Polyurethanes and Polyallophanates via Sequence-Selective Copolymerization of Epoxides and Isocyanates.

Aryl isocyanates are introduced as comonomers for ring-opening copolymerization (ROCOP) with epoxides. Informed by studies of reaction kinetics, we show that divergent sequence selectivity for AB- and ABB-type copolymers can be achieved with a single dimagnesium catalyst. The resulting materials respectively constitute a new class of polyurethanes (PUs) and a new class of materials featuring an unprecedented backbone structure, the polyallophanates (PAs). The successful use of isocyanate comonomers in this way marks a new direction for the field of ROCOP while providing distinct opportunities for expansion of PU structural diversity. Specifically, the methodology reported herein delivers PUs featuring fully substituted (tertiary) carbamyl nitrogen atoms, a structural motif that is almost inaccessible via extant polymerization strategies. Thus, in one step from commercially available comonomers, our methodology expands the scope of ROCOP and gives access to diverse materials featuring both privileged (PU) and unexplored (PA) microstructures.

Recognition and Sensing of Creatinine.

Current methods for creatinine quantification suffer from significant drawbacks when aiming to combine accuracy, simplicity, and affordability. Here, an unprecedented synthetic receptor, an aryl-substituted calix[4]pyrrole with a monophosphonate bridge, is reported that displays remarkable affinity for creatinine and the creatininium cation. The receptor works by including the guest in its deep and polar aromatic cavity and establishing directional interactions in three dimensions. When incorporated into a suitable polymeric membrane, this molecule acts as an ionophore. A highly sensitive and selective potentiometric sensor suitable for the determination of creatinine levels in biological fluids, such as urine or plasma, in an accurate, fast, simple, and cost-effective way has thus been developed.

Chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles: combining hydrogen bonds and anion-π interactions to achieve optimum performance.

The performance of chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso-positions. When the meso-phenyl groups are decorated with strong electron-withdrawing substituents, attractive anion-π interactions may exist between the receptor's aromatic walls and the sandwiched anion. These anion-π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p-nitro withdrawing group on each of the meso-phenyl rings, afforded sensors that display anti-Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion-specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids.

Thermodynamic characterization of halide-π interactions in solution using "two-wall" aryl extended calix[4]pyrroles as model system.

Herein, we report our latest experimental investigations of halide-π interactions in solution. We base this research on the thermodynamic characterization of a series of 1:1 complexes formed between halides (Cl(-), Br(-), and I(-)) and several α,α-isomers of "two-wall" calix[4]pyrrole receptors bearing two six-membered aromatic rings in opposed meso positions. The installed aromatic systems feature a broad range of electron density as indicated by the calculated values for their electrostatic surface potentials at the center of the rings. We show that a correlation exists between the electronic nature of the aromatic walls and the thermodynamic stability of the X(-)⊂receptor complexes. We give evidence for the existence of both repulsive and attractive interactions between π systems and halide anions in solution (between 1 and -1 kcal/mol). We dissect the measured free energies of binding for chloride and bromide with the receptor series into their enthalpic and entropic thermodynamic quantities. In acetonitrile solution, the binding enthalpy values remain almost constant throughout the receptor series, and the differences in free energies are provoked exclusively by changes in the entropic term of the binding processes. Most likely, this unexpected behavior is owed to strong solvation effects that make up important components of the measured magnitudes for the enthalpies and entropies of binding. The use of chloroform, a much less polar solvent, limits the impact of solvation effects revealing the expected existence of a parallel trend between free energies and enthalpies of binding. This result indicates that halide-π interactions in organic solvents are mainly driven by enthalpy. However, the typical paradigm of enthalpy-entropy compensation is still not observed in this less polar solvent.

Single-molecule-magnet behavior in the family of [Ln(OETAP)2] double-decker complexes (Ln=lanthanide, OETAP=octa(ethyl)tetraazaporphyrin).

Double-decker complexes of lanthanide cations can be readily prepared with tetraazaporphyrins (porphyrazines). We have synthesized and characterized a series of neutral double-decker complexes [Ln(OETAP)2 ] (Ln=Tb(3+), Dy(3+), Gd(3+), Y(3+); OETAP=octa(ethyl)tetraazaporphyrin). Some of these complexes show analogous magnetic features to their phthalocyanine (Pc) counterparts. The Tb(3+) and Dy(3+) derivatives exhibit single-molecule magnet (SMM) behavior with high blocking temperatures over 50 and 10 K, respectively. These results confirm that, in double-decker complexes that involve Tb or Dy, the (N4)2 square antiprism coordination mode has an important role in inducing very large activation energies for magnetization reversal. In contrast with their Pc counterparts, the use of tetraazaporphyrin ligands endows the presented [Ln(OETAP)2] complexes with extraordinary chemical versatility. The double-decker complexes that exhibit SMM behavior are highly soluble in common organic solvents, and easily processable even through sublimation.

Hydrogen bonded supramolecular capsules with functionalized interiors: the controlled orientation of included guests.

This tutorial review aims to present and describe selected examples of still quite rare endo-functionalized supramolecular capsules. Only capsules assembled through the use of neutral or polar hydrogen bonding interactions are covered. The ability of these capsules to orient and control the position of the encapsulated guest molecules represents their stand-out feature. Thus, the way in which guests interact with the functionalized interior of the capsules is discussed in detail. Several of the described capsular assemblies display chiral architectures. The manner in which chirality is manifested in these assemblies is far from trivial. For this reason, we also offer explanations of the chiral features expressed by the relevant capsules and their encapsulation complexes.

Quantification of nitrate-π interactions and selective transport of nitrate using calix[4]pyrroles with two aromatic walls.

Herein we disclose the results of our investigations regarding the interactions between the biologically relevant nitrate oxoanion and several "two-wall" aryl-extended calix[4]pyrroles. There exists a clear relationship between the electronic nature of the aromatic walls of the calix[4]pyrroles and the stability of the nitrate⊂calix[4]pyrrole complex. This suggests that NO3(-)-π interactions have an important electrostatic component. We provide energetic estimates for the interaction of nitrate with several phenyl derivatives. Additionally, we report solid-state evidence for a preferred binding geometry of the nitrate anion included in the calix[4]pyrroles. Finally, the "two-wall" aryl-extended calix[4]pyrroles show excellent activity in ion transport through lipid-based lamellar membranes. Notably the best anion transporters are highly selective for transport of nitrate over other anions.

Chiral analysis of helquats by capillary electrophoresis: resolution of helical N-heteroaromatic dications using randomly sulfated cyclodextrins.

Enantiomers of helical N-heteroaromatic dications, helquats, were separated by CE. An acidic 22/35 mM sodium/phosphate background electrolyte, pH 2.4, with addition of randomly sulfated α-, ß- and γ- cyclodextrins allowed enantioresolution of a series of helquats, which comprised 5, 6 and 7 fused rings participating in the helical backbone. In general, at least one of the chiral selectors was found to provide baseline separation for 22 out of 24 helquats and partial separation for the remaining two. Individually, the sulfated γ-cyclodextrin turned out to separate 79% of the helquats, followed by the ß- and α-congeners with 54 and 42% of the resolved compounds, respectively. Migration order of enantiomers was inspected for selected helquats and a relation of molecular size of the analytes to a cavity of the cyclodextrin selectors is discussed.

Helquats, helical extended diquats, as fast electron transfer systems.

Helicene-viologen structural hybrids, like [5]helquat, 6,7,10,11-tetrahydrodipyrido[2,1-a:1',2'-k][2,9]phenanthrolinediium, and its four methylated derivatives, are characterized by electrochemical admittance and EPR spectroscopy. All compounds are reversibly reduced in two one-electron steps. Formal redox potentials correlate with the calculated LUMO energies. The electron transfer is coupled with a weak adsorption of the reactants. The analysis of the frequency dependence of the electrode admittance is used for the separation of Faradaic and double layer contributions and finally to the estimation of heterogeneous rate constants. Heterogeneous rate constants determined this way are in the range 0.1 to 3 cm s(-1). In all cases the second electron transfer is faster than the first redox step by a factor of three. The Frumkin correction for the acceleration by the double layer potential further amplifies this difference. The heterogeneous rate constants of derivatives correlate with the solvent reorganization energy estimated from the Marcus model. EPR spectra confirm the radical cation formation. The radical of [5]helquat participates in an extremely fast self-exchange process with the parent dication characterized by the self-exchange rate constant k(ET) = (2.4 +/- 0.5) x 10(9) M(-1) s(-1).

Characterization of a new ionophore-based ion-selective electrode for the potentiometric determination of creatinine in urine.

The optimization, analytical characterization and validation of a novel ion-selective electrode for the highly sensitive and selective determination of creatinine in urine is presented. A newly synthesized calix[4]pyrrole-based molecule is used as an ionophore for the enhanced recognition of creatininium cations. The calculation of the complex formation constants in the polymeric membrane with creatininium, potassium and sodium confirms the strong selective interactions between the ionophore and the target. The optimization of the potentiometric sensor presented here yields an outstanding analytical performance, with a linear range that spans from 1µM to 10mM and limit of detection of 10-6.2M. The calculation of the selectivity coefficients against most commonly found interferences also show significant improvements when compared to other sensors already reported. The performance of this novel sensor is tested by measuring creatinine in real urine samples (N=50) and comparing the values against the standard colorimetric approach (Jaffé's reaction). The results show that this sensor allows the fast and accurate determination of creatinine in real samples with minimal sample manipulation.

Novel heterobimetallic radiotheranostic: preparation, activity, and biodistribution.

A novel Ru(II) (arene) theranostic complex is presented. It is based on a 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid macrocycle bearing a triarylphosphine and can be tracked in vivo by using the γ emission of (153) Sm atoms. Notably, the heteroditopic ligand can be selectively metalated with ruthenium at the phosphorus atom despite the presence of other functionalities that are prone to metal coordination. Subsequent labeling with radionuclides such as (153) Sm can then be performed easily. The resulting heterobimetallic complex exhibits favorable solubility and stability properties in biologically relevant media. It also shows in vitro cytotoxicity in line with that expected for this type of metallodrug, and is nontoxic to the organism as a whole. As a proof of concept, initial studies in healthy mice were performed to obtain information about the uptake, biodistribution, and excretion of the radiolabeled complex.

Beta-amino acids to piperidinones by Petasis methylenation and acid-induced cyclization.

Ester-imine derivatives of beta-amino acids were methylenated with dimethyltitanocene under microwave irradiation and the resulting enol ethers cyclized with Brönsted acid or triisopropylaluminium to give 2,6-syn-disubstituted piperidinones in good yield and diastereoselectivity. The method is analogous to the Petasis-Ferrier rearrangement of 1,3-dioxan-4-ones to give tetrahydropyranones.