All i need is a poster presentation for my thesis, i will include my thesis and also 2 sample posters
Glossary: TDDFT- Time Dependent Density-Functional Theory UV- Ultraviolet LD- Lethal Dose SERS- Surface-enhanced Raman spectroscopy DFT- Density Functional Theory B3LYP- Becke, 3-Parameter, Lee-Yang-Parr) TD- Time Dependant AQ- Anthraquinones SCRF- Self-Consistent Reaction Field PCM- Polarizable Continuum Model IEFPCM- Integral Equation formalism FMO- Frontier Molecular Orbital CPCM- Conductor-like polarisable Continuum Model LLC-BLYP- Lyotropic Liquid Crystal- Becke Lee-Yang-Parr LUMO- Lowest Unoccupied Molecular Orbital HOMO- Highest Occupied Molecular Orbital NLMO- Natural Localised Molecular Orbital DHAQ- Dihydroxyanthraquinone CAAQ- Cis-Aconitic Anthraquinones AYAAQ- Acylamino anthraquinones HPAQ- Hypothalamic- Pituitary- Adrenal MO- Molecular Orbitals Table of Contents 1.Objective7 2.Introduction7 3.Methodology13 3.1.Building of Models13 3.1.1.Chemcraft14 3.1.2.Gaussian application15 3.1.3.Plotting of orbital isosurfaces17 3.1.4.Role of the TDDFT, SCRF and the PCM in the process19 3.1.5.The SCRF Functionality19 3.1.6.Undertaking the calculations20 4.Results:21 4.1.Absorption spectra and the FMO analysis27 4.2.Correlation vs. accuracy, trends in errors:29 5.1. Conclusions:30 6.1. References31 7.1. Appendix37 List of Figure and Tables Figure 1: 9,10-Anthraquinones13 Figure 2: Edit option on Chemcraft14 Figure 3: Input file using Gaussian (Smaller Basis Set)15 Figure 4: Optimized Geometry of 1,4-NH2 AQ using B3LYP functional16 Figure 5: TD Spectrum of 1,4-NH2 AQ17 Figure 6: Input file using Gaussian (Larger Basis Set)18 Figure 7: Atoms and bond length of 1,2-NH2-Anthraquinone20 Figure 8: Plots of calculated vs. experimental transition energies (6-31G(d) basis set)24 Figure 9:Plots of calculated vs. experimental transition energies (6-311G+(d,p)24 Figure 10: Orbital energy gap vs. Experimental transition energies25 Figure 11: Alpha Molecular orbital 62 at occupied state27 Figure 12: Alpha Molecular orbital 63 at unoccupied state27 Table 1: Calculated transition energies, wavelengths, oscillator strengths, and experimental wavelengths/transition energies22 Table 2: Table of orbital # assignments and orbital energies, orbital energy gaps24 Table 3: Analysis of above including mean signed errors and rms29 Table 4: Table comparing R2, average signed errors and rms errors for your functional vs. other functionals.29 1. Objective To investigate the applicability of selected time-dependent density functional (TDDFT) methods to the prediction of electronic spectra of substituted 1,10-anthraquinones. 2. Introduction Anthraquinones, also known as 9,10 anthraquinones or 9,10-dioxoanthracenes, have long been considered as important in the chemical industry and in medicine as an ingredient in various medications for constipation, arthritis, multiple sclerosis, and cancer, even with the attributed safety concerns related to the presence of quinone moiety. They have also been used as colorants for various applications but are widely known for their anti-inflammatory and antimicrobial uses. While their uses have been generally for synthetic purposes in recent years, this chemical is naturally derived. It can be found in foods usually consumed by humans, including vegetables such as peas, cabbage, lettuce, and beans. They play an important part in breaking down vegetables during digestion and metabolizing plants using the electron transport chain. This group is structurally derived from an anthracene ring, which is a tricyclic aromatic ring, with carbonyl groups at positions 9 and 10, thus its name. As this chemical could be found in bacteria, fungi, plants, and animals, several extraction methods are available for research, including ultrasonic-assisted, microwave, pressurized fluid, supercritical fluid extraction, capillary electrophoresis, thin layer, liquid, gaseous, countercurrent, and supercritical fluid. Their commercial use has been greatly dependent on the avoidance of side effects brought by synthetic products and the high preference being given to naturally sourced chemicals for use. The natural sourcing of this chemical has been indicated for use against diabetes mellitus and its autoimmune form. It has also been indicated for its anti-plasmodial effects after being synthesized through Friedel-Crafts reaction and assayed against Plasmodium falciparum. This various evidence of this chemical's relevance would make an undertaking on its other effects to be important for further research, especially on the effective indications. The chemical itself has numerous derivatives that have their own effects and mode of action that contribute to its use for effective medications and other uses. Unfortunately, much of its chemical action is not that understood as of the moment despite its use having been made for many years. It also has several sources, some of which were already mentioned, but those were vegetables that are frequently eaten by human beings. Recent discoveries have shown that a chemical could also be sourced from other plants, including Knoxia valerianoides, from which nine new derivatives were collected and tested for antiviral properties. It is important for further studies to be done to ensure that the discoveries are maximized and that other properties of the chemical will be discovered. In terms of its colorant activity, a spectroscopic study was done on some of its derivatives, including purpurin, alizarin, carminic acid, and 2-(hydroxymethyl)-9,10-anthraquinone. Interestingly, the findings showed that there were protonation and deprotonation equilibria of hydroxyanthraquinones in the aprotic solvent and a subsequent formation of reactive oxygen species generation when these were subjected to UVA photoexcitation. These findings are important to consider when the chemicals are being subjected to spectrophotometric studies such as this study. Since this chemical has various uses and can become other medications that could be effective even in treating cancer, doing studies using this chemical would be universally relevant, and would even constitute a service to the human population all around the world. In studying the electronic structure and its dynamics in atoms and molecules, the methods would entail both experimental and theoretical information to carry out the understanding both in theory and in action. Most studies related to anthraquinones is for the spectra's effect on the degradation of the colorant factor of the chemical since it is one of its widely spread use in the world today. For this reason, anthraquinones are also characterized by how the chemical reacts with the alkaline medium as it transforms into another form. The results would further determine how the chemical could be used for better purposes and for other indicated studies especially those relating to health sciences. Various ways to produce 9,10-anthraquinone has been established for many years including the following: oxidizing anthracene typically using chromium(IV) as oxidant; Friedel-Crafts reaction of benzene and phthalic anhydride in presence of aluminum chloride to produce o-benzoyl benzoic acid and then to undergo cyclization; Diels-Alder reaction of naphthoquinone and butadiene then subjected to oxidative dehydrogenation; acid-catalyzed dimerization of styrene to give a 1,3-diphenylbutene, which will subsequently be transformed to the anthraquinone; and through the Rickert-Alder reaction. These methods allow for the wide use of the chemical in various industries. As a potent chemical, anthraquinones have the same mechanism of action as other quinones in that they are alpha-beta-unsaturated ketones that react with sulfhydryl (-SH) groups thus inhibiting the -SH groups of enzymes like amylase and carboxylase. This would explain the fungicidal mechanism in which there is a change in the redox potential of the system. Even though anthraquinones have long been known to science, and in their crude form in antiquity, much is yet to be known about this chemical. Some that are established and are well-known in science and industry include the following: The chemical is used as a digester additive in papermaking through alkaline processes and acts as the redox catalyst in the reaction involving a single electron transfer. Through this mechanism, the anthraquinone would oxidize the reducing end of the polysaccharides in the pulp such as cellulose making the paper more digestible for further processing. This means that there will be an increase in the amount of paper pulp produced. The chemical is also known as a big factor in the function of flow batteries acting as an electrolyte to produce long-term storage of electricity. This is among the widely novel studies being undertaken on the subject. Other uses would include having the chemical as a bird repellant added on seeds and as gas generated for satellite balloons. Its potential power against invading animals on both livestock and agriculture, especially birds, has been very valuable in that its use has been indicated even to endangered species that would be harmful to human production. Anthraquinone has been noted to be insoluble in water making it hard to test it for toxicity levels. For instance, it has no recorded LD50 as of this writing, yet many drugs are already having their derivatives as major components for the actual drugs. Another source of anthraquinones that was subjected to spectra studies is Cassia occidentalis and are undergoing glutathione conjugates. The plant has been known for its emetic effects in children but is used in constipation and weight loss. This cytotoxicity is linked to the DNA binding affinity of the anthraquinone. There is an indication that the chemical can be most toxic in HepG2 cells and rat primary hepatocytes and has the maximum binding affinity to bovine serum albumin. This has also been causing the relevant toxicity that is experienced by people who may knowingly or unknowingly be consuming the products. As such, it is important that in extracting these products for use in medications and food products that the cytotoxic activity is understood completely. This is why some researchers are wary of the extreme use of the product as it could be possible that there are persons who may display hypersensitivity to the effects of the chemical. Among the notable findings of anthraquinones in modern times is the additional medical uses that indicate its potential of being an antioxidant and its nematocidal ability extracted from Rheum emodi. This would be another breakthrough in the active actions that the substance has been noted before. It is expected that much is still to be discovered as long as the goal is to promote the benefit of humanity. Thus, will also be the interest for such research topics to be done. Proper detection and identification of plants that possess the substance would also be important as reports of effects of the quinone in some food and drinks have been established in the literature. This has been found in tea products, which prompted the European Union to limit the possible anthraquinone content of the drink at 0.02 mg/kg. It was found that a great deposit of the chemical has been situated near a source of the tea leaves processed for this export with the degradation of the chemical even found in brewing the tea. If the leaching of the chemical would reach at least 10% to these tea leaves, it has been deemed unsuitable for consumption and may result in havoc for the health. While no standing warnings about this quinone contamination in place in certain products, it would be appropriate if future research on the matter would try to provide the possibility of checking the contamination of the chemical in food products. It has been mentioned that anthraquinone derivatives have been used for antibacterial purposes and pesticides that could also seep into food products. For this cause, it would be imperative to devise such a venture. Anthraquinones, together with naphthoquinones and benzoquinones, have been found to have molecular docking capabilities that could be used against cardiovascular diseases because of their inhibition of the human serum paraoxonase‐1. Yet it has also been indicated that the use of quinone-based drugs would also pose as hazardous to persons