Induced Protic Behaviour in Aprotonic Ionic Liquids by Anion Basicity for Efficient Carbon Dioxide Capture

The interactions between aprotonic tetrabutylphosphonium carboxylate ionic liquids (ILs), [P_{4 4 4 4}][C_nCOO] (n=1, 2 and 7), and water were investigated. The cation-anion interactions occur via the α-¹H on [P_{4 4 4 4}]⁺ and the carboxylate headgroup of the anion. Upon addition, H₂O localises around the carboxylate headgroups, inducing an electron inductive effect towards the oxygens, leading to ion-pair separation. Studies with D₂O and [P_{4 4 4 4}][C_nCOO] revealed protic behaviour of the systems, with proton/deuterium exchange occurring at the α-¹H of the cation, promoted by the basicity of the anion, forming an intermediate ylide. The greater influence of van der Waals forces of the [P_{4 4 4 4}][C₇COO] system allows for re-orientation of the ions through larger interdigitation. The protic behaviour of the neat ILs allows for CO₂ to be chemically absorbed on the ylide intermediate, forming a phosphonium-carboxylate zwitterion, signifying proton exchange occurs even in the absence of H₂O. The absorption of CO₂ in equimolar IL-H₂O mixtures forms a hydrogen carbonate, through a proposed reaction of the CO₂ with an intermediate hydroxide, and carboxylic acid.     

Formation of lanthanide ion networks by orientation of the mesophases of their complexes in magnetic fields

A complex of a Tm(III) perfluoroalkylsulsphate with salicylaldimine Schiff's base was synthesized and its liquid crystallinity characterized by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. An additional phase transition was detected. 2D or 3D anisotropically-organized media were obtained by cooling of the lanthanide complex from different phases in an applied magnetic field. A huge positive magnetic anisotropy was observed for the resulting material.     

Measurement of Hydroxyl-Radical Formation in the Rat Striatum by In Vivo Microdialysis and GC-MS

A GC-MS method was developed for measuring hydroxyl-radical capture products of salicylic acid, a common trapping agent for this reactive oxygen species, in samples obtained by in vivo cerebral microdialysis experiments. The assay employed liquid–liquid extraction followed by derivatization of 2,3- and 2,5-dihydroxybenzoic acid, along with 3,5-dihydroxybenzoic acid added as an internal standard. Due to their simple electron ionization mass spectra featuring [M–57]⁺ ions through the loss of tertiary alkyl group from the corresponding molecular ions, tert-butyldimethylsilyl (TBDMS) derivatives afforded straightforward method development based on selected-ion monitoring. In addition, tandem mass spectrometry probing collision-induced dissociation of [M–57]⁺ ions obtained from the isomeric tert-butyldimethylsilyl derivatives revealed characteristic differences in the resultant product-ion spectra. Our work has demonstrated the applicability of GC-MS for the assay of microdialysates for 2,3- and 2,5-dihydroxybenzoic acid by confirming that local administration of the excitotoxic glutamate into the rat striatum significantly increased in vivo hydroxyl-radical production in this brain region and that subsequent systemic administration of α-phenyl-tert-butylnitrone reversed glutamate-induced oxidative stress.     

A Benchtop Method for Appending Protic Functional Groups to N-Heterocyclic Carbene Protected Gold Nanoparticles

The remarkable resilience of N-heterocyclic carbene (NHC) gold bonds has quickly made NHCs the ligand of choice when functionalizing gold surfaces. Despite rapid progress using deposition from free or CO₂-protected NHCs, synthetic challenges hinder the functionalization of NHC surfaces with protic functional groups, such as alcohols and amines, particularly on larger nanoparticles. Here, we synthesize NHC-functionalized gold surfaces from gold(I) NHC complexes and aqueous nanoparticles without the need for additional reagents, enabling otherwise difficult functional groups to be appended to the carbene. The resilience of the NHC−Au bond allows for multi-step post-synthetic modification. Beginning with the nitro-NHC, we form an amine-NHC terminated surface, which further undergoes amide coupling with carboxylic acids. The simplicity of this approach, its compatibility with aqueous nanoparticle solutions, and its ability to yield protic functionality, greatly expands the potential of NHC-functionalized noble metal surfaces.     

Construction of pyrazolo[3,4-b]pyridines and pyrazolo[4,3-c]pyridines by ring closure of 3-acylpyridine N-oxide tosylhydrazones

3-Acylpyridine N-oxide tosylhydrazones give good overall yields of a mixture of pyrazolo[3,4-b]pyridines and pyrazolo[4,3-c]pyridines when treated with an electrophilic additive and an amine base. (Z)-Hydrazones cyclize readily, while (E)-hydrazones fail to react under the reported conditions. The reaction takes place at room temperature, and moderate regiocontrol over the cyclization can be achieved by varying the electrophile/solvent combination.     

Spatial Filters on Demand Based on Aperiodic Photonic Crystals

Photonic Crystal spatial filters, apart from stand‐alone spatial filtering function, can also suppress multi‐transverse‐mode operation in laser resonators. Here it is shown that such photonic crystals can be designed by solving the inverse problem: for a given spatial filtering profile. Optimized Photonic Crystal filters were fabricated in photosensitive glass. Experiments have shown that such filters provide a more pronounced filtering effect for total and partial transmissivity conditions.     

Coherent third-order spectroscopic probes of molecular chirality

The third-order optical response of a system of coupled localized anharmonic vibrations is studied using a Green's function solution of the nonlinear exciton equations for bosonized excitons, which are treated as interacting quasiparticles. The explicit calculation of two-exciton states is avoided and the scattering of quasiparticles provides the mechanism of optical nonlinearities. To first-order in the optical wave vector we find several rotationally invariant tensor components for isotropic ensembles which are induced by chirality. The nonlocal nonlinear susceptibility tensor is calculated for infinitely large periodic structures in momentum space, where the problem size reduces to the exciton interaction radius. Applications are made to alpha and 3(10) helical infinite peptides.