in a particular class of photochemically driven molecular abacus, which has the molecular structure of BR-I6+ in its Mark I prototype (Ashton et al., Chem. Eur. J. 2000, 6, 3558), we have synthesized and characterized a Mark II version of this kind of two-station rotaxane comprised of six molecular modules, namely (a) a bisparaphenylene[34]crown-10 electron donor macrocycle M and its dumbbell-shaped component which contains (b) a Ru(ii)-polypyridine photoactive unit P2+ as one of its stoppers, (c) a p-terphenyl-type ring system as a rigid spacer S, (d) 4,4′-bipyridinium (A12+) and (e) 3,3′-dimethyl-4,4′-bipyridinium (A22+) electr…
Multiple interactions between molecular and supramolecular ordering
1999
We report studies of the interplay among processes of molecular conformational changes, spinodal demixing of the solution, and molecular crosslinking involved in the physical gelation of a biopolysaccharide-water system. Multiple interactions and kinetic competition among these processes were studied under largely different absolute and relative values of their individual rates by appropriate choices of the quenching temperature at constant polymer concentration. Quenching temperature strongly affects the rate of growth but not the final value of the fractal dimension of the gel. Kinetic competition plays a central role in determining the final conformation of individual molecules and the s…
Receptors for Nucleotides
2012
Recognition and activation of nucleotides by polyammonium receptors constitute an important target in supramolecular chemistry since the very beginning of this field. Nucleotides have three components: (i) the polyphosphate chain, (ii) the sugar moiety, and (iii) the nucleobase, which permit their multipoint binding through attractions between opposite charges, hydrogen bonding, π-stacking, CH–π interactions, and so on. In this chapter, different receptors for nucleotides, most but not all of them consisting polyamines, are examined, focusing on their molecular structure that enables different binding modes to be operated. Also, a number of examples of nucleotide binding through metal compl…