Linear polyamines

Complex linear polyamines are best designated by replacement nomenclature. These trivial names are retained aniline, benzidene, phenetidine, toluidine, and xylidine. 

Macrocyclic polyamines may be viewed as an extended form of linear polyamines 13-161 with one less degree of saturation. Polyamines with lower degrees of saturation, have important biological functions. Compounds such as macrocyclic polyimines 171 and porphyrines 18), function as 02 carriers and activators, promote photosynthesis, form the basic structure of vitamine B12, etc., and for these reasons have been subjects of intense investigation. 

The term chitosan describes a series of chitosan polymers with different molecular weight (MW), viscosity, and degree of deacetylation (DD) (40-98%). It is a linear polyamine with a number of amino groups that are readily available for chemical reaction and salt formation with acids. 

Another approach to the problem of the structural assignment of isomers formed by Co111 and linear polyamines is the use of structure-reactivity patterns. In particular it has been observed that in chloropentaaminecobalt(III) complexes containing a planar (meridional)—NH(CH2)INH(CH2) NH—moiety, base hydrolysis is (Chapter 7.1) several orders of magnitude more rapid than in isomeric analogs with this feature absent.15,34... 

All the linear triamines (27)-(31) are commerically available and there are others, such as 6,6-tri, which, as yet, do not appear to have been used in the preparation of coordination complexes. These linear polyamine ligands can coordinate in either meridional or facial topology and both bis(tri-amine) and mono(triamine) complexes are possible for octahedral central metal ions. 

Table It TV-Alkylated and C-Alkylated N4 Linear Polyamines Used in the Formation of Cora Complexes...

Linear arrays of protonatable or hydrogen bonded sites may allow the directed long range transfer of protons, thus functioning as proton-conducting channel, i.e., as proton wire. Relevant systems would be linear polyamines or polyphenolic condensed aromatic units [8.218], self-assembled hydrogen bonded heterocyclic ribbons such as 116 (see Section 9.4.4) or polyelectrolyte membranes [8.219] in which collective proton motion may take place and lead to proton conductivity. 

Well-expressed correlations between headgroup structure and transfection activity have been found for cholesterol-based cationic derivatives. Polyamine derivatives with T-shaped structure exhibit considerably higher levels of transfection as compared to lipids with linear polyamine headgroups (Fig. 6) [36]. Varying... 

Pu(IV) and Am(III) at the appropriate denticity can be achieved. The polyamines used have been linear or aromatic polyamines or cyclic polyamines. For the linear polyamines ligand (29) is separated by 3 and 4 methylene units or 3, 4 and 3 methylene units, thus resulting in the acronyms 3,4-LICAM254), 3,4-LICAMC260) and 3,4-LICAMS261), (30, 3,4,3-LICAMC, R as in 29). Alternatively various cyclic polyamines were used e.g., (31, R as in 29) which leads to an acronym series CYC AM257). 

Electrostatic self-assembly was combined with supramolecular chemistry to obtain inclusion complexes of a polymeric nonlinear optical (NLO) active dye and modified [3-cyclodextrin with induced chromophore orientation [37], The polyanion is a N,N-diallyl-aniline and sodium-2-acrylamido-2-methylpropanesulfonate copolymer functionalized with pendant azo group. The modified /i-cyclodextrin oligo-cation was obtained by treatment of hcptakis(6-dco y-6-iodo-/i-cyclodcxtrin) with excess pyridine. A linear polyamine, chitosan, was also combined with the polyanion, for comparison. Films were deposited on glass slides by dipping them alternatively in aqueous solutions of the cation and the polyanion. UV-visible spectra indicate dye aggregation and suggest the formation of an inclusion complex of the dye with the cyclodextrin, thus isolating the chromophores. 

Stabilizing Role of linear Polyamines as Pore Fillers During the Crystallization of Zeolite NU-10... 

PELLEGRINO ETAL. Linear Polyamines as Pore Fillers... 

A variety of mono-, di-, tetra-, and polydendron PAMAMs have been synthesized from simple amines as well as linear polyamine cores [2, 83, 124]. Linear poly(ethylenimines) with core multiplicities (Nc of ca. 300-400) have been shown to produce high-aspect ratio, rod-like dendrimers at generation 3 or 4 [2]. Their length is determined by the degree of polymerization (n) of the initiator core and their diameter is derived from the number of generations (see Scheme 3). 

This sequence is representative of the preparation of differentially /V-protected polyazacycles involving a malonate condensation of a linear polyamine. 

If a C3 unit needs to be introduced bearing a carbon chain, then there are several options. A P-amino add could be used as a precursor in a parallel synthesis to those discussed above. Alternatively, a strategy based on malonate syntheses could be employed. Co-condensation of a C-substituted malonate with a primary diamine in boiling ethanol gives reasonable yields of cyclic diamide which may be reduced with borane in THF to yield the desired polyamine (Scheme 1.12 and Protocol 5).18 Another possibility is to prepare a linear bis-toluenesulfonate ester from a malonate by reduction (e.g. LiBH4) and tosylation, followed by a standard toluenesulfonamide cyclisation reaction. Yet another variant, this time giving racemic product, is to react a coumarin derivative with a linear polyamine (Scheme 1.12).1819 In this case, a... 

There are also systematic trends in stability constants when frve-memberedpolyamine rings are replaced by six-membered rings, or when linear polyamine ligands are replaced by macrocyclic ligands of a similar strain see Chelate Effect). These effects can be well accounted for in terms of enthalpy contributions to the formation constant. ... 

According to Saegusa et al. [13], linear polyamines (PEI and PPI) were synthesized starting from oxazolines or 1,3-oxazines with subsequent hydrolysis or methylation, respectively [11]. The degree of polymerization was varied between 10 and 20. Here we present results of investigations on PEI withPn= 8-9 and on PPI withP = 12 - 13. 

Repetitive strategy is a fundamental principle for the synthesis of dendrimers, that was first coined, to the best of our knowledge in our seminal cascade paper.1 It implies a repetitious sequence of the same reaction steps, as initially demonstrated in the synthesis of linear polyamines,1 by sequential Michael addition, followed by a facile nitrile reduction (Scheme 1). The preparation of Newkome s arborols5 is an-... 

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