Hybrid GMP-polyamine hydrogels as new biocompatible materials for drug encapsulation.

Here we present the preparation and characterization of new biocompatible materials for drug encapsulation. These new gels are based on positively charged [1+1] 1H-pyrazole-based azamacrocycles which minimise the electrostatic repulsions between the negatively charged GMP molecules. Rheological measurements confirm the electroneutral hydrogel structure as the most stable for all the GMP-polyamine systems.

Separating the coherence transfer from chemical shift evolution in high-resolution pure shift COSY NMR.

Recent developments in data sampling and processing techniques have made it possible to acquire 2-dimensional NMR spectra of small molecules at digital resolutions in both dimensions approaching the intrinsic limitations of the equipment and sample on a realistic timescale. These developments offer the possibility of enormously increased effective resolution (peak dispersion) and the ability to effectively study samples where peak overlap was previously a limiting factor. Examples of such spectra have been produced for a number of 2-dimensional techniques including TOCSY and HSQC.

Guanosine-5'-Monophosphate Polyamine Hybrid Hydrogels: Enhanced Gel Strength Probed by z-Spectroscopy.

The self-assembling tendencies of guanosine-5'-monophosphate (GMP) can be drastically increased using polyamines, with potential applications in the production of biocompatible smart materials, as well as for the design of antitumor drugs based on G-quadruplex stabilization. Results from scanning electron microscopy (SEM), wide angle X-ray scattering (WAXS), rheology, and nuclear magnetic resonance (NMR) z-spectroscopy studies are presented.

Exceedingly Fast Oxygen Atom Transfer to Olefins via a Catalytically Competent Nonheme Iron Species.

The reaction of [Fe(CF3 SO3 )2 (PyNMe3 )] with excess peracetic acid at -40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [Fe(III) (OOAc)(PyNMe3 )](2+) and [Fe(V) (O)(OAc)(PyNMe3 )](2+) , in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the substrate on the reaction rate could be elucidated, and the relative reactivities determined for the catalytic oxidations could be reproduced by kinetic studies.

Synthesis and Structural Characterization of a Cyclen-Derived Molecular Cage.

Reaction of a tetrafunctionalized cyclen derivative containing four aldehyde groups with an appropriate diamine followed by reduction and demetalation highly efficiently affords a bis(cyclen)-derived molecular cage. Potentiometric investigations show that this compound forms dimetallic complexes with copper(II), with the two metal ions selectively coordinated to the cyclen units. X-ray crystallography indicates that these complexes could give rise to new cascade complexes after incorporation of anions between the metal centers.

"3 + 1 = 6 + 2" in Cu(II) coordination chemistry of 1H-pyrazole aza cryptands.

A polyazamacrocycle formed from two tris(2-aminoethyl)amine units connected by 1H-pyrazole units shows unique hexanuclear Cu(ii) complexes by combination of two binuclear Cu(ii) cryptand complexes through pyrazolate moieties belonging to both cryptands. The formation of these dimeric entities has been proven both in solution by potentiometric studies and mass spectroscopy and in the solid state by X-ray diffraction of crystals of three different batches of formulae [Cu6(H-3)2(H2O)2](TsO)6·22H2O (), [Cu6(H-3)2(NO3)2](NO3)4·2H2O () and [Cu6(H-3)2Cl2]Cl4·(C4H5N3O2)2·14.35H2O ().

Selective recognition of sulfate anions by a cyclopeptide-derived receptor in aqueous phosphate buffer.

A cyclopeptide-based anion receptor containing alternating 6-aminopicolinic acid and substituted (4R)-4-aminoproline subunits with appended β-alanine residues binds sulfate anions in water. Importantly, appreciable sulfate binding is even observed in phosphate buffer, hence in the presence of anions of similar structure but with a different degree of protonation. The cause for the high selectivity of this receptor is related to the mode of action of the sulfate-binding protein.

Homo- and heterobinuclear Cu²⁺ and Zn²⁺ complexes of abiotic cyclic hexaazapyridinocyclophanes as SOD mimics.

The new receptor 3,7,11,15,19,23-hexaaza-1(2,6)-pyridinacyclotetracosaphane (L1) containing a complete sequence of propylenic chains has been synthesised. The acid-base behaviour and Cu²⁺ and Zn²⁺ coordination have been analysed by potentiometric measurements in 0.15 M NaClO₄ for L1 and for the related compounds 3,7,11,14,18,22-hexaaza-1(2,6)-pyridinacyclotricosaphane (L2), 3,7,10,13,16,20-hexaaza-1(2,6)-pyridinacycloheneicosaphane (L3) and 3,7,10,12,15,19-hexaaza-1(2,6)-pyridinacycloicosaphane (L4).

Zn(II)-coordination and fluorescence studies of a new polyazamacrocycle incorporating 1H-pyrazole and naphthalene units.

The synthesis and Zn(2+) coordination properties of a new macrocycle (L1) obtained by dipodal (2 + 2) condensation of the polyamine 3-(naphthalen-2-ylmethyl)pentane-1,5-diamine with 1H-pyrazole-3,5-dicarbaldehyde are reported. pH-metric studies show that L1 bears five measurable protonation steps in the 2.0-11.

Synthesis and coordination properties of an azamacrocyclic Zn(II) chemosensor containing pendent methylnaphthyl groups.

The synthesis of a polyazamacrocycle constituted by two diethylenetriamine bridges functionalized at their central nitrogen with naphth-2-ylmethyl units and interconnected through 2,6-dimethylpyridine spacers (L1) is reported. The protonation behaviour of the new macrocycle in water and in water-ethanol 70/30 v/v mixed solvent has been examined by means of pH-metric, UV-Vis and steady-state fluorescence techniques. The fluorescence emission is slightly quenched following the deprotonation of the central tertiary amines and more deeply quenched upon deprotonation of the secondary amino groups.