School of Chemistry - Research Publications
Permanent URI for this collection
Search Results
1 - 10 of 452
-
ItemSelenoproteins in Health(MDPI AG, 2023-12-25)Selenium (Se) is a naturally occurring essential micronutrient that is required for human health. The existing form of Se includes inorganic and organic. In contrast to the inorganic Se, which has low bioavailability and high cytotoxicity, organic Se exhibits higher bioavailability, lower toxicity, and has a more diverse composition and structure. This review presents the nutritional benefits of Se by listing and linking selenoprotein (SeP) functions to evidence of health benefits. The research status of SeP from foods in recent years is introduced systematically, particularly the sources, biochemical transformation and speciation, and the bioactivities. These aspects are elaborated with references for further research and utilization of organic Se compounds in the field of health.
-
ItemPredicting valence tautomerism in diverse cobalt-dioxolene complexes: elucidation of the role of ligands and solvent(ROYAL SOC CHEMISTRY, 2024-04-17)The ability of molecular switches to reversibly interconvert between different forms promises potential applications at the scale of single molecules up to bulk materials. One type of molecular switch comprises cobalt-dioxolene compounds that exhibit thermally-induced valence tautomerism (VT) interconversions between low spin Co(iii)-catecholate (LS-CoIII-cat) and high spin Co(ii)-semiquinonate (HS-CoII-sq) forms. Two families of these compounds have been investigated for decades but have generally been considered separately: neutral [Co(diox)(sq)(N2L)] and cationic [Co(diox)(N4L)]+ complexes (diox = generic dioxolene, N2L/N4L = bidentate/tetradentate N-donor ancillary ligand). Computational identification of promising new candidate compounds prior to experimental exploration is beneficial for environmental and cost considerations but requires a thorough understanding of the underlying thermochemical parameters that influence the switching. Herein, we report a robust approach for the analysis of both cobalt-dioxolene families, which involved a quantitative density functional theory-based study benchmarked with reliable quasi-experimental references. The best-performing M06L-D4/def2-TZVPP level of theory has subsequently been verified by the synthesis and experimental investigation of three new complexes, two of which exhibit thermally-induced VT, while the third remains in the LS-CoIII-cat form across all temperatures, in agreement with prediction. Valence tautomerism in solution is markedly solvent-dependent, but the origin of this has not been definitively established. We have extended our computational approach to elucidate the correlation of VT transition temperature with solvent stabilisation energy and change in dipole moment. This new understanding may inform the development of VT compounds for applications in soft materials including films, gels, and polymers.
-
ItemAb initio-based determination of lanthanoid-radical exchange as visualised by inelastic neutron scattering(ROYAL SOC CHEMISTRY, 2024-03-20)Magnetic exchange coupling can modulate the slow magnetic relaxation in single-molecule magnets. Despite this, elucidation of exchange coupling remains a significant challenge for the lanthanoid(iii) ions, both experimentally and computationally. In this work, the crystal field splitting and 4f-π exchange coupling in the erbium-semiquinonate complex [ErTp2dbsq] (Er-dbsq; Tp- = hydro-tris(1-pyrazolyl)borate, dbsqH2 = 3,5-di-tert-butyl-1,2-semiquinone) have been determined by inelastic neutron scattering (INS), magnetometry, and CASSCF-SO ab initio calculations. A related complex with a diamagnetic ligand, [ErTp2trop] (Er-trop; tropH = tropolone), has been used as a model for the crystal field splitting in the absence of coupling. Magnetic and INS data indicate antiferromagnetic exchange for Er-dbsq with a coupling constant of Jex = -0.23 meV (-1.8 cm-1) (-2Jex formalism) and good agreement is found between theory and experiment, with the low energy magnetic and spectroscopic properties well modelled. Most notable is the ability of the ab initio modelling to reproduce the signature of interference between localised 4f states and delocalised π-radical states that is evident in the Q-dependence of the exchange excitation. This work highlights the power of combining INS with EPR and magnetometry for determination of ground state properties, as well as the enhanced capability of CASSCF-SO ab initio calculations and purposely developed ab initio-based theoretical models. We deliver an unprecedentedly detailed representation of the entangled character of 4f-π exchange states, which is obtained via an accurate image of the spin-orbital transition density between the 4f-π exchange coupled wavefunctions.
-
ItemJohn Atherton Young 1936–2004(CSIRO Publishing, 2024)John Atherton Young (1936–2004) graduated in medicine at the University of Queensland and undertook research in physiology at the Kanematsu Institute in Sydney for which he was awarded his PhD. After postdoctoral studies in Germany, he joined the department of physiology at the University of Sydney, rising to professor, then Dean of the Faculty of Medicine and finally Pro-Vice-Chancellor for Health Sciences. His research on the physiology of epithelial ducts, beginning with those of the kidney but later centring on salivary glands and the pancreas, brought him international recognition as a leader in the field. He made significant contributions to professional societies and was recognised with international and national awards including membership of the Order of Australia. A bronze portrait head of Young by sculptor Dan Lake is displayed in the foyer of the Edward Ford building at the University of Sydney. He was a man of great culture, a witty conversationalist and a great scientist.
-
ItemNo Preview AvailableResolving conjugated polymer film morphology with polarised transmission and time-resolved emission microscopy(IOP Publishing, 2024-07-01)The alignment of chromophores plays a crucial role in determining the optoelectronic properties of materials. Such alignment can make interpretation of fluorescence anisotropy microscopy (FAM) images somewhat ambiguous. The time-resolved emission behaviour can also influence the fluorescence anisotropy. This is particularly the case when probing excitation energy migration between chromophores in a condensed phase. Ideally information concerning the chromophoric alignment, emission decay kinetics and fluorescence anisotropy can be recorded and correlated. We report on the use of polarised transmission imaging (PTI) coupled with both steady-state and time-resolved FAM to enable accurate identification of chromophoric alignment and morphology in thin films of a conjugated polydiarylfluorene. We show that the combination of these three imaging modes presents a comprehensive methodology for investigating the alignment and morphology of chromophores in thin films, particularly for accurately mapping the distribution of amorphous and crystalline phases within the thin films, offering valuable insights for the design and optimization of materials with enhanced optoelectronic performance.
-
ItemChemical vapor deposition growth of phase-selective inorganic lead halide perovskite films for sensitive photodetectors(ELSEVIER SCIENCE INC, 2021-01)Inorganic lead halide perovskites are attractive optoelectronic materials owing to their relative stability compared to organic cation alternatives. The chemical vapor deposition (CVD) method offers potential for high quality perovskite film growth. The deposition temperature is a critical parameter determining the film quality owing to the melting difference between the precursors. Here, perovskite films were deposited by the CVD method at various temperatures between 500−800 °C. The perovskite phase converts from CsPb2Br5 to CsPbBr3 gradually as the deposition temperature is increased. The grain size of the perovskite films also increases with temperature. The phase transition mechanism was clarified. The photoexcited state dynamics were investigated by spatially and temporally resolved fluorescence measurements. The perovskite film deposited under 750 °C condition is of the CsPbBr3 phase, showing low trap-state density and large crystalline grain size. A photodetector based on perovskite films shows high photocurrent and an on/off ratio of ∼2.5 × 104.
-
ItemMorphological Requirements for Nanoscale Electric Field Buildup in a Bulk Heterojunction Solar Cell(AMER CHEMICAL SOC, 2021-01-14)The morphology of organic semiconductors is critical to their function in optoelectronic devices and is particularly crucial in the donor-acceptor mixture that comprises the bulk heterojunction of organic solar cells. Here, energy landscapes can play integral roles in charge photogeneration, and recently have been shown to drive the accumulation of charge carriers away from the interface, resulting in the buildup of large nanoscale electric fields, much like a capacitor. In this work we combine morphological and spectroscopic data to outline the requirements for this interdomain charge accumulation, finding that this effect is driven by a three-phase morphology that creates an energetic cascade for charge carriers. By adjusting annealing conditions, we show that domain purity, but not size, is critical for an electro-absorption feature to grow-in. This demonstrates that the energy landscape around the interface shapes the movement of charges and that pure domains are required for charge carrier buildup that results in reduced recombination and large interdomain nanoscale electric fields.
-
ItemElectronic spectroscopy and photophysics of calix[4]azulene(ELSEVIER SCIENCE SA, 2021-01-15)Calix[4]azulene is a non-alternant aromatic calixarene composed of four azulene chromophores linked by methylene groups. Its photochemical stability, photophysical properties and an analysis of its electronic spectra are reported using monomeric azulene as a known reference standard. The molecule is stable when excited in its visible and near uv absorptions and, unlike azulene, produces no measurable “anti-Kasha” fluorescence when excited to its second excited singlet state, S2. This lack of fluorescence places the lifetime of the initially excited, photochemically stable S2 species at less than 1 picosecond. A significant, bathochromic shift of the S2 absorption band system in the calixarene, and the appearance of an additional weak, broad absorption immediately to the red signals significant intramolecular chromophore interaction. Femtosecond transient absorption spectroscopy using excitation in this red-shifted tail of the S2 band system reveals a very weak transient signal most of which decays within one ps, but with suggestions of a slightly longer-lived underlying component. No longer-lived T1 triplet transient is observed. A complete analysis of the data using monomeric azulene as a reference suggests, following elimination of several alternate mechanisms, that the initially excited S2 species may be relaxing via a novel singlet-singlet fission process.
-
ItemUltrafast Nanodrum-on-Chip Pixels(AMER CHEMICAL SOC, 2024-03-15)Environmentally friendly, ultrafast display pixels of micrometer sizes are fabricated with nanometer-thick gold films and Si/SiO2 wafers. The color displayed is due to both the plasmon response of the gold film and the optical interference from the Fabry-Peerot cavity formed by the underlying silicon substrate, the semitransparent gold film and the air gap between them. When an electric potential is applied to the gold film, the electrostatic force induces an attraction between the gold film and the silicon wafer. Due to the flexibility of the film, the size of the air gap changes, resulting in a changing color. By applying different driving signals, we have achieved cyan, magenta, and yellow reflected colors. The maximum switching rate of the pixel is primarily determined by the thickness dependence of the metal drum and its Young's modulus and is typically in the MHz regime.
-
ItemNo Preview AvailableFingerprints of Chalcogen Bonding Revealed Through 77Se-NMR.(Wiley, 2024-03-20)77Se-NMR is used to characterise several chalcogen bonded complexes of derivatives of the organoselenium drug ebselen, exploring a range of electron demand. NMR titration experiments support the intuitive understanding that chalcogen bond donors bearing more electron withdrawing substituents give rise stronger chalcogen bonds. The chemical shift of the selenium nucleus is also shown to move upfield as it participates in a chalcogen bond. Solid-state NMR is used to explore chalcogen bonding in co-crystals. Due to the lack of molecular reorientation on the NMR timescale in the solid state, the shape of the chemical shift tensor can be determined using this technique. A range of co-crystals are shown to have extremely large chemical shift anisotropy, which suggests a strongly anisotropic electron density distribution around the selenium atom. A single crystal NMR experiment was conducted using one of the co-crystals, affording the absolute orientation of the chemical shift tensor within the crystal. This showed that the selenium nucleus is strongly shielded in the direction of the chalcogen bond (due to the approach of the lone pair of the Lewis base), and strongly deshielded in the perpendicular direction. The orientation of the deshielded axis is consistent with the presence of a second σ-hole which is not participating in a chalcogen bond, showing the profound effect of electron density anisotropy on the chemical shift.