Functionalized polydiacetylenes with

Functionalized Polydiacetylenes with Polar, Hydrogen Bonding and Metal-Containing Groups... 

The sensors discussed so far are based on ligands covalently bound to the polymer backbone. Other methods of detection - often referred to as mix and detect methods - work by simple noncovalent incorporation of the polymer with the ligand of interest. Reichert et al. generated liposomes of polydiacetylene with sialic acid for the same purpose of detection as Charych s surface-bound polymers, but realized that covalent functionalization of the polymer was not necessary [17]. Through simple mixing of the lipid-bound sialic acid with the polymer before sonication and liposome formation, they were able to form a functional colorimetric recognition system (Fig. 8). 

Rangin M, Basu A. Lipopolysaccharide identification with functionalized polydiacetylene liposome sensors. J Am Chem Soc 2004 126 5038-5039. 

Wang C, Ma Z, Su Z. Facile method to detect ohgonucleotides with functionalized polydiacetylene vesicles. Sens Actual B Chem 2006 B113 510-515. 

Zhang Y, Fan Y, Sun C, Shen D, Li Y, Li J. Functionalized polydiacetylene-glycoUpid vesicles interacted with Escherichia coli under the Ti02 colloid. CoUoids Surf B Biointerfaces 2005 40 137-142. 

Camacho, M.A., Kar, A.K., Lindsell, W.E.. Murray, C., Preston, P.N., Wherrett, B.S. Synthesis and nonlinear optical properties of functionalized polydiacetylenes and their complexes with transition metals. J. Mater. Chem. 9, 1251-1256 (1999)... 

Polydiacetylenes with appropriate amphiphilic structures can be used to fabricate thin films in this way, e.g., heptadeca-4,6-diyne-l-ol and the corresponding add. It is often found that the stability of the monolayers is a function of the stmcture of the molecules. It has also been found advantageous to use the neutralized form of acid derivatives, and diacetylene monocarboxylic acids generally form much more stable films if the cadmium salt is used initially, where the Cd + ion is then present in the aqueous phase as a counterion. 

Single-handed helicity induction was also achieved in gels and films of polyphenylacetylene derivatives. Gels obtained by copolymerization of (4-carboxyphenyl)acetylene with a bis(phe-nylacetylene) or by cross-linking of 168 responded to chirality to nonracemic amines in DMSO and alkaline water. Compound 174 formed an optically active gel upon complexation with optically active bis (amino acid)s. A cast film of 168 exhibited ICD in response to the chirality of liquid and solid chiral amines. Polydiacetylenes with a 4-carboxyIphenyI functions also showed ICD in the presence of optically active amines in dispersion and in the solid state. Helicity induction was also realized for polyphosphazene derivative 185 as (P)-phenethylamine as the chiral additive. ... 

In order to prepare polydiacetylenes with aromatic rings directly attached to the polymer backbone an interesting strategy has been employed. The aromatic ring is attached to one position of the diyne and a functionality for proper self-assembly (Fig. 1) is attached to the other position of the di5me. A carbamate functionality has commonly been used to provide the proper supramolecular stnictiu-e (Fig. 5). Advantages of this scheme are that the reduced nonbonded interactions... 

Reichert A, Nagy JO, Spevak W, Charych D (1995) Polydiacetylene liposomes functionalized with sialic-acid bind and colorimetrically detect influenza-virus. J Am Chem Soc 117 829-830... 

Guo CX, Boullanger P, Liu T, Jiang L. Size effect of polydiacetylene vesicles functionalized with glycolipids on their colorimetric detection ability. J Phys Chem B Condens Matter Mater Surf Interfaces Biophys 2005 109 18765-18771. 

The values for functionalized polymers, listed in Table 2 compare also well with conjugated polymers which form good optical quality amorphous thin films like polydiacetylene poly-4BCMU and functionalized polythiophenes po-ly(3-decyl)thiophene (P3DT) and poly(4-,4 -didecyl-2,2 Ibithiophene (PDDBT)... 

Reichert, A., J.O. Nagy, W. Spevak, and D. Charych. 1995. Polydiacetylene liposomes functionalized with sialic-acid bind and colorimetrically detect influenza-vims. J Am Chem Soc 117 (2) 829-830. Charych, D., Q. Cheng, A. Reichert, G. Kuziemko, M. Stroh, J.O. Nagy, W. Spevak, and R.C. Stevens. 1996. A Htmus test for molecular recognition using artificial membranes. Chem Biol 3 (2) 113-120. 

Clickable , polymerized liposomes as a general liposomal platform for rapid attachment of functional moieties to their peripheries via click chemistry. The platform was based on polydiacetylene lipids terminated with alkynyl groups... 

Preparation of Polydiacetylene. The preorganization for the 1,4-polymerization of diacetylenes has been discussed previously (7,14,15). Successful polymerization occurs when the diacetylenes have a translational repeat distance (d) of about 0.49 nm and an angle (tt) of about 45° with respect to the translational direction and van der Waals contact (i v) of the polydiacetylene functionalities (Fig. 1). If these structural parameters are met then the Cl and C4 carbon atoms of adjacent diacetylenes will be in a position for a topochemically controlled polymerization. Because the 0.49 nm translational repeat distance (d) of the monomer is about the same as the repeat distance in the polymer, the pol5nnerization process can occur with little disruption of the reactant packing. 

A sensor is a system that displays a readily detectable response in the presence of a specific analyte. Indeed, stimulus-responsive vesicles have been tailor-made to function as highly specific sensors. The overwhelming majority of vesicle-based sensors are based on a very simple type of amphiphile polydiacetylenes. These polymeric amphiphiles are easily formed from simple diacelylene amphiphiles by in situ photopolymerization of vesicles. If the vesicles are additionally equipped with ligand or receptor groups, the absorbance and fluorescence of the conjugated polymer backbone is highly sensitive to the presence of metal ions, anions, and small as well as large... 

---