Cubane-1,3-dicarboxamides as structural isosteres for isophthalamides in hydrogen bond templated interlocked molecules.

The synthesis and characterization of the first examples of cubane containing interlocked molecules are reported. Catenanes and rotaxanes have been prepared by hydrogen bond templation with cubane-1,3-dicarboxamides replacing isophthalamide motifs.

Synthesis of a [2]catenane by ring closing metathesis of a [2]rotaxane prepared by crown ether active templation.

The high yielding synthesis and spectral characterization of a [2]catenane prepared by Grubbs catalyzed ring closing metathesis of a [2]rotaxane prepared by crown ether active template synthesis is described.

Rapid synthesis of hydrogen bond templated handcuff rotaxanes.

The rapid synthesis of hydrogen bond templated handcuff rotaxanes is described. The isolated rotaxanes were characterized by NMR and IR spectroscopies and high resolution mass spectrometry. This report represents a rare demonstration of preparing (2)handcuff [2]rotaxanes by covalently linking separate axles threaded through the rings of a bis-macrocycle by use of the copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction.

A pyridine--oxide catenane for cation recognition.

The rapid preparation of a pyridine--oxide containing [2]catenane is described. The [2]catenane was characterized by NMR spectroscopy, mass spectrometry and X-ray single crystal structure determination. H NMR titration experiments reveal the [2]catenane may be reversibly protonated, as well as an ability to bind lithium cations more strongly than sodium cations.

Brief High-Velocity Motor Skill Training Increases Step Frequency and Improves Length/Frequency Coordination in Slow Walkers With Chronic Motor-Incomplete Spinal Cord Injury.

Objective: To quantify spatiotemporal coordination during overground walking among persons with motor-incomplete spinal cord injury (PwMISCI) by calculating the step length (SL)/step frequency (SF) ratio (ie, the Walk Ratio [WR]) and to examine the effects of motor skill training (MST) on the relationship between changes in these parameters and walking speed (WS).

Design: Between-day exploratory analysis.

Setting: Research laboratory in a rehabilitation hospital PARTICIPANTS: PwMISCI (N=26).

Anion Modulated Expression of Chirality in Hydrogen Bond Templated Mechanically Chiral [2]Rotaxanes.

The syntheses of two novel mechanically chiral rotaxanes containing urea and squaramide motifs (in yields of 33 % and 22 %, respectively) are presented. H NMR spectroscopic titrations reveal shuttling of the macrocycle - detectable by modulation of the expression of mechanical chirality in the NMR spectrum - is possible through the addition of achiral chloride anions, a process which is reversed by the addition of sodium cations.

Hydrogen bond templated synthesis of catenanes and rotaxanes from a single isophthalic acid derivative.

Hydrogen bond templated [2]catenanes and [2]rotaxanes have been synthesized using azide precursors derived from a single isophthalic acid derivative precursor. The interlocked molecules were prepared using either stoichiometric or near stoichiometric amounts of macrocycle and CuAAC "click" precursors, with yields of up to 70% for the mechanical bond formation step. Successful preparation of the interlocked structures was confirmed by NMR spectroscopy and mass spectrometry, with detail of co-conformational behaviour being elucidated by a range of H NMR spectroscopic experiments.

Walking and Balance Outcomes Are Improved Following Brief Intensive Locomotor Skill Training but Are Not Augmented by Transcranial Direct Current Stimulation in Persons With Chronic Spinal Cord Injury.

Unlabelled: Motor training to improve walking and balance function is a common aspect of rehabilitation following motor-incomplete spinal cord injury (MISCI). Evidence suggests that moderate- to high-intensity exercise facilitates neuroplastic mechanisms that support motor skill acquisition and learning. Furthermore, enhancing corticospinal drive via transcranial direct current stimulation (tDCS) may augment the effects of motor training.

A Pilot Study of Intensive Locomotor-Related Skill Training and Transcranial Direct Current Stimulation in Chronic Spinal Cord Injury.

Background And Purpose: Improved walking function is a priority among persons with motor-incomplete spinal cord injury (PwMISCI). Accessibility and cost limit long-term participation in locomotor training offered in specialized centers. Intensive motor training that facilitates neuroplastic mechanisms that support skill learning and can be implemented in the home/community may be advantageous for promoting long-term restoration of walking function.

An amide hydrogen bond templated [1]rotaxane displaying a peptide motif - demonstrating an expedient route to synthetic mimics of lasso peptides.

The rapid synthesis of an amide hydrogen bond templated [1]rotaxane is reported - demonstrating a potential pathway to synthetic analogues of lasso peptides. The structures of the [1]rotaxane and its unthreaded isomer have been characterized by NMR spectroscopy and modelled using DFT calculations.

Lanthanide-Containing Rotaxanes, Catenanes, and Knots.

The valuable luminescence, magnetic, and catalytic properties of lanthanide cations are beginning to be exploited in conjunction with structurally exotic mechanically interlocked molecules (MIMs) such as rotaxanes, catenanes and knots. This Minireview provides an account of this rapidly developing research area commencing with the use of lanthanides in extended MIM-containing frameworks. Then, attention turns to discrete lanthanide-containing pseudorotaxanes, followed by fully interlocked rotaxanes, catenanes and knots - where lanthanides have not only been incorporated into MIM architectures but have also been used to template formation of the interlocked structure.

Modulating the expression of chirality in a mechanically chiral rotaxane.

The expression of mechanical chirality by a hydrogen bond templated rotaxane, as detected by 1H NMR spectroscopy, may be modulated by affecting the co-conformational behaviour of the rotaxane through varying solvent or by addition of acid and base.

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications.

Molecular chirality provides a key challenge in host-guest recognition and other related chemical applications such as asymmetric catalysis. For a molecule to act as an efficient enantioselective receptor, it requires multi-point interactions between host and chiral guest, which may be achieved by an appropriate chiral 3D scaffold. As a consequence of their interlocked structure, catenanes and rotaxanes may present such a 3D scaffold, and can be chiral by inclusion of a classical chiral element and/or as a consequence of the mechanical bond.

Rapidly accessible "click" rotaxanes utilizing a single amide hydrogen bond templating motif.

The synthesis of hydrogen bond templated rotaxanes using the CuAAC click reaction has been achieved in yields of up to 47%, employing near stoichiometric equivalents of macrocycle and readily prepared azide and alkyne half-axle components. Interlocked structure formation has been confirmed by NMR spectroscopy and mass spectrometry. Density functional theory calculations support H NMR spectroscopic analysis that the macrocycle resides over the amide of the axle component, rather than the newly formed triazole, as a result of more favourable hydrogen bond interactions.

The synthesis of a pyridine-N-oxide isophthalamide rotaxane utilizing supplementary amide hydrogen bond interactions.

The synthesis of a pyridine-N-oxide containing rotaxane, not requiring an additional ionic template, has been achieved in 32% yield. Successful rotaxane formation is dependent upon the structure of the isophthalamide macrocycle used, an observation which has been rationalised by a combination of NMR spectroscopy, X-ray crystallography and computational modelling.

The rapid synthesis and dynamic behaviour of an isophthalamide [2]catenane.

A serendipitous [2]catenane has been prepared in three steps from commercially available starting materials. The interlocked topology of the catenane has been confirmed by single crystal X-ray structural determination. The rings of the catenane may rotate relative to one another - a process that may be controlled by varying solvent or temperature.

Advances in anion supramolecular chemistry: from recognition to chemical applications.

Since the start of this millennium, remarkable progress in the binding and sensing of anions has been taking place, driven in part by discoveries in the use of hydrogen bonding, as well as the previously under-exploited anion-π interactions and halogen bonding. However, anion supramolecular chemistry has developed substantially beyond anion recognition, and now encompasses a diverse range of disciplines. Dramatic advance has been made in the anion-templated synthesis of macrocycles and interlocked molecular architectures, while the study of transmembrane anion transporters has flourished from almost nothing into a rapidly maturing field of research.

Progress in the synthesis and exploitation of catenanes since the Millennium.

Catenanes - molecules consisting of interlocked macrocyclic rings - have been prepared by templation strategies for some thirty years. The utilization of Cu(I) cation, aromatic donor-acceptor interactions and hydrogen bonding assisted self-assembly strategies has led to the construction of numerous examples of these aesthetically pleasing species. This review seeks to discuss key developments in the synthesis and functional application of catenanes that have occurred since the Millennium.

Utility of tris(4-bromopyridyl) europium complexes as versatile intermediates in the divergent synthesis of emissive chiral probes.

The synthetic utility of europium complexes with three coordinated 4-bromopyridyl groups for chromophore elaboration has been assessed in palladium-catalysed Sonogashira coupling reactions, and in copper(i) mediated click reactions of the triazide derivative, generated in situ. The crystal structure of the Eu complex of a p-OMe-phenyl substituted triazole at 100 K is reported in which the pendant triazole sensitising moieties interdigitate in the solid-state lattice. The triazole complex can be separated into Δ and Λ enantiomers by chiral HPLC but is weakly emissive in methanol (ε 5.

Complete stereocontrol in the synthesis of macrocyclic lanthanide complexes: direct formation of enantiopure systems for circularly polarised luminescence applications.

Mono-C-substitution of the 1,4,7-triazacyclononane ring induces formation of single enantiomers of Eu(III) complexes with nonadentate N6O3 ligands. The absolute configuration of each complex is determined by the stereogenicity of the C-substituent, revealed by comparison of the sign and sequence of CPL transitions for a series of complexes.

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence.

Optical probes that provide information about local chirality have been developed based on changes to the circular polarisation of emitted light. Highly emissive complexes of lanthanide ions are ideally suited for CPL spectroscopy and the design criteria for developing such probes are defined, based on a rigorous stereochemical analysis. The perturbation of a dynamically racemic complex may occur either by a change in complex constitution or by non-covalent association.

Isostructural series of nine-coordinate chiral lanthanide complexes based on triazacyclononane.

Nonadentate ligands based on triazacyclononane incorporating pyridyl-2-phosphinate groups form an isostructural series of complexes with Ln ions in the solid state and in solution. The Ln ion is effectively shielded from the solvent environment. Crystal structures reveal a rigid C(3)-symmetric tricapped trigonal-prismatic coordination geometry that is maintained in solution for the methyl and phenylphosphinate series, as shown by multinuclear NMR analysis.

Surface-attached sensors for cation and anion recognition.

The development of surface-attached sensors for cationic and anionic guests is of intense current research interest. In addition to the environmental flexibility, robustness and reusability of such devices, surface-confined sensors typically exhibit an amplified response to target analytes owing to preorganization of the receptor. Whereas redox-active cations may be sensed by studying the cyclic voltammetry of host-guest systems containing ion-selective receptors attached to an appropriate electrode, redox-inactive ionic species require the use of electrochemical impedance spectroscopy, with appropriately functionalized electrodes and redox probes.

A 1,2,3,4,5-pentaphenylferrocene-stoppered rotaxane capable of electrochemical anion recognition.

The chloride anion templated synthesis of an electrochemical anion sensory interlocked host system, prepared by the integration of redox-active 1,2,3,4,5-pentaphenylferrocene stopper groups into the structure of a rotaxane capable of binding anionic guests is described. Extensive (1)H NMR and electrochemical titration investigations were used to probe the anion recognition and sensing properties of the rotaxane, compared to the axle and model system components. A characteristic electrochemical response was observed for chloride binding by the rotaxane, which was attributed to the topologically constrained cavity of the interlocked host molecule.