Conformations and dynamics of 1,5-diaza-3,7-diphosphacyclooctane (1) with chiral l-menthyl substituents on the phosphorus atoms and several metal complexes thereof were investigated by a variety of DNMR methods. In solution 1 adopts a C(2) symmetrical "crown"-like conformation (CW) and the conformational preference and dynamics of the complexes depend on the type of metal: for the Cu complex the CW form is preferred, whereas the Pd, Pt, or Mo complexes exist in an equilibrium of two "chair-boat"-like conformations (CB/CB*). The barriers of interconversion between these two conformations for the Pd and Pt complexes are about 2 times higher than for the Mo complex. Quantum chemical calculations (B3LYP/6-31G(d)) are in agreement with experimental findings.

Novel mono- and dicationic pyrimidinic surfactants are synthesized and their aggregation behavior is studied by methods of tensiometry and nuclear magnetic resonance (NMR) self-diffusion. To estimate their potentiality as gene delivery agents, the complexation with oligonucleotides (ONus) is explored by dynamic light scattering (DLS) and zeta-potential titration methods and ethidium bromide exclusion experiments. Bola-type pyrimidinic amphiphile (BPM) demonstrates rather a weak affinity to ONus. Although it induces mixed associations with ONus, only slight charge compensation changes occur at a large excess of bola, with no recharging reached. Similarly, the ethydium bromide exclusion study reveals a slow increase in the binding capacity toward an ONu with an increment in BPM concentration. The monocationic pyrimidinic surfactant (MPM) and its gemini analogue (GPM-1) are ranked as intermediates in both their aggregative activity and complexing properties toward ONus. They both form mixed associates with ONus well below the critical micelle concentrations (cmcs) of 2 and 15 mM respectively. However, GPM-1 has a much lower isoelectric point at the molar ratio surfactant/ONu r~1 compared to r~3 for MPM. This probably indicates a larger electrostatic contribution to the ONu complexation in the case of GPM-1. The most hydrophobic pyrimidinic surfactant (GPM-2), bearing three alkyl tails, demonstrates enhanced aggregative activity and binding capacity toward ONus as compared to former pyrimidinic surfactants. Due to effective aggregative (low cmc of 0.04 mM) plus binding properties (fraction of bound ONu β=0.76 at r=2.5), GPM-2 may be ranked as a promising agent for wider biological applications.

Supramolecular nanoaggregates formed through the association of amphiphilic sulfonatomethylated calix[4]resorcinarenes with different substituents on the lower rim (methyl, pentyl, heptyl) and number of aromatic, aliphatic, and cationic guests differing in their shapes and sizes were investigated in aqueous solution by various NMR techniques ((1)H, 2D NOESY, FT-PGSE). It was shown that slight variations of the alkyl chain length on the lower rim of calixresorcinarenes dramatically change their aggregation behavior. Unlike the other calixresorcinarenes studied, the "head-to-tail" packing mode is observed for calixresorcinarene with pentyl moieties on the lower rim, which is unusual for amphiphilic calixarene aggregates. This calixresorcinarene demonstrates the stronger binding capacity toward the guest molecules due to their encapsulation into the capsule-like aggregate subunits. The guest-host complexation modifies the properties of both components, with the size of the resulted colloid particles being controlled by the guest nature.

A systematic study of the aggregation behavior of alkyltriphenylphosphonium bromides (TPPB-n; n=8, 10, 12, 14, 16, 18; here n is the number of carbon atoms in alkyl groups) in aqueous solutions has been carried out and compared with trimethyl ammonium bromides (TMAB-n). Critical micelle concentrations (cmcs) of TPPB-n and TMAB-n decrease with the number of carbon atoms with the slope parameter of ca.0.3. The low cmcs and effective solubilization power toward Orange OT indicate high micellization capacity of phosphonium surfactants. The low counterion binding parameter β is revealed for TPPB-10 and TPPB-12, while high counterion binding of ⩾80% is observed for high TPPB-n homologs. Values of the surface potential ψ calculated on the basis of pK(a) shifts of p-nitrophenols is similar for both series and monotonously increase with alkyl chain length. Several points indicate non-monotonic changes within TPPB-n series. There are peculiarities of the tensiometry and solubilization plots for high homologs and above mentioned increases in counterion binding on transiting from low to high molecular weight surfactants. Differences in aggregation behavior between TPPB and TMAB series and between low and high homologs can be due to the specific structural character of the TPP(+) cation, which is supported by X-ray data.

Electrocatalytic generation of nickel catalysts in low oxidation states by reduction of nickel complexes with various ligands (2,2'-bipyridine, 2,2':6',2''-terpyridine,(S,S)-2,6-bis(4-phenyl-2-oxazolin-2-yl)-pyridine) in the presence of olefinic substrates and fluoroalkyl halides leads to new organic products derived from addition-dimerization processes. Due to the presence of two stereocenters in the dimerization products two diastereomers were characterized by a variety of analytical techniques including multi-dimensional NMR methods and X-ray single crystal diffraction. The formation of dimers was prevented by the inclusion of the hydrogen atom donor tributyltin hydride. The cyclic voltammetry study of selected nickel complexes along with fluoroalkyl halides demonstrated that Ni(I)L is the active form of the catalyst.

Mixed association of calix[4]resorcinarene with ethyl sulfonate groups on the lower rim and dimethylaminomethyl groups on the upper rim (CR) and cationic surfactant 4-aza-1-hexadecyl-azoniabicyclo[2.2.2]octane bromide (DABCO-16) is studied by methods of tensiometry, conductometry, potentiometry and NMR spectroscopy at fixed CR concentration and varied surfactant concentration. Beyond ca. 0.4 mM of DABCO-16, mixed aggregates enriched by CR are proved to be formed due to electrostatic forces, while beyond ca. 5 mM, aggregates enriched by surfactant occur due to the hydrophobic effect. Spectrophotometry monitoring of the solubilization of a hydrophobic dye, Orange OT, demonstrated that only the second type of mixed aggregate enriched by DABCO-16 is capable of binding the organic probe, while the mixed system where the surfactant is a minor component shows no binding capacity towards Orange OT. This finding can be used for the design of nanocontainers with controllable binding/release properties.

Reactions of pyrimidinophanes with two 6-methylthiocytosine and one 5(6)-alkyluracil moieties bridged with each other by polymethylene spacers with methyl or nonyl p-toluenesulfonate, p-toluenesulfonic acid, methanesulfonate and trifluorosulfonate afforded amphiphilic macrocyclic bis-p-toluene-, methane- and trifluorosulfonates. Despite the presence of several reaction centers in the initial pyrimidinophane molecules, protonation and methylation occurred only at the N(1) atom (with quaternization) of the 6-methylthiocytosine moieties. The bacteriostatic and fungistatic activity of the products was estimated. Macrocyclic tosylates exhibit a remarkable selectivity towards Staphylococcus aureus, with MIC values comparable with a reference drug. Bacteriostatic activity of the amphiphilic pyrimidinophanes depends on the size of the macrocycles, and the highest activity corresponds to definite lengths of polymethylene bridges. Besides, the antimicrobial activity of the screened pyrimidine derivatives depends on their topology. While macrocyclic tosylates are more active against bacteria than against fungi, acyclic tosylate with the same structural fragments shows a dramatical decrease of MIC towards mold and yeast with respect to the corresponding macrocycle. It is found that macrocyclic and acyclic tosylates in high dilutions decrease the extracellular lipase activity.

The reactions of such cyclic α-diketones as acenaphthenequinone, aceanthrenequinone, and N-alkylisatins, with hexaethyltriaminophosphine in the presence of the fullerene C(60), lead to the formation of methanofullerene derivatives under mild conditions. This process proceeds via deoxygenation of the dicarbonyl compound by the P(III) derivative and is likely to involve the intermediate formation of α-ketocarbenes. The structure of some methanofullerenes has been confirmed by NMR and XRD. The electrochemical behavior of the methanofullerenes was also investigated.

The combined use of two-dimensional NMR correlation experiments and gauge including atomic orbital density functional theory in (13)C NMR chemical shift (CS) calculations allowed reliable and simple structural determination of regioisomeric heterocyclic systems that originate from the reactions of acylquinolinones with substituted hydrazines. Moreover, the results of differential analysis between the calculated (15)N NMR CSs for hypothetical structures and the experimental data of the title azaheterocyclic systems were even more advantageous with respect to (13)C because there was no need for correlational analysis: structures of the regioisomeric compounds could be determined just by direct comparison.