Naphthalene diimide-amino acid conjugates as novel fluorimetric and CD probes for differentiation between ds-DNA and ds-RNA.

Two novel unnatural amino acids, prepared by linking a dicationic purple-coloured and fluorescent naphthalene diimide (NDI) at core position to amino acid side chains of variable length, strongly interacted with ds-DNA/RNA by threading intercalation. Different from a reference NDI dye with identical visible range absorbance (520-540 nm) and Stokes shifts in emission (+60 nm, quantum yield > 0.2), only these amino acid-NDI conjugates showed selective fluorimetric response for GC-DNA in respect to AT(U)-polynucleotides.

Guest exchange in dimeric capsules formed by tetra-urea calix[4]arenes.

Ten tetra-urea calix[4]arene derivatives with different ether residues (methyl, pentyl, benzyl, all combinations of methyl and pentyl, 1,3-dibenzyl-2,4-dipentyl), including also the tetrahydroxy compound and the 1,3-dipentyl ether, were synthesised. Their urea groups were substituted with a lipophilic residue to ensure sufficient solubility in cyclohexane. Thus, kinetics for the exchange of the included guest (benzene) against the solvent (cyclohexane) could be followed by 1H NMR spectroscopy.

Calix[4]arene-based bis[2]catenanes: synthesis and chiral resolution.

The exclusive formation of hydrogen-bonded dimers between tetraaryl and tetratosylurea calix[4]arenes has been used to prepare a series of ten "bisloop" tetraurea calix[4]arenes 3, in which adjacent phenylurea groups are covalently linked through alpha,omega-dioxyalkane chains. This dimerization with tetratosylurea 2 as template preorganizes the alkenyl residues of tetra(m-alkenyloxyphenyl) ureas 1 and enables their selective connection in high yield (up to 95 %) by olefin metathesis followed by hydrogenation. The "bisloop" calixarenes 3 also exclusively form heterodimers with 1.

Guest exchange in dimeric capsules of a tetraurea calix[4]arene in the solid state.

A solid powder of hydrogen bonded dimers of a tetraurea calix[4]arene is able to exchange the encapsulated guest in contact with the vapor of a second guest. The molecules of a guest-free powder obtained from a polar solvent cannot rearrange in the solid phase to form new guest-filled capsules under these conditions.

Topologically novel multiple rotaxanes and catenanes based on tetraurea calix[4]arenes.

Calix[4]arenes bearing at their wide rim four urea residues easily form hydrogen bonded dimeric capsules. This has been used to preorganise alkenyl functions attached to these urea groups for their controlled connection via metathesis reaction. Multimacrocyclic tetraurea derivatives are thus obtained in excellent yields via heterodimers which are formed exclusively with tetratosylurea derivatives.

Orientational preferences of aromatic guests in dimeric capsules of tetraurea calix[4]arenes--MD and NMR studies.

Molecular dynamics (MD) simulations have been performed for complexes of a dimeric capsule of a tetraurea calixarene with a series of twelve aromatic guests. A distinct orientational preference and a restriction of the internal mobility was found which depend on the size and electronic properties of the guests. The results are in agreement with the CIS values obtained from (1)H NMR spectroscopic measurements and with complexation selectivities obtained by competition experiments.

Wide rim urethanes derived from calix[4]arenes: synthesis and self-assembly.

[reaction: see text] Calix[4]arenes 4, substituted at the wide rim by four N-tolyl-urethane groups, were synthesized, as well as derivatives 10a,b bearing two or three tolyl-urea groups beside of one or two urethane group(s). In contrast to tetra-tolyl urea 11, the urethane derivatives do not form hydrogen-bonded, dimeric capsules in CDCl3 or benzene-d6, but the dimerization can be induced for the triurea 10b by tetraethylammonium cations as guests. The quantitative formation of heterodimers is observed for all urethanes 4 and 10a,bin benzene-d6 in mixtures with a "tetra-loop" tetraurea 14, while "bisloop" tetraureas 13 require di- or triurea derivatives 10a,b for a clean heterodimerization.

Energy transfer in calixarene-based cofacial-positioned perylene bisimide arrays.

The synthesis of multichromophoric perylene bisimide-calix[4]arene arrays with up to five perylene units (containing orange, violet, and green perylene bisimide chromophores) and of monochromophoric model compounds was achieved by subsequent imidization of mono-Boc functionalized calix[4]arene linkers with three different types of perylene bisimide dye units. The optical properties of all compounds were studied with UV/vis absorption and steady state and time-resolved fluorescence spectroscopy. Upon excitation of the inner orange dye at 490 nm of array 3, strong fluorescence emission of the outer green perylene bisimide (PBI) chromophore at 744 nm is observed.

Fourfold [2]rotaxanes based on calix[4]arenes.

Tetraurea calix[4]arenes with four loops form exclusively heterodimers with open-chain urea calix[4]arenes when they are dissolved in aprotic solvents. These assemblies can be considered as pseudorotaxanes. If open-chain tetraureas ending with maleic imide functions are used, their Diels-Alder reaction with 1,4,5,8-tetrapentoxyanthracene leads to tetra[2]rotaxanes which cannot be split into the single calixarene parts by hydrogen bond breaking solvents.

Synthesis of huge macrocycles using two calix[4]arenes as templates.

Macrocycles with up to 100 atoms have been synthesised using two calix[4]arenes as templates: first, (3,5-dialkenyloxy)phenyl groups are attached to the wide rim of a calix[4]arene via urea links, then the alkenyl groups are connected via a metathesis reaction using a tetratosylurea calix[4]arene for their correct prearrangement and finally the urea functions are cleaved to detach the newly formed macrocycles.

Preferred dimerization of tetra-tolyl- and tetra-tosylurea derivatives of flexible and rigidified calix[4]arenes.

The dimerization of tetratolyl- and tetratosyl-urea derivatives 1 and 2, derived from a tetrapentoxy calix[4]arene in the cone conformation and of the corresponding tetra-urea derivatives 3 and 4, in which the cone conformation is rigidified by the two crown-3 tethers, have been studied. All six possible equimolar mixtures were examined by 1H NMR using CDCl3 and CD2Cl2 as solvents. While no heterodimers are found for the combinations 1/3 and 2/4 in either solvent, all remaining combinations lead to the (exclusive) formation of heterodimers in CD2Cl2.

Enhanced thermodynamic and kinetic stability of calix[4]arene dimers locked in the cone conformation.

Wide rim tetraurea derivatives (2a,b) have been prepared from a calix[4]arene rigidified in the cone conformation by two diethyleneglycol ether bridges between adjacent oxygens. In comparison to the analogous tetraurea derivatives (3a,b) of a tetrapentoxy calix[4]arene, 2a,b show an increased thermodynamic stability in mixtures of CDCl(3) and DMSO-d(6). Their kinetic stability as expressed by the rate of guest exchange (benzene or cyclohexane against the solvent benzene-d(6)) is also strongly increased by factors of 30-38.

Rational synthesis of multicyclic bis[2]catenanes.

Bis-loop tetraurea calix[4]arene 6 has been prepared by acylation of the wide-rim calix[4]arene tetraamine 1 with the activated bis(urethane) 8 under dilution conditions. Similarly the bis(Boc-protected) tetraamine 2 is converted into the mono-loop derivative 3 which after deprotection and acylation gives the bisalkenyl derivative 5. In apolar solvents this tetraurea calix[4]arene 5 forms regioselectively a single hydrogen-bonded homodimer, from which the bis[2]catenane 10a is formed in 49% by a metathesis reaction followed by hydrogenation.

Multiple catenanes derived from calix[4]arenes.

A multicatenane is described in which two belts consisting of four annelated rings attached to the wide rims of two calix[4]arenes are interwoven in such a way that each ring of one belt penetrates two adjacent rings of the other belt and vice versa. The key step of the synthesis of this [8]catenane is the exclusive formation of preorganized heterodimers between a multimacrocyclic tetraurea calix[4]arene and an "open-chain" tetraurea calix[4]arene containing eight omega-alkenyl groups. When a tetraurea calix[4]arene containing four alkenyl groups is used, a bis-[3]catenane is formed analogously.

Sterically and guest-controlled self-assembly of calix[4]arene derivatives.

In solvents such as chloroform or benzene, tetraurea calix[4]arenes 1 form dimeric capsules in which one solvent molecule is usually included as guest. To explore the structural requirements for the formation of such hydrogen-bonded dimers we replaced one p-tolylurea residue by a simple acetamide function. The resulting calix[4]arene 2 a, substituted at its wide rim with one acetamide and three p-tolylurea functions, assumes a C(1)-symmetrical conformation in apolar solvents as shown by (1)H NMR, which is not compatible with the usual capsule.

Compensation of steric demand by cation-pi interactions, cobaltocenium cations as guests in tetraurea calix[4]arene dimers.

The affinities of ferrocene (2) and the cobaltocenium cation (3+), which have roughly the same size and differ in their charge, towards the inner cavity of the dimeric capsule formed by tetraurea calix[4]arene (1) were studied in C2D4Cl2 solutions. While 3+, which occupies more than 75% of the internal volume of the dimer, is readily encapsulated this is not the case for 2. This is probably due to cation-pi interactions, which operate only between 3+ and the aromatic rings of the calix[4]arene dimer.

New molecular topologies by fourfold metathesis reactions within a hydrogen-bonded calix[4]arene dimer.

A calix[4]arene tetrapentyl ether in the cone conformation substituted at its wide rim by four m-(omega-octenyloxy)phenyl urea groups forms hydrogen-bonded dimeric capsules in dichloromethane/benzene (95:5). Metathesis reaction with Grubbs' catalyst under high-dilution conditions (1.1 x 10(-4) M) followed by hydrogenation leads to a covalent connection of all the urea groups within a dimer.

Self-assembled dimers with supramolecular chirality.

The possibilities to form dimeric capsules with supramolecular chirality from tetraurea calix[4]arenes composed of two different phenolic urea units are discussed in general and demonstrated experimentally for various selected examples.

Calix[4]arene-functionalized naphthalene and perylene imide dyes.

[reaction: see text] Calix[4]arenes bearing one, two, or four 1,8-naphthyl imide groups at the wide rim and bis-calix[4]arenes connected via perylene-bisimide dye spacers have been synthesized. The low-temperature NMR spectrum of the tetranaphthylimide suggests, in agreement with a crystal structure, a C2-symmetrical pinched cone conformation stabilized via face-to-face pi-pi interactions between opposite naphthylimide groups. UV-vis and fluorescence studies have been carried out for the perylene bis-calix[4]arene dyes.

1H and (13)C NMR and Molecular Dynamics Study of Chiral Recognition of Camphor Enantiomers by alpha-Cyclodextrin.

1H and (13)C NMR spectra of the complexes of camphor enantiomers with alpha-cyclodextrin in D(2)O manifest splittings due to chiral recognition. The complexes were found to be of 1:2 guest-to-host stoichiometry. Free energies of the complex formation obtained from (1)H NMR titration data are equal to -7.

Noncovalent Assembly of [2]Rotaxane Architectures.

Reversible zinc-pyridine coordination and hydrogen-bonding interactions have been used to assemble a [2]rotaxane from three components. Cooperativity in the macrocyclization process that results in the porphyrin dimer makes the system exceptionally stable. However, the kinetic lability of the zinc-porphyrin interaction means the dimer is in dynamic equilibrium with its monomer, and this has been exploited in the construction of a [2]rotaxane.