15 resultados para QUANTUM CHEMISTRY AND THERMOCHEMISTRY

em Deakin Research Online - Australia


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A novel electrochemical sensor for highly sensitive and selective detection of dopamine (DA) was developed based on a graphene quantum dots (GQDs) and Nafion composite modified glassy carbon electrode (GCE). GQDs were synthesized by a hydrothermal approach for cutting graphene sheets into GQDs and characterized by TEM, UV-vis, photoluminescence, and FT-IR spectra. The GQDs had carboxyl groups with a negative charge, which not only provided good stability, but also enabled interaction with amine functional groups in DA through electrostatic interaction to enhance the specificity of DA. The interaction and electron communication between GQDs and DA can be further strengthened via π-π stacking force. Nafion was used as an anchoring agent to increase the robustness of GQDs on the electrode surface and sensor stability and reproducibility. The GQDs-Nafion composite exhibits a good linear range of 5 nM to 100 μM and a limit of detection as low as 0.45 nM in the detection of DA. The proposed electrochemical sensor also displays good selectivity and high stability and could be used for the determination of DA in real samples with satisfactory results. The present study provides a powerful avenue for the design of an ultrasensitive detection method for clinical application.

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The Mediterranean diet is associated with a lower incidence of atherosclerosis, cardiovascular disease, and certain types of cancer. The apparent health benefits have been partially attributed to the dietary consumption of virgin olive oil by Mediterranean populations. Most recent interest has focused on the biologically active phenolic compounds naturally present in virgin olive oils. Studies (human, animal, in vivo and in vitro) have shown that olive oil phenolics have positive effects on certain physiological parameters, such as plasma lipoproteins, oxidative damage, inflammatory markers, platelet and cellular function, and antimicrobial activity. Presumably, regular dietary consumption of virgin olive oil containing phenolic compounds manifests in health benefits associated with a Mediterranean diet. This paper summarizes current knowledge on the physiological effects of olive oil phenolics. Moreover, a number of factors have the ability to affect phenolic concentrations in virgin olive oil, so it is of great importance to understand these factors in order to preserve the essential health promoting benefits of olive oil phenolic compounds.

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pH-detachable poly(styrene) brushes formed on indium−tin oxide (ITO) glass substrates using metal complex chemistry and reversible addition−fragmentation chain transfer (RAFT) polymerization was described. These pH-detachable polymeric brushes were generated using both “graft-from” and “graft-to” methodologies. The methodologies involved either the surface self-assembly of catechol-functional RAFT agents (graft-from) or catechol-terminal polymer chains (graft-to) onto the ITO substrate via titanium−diol coordination. The stepwise functionalization of the ITO glass surfaces was characterized successfully using X-ray photoelectron spectroscopy (XPS) and contact angle measurement. Poly(styrene) brushes generated using the “graft-from” method were denser than those generated using the “graft-to” method, as exemplified by atom force microscopy (AFM) and quantified using cyclic voltammetry. Poly(styrene) brushes assembled using both methods could be detached easily by manipulating the pH of the brush environment. Cyclic voltammetry was utilized to calculate precisely the surface coverage of the RAFT functionality and polymeric brush density.

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This Account covers research dating from the early 1960s in the field of low-melting molten salts and hydrates,which has recently become popular under the rubric of “ionic liquids”. It covers understanding gained in the principal author’s laboratories (initially in Australia, but mostly in the U.S.A.) from spectroscopic, dynamic, and thermodynamic studies and includes recent applications of this understanding in the fields of energy conversion and biopreservation. Both protic and aprotic varieties of ionic liquids are included, but recent studies have focused on the protic class because of the special applications made possible by the highly variable proton activities available in these liquids.

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Interfacial chemistry and adhesion between titanium dioxide (TiO2) nanotube layers and titanium (Ti) substrates were studied in this Article. TiO2 nanotube layers were produced on pure Ti by anodization and annealed in air for different time durations. The adhesion of the TiO2 nanotube layers was then investigated by Rockwell C indentation test. Results show that adhesion of TiO2 nanotube layers improved with the extension of annealing time. This improvement in adhesion of TiO2 nanotube layers was analyzed from the viewpoint of interfacial chemistry using energy dispersive X-ray spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS). It suggests that more Ti-O bonds formed in the interface after annealing, and this led to the improved adhesion of the TiO2 nanoube layers.

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This paper reports a fast, accurate, and non-destructive three-dimensional imaging approach based on using quantum dots and confocal laser scanning microscopy to get three-dimensional images of internal pore structure of the nanofibrous materials. A practical method of making the fiber fluorescent using quantum dots was applied before three-dimensional imaging by confocal laser scanning microscopy. Fibrous scaffolds with different porosity parameters produced by electrospinning and their three-dimensional pore structure was evaluated by this approach. Furthermore, the introduced approach can be used to measure the pore interconnectivity of the scaffold

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This work presents a comprehensive investigation of the quantum capacitance and the associated effects on the carrier transit delay in armchair-edge graphene nanoribbons (A-GNRs) based on semi-analytical method. We emphasize on the realistic analysis of bandgap with taking edge effects into account by means of modified tight binding (TB) model. The results show that the edge effects have significant influence in defining the bandgap which is a necessary input in the accurate analyses of capacitance. The quantum capacitance is discussed in both nondegenerate (low gate voltage) and degenerate (high gate voltage) regimes. We observe that the classical capacitance limits the total gate (external) capacitance in the degenerate regime, whereas, quantum capacitance limits the external gate capacitance in the nondegenerate regime. The influence of gate capacitances on the gate delay is studied extensively to demonstrate the optimization of switching time. Moreover, the high-field behavior of a GNR is studied in the degenerate and nondegenerate regimes. We find that a smaller intrinsic capacitance appears in the channel due to high velocity carrier, which limits the quantum capacitance and thus limit the gate delay. Such detail analysis of GNRs considering a realistic model would be useful for the optimized design of GNR-based nanoelectronic devices.

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The use of zinc oxide (ZnO) nanoparticles as ultraviolet (UV) absorbers for many organic substrates is limited because of the high photocatalytic activity of ZnO. In this study, a facile and efficient technique for the preparation of a hybrid material of silica-coated ZnO nanoparticles was used to reduce the photocatalytic activity of ZnO. Monodispersed ZnO nanopartcles were prepared by wet chemistry and the particle surface was modified by tetraethylorthosilicate to form a silica coating via the Sto¨ ber method. ZnO samples, both before and after the coating process, were investigated by transmission electron microscopy, X-ray diffraction, dynamic light scanning, infrared, and UV-Vis absorption spectroscopy. The effect of the surface modification on the photocatalytic activity of ZnO was studied by monitoring the degradation of Rhodamine B caused by photo-generated free radicals. The results implied that the photo-generation of free-radicals was strongly quenched by the presence of silica on the particle surface.

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Chemiluminescence, the production of light from a chemical reaction, has found widespread use in analytical chemistry. Both tris (2, 2’-bipyridyl) ruthenium (II) and acidic potassium permanganate are chemiluminescence reagents that have been employed for the determination of a diverse range of analytes. This thesis encompasses some fundamental investigations into the chemistry and spectroscopy of these chemiluminescence reactions as well as extending the scope of their analytical applications. Specifically, a simple and robust capillary electrophoresis chemiluminescence detection system for the determination of codeine, O6-methylcodeine and thebaine is described, based upon the reaction of these analytes with chemically generated tris(2,2'-bipyridyl)ruthenium(III) prepared in sulfuric acid (0.05 M). The reagent solution was contained in a glass detection cell, which also held both the capillary and the cathode. The resultant chemiluminescence was monitored directly using a photomultiplier tube mounted flush against the base of the detection cell. The methodology, which incorporated a field amplification sample introduction procedure, realised detection limits (3a baseline noise) of 5 x 10~8 M for both codeine and O6-methylcodeine and 1 x 10~7 M for thebaine. The relative standard deviations of the migration times and the peak areas for the three analytes ranged from 2.2 % up to 2.5 % and 1.9 % up to 4.6 % respectively. Following minor instrumental modifications, morphine, oripavine and pseudomorphine were determined based upon their reaction with acidic potassium permanganate in the presence of sodium polyphosphate. To ensure no migration of the permanganate anion occurred, the anode was placed at the detector end whilst the electroosmotic flow was reversed by the addition of hexadimethrine bromide (0.001% m/v) to the electrolyte. The three analytes were separated counter to the electroosmotic flow via their interaction with a-cyclodextrin. The methodology realised detection limits (3 x S/N) of 2.5 x 10~7 M for both morphine and oripavine and 5 x 10~7 M for pseudomorphine. The relative standard deviations of the migration times and the peak heights for the three analytes ranged from 0.6 % up to 0.8 % and 1.5% up to 2.1 % respectively. Further improvements were made by incorporating a co-axial sheath flow detection cell. The methodology was validated by comparing the results realised using this technique with those obtained by high performance liquid chromatography (HPLC), for the determination of both morphine and oripavine in seven industrial process liquors. A complimentary capillary electrophoresis procedure with UV-absorption detection was also developed and applied to the determination of morphine, codeine, oripavine and thebaine in nine process liquors. The results were compared with those achieved using a standard HPLC method. Although over eighty papers have appeared in the literature on the analytical applications of acidic potassium permanganate chemiluminescence, little effort has been directed towards identifying the origin of the luminescence. It was found that chemiluminescence was generated during the manganese(III), manganese(IV) and manganese(VII) oxidations of sodium borohydride, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689 ± 5 nm and 734 ± 5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate or orthophosphoric acid environments respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K, exhibited two peaks with maxima at 688 nm and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution phase chemically induced phosphorescence of manganese(II). Thereby confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species. Additionally, these findings have had direct analytical application in that manganese(IV) was evaluated as a new reagent for chemiluminescence detection. The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 x S/N) for Mn(II), Fe(II), morphine and codeine of 5 x 10-8 M, 2.5 x 10-7 M, 7.5 x 10-8 M and 5 x 10-8M, respectively. The corrected emission spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm indicating that these chemiluminescence reactions also shared a common emitting species, excited manganese(II). Whilst several analytical problems were addressed in this thesis and answers to certain questions regarding the fundamentals of acidic potassium permanganate chemiluminescence were proposed, there are several areas that would benefit from further research. These are outlined in the final chapter of this thesis.

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This research focuses on surveying in an attractive field of quantum computing. The paper begins by highlighting a brief history of quantum mechanics. Major elements of quantum computing such as quantum superposition, quantum tunnelling and qubits are addressed at next from a physics perspective. In addition, various methods and applications of quantum physics are also examined. This paper discusses the power and efficiencies that a quantum computer provides and the basis for these claims. Furthermore, the level of research in quantum computing and it’s commercial markets assays to find out the major contributions and developments in the field of quantum computing. The top two leading organisations in quantum computing are picked and reviewed with their up to date contributions. This paper expresses the methods and techniques which are being used by these two organisations to implement a quantum processor and the level of success that has been achieved. This research attempts to log the challenges and limitations that these organisations face in the development of quantum computing. Finally, the research compares quantum model with classical computing model.