Microwave-accelerated 1,3-dipolar cycloaddition for the formation of fused [n]polynorbornanes

Microwave irradiation induces the 1,3-dipolar cycloaddition of cyclobutane epoxides with norbornenes to afford [n]polynorbornane scaffolds. Greatly enhanced reaction rates and significantly reduced levels of decomposition were observed.

A novel approach to the functionalisation of pristine carbon fibre using azomethine 1,3-dipolar cycloaddition

We demonstrate the utilisation of an azomethine 1,3-dipolar cycloaddition reaction with carbon fibre to graft complex molecules onto the fibre surface. In an effort to enhance the interfacial interaction of the fibre to the matrix, the functionalised fibres possessed a pendant amine that is able to interact with epoxy resins. Functionalisation was supported by X-ray photoelectron spectroscopy and the grafting process had no detrimental effects on tensile strength compared with the control (untreated) fibres. Also, microscopic roughness (as determined by atomic force microscopy) and fibre topography were unchanged after the described treatment process. This methodology complements existing methodology aimed at enhancing the surface of carbon fibres for advanced material applications while not compromising the desirable strength profile. Single-fibre fragmentation tests show a statistically significant decrease in fragment length compared with the control fibres in addition to transverse cracking within the curing resin, both of which indicate an enhanced interaction between fibre and resin.

Incorporation of a molecular hinge into molecular tweezers by using tandem gycloadditions onto 5,6-Dimenthylenenorbornene

Site-selective 1,3-dipolar coupling at the norbornene p-bond of 5,6-dimethylenenorbornene 1 yields cycloadducts with an end-fused 1,3-diene system which have been reacted with N=N (or C=C) dienophiles to produce ribbon molecules, in which the internal diazacyclohexene (or cyclohexene) subunits are capable of acting as conformational hinges. Direct coupling of 5,6-dimethylenenorbornene with 1,3,4-oxadiazoles or dual coupling with bis(cyclobutene epoxides) afforded bis(1,3-dienes) that diastereoselectively react with dienophiles to produce new, conformationally mobile, molecular tweezers.

Approaches to the synthesis of peptide substituted frameworks

The 1,3 dipolar cycloaddition between carbonyl ylids (generated from cyclobutene epoxides flanked by esters) and norbornyl alkenes – the ACE reaction – offers a facile method for the construction of polynorbornyl molecular frameworks. This reaction has, as described in this dissertation, underpinned the construction of molecular frameworks that have peptides and amino acids attached. Such highly rigid peptide-frameworks are of use in the field of peptidomimetics; the template molecule governs the final positioning of any attached groups such that a precise arrangement of amino acids can be achieved without the need to construct entire proteins. In the course of any ACE reaction the ester flanked cyclobutene epoxide is transformed to a 1,3 dipole, the esters serve to stablise this reactive intermediate and are as a consequence incorporated in the reaction product. Modification of these esters provides pseudo-equatorial points for peptide attachment. These methyl esters were replaced with tert-butyl esters to provide pseudo-axial attachment points that could be selectively addressed. The optimal strategy for peptide-framework construction involved direct condensation of carboxyl protected amino acids to bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid as well as condensation of amino acids to cyclobutene epoxides derived from this acid. The ACE reaction of (±) bicycloheptene-2-endo-carboxylic acid derivatives with cyclobutene epoxides synthesised from such racemic acid derivatives provided a mixture of enantiomers and meso compounds. In order to control the position of the attachment points – and hence the final location of the attached peptides – the ACE reaction required chiral starting materials. Accordingly, all peptidoframeworks were derived from the chiral (2S)-(-)-bicycloheptene carboxylic acid. The ACE reaction of this (S)-norbornene with the (S)-epoxide provided a peptide framework in which the attached amino acids were positioned pseudo-axially. Deprotection of the amino acid allowed peptide chain building in the pseudo-axial direction. Using this strategy a framework with an alanine residue and a triglycine peptide was synthesised. By combining this strategy with the ter-butyl ester variant a framework with pseudo-axial alanine and pseudo-equatorial glycine residues was manufactured.

New heterocycles from nitrile imines

Heterocycles, cyclic organic molecules containing atoms other than carbon, have displayed a wide and varied range of reactivity and application. This project employed the 1,3-dipolar cycloaddition chemistry of nitrile imines to synthesise new and novel heterocycles, with a focus on their potential as insecticidal agents.

13 C NMR spin–lattice relaxation times as a probeof local polymer dynamics in plasticized polyethers

¹³C NMR spin–lattice relaxation times T₁ are used to investigate the effect of low molecular weight diluents, including N,N-dimethylformamide, N-methylformamide, propylene carbonate, γ-butyrolactone, triglyme and tetraglyme, on the local polymer segmental motion in polyether–urethane networks. In all cases, an increase in the local mobility is deduced from the increasing T₁ measurements consistent with a decreasing glass transition temperature. The extent of plasticization, however, is dependent on the nature of the small molecules. Those molecules which can either form strong polymer-diluent interactions (for example through dipolar interactions) or are themselves rigid, give the least enhancement of polymer mobility and the greatest deviation from the Fox equation for T_g. In the presence of alkali metal salts, N,N-dimethylformamide and propylene carbonate are shown to have opposite effects on the local polymer motion, as seen from the T₁ measurements. In both cases, addition of the plasticizers increases the ¹³C T₁ relaxation times for the plasticizer. However, propylene carbonate decreases the polymer ¹³C T₁ whilst N,N-dimethylformamide results in the expected increase in polymer ¹³C T₁.

Solid state NMR characterization of lithium conducting ceramics

⁷Li solid state NMR has been used to characterize lithium aluminium titanium phosphate and lithium lanthanum titanate ceramics. Both materials have high ionic mobilities at room temperature and this is reflected in their static ⁷Li powder patterns. In the case of the phosphate based ceramic, a narrow Lorentzian peak is observed above 300 K, which narrows further with increasing temperature. The accompanying quadrupolar structure, with C_Q (quadrupolar coupling constant) ~ 40 kHz, suggests that the lithium ions are hopping rapidly between equivalent, high electric field gradient sites. The ²⁷Al and ³¹P magic angle spinning (MAS) spectra reveal an asymmetric phosphorus peak and two distinct aluminium resonances. The room temperature powder pattern of Li_0.33La_0.57TiO₃ shows a dipolar broadened peak which narrows quite suddenly at 310 K revealing quadrupolar satellites with C_Q ~ 900 Hz. A second lithium site is also observed in this material, as indicated by a further, weaker quadrupolar structure (C_Q ~ 40 kHz).

Dipole time correlation functions of the Stockmayer fluid in the microcanonical and canonical ensembles

Computer simulations of Stockmayer fluids were performed to generate dipole time correlation functions (TCF) at three temperatures and three dipole moments in both the microcanonical and canonical ensembles. The effect of Nosé constant-temperature dynamics on time-dependent quantities is discussed, and empirical results are given to show that the choice of thermal inertia parameter influences the speed with which a system moves through its phase space. The time correlation functions from the simulations were analyzed in terms of current theories for dipolar systems. A functional form is proposed to cover both the longtime and short-time behavior of the time correlation functions of dipoles. The relationship between this functional form and the dielectric function of the Stockmayer system is also discussed.

High frequency dielectric response of the ionic liquid N-methyl-N-ethylpyrrolidinium dicyanamide

A study of the room-temperature ionic liquid N-methyl-N-ethylpyrrolidinium dicyanamide by dielectric relaxation spectroscopy over the frequency range 0.2 GHz ≤ ν ≤ 89 GHz has revealed that, in addition to the already known lower frequency processes, there is a broad featureless dielectric loss at higher frequencies. The latter is probably due to the translational (oscillatory) motions of the dipolar ions of the IL relative to each other, with additional contributions from their fast rotation.

Orientation relationship, texture and microstructure in electromagnetic processed materials (EPM)

In this work, some of our recent results in microstructure, texture and orientation relationship resulting from the application of an external high magnetic field during diffusional and non-diffusional phase transformation in both steel and functional metallic materials have been summarized. A 12-T magnetic field was applied to the diffusional decomposition of austenite in 0.81C-Fe alloy and martensitic transformation of a Ni-Mn-Ga magnetic shape memory alloy. For the 0.81C-Fe alloy, it was found that the magnetic field induces the formation of proeutectoid ferrite and slightly enhances the <001> fiber component in ferrite in the transverse field direction. The magnetic dipolar interaction between Fe atoms in the transverse field direction accounts for this phenomenon. The magnetic field favors the formation of pearlite with Pitsch-Petch 2 (P-P 2) and Isaichev (IS) orientation relationships (OR) between the lamellar ferrite and cementite. For the Ni-Mn-Ga magnetic shape memory alloy, the magnetic field makes the martensite lamellas to grow in some specific directions with their c-axes [001] orientated to the field direction and transverse field direction.

Investigating nanoparticle-substrate interaction in LSPR biosensing using the image-charge theory

Localized surface plasmon resonance (LSPR) has been used to develop optical biosensors. Tuning the resonance wavelength to detect target biomolecules with a particular dipolar resonance is essential when designing LSPR biosensors. In this paper, the interaction of nanoparticles (NPs) with glass substrate (SiO2) for LSPR wavelength is investigated using the concept of the image-charge theory. Using the FDTD method, it is shown how the NP and substrate size change the plasmon wavelength. Next, this phenomenon is interpreted using the analytical electrostatic eigenvalue method.

Rapid domino [3+2] cycloaddition, [4+2] cycloreversion, ring-opening and aromatisation of a fused oxanorbornane substrate

Heating a dioxa-bridged diene with a cyclobutane epoxide for 10 min under microwave conditions (150 °C) gave an unexpected aryloxanorbornane product (20%). This adduct is proposed to occur via a [3+2] dipolar cycloaddition, retro-Diels-Alder reaction, ring-opening and subsequent aromatisation.