Polyallylamines

Nishiyama Kand Fujihira M 1988 Cis-trans reversible photoisomerization of an amphiphilio azobenzene derivative in its pure LB film prepared as polyion oomplexes with polyallylamine Chem. Lett. 1257-60... 

The penetration of ions from the subphase into the shell of spread particles is a general phenomenon and can be used to modify and functionalize the particle surface. For example, metal ions, such as Ba and Fe, or cationic polyelectrolytes, such as the polycation of polyallylamine, can be adsorbed at anionic particles, while anionic water-soluble dyes, such as phthalocyanine tetrasulfonic acid and 1.4-diketo-3.6-diphenylpyrrolo[3.4-c]pyrrole-4, 4 -disulfonic acid (DPPS) [157], can be adsorbed at cationic particles. However, since only a monolayer of the dye is adsorbed, a deep coloration of the particles is not obtained unless a dye with very high absorption coefficient is used [156],... 

Serizawa and Akashi [95] analyzed the monolayer adsorption of polystyrene latex particles with cationic polyvinylamine grafted on their surface, while Serizawa et al. [96,97] used commercial anionic latex particles. Both types of particles were adsorbed on polyelectrolyte-coated substrates previously prepared by alternating adsorption of cationic and anionic polyelectrolytes such as polyallylamine hydrochloride (PAH) and polystyrene sulfonate sodium salt (PSS) according to the method described by Decher [164]. Using... 

In the presence of the polyelectrolyte polyallylamine hydrochloride (PAAN), the formation of a pearl-necklace structure between AOT-reversed micelles and PAAN was... 

Figure 23 Heparin release rate (normalized to pg/15 min per 50 mg device) from hepa-rin-polyallylamine complex matrix with the application of step function electric current in PBS (pH 7.4) solution (mean SD). (O, , A) Off state ( ) 20 mA ( ) 15 mA (A) 10 mA. (From Ref. 48.)...

The basic idea was to randomly acylate polyallylamine (MW = 50,000-65,000) all at once with eight different activated carboxylic acids. The relative amounts of acids used in the process was defined experimentally. Since the positions of attack could not be controlled, a huge family of diverse polymers (4) was formed. In separate runs the mixtures were treated with varying amounts of transition metal salts and tested in the hydrolysis reaction (1) —> (2) (Equation (1). The best catalyst performance was achieved in a particular case involving Fe3+, resulting in a rate acceleration of 1.5 x 105. The weakness of this otherwise brilliant approach has to do with the fact that the optimal system is composed of many different Fe3+ complexes, and that deconvolution and therefore identification of the actual catalyst is not possible. A similar method has been described in other types of reaction.30,31... 

Polyallylamine Low Induced High Flexible Linear Backbone Moderate... 

Xanthan 0.025% Polylysine/ 5% Polyallylamine NT Spherical, Smooth, Good Mechanical Stability 16/13... 

The last work pertaining to the discovery of new catalysts is perhaps the most novel approach to be reported thus far. In one of the earliest approaches taken toward catalyst development, Menger et al. (61) attempted to find catalysts for phosphate ester hydrolysis. A series of eight functionalized carboxylic acids were attached to polyallylamine in various combinations. Each of these polymers were then treated with one of three metals, Mg2+, Zn2+, or Fe3+. The different members of each library were identified by the relative percentages of each carboxylic acid attached to the polyamine. For example, one polymer possessed 15% Oct, 15% Imi, 15% Phe, and 5% Fe3+. There is no attempt to identify the location of the various carboxylic acids in a given polymer. This approach is novel since each system consists of an ensemble of different ligands with the carboxylic acids positioned in various locations. Each polymer within a given ratio of carboxylic acids consists of a combinatorial library of potential catalysts. 

The basic goal behind this approach is to find systems that perform the desired reaction without particular interest in the absolute structure of the active species. In an ensemble that possesses activity, there are likely many catalysts that are not active. The analogy to catalytic antibodies is made. Just as in the polyallylamine system reported, the identity and structure of catalytic antibodies is not determined. At this time, the authors are not interested in sorting out which species are active and which are not. Their stated goal is to find a system that catalyzes the desired reaction. 

Fig. 16. CEC separation of naphthalene (1), fluorene (2), phenanthrene (3), anthracene (4), pyrene (5),triphenylene (6),andbenzo(a)pyrene (7) using capillary filled with CIO alkyl substituted polyallylamine. (Reprinted with permission from [86]. Copyright 1997 Elsevier). Conditions capillary 50 pm i.d., 48 cm total length, 33 cm active length, field strength 400 V/cm, carrier concentration 20 mg/ml, mobile phase 60 40 methanol-20 mmol/1 borate buffer pH=9.3...

PVP-Os Osmium-bipyridyl-modified quaternized poly 4-vinylpyridine) [102,206,207] PAH-Fc Ferrocene-modified polyallylamine [77, 101, 208] P(CM-FcJ Poly(vynil ferrocene) copolymer [224] PVn Polyalkylviologens (PVn, n number of methylene groups) [67, 104,... 

Amperometric glucose Ferrocene-modified polyallylamine (PAFi-Fc) Glucose oxidase (GOx) (77)... 

The binding of pyridoxal 5 -phosphate (vitamin Be) to enzymes has been modelled using homo- and co-polypeptides containing L-lysine as a source of reactive amino groups. This has now been extended to reaction of pyridoxal with polyallylamine, with the polymer acting as a control that cannot provide amido -CO- or -NH- functions to stabilize the Schiff base products, as occurs in enzymes and polypeptides. Rate constants for the formation and hydrolysis of the imines have been measured and interpreted in terms of formation of the carbinolamine (in its neutral or zwitterionic form). 

Recently, polymerization of sodium acrylate on polyallylamine hydrochloride template was described. In aqueous solution, sodium acrylate molecules are adsorbed onto a template with ammonium cationic pendant groups. The complex was polymerized in water solution using AIBN or K2S2O8 as initiators. Polymerization proceeds according to reaction ... 

Figure 12.5 (a) Layer-by-layer deposition of glucose oxidase and the polyallylamine Os3 +n + -polypyridine polyelectrolyte on the electrode, (b) Typical catalytic current responses for different glucose concentrations obtained by self-assembled nanostructured thin films based on different architectures (i) PAH/Os/GOx, (ii) cysteamine/GOx/PAH-Os, (iii) PAH/GOx/ -Os, and (iv) (PAH-Os)2/(GOx)i. All measurements were performed in 0.1 M tris buffer at pH 7.5. Part (b) Reproduced with permission from Ref. 34a. Copyright Wiley-VCH Verlag GmbH Co. KGaA. 

Studies by Nishiyama and Fujihara [149] utilizing azobenzene derivative (27) as isomerizable chromophores have demonstrated the importance of reaction cavity free volume in L-B films. The L-B films of amphiphilic derivative 4-octyl-4 -(3-carboxytrimethyleneoxy)-azobenzene (27) upon irradiation was found to be stable, no geometric isomerization of the azobennzene moiety occurred. This compound forms L-B films with water soluble polyallylamine 28 at an air-water interface. Reversible cis-trans photoisomerization occurs in the film containing 28. The reversible photoisomerization reaction in polyion complexed films is thought to occur because of the increased area per molecule provided in the film. The cross sections of molecule 27 in the pure film and in film containing 28 were estimated to be 0.28 and 0.39 nm2. Such an increased area per molecule... 

Complexation of poly(allylamine hydrochloride), — (CH—(CH2NH3C1)—CH2) —, with transition metal ions in aqueous solution appears to proceed in one step, in contrast to that of the corresponding low molecular weight metal complex. Interaction between polyallylamine and Cu2+, Ni2 +, Co2+, Zn2+, and Mg2+ has been reported 21). 

Boussif, O., Delair, T., Brua, C., Veron, L., Pavirani, A. and Kolben, H.V.J. (1999) Synthesis of polyallylamine derivatives and their use as gene transfer vectors in vitro. Bioconjug. Chem., 10, 877-883. 

---