Aromatic amines intercalation

The monofunctional complexes [PtCl(dien)]+, [PtCl(NH3)3]+, and the active d.v-compounds cA-[PtCl(NH3)2 (Am)]+, where Am is an heterocyclic or aromatic amine ligand like pyridine, pyrimidine, purine, or aniline, only form stable monoadducts with DNA [50][51]. However, when Am = A-methyl-2,7-diazapyrenium (a strong intercalator), the monoadduct is stable only on single-stranded DNA. On double-stranded DNA it is hydrolyzed with release of c T-[Pt(NH3)2(Am)(H20)]3+ or of Am generating the aqua monoadduct of cisplatin [52],... 

Ffowever, such DNA ligands are often toxic or carcinogenic. Nowadays it is well known that several pollutants exhibit carcinogenicity through intercalation into DNA. Some examples are PAFfs or aromatic amines, and some endocrine disruptors, in coal tar, atmospheric pollutants, automobile exhaust, and cigarette smoke. PCDDs, PCDFs, and PCBs have especially emerged as... 

Babushkina, T.A. Seiymkova, I.V. NQR l spectroscopy of layered inorganic compounds intercalated with aromatic amines. Z. Naturforsch. 1998. 53a, 585-589. 

On the other hand, clays modified with salts of aromatic amines, in which the N atom is directly linked to aromatic ring, exhibited higher thermal stability then those modified with alkylammonium compounds [117, 118]. The use of a combination of aromatic and aliphatic ammonium compounds was an effective strategy for synthesis of clays with sufficient thermal stability for thermoset polyimide resin (PI) [117]. In that case, the aromatic component of OLS provided higher thermal stability and the aliphatic component promoted intercalation. The benefits of combining aromatic and aliphatic surfactants to treat clay are also reported by other authors [ 119]. It was shown that clay treated with a 1 1 molar mixture of methylene dianihne (MDA) and dodecylamine resulted in an improvement in thermooxidative stability of Pl-based nanocomposites. 

The intercalation of platinum complexes containing bidentate or tridentate aromatic amines was first proposed for binding to tRNA and then to DNA [53]. The structures of the relevant complexes of palladium and platinum are shown in Figure 1.5 and a requisite is the presence of planar ligands such as bipyridine, terpyridine, or o-phenanthroline, which are coplanar with the coordination plane formed by the four ligand donor atoms and the metal ion. The similar pyridine derivative, [Pt(en)py2], where the pyridine Ugands are forced by nonbonded steric constraints to be out of the coordination plane, does not intercalate. 

First reported by Fredenhagen in 1926 F3, F4), the graphite-alkali-metal compounds possess a relative simplicity with respect to other intercalation compounds. To the physicist, their uncomplicated structure and well defined stoichiometry permit reasonable band-structure calculations to be made S2,12) to the chemist, their identity as solid, "infinite radical-anions frequently allows their useful chemical substitution for such homogeneous, molecular-basis reductants as alkali metal-amines and aromatic radical anions N2, B5). 

Yang XB, Fu X-K, Zeng R-Q (2010) Intercalation of non-aromatic heterocyclic amines into layered zirconium glycine-N, N-dimethylphosphonate. Chem Paper 64( 1) 118-122... 

As shown in Scheme 17, a tridentate amine was coupled to an intercalating aromatic molecule such as pyrene or anthrachinon and was labelled with 99mTc. 

The key to many of these degradation processes is oxidative metabolism by the cytochrome P450 enzyme family [10]. Cytochrome P450 oxidation is most easy for electron-rich -electron systems, for example aromatic moieties or olefinic substructures, from which epoxides are generated. These epoxides are often potent electrophiles, intercalating into DNA and reacting with all kinds of nucleophile, for example nucleobases, amines, or thiols. Metabolic processes like this are the reason for the mutagenicity of many polycyclic arenes. 

Aromatic and aliphatic amines [23,24] can also be intercalated into barium phenylphosphonates it has been verified that the total amount of intercalated amines is related to the basicity of such compounds, with exothermic enthalpy values, in all cases. 

A characteristic property of the crystalline silicic acids is their ability to intercalate polar organic molecules. Various types of guests are intercalated short-chain fatty acid amides, urea and derivatives, S- and V-oxides, amines, aromatic bases. 

All acids intercalate alkylamines, and the interlayer expansion can be very large for long-chain amines (Table 15). Other types of amines and aromatic bases and the other groups of guest compounds are only intercalated by certain acids. The interlamellar adsorption of urea derivatives, alcohols, nitriles, and ketones is restricted to the most reactive acids (Table 16). The reactivity of guest molecules follows this order alkylamines > N- and 5-oxides > acid amides > various bases > urea derivatives > alcohols. 

Table 15 Intercalation of Amines and Aromatic Bases into the Crystalline Silicic Acid H2Si205-I (A) and H2Sii4029 XU2O (from Magadiite, Air-Dried) (B)... 

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