25 research outputs found
Recommended from our members
A Ferrocene-Based Catecholamide Ligand: the Consequences of Ligand Swivel for Directed Supramolecular Self-Assembly
A ferrocene-based biscatecholamide ligand was prepared and investigated for the formation of metal-ligand supramolecular assemblies with different metals. Reaction with Ge(IV) resulted in the formation of a variety of Ge{sub n}L{sub m} coordination complexes, including [Ge{sub 2}L{sub 3}]{sup 4-} and [Ge{sub 2}L{sub 2}({mu}-OMe){sub 2}]{sup 2-}. The ligand's ability to swivel about the ferrocenyl linker and adopt different conformations accounts for formation of many different Ge{sub n}L{sub m} species. This study demonstrates why conformational ligand rigidity is essential in the rational design and directed self-assembly of supramolecular complexes
La Paz : periódico de noticias, avisos y fomento de la provincia de Murcia: Año XXX Número 9243 - 1887 Agosto 18
Isotope effects (IEs), which arise from differences in zero point energies (ZPEs) between a parent and isotopically substituted bond, have been used extensively by chemists to probe molecular interactions and reactivity. Due to the anharmonicity of the C-H/D vibrational potential energy function and the lower ZPE of a C-D bond, the average C-D bond length is typically {approx}0.005 {angstrom} shorter than an equivalent C-H bond. It is this difference in size that is often invoked to explain the observation of secondary, inverse kinetic isotope effects (KIEs) in chemical processes which proceed through a sterically strained transition state. This so-called 'steric isotope effect' (SIE) has been observed in processes such as the racemization of ortho-substituted biphenyls[6] and phenanthrenes, ring flipping of cyclophanes, and more recently in the deslipping of rotaxanes, where substitution of the sterically less demanding deuterium for protium results in rate accelerations for these processes. Herein, we use deuterium substitution in a cationic guest molecule to probe the sensitivity limits of the guest exchange process from a highly-charged supramolecular host
Recommended from our members
High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions
Isotope effects (IEs) are a powerful tool for examining the reactivity of, and interactions between, molecules. Recently, secondary IEs have been used to probe the nature of noncovalent interactions between guest and host molecules in supramolecular systems. While these studies can provide valuable insight into the specific interactions governing guest recognition and binding properties, IEs on noncovalent interactions are often very small and difficult to measure precisely. The Perrin group has developed an NMR titration method capable of determining ratios of equilibrium constants with remarkable precision. They have used this technique to study small, secondary equilibrium isotope effects (EIEs) on the acidity of carboxylic acids and phenols and on the basicity of amines, measuring differences down to thousandths of a pK{sub a} unit. It occurred to us that this titration method can in principle measure relative equilibrium constants for any process which is fast on the NMR timescale and for which the species under comparison are distinguishable by NMR. Here we report the application of this method to measure very small EIEs on noncovalent host-guest interactions in a supramolecular system
Equilibrium Isotope Effects on Noncovalent Interactions in a Supramolecular Host–Guest System
The self-assembled supramolecular complex [Ga<sub>4</sub>L<sub>6</sub>]<sup>12‑</sup> (<b>1</b>; L = 1,5-bisÂ[2,3-dihydroxybenzamido]Ânaphthalene)
can act as a molecular host in aqueous solution and bind cationic
guest molecules to its highly charged exterior surface or within its
hydrophobic interior cavity. The distinct internal cavity of host <b>1</b> modifies the physical properties and reactivity of bound
guest molecules and can be used to catalyze a variety of chemical
transformations. Noncovalent host–guest interactions in large
part control guest binding, molecular recognition and the chemical
reactivity of bound guests. Herein we examine equilibrium isotope
effects (EIEs) on both exterior and interior guest binding to host <b>1</b> and use these effects to probe the details of noncovalent
host–guest interactions. For both interior and exterior binding
of a benzylphosphonium guest in aqueous solution, protiated guests
are found to bind more strongly to host <b>1</b> (<i>K</i><sub>H</sub>/<i>K</i><sub>D</sub> > 1) and the preferred
association of protiated guests is driven by enthalpy and opposed
by entropy. Deuteration of guest methyl and benzyl C–H bonds
results in a larger EIE than deuteration of guest aromatic C–H
bonds. The observed EIEs can be well explained by considering changes
in guest vibrational force constants and zero-point energies. DFT
calculations further confirm the origins of these EIEs and suggest
that changes in low-frequency guest C–H/D vibrational motions
(bends, wags, etc.) are primarily responsible for the observed EIEs
Recommended from our members
External and Internal Guest Binding of a Highly Charged Supramolecular Host in Water: Deconvoluting the Very Different Thermodynamics
NMR, UV-vis and isothermal titration calorimetry (ITC) measurements probe different aspects of competing host-guest equilibria as simple alkylammonium guest molecules interact with both the exterior (ion-association) and interior (encapsulation) of the [Ga{sub 4}L{sub 6}]{sup 12-} supramolecular assembly in water. Data obtained by each independent technique measure different components of the host-guest equilibria and only when analyzed together does a complete picture of the solution thermodynamics emerge. Striking differences between the internal and external guest binding are found. External binding is enthalpy driven and mainly due to attractive interactions between the guests and the exterior surface of the assembly while encapsulation is entropy driven as a result of desolvation and release of solvent molecules from the host cavity
Impedance Changes and Fibrous Tissue Growth after Cochlear Implantation Are Correlated and Can Be Reduced Using a Dexamethasone Eluting Electrode.
BACKGROUND:The efficiency of cochlear implants (CIs) is affected by postoperative connective tissue growth around the electrode array. This tissue formation is thought to be the cause behind post-operative increases in impedance. Dexamethasone (DEX) eluting CIs may reduce fibrous tissue growth around the electrode array subsequently moderating elevations in impedance of the electrode contacts. METHODS:For this study, DEX was incorporated into the silicone of the CI electrode arrays at 1% and 10% (w/w) concentration. Electrodes prepared by the same process but without dexamethasone served as controls. All electrodes were implanted into guinea pig cochleae though the round window membrane approach. Potential additive or synergistic effects of electrical stimulation (60 minutes) were investigated by measuring impedances before and after stimulation (days 0, 7, 28, 56 and 91). Acoustically evoked auditory brainstem responses were recorded before and after CI insertion as well as on experimental days 7, 28, 56, and 91. Additionally, histology performed on epoxy embedded samples enabled measurement of the area of scala tympani occupied with fibrous tissue. RESULTS:In all experimental groups, the highest levels of fibrous tissue were detected in the basal region of the cochlea in vicinity to the round window niche. Both DEX concentrations, 10% and 1% (w/w), significantly reduced fibrosis around the electrode array of the CI. Following 3 months of implantation impedance levels in both DEX-eluting groups were significantly lower compared to the control group, the 10% group producing a greater effect. The same effects were observed before and after electrical stimulation. CONCLUSION:To our knowledge, this is the first study to demonstrate a correlation between the extent of new tissue growth around the electrode and impedance changes after cochlear implantation. We conclude that DEX-eluting CIs are a means to reduce this tissue reaction and improve the functional benefits of the implant by attenuating electrode impedance
Solvent and Pressure Effects on the Motions of Encapsulated Guests: Tuning the Flexibility of a Supramolecular Host
The
supramolecular host assembly [Ga<sub>4</sub>L<sub>6</sub>]<sup>12‑</sup> [<b>1</b>; L = 1,5-bisÂ(2,3-dihydroxybenzamido)Ânaphthalene]
contains a flexible, hydrophobic interior cavity that can encapsulate
cationic guest molecules and catalyze a variety of chemical transformations.
The Ar–CH<sub>2</sub> bond rotational barrier for encapsulated
ortho-substituted benzyl phosphonium guest molecules is sensitive
to the size and shape of the host interior space. Here we examine
how changes in bulk solvent (water, methanol, or DMF) or applied pressure
(up to 150 MPa) affect the rotational dynamics of encapsulated benzyl
phosphonium guests, as a way to probe changes in host cavity size
or flexibility. When host <b>1</b> is dissolved in organic solvents
with large solvent internal pressures (∂<i>U</i>/∂<i>V</i>)<sub><i>T</i></sub>, we find that the free energy
barrier to Ar–CH<sub>2</sub> bond rotation increases by 1–2
kcal/mol, compared with that in aqueous solution. Likewise, when external
pressure is applied to the host–guest complex in solution,
the bond rotational rates for the encapsulated guests decrease. The
magnitude of these rate changes and the volumes of activation obtained
using either solvent internal pressure or applied external pressure
are very similar. NOE distance measurements reveal shorter average
host–guest distances (∼0.3 Å) in organic versus
aqueous solution. These experiments demonstrate that increasing solvent
internal pressure or applied external pressure reduces the host cavity
size or flexibility, resulting in more restricted motions for encapsulated
guest molecules. Changing bulk solvent or external pressure might
therefore be used to tune the physical properties or reactivity of
guest molecules encapsulated in a flexible supramolecular host
Shifts in hearing thresholds obtained on day 0 before (A) and after surgery (B) until day 91 are plotted (ΔdB) for all tested frequencies.
<p>At 4, 8, 32 and 40 kHz no differences in ΔdB between treatment groups were observed for day 0 (pre-operative) and day 91. 10% DEX treatment resulted in significantly greater threshold shifts at 1 and 16 kHz than 0% DEX + ES (p<0.05) or 0% DEX without-ES at 16 kHz (p<0.05) (A). No differences between groups where observed when relating the final threshold (day 91) to the day 0 threshold measured after surgery (B). Error bars: SEM.</p