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The melting points of rigid, hydrogen bonding, and non-hydrogen bonding organic compounds have been estimated from their chemical structure. The estimation was accomplished through the use of both additive and non-additive non-constitutive properties of the molecule. The melting points of the aforementioned compounds can be estimated by the equation: TM = TMPN + TIHBN + TPACK + 8.9*EXPAN + 73.1*SIGMAL + 196.3 where the dependent variable, TM, is the melting point of the compound in Kelvin, SIGMAL is the logarithm of the symmetry number for the molecule, EXPAN is the eccentricity of the molecule taken to the third power, TMPN is the summation of the melting point number for each functional group in the molecule, TIHBN is the summation of an intramolecular hydrogen bonding index and TPACK is a packing efficiency index. The solubility of naphthalene in binary, ternary, and quinary cosolvent-water mixtures was determined by HPLC analysis. The samples were equilibrated for 48 hours on a test tube rotator, centrifuged, diluted with acetonitrile, and then injected onto a C8 10 micron column. The cosolvent mixtures used were hydro-organic solutions consisting of water with either methanol, ethanol, isopropanol, acetone, acetonitrile, propylene glycol or a combination of these as the cosolvent. The propylene glycol-water mixtures were allowed to equilibrate for 10 days. In all cases, naphthalene solubilities in binary cosolvent mixtures were found to obey log-linear relationships: log X = SIGMA(FRAC) - log X(w) where X is the mole fraction solubility of naphthalene in the mixture, X(w) is the mole fraction solubility in pure water, FRAC is the volume fraction of the cosolvent, and SIGMA is the slope. SIGMA can be estimated by using the UNIFAC method to predict the solubility in 100% cosolvent and by using the generalized solubility equation of Yalkowsky to estimate the water solubility. These binary equations can then be used to generate ternary and higher multicomponent equations.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Inductively-Coupled Plasma Optical Emission Spectrometry (ICP-OES) is evaluated as a method for the selective determination of several non-metals which emit light in the Vacuum Ultraviolet (VUV) region of the spectrum. In this study, emphasis is placed on those elements which are totally unobservable with standard techniques or have very weak lines in the UV-VIS region of the spectrum. The sensitivity and accuracy of the apparatus and methods devised allows the determination of empirical formulas of gas chromatographic effluents. The results of this study indicate that the background emission of the ICP in the VUV is low level and nearly constant over the entire spectral region investigated (125 - 185 nm.). Promising analytical lines for oxygen, nitrogen, chlorine, bromine, and carbon are also observed in this region. A progression of four experimental configurations were constructed, employing a purged optical path and a unique coolant tube design. The last of these configurations has the capability of spatial resolution of individual portions of the discharge so that emission maps and profiles could be constructed. The results of the maps generated indicate that the region of highest emission intensity is always centered in the discharge. However, the vertical position of this region is found to be dependent upon r.f. power and argon flow rates. Detection limits in the low nanogram region are observed for each non-metal. The dynamic range for each element is in excess of 10⁴ and the selectivity ratio versus carbon is above 100 in each case. A method was developed for determining the elemental composition of the effluents of a GC. Using internal standards, the method is independent of the weight of each component eluted thus sampling errors are eliminated. The average relative errors in multielement analysis are 0.89%, 0.75%, 2.1%, 0.55%, and 0.64% for the percent carbon, oxygen, nitrogen, chlorine, and bromine, respectively.

Physical properties are fundamental to all chemical, biochemical and environmental industries. One of these properties is the normal boiling point of a compound. However, experimental values in literature are quite limited and measurements are expensive and time consuming. For this reason, group contribution estimation methods are generally used. Group contribution is the simplest form of estimation requiring only the molecular structure as input. Consequently, the aim of this project was the development of a reliable group contribution method for the estimation of normal boiling points of non-electrolytes applicable for a broad range of components. A literature review of the available methods for the prediction of the normal boiling points from molecular structure only, was initially undertaken. From the review, the Cordes and Rarey (2002) method suggested the best scientific approach to group contribution. This involved defining the structural first-order groups according to its neighbouring atoms. This definition also provided knowledge of the neighbourhood and the electronic structure of the group. The method also yielded the lowest average absolute deviation and probability of prediction failure. Consequently, the proposed group contribution method was then developed using the Cordes and Rarey method as a starting point. The data set included experimental data for approximately 3000 components, 2700 of which were stored in the Dortmund Data Bank (DDB) and about 300 stored in Beilstein. The mathematical formalism was modified to allow for separate examination and regression of individual contributions using a meta-language filter program developed specifically for this purpose. The results of this separate examination lead to the detection of unreliable data, the re-classification of structural groups, and introduction of new structural groups to extend the range of the method. The method was extended using steric parameters, additional corrections and group interaction parameters. Steric parameters contain information about the greater neighbourhood of a carbon. The additional corrections were introduced to account for certain electronic and structural effects that the first-order groups could not capture. Group interactions were introduced to allow for the estimation of complex multifunctional compounds, for which previous methods gave extraordinary large deviations from experimental findings. Several approaches to find an improved linearization function did not lead to an improvement of the Cordes and Rarey method. The results of the new method are extensively compared to the work of Cordes and Rarey and currently-used methods and are shown to be far more accurate and reliable. Overall, the proposed method yielded an average absolute deviation of 6.50K (1.52%) for a set of 2820 components. For the available methods, Joback and Reid produced an average absolute deviation of 21.37K (4.67%) for a set of 2514 components, 14.46K (3.53%) for 2578 components for Stein and Brown, 13.22K (3.15%) for 2267 components for Constantinou and Gani, 10.23 (2.33%) for 1675 components for Marrero and Pardillo and 8.18K (1.90%) for 2766 components for Cordes and Rarey. This implies that the proposed method yielded the lowest average deviation with the broadest range of applicability. Also, on an analysis of the probability of prediction failure, only 3% of the data was greater than 20K for the proposed method. This detailed comparison serves as a very valuable tool for the estimation of prediction reliability and probable error. Structural groups were defined in a standardized form and the fragmentation of the molecular structures was performed by an automatic procedure to eliminate any arbitrary assumptions. / Thesis (M.Sc.Eng.)-University of Natal, Durban, 2004.

We aimed to identify the volatile compounds in inflorescences of Rudbeckia hirta that may be responsible for the olfactory attraction of the crab spider Misumenoides formosipes to this plant. Our approach was to use ultrasonic extraction, separate the extract into fractions using flash chromatography with different solvent systems, and test the attraction of the male spiders to the pooled fractions using a y-tube olfactometer. Ultrasonic extraction is carried out using a mixture of 1:2 hexane/diethyl ether with 10 g of inflorescences for 30 minutes. Bioassay results indicated that male spiders chose the inflorescences, bulk ultrasonic extract, and the pooled 100% dichloromethane fractions over controls. Nuclear magnetic resonance experiments and infrared spectroscopy experiments were carried out on the 100% dichloromethane fractions and these experiments indicated that a long chain hydrocarbon is the main component in the 100% dichloromethane fractions / Chromatographic method and bioassay development method -- M. formosipes olfactory response to R. hirta -- Separation and identification of the possible attractants in the 100% dichloromethane fractions. / Department of Chemistry

The 207Pb and 119Sn NMR chemical shift were used to study the effect of temperature on Ph3MCl (M= Pb and Sn) adducts in the presence of 10% excess pyridine. The 207Pb and 119Sn chemical shift indicate a slow exchange at low temperatures below -90 0C and a significant exchange at higher temperatures above 10 0C. A plot of temperature against 207Pb or 119Sn chemical shift showed a curve with gentle slope at lower and a steep slope at higher temperatures. A good linear correlation (coefficient. of 0.95) between Hammett substituent constant and 207Pb or 119Sn chemical shift of para-substituted derivatives of Ph3MCl.py* (py* = NMe2, OMe, Me, Ph, H, Br, COPh and COMe; at -90 0C in CD2Cl2/CH2Cl2) was found. Both 207Pb and 119Sn chemical shift ranges are characteristic of five coordinate systems resolving into trigonal bipyramidal geometry as shown by X-ray crystal structures. New complexes of the type [CpFe(CO)(SnPh3)L] (L = PPh3, PBu3, PCy3, PMe3, P(NMe2)3, PMePh2, PMe2Ph, P(p-FC6H5)3, P(p-OMeC6H4)3, P(p-tolyl)3, P(OMe)3, and P(OPh)3 were synthesized by ultraviolet irradiation of [CpFe(CO)2(SnPh3)] and the appropriate phosphine or phosphite ligand. 57Fe NMR studies of the complexes showed an increasing linear relationship with Tolman’s steric parameter, whereas with Tolman’s electronic parameter the 57Fe chemical shift showed a decrease. The X-ray crystallographic profile of the selected new piano stool type complexes shows a significant correlation to the NMR data (solution state), i.e. Fe-Sn, Fe-P bond length and Sn-Fe-P bond angle against chemical shifts of 207Pb and 119Sn. Disubstituted complexes of the type [CpFe(SnPh3)L2] (L = PMe3, PMe2Ph, P(OMe)3 and P(OPh)3 were synthesized under similar conditions as monosubstituted compounds. The correlation trends between the NMR data and X-ray crystallographic profiles are similar to those found for monocarbonylated complexes. Tungsten phosphine complexes of the type [W(CO)5(PR3)] (prepared from [W(CO)6] under thermal conditions) and [W(CO)4(NCMe)(PR3)] (prepared from [W(CO)5(PR3)] by use of Me3NO-promoted decarbonylation) were synthesized and characterized by, among other methods X-ray diffraction techniques (R = Ph, p-tolyl, p-OMeC6H4, p-FC6H4, p-CF3C6H4, and NMe2). The tungsten complexes [W(CO)4(NCMe)(PR3)] react with [(dppp)Pt{C≡C-C5H4N}2] at room temperature to form new complexes of the type [(dppe)Pt{C≡C-C5H4N-W(CO)4(PR3)}2] which were characterized unambiguously by NMR spectroscopy. There is a fair correlation between 195Pt and 183W NMR chemical shifts and Tolman’s electronic parameter which indicates a fair influence by the substituents of the phosphorus atom on both metal centres. Tungsten complexes of the type [W(CO)4(NCMe)(L)] (L= PPh3, P(p-FC6H4)3, P(p-OMeC6H4)3, P(p-tolyl)3, P(p-CF3C6H4)3, PMePh2, and PPh2(C6F5) react with [(PPh3)2Rh(H)2(pytca)] (pytca = 2-(4-pyridyl)thiazole-4-carboxylate) to form new complexes of the type [(PPh3)2Rh(H)2(pytca)- W(CO)4(L)] under mild conditions. These complexes were characterized principally by NMR spectroscopy and X-Ray crystallography (L = P(p-tolyl)3). Crystallographic evidence was found for π-π-π interactions involving two phenyl rings, one of the two phosphines bonded to rhodium atom, one of the three phosphines bonded to tungsten and the pyridyl ring of the thiazole corboxylate group. A second π-π interaction is found between a thiazole and a phenyl ring of the phosphine ligand bonded to the rhodium atom. A fair correlation was found between the rhodium and tungsten chemical shift measured from this series of complexes as a result of varied paraphenyl substituent of phosphine ligand bonded to the tungsten atom. This therefore implies the possible existence of electronic communication between the two bridged metal centres.

Current research in natural products has heavily focused on the identification of potent biologically active compounds, specifically for drug development. The project detailed in this thesis focuses on the extraction of compounds from marine invertebrates as well as defining the absolute configuration for a compound. Utilizing marine invertebrates, the sonications method developed in this thesis provides an alternative approach to rapidly extract compounds for primary screening. This method is viable compared to a traditional overnight extraction method, without suffering compound degredation... Previously, clathric acid was isolated from an unknown Clathria sp. This compound is a bibyblic C-21 terpenoid shown to have mild antimicrobial activity against gram positive bacteria. With only its relative configuration established, additional amounts of clathric acid were required to define the overall absolute configuration. Identifying the Clathria sp. to be Clathria compressa, through spicule analysis, additional sponge tissues were then collected off the coast of Boca Raton, Florida to isolate additional quatities of clathric acid. The absolulte configuration was determined through circular dichroism and the octant rule to establish a final configuration for clathric acid's four carbon stereocenters to be: (3S, 7S, 8R, and 12S). / by Rolando Rueda de Leâon. / Thesis (M.S.)--Florida Atlantic University, 2012. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

Lam, Hon Yiu. / "November 2011." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 122-135). / Abstracts in English and Chinese. / Abstract (in English) --- p.i / Abstract (in Chinese) --- p.iv / Acknowledgement --- p.vi / Contents --- p.vii / List of Abbreviations --- p.xiii / List of Figures --- p.xiv / List of Tables --- p.xvii / Chapter 1 --- Literature review / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.2 --- Flavor of fish --- p.3 / Chapter 1.2.1 --- Carbonyls (aldehydes and ketones) and alcohols --- p.4 / Chapter 1.2.2 --- Sulfur-containing compounds --- p.5 / Chapter 1.2.3 --- Thermally-induced flavor --- p.5 / Chapter 1.2.4 --- Deteriorated fish flavor --- p.6 / Chapter 1.2.5 --- Autoxidation --- p.7 / Chapter 1.2.6 --- Bromophenols --- p.8 / Chapter 1.3 --- Bromophenols in aquaculture --- p.8 / Chapter 1.3.1 --- General properties of bromophenols --- p.9 / Chapter 1.3.2 --- Biosynthetic pathway of bromophenol in marine algae --- p.12 / Chapter 1.3.3 --- Thresholds of bromophenols --- p.14 / Chapter 1.3.4 --- Toxicity of bromophenols --- p.17 / Chapter 1.4 --- Giant Grouper --- p.19 / Chapter 1.4.1 --- Living Habitat of Giant Grouper --- p.19 / Chapter 1.4.2 --- Biological features of Giant Grouper --- p.23 / Chapter 1.4.3 --- Aquaculture of Giant Grouper --- p.23 / Chapter 1.5 --- Flavor analysis and extraction methods --- p.23 / Chapter 1.5.1 --- Solvent extraction --- p.25 / Chapter 1.5.2 --- Simultaneous Steam Distillation/Extraction --- p.25 / Chapter 1.5.3 --- Headspace sampling --- p.27 / Chapter 1.5.4 --- Gas Chromatography/Olfactometry (GCO) --- p.28 / Chapter 1.5.5 --- Food chemistry and Odor Threshold Value --- p.30 / Chapter 2 --- Distribution of bromophenols in selected Hong Kong dried seafood / Chapter 2.1 --- Introduction --- p.33 / Chapter 2.2 --- Materials and Methods --- p.34 / Chapter 2.2.1 --- Sample preparation --- p.34 / Chapter 2.2.2 --- "Preparation of the internal standard, Pentachloroanisole" --- p.35 / Chapter 2.2.3 --- Simultaneous steam distillation-solvent extraction (SDE) --- p.35 / Chapter 2.2.4 --- Gas chromatography-mass spectrometry (GC-MS) --- p.36 / Chapter 2.2.5 --- Compound identification --- p.37 / Chapter 2.2.6 --- Quantification of compounds --- p.37 / Chapter 2.2.7 --- Recovery --- p.37 / Chapter 2.2.8 --- Odor activity value (OAV) --- p.38 / Chapter 2.2.9 --- Statistical Analysis --- p.38 / Chapter 2.3 --- Results and discussion --- p.39 / Chapter 2.3.1 --- Distribution of bromophenols in dried seafoods --- p.39 / Chapter 2.3.2 --- Bromophenol contents in dried seaweeds --- p.51 / Chapter 2.3.3 --- Bromophenol contents in dried crustacean --- p.52 / Chapter 2.3.4 --- Bromophenol contents in dried mollusks --- p.53 / Chapter 2.3.5 --- Bromophenol contents in dried-salted fishes --- p.54 / Chapter 2.3.6 --- Relationship between living habitat and bromophenol contents --- p.55 / Chapter 2.3.7 --- Flavor impact of bromophenols in dried seafood --- p.57 / Chapter 2.3.8 --- Comparison of bromophenol content in purchased dried laminaria with Qingdao seaweed powder and bloodworms --- p.64 / Chapter 2.4 --- Conclusion --- p.67 / Chapter 3 --- Bromophenol content retention and fish quality in giant grouper / Chapter 3.1 --- Introduction --- p.70 / Chapter 3.2 --- Materials and Methods --- p.71 / Chapter 3.2.1 --- Abbreviation of treatment groups --- p.71 / Chapter 3.2.2 --- Sample preparation --- p.72 / Chapter 3.2.3 --- Ingredients --- p.72 / Chapter 3.2.4 --- Production of fish feed --- p.73 / Chapter 3.2.5 --- Preparation of the internal standard，Pentachloroanisole --- p.73 / Chapter 3.2.6 --- Simultaneous steam distillation-solvent extraction (SDE) --- p.75 / Chapter 3.2.7 --- Gas chromatography-mass spectrometry (GC-MS) --- p.75 / Chapter 3.2.8 --- Bromophenol identification and quantification --- p.76 / Chapter 3.2.9 --- Recovery of bromophenols --- p.76 / Chapter 3.2.10 --- Muscle color determination --- p.76 / Chapter 3.2.11 --- Texture analysis --- p.77 / Chapter 3.2.12 --- Moisture determination --- p.78 / Chapter 3.2.13 --- Ash determination --- p.78 / Chapter 3.2.14 --- Fat determination --- p.78 / Chapter 3.2.15 --- Protein determination --- p.79 / Chapter 3.2.16 --- Statistical Analysis --- p.80 / Chapter 3.3 --- Results and discussion --- p.80 / Chapter 3.3.1 --- Muscle color of giant grouper --- p.81 / Chapter 3.3.2 --- Texture of giant grouper --- p.85 / Chapter 3.3.3 --- Proximate analysis of giant grouper --- p.86 / Chapter 3.3.4 --- Bromophenol depuration of giant grouper --- p.92 / Chapter 3.4 --- Conclusion --- p.101 / Chapter 4 --- Volatile compounds in giant grouper / Chapter 4.1 --- Introduction --- p.102 / Chapter 4.2 --- Materials and Methods --- p.103 / Chapter 4.2.1 --- Sample preparation --- p.103 / Chapter 4.2.2 --- "Preparation of the internal standard, 2,4,6Trimethylpyridine (TMP)" --- p.104 / Chapter 4.2.3 --- Dynamic headspace (purge-and-trap) --- p.104 / Chapter 4.2.4 --- Simultaneous steam distillation-solvent extraction (SDE) --- p.105 / Chapter 4.2.5 --- Gas chromatography-mass spectrometry (GC-MS) --- p.105 / Chapter 4.2.6 --- Compound identification --- p.106 / Chapter 4.2.7 --- Quantification of compounds --- p.106 / Chapter 4.2.8 --- Recovery --- p.107 / Chapter 4.2.9 --- Odor activity value (OAV) --- p.108 / Chapter 4.2.10 --- Statistical analysis --- p.108 / Chapter 4.3 --- Results and discussion --- p.108 / Chapter 4.3.1 --- Comparison of extraction between dynamic headspace and SDE --- p.108 / Chapter 4.3.2 --- Flavor profile of giant grouper --- p.113 / Chapter 4.3.2.1 --- carbonyls and alcohol --- p.113 / Chapter 4.3.2.2 --- Other aroma volatile compounds in giant grouper --- p.116 / Chapter 4.3.3 --- Giant grouper tainted by water contamination --- p.116 / Chapter 4.4 --- Conclusion --- p.118 / Chapter 5 --- General conclusion --- p.119 / References --- p.122 / Appendix --- p.136

Our research involves the isolation and identification of the possible chemical compounds in black-eyed Susans that may be responsible for the olfactory attraction of the crab spider Misumenoides formosipes to the inflorescences of these plants. In olfactometric bioassays, 80% of 30 male spiders moved towards olfactory-only cues from R. hirta inflorescences over a water control (P = 0.0014). The bulk extract was separated using flash column chromatography (silica column) with a series of solvents. Spiders in olfactometer bioassays showed a significant preference for the fractions collected using 100% dichloromethane over the solvent-only control (P=0.039). The 100% dichloromethane pooled fractions were separated using solid phase extraction (SPE). Three compounds were isolated and identified using TLC, infrared and NMR spectroscopy. Two compounds were identified as contaminants, di(2-ethylhexyl) phthalate and erucamide, found in the flash column chromatography apparatus and SPE apparatus, respectively. A long-chain crystalline hydrocarbon wax was extracted from R. hirta inflorescences. Research shows that several insects use the lipids of the wax layer, specifically various long-chain alkanes and alcohols, as cues in host plant selection or as kairomones, chemical cues used in communication from one organism to another [3]. It also shows that the waxes can act as absorbents or release agents for biologically active material. Thus, the long-chain hydrocarbon wax interacting with the volatile components could play a major role in attracting the male crab spiders to the R. hirta inflorescences / Introduction and background -- Olfactory bioassay studies of M. formosipes -- Chromatographic separation of components in the 100% dichloromethane fractions -- Identification of the possible attractants in the 100% dichloromethane fractions using spectroscopic methods. / Department of Chemistry