No description available.

The purpose of this research was to design and develop a facile synthesis of a series of multi-headed, two-tailed anionic surfactants (3CAm1(n)2) as anti-HIV microbicides, and to compare the biological activities of these compounds to the activities of their straight-acyl chain derivatives. The synthesis requires coupling reaction of dialkylacetic acid (R2CHCOOH) (R2= n-C6H13, n-C7H15, n-C8H17, n-C9H19, n-C10H21) and Behera's amine (H2NC(CH2CH2COOtBu)3). Commercially available diethyl malonate and straight chain alkyl bromide were selected to produce dialkylacetic acid. Sodium methoxide (MeONa) was used as a base to deprotonate the acidic protons of diethyl malonate. The monoalkylmalonate (RCH(COOEt)2) was separated by vacuum distillation and then used as the starting material of the dialkylation step. This modification improved the yields of this reaction by about 10 percent from the routine procedure of introducing both alkyl groups in the same reaction. The Behera's amine was prepared from the nitrotriester (O2NC(CH2CH2COOtBu)3) by Zn° reduction. The Behera's amine was then converted into an HCl salt by using a diluted HCl solution in 1:1 EtOH/H2O. By doing so, lactam impurity can be separated by solid-liquid extraction in hexane with sonication. The Behera's amine HCl salt was then separated and converted back into Behera's amine by Et3N in dry CH2Cl2. Dialkylacetic acid was converted into its sodium salt by using aqueous NaOH solution; the sodium salt was then added to SOCl2 to yield the acyl chloride (R2CHCOCl). The coupling reaction of Behera's amine and acyl chloride was done in dry CH2Cl2 with 2.2 eq Et3N under sonication to give crude (R2CHCONHC(CH2CH2COOtBu)3), which was identified by ¹H NMR. The crude product from coupling reaction was treated with formic acid. The resulting product was the purified and isolated as a white solid by gravity column chromatography in 100:100:0.5 Hexane/EtOAc/AcOH. Five homologues (R2CHCONHC(CH2CH2COOH)3 R2= n-C6H13, n-C7H15, n-C8H17, n-C9H19, n-C10H21) were produced by this method; all were fully characterized by ¹H and ¹³C NMR, IR, and HRMS. Future improvements can be achieved by replacing the carboxylate groups with the other anionic groups, such as sulfate and phosphate, or add making tri-tailed surfactants, and by, exploring other possible way to improve the biological activities. / Master of Science

No description available.

No description available.

No description available.

Arborescent polymers are characterized by a tree-like architecture and a high branching functionality. This type of polymer can be synthesized by different techniques, but the ‘grafting onto’ method is attractive because it provides good control over the molecular weight of the graft polymer and the side-chains used as building blocks. This method was applied to the synthesis of arborescent polybutadiene, using cycles of epoxidation and anionic grafting reactions. The research focused on optimization of the grafting yield for the synthesis of the G0 polymers, obtained by grafting side-chains onto a linear epoxidized substrate, with the ultimate goal of synthesizing successive generations of graft polymers using these optimized conditions. Two additives potentially useful as reactivity modifiers, N,N,N’,N’-tetramethylethylenediamine (TMEDA) and lithium bromide (LiBr), were investigated to increase the grafting yield. The influence of solvent polarity was also examined, and the reaction time was varied from one day to one week while monitoring the grafting yield. Optimal results (with grafting yields reaching up to 85% in one week) were obtained in cyclohexane-tetrahydrofuran mixtures, in the presence of LiBr, with only small (2-3%) yield increases observed after 24 h of reaction. These optimal conditions, when applied to the synthesis of G1 and G2 polymers, led to grafting yields of 78-80% when using a 1:1 ratio of epoxide groups to living ends. The influence of excess substrate was also examined individually for each generation, and likewise led to small (2-4%) increases in grafting yield. The results obtained showed that the grafting reaction was successful on the basis of 1H NMR spectroscopy and size exclusion chromatography analysis, and was sensitive to parameters such as the substitution level of the epoxidized substrate, the solvent composition, and the presence of additives.

Poly(methyl methacrylate) (PMMA) homopolymers synthesised using 'classical' anionic methods and subsequently studied by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) are discussed. Specifically, the attempts at different end-group functionalisation reactions, their varying degrees of success, and the characterisation of these functionalized polymers via MALDI are reported. Extra peaks were observed in the spectra of samples containing a tertiary amine end-group. A mechanism for the in situ elimination of H(_2)(g) involving these end-groups, which would fit the observations, is proposed. Two alternative, 'non-classical' routes to the desired materials were investigated, as difficulties in successfully performing capping reactions to give end functionalised PMMA were noted. The first method was a variation of standard anionic polymerisation that involved the use of lithium silanolates, which could be performed at a higher temperature than normal. The second was a controlled free-radical technique known as Reversible Addition-Fragmentation Chain Transfer (RAFT). A lack of control of the polymerisation to the desired degree was observed with the former method. A well-defined RAFT sample was observed to undergo in situ eliminadon also, for which a mechanism involving the dithioester end-group is proposed, and which is supported by MALDI-collision induced dissociation (CID) evidence. The synthesis of block copolymers of various compositions of MMA with r-butyl methacrylate (t-BMA) and hexyl methacrylate (HMA), along with their homopolymers, and their subsequent characterisation is reported. PHMA was analysed easily, in contrast to Pt-BMA. Only copolymers with a high PMMA content were analysed successfully and this has been rationalised in terms of the factors that affect cationisation. The characterisation of equimolar blends of various end-functionalised PMMA samples is reported also. Samples that favour the binding of a metal ion over protonation appear to have a higher ion yield. Once more, these observations are rationalised in terms of the factors that affect cationisation.

Arborescent polymers are characterized by a tree-like architecture and a high branching functionality. This type of polymer can be synthesized by different techniques, but the ‘grafting onto’ method is attractive because it provides good control over the molecular weight of the graft polymer and the side-chains used as building blocks. This method was applied to the synthesis of arborescent polybutadiene, using cycles of epoxidation and anionic grafting reactions. The research focused on optimization of the grafting yield for the synthesis of the G0 polymers, obtained by grafting side-chains onto a linear epoxidized substrate, with the ultimate goal of synthesizing successive generations of graft polymers using these optimized conditions. Two additives potentially useful as reactivity modifiers, N,N,N’,N’-tetramethylethylenediamine (TMEDA) and lithium bromide (LiBr), were investigated to increase the grafting yield. The influence of solvent polarity was also examined, and the reaction time was varied from one day to one week while monitoring the grafting yield. Optimal results (with grafting yields reaching up to 85% in one week) were obtained in cyclohexane-tetrahydrofuran mixtures, in the presence of LiBr, with only small (2-3%) yield increases observed after 24 h of reaction. These optimal conditions, when applied to the synthesis of G1 and G2 polymers, led to grafting yields of 78-80% when using a 1:1 ratio of epoxide groups to living ends. The influence of excess substrate was also examined individually for each generation, and likewise led to small (2-4%) increases in grafting yield. The results obtained showed that the grafting reaction was successful on the basis of 1H NMR spectroscopy and size exclusion chromatography analysis, and was sensitive to parameters such as the substitution level of the epoxidized substrate, the solvent composition, and the presence of additives.

Thesis--Auburn University, 2009. / Abstract. Vita. Includes bibliographical references (p. 118-121).

The DLVO theory states that the interaction between two lyophobic particles in aqueous media can be predicted by the sum of two surface forces, i.e., the electrical double-layer and van der Waals forces. This theory, which was developed 50 years ago, served as a backbone for colloid chemistry. However, various experiments conducted in recent years showed that it is applicable only to those particles whose advancing water contact angles (qa) are in the range of 15-60o. For example, direct surface force measurements conducted between silica substrates, whose qa values are less than 15o, exhibited the existence of repulsive hydration forces at relatively short separation distances. On the other hand, substrates, for which qa is greater than 60o, exhibit long-range attractive hydrophobic forces not considered in the DLVO theory . These extraneous attractive forces play important roles in many industrial applications. It is, therefore, the objective of the present study to measure the hydrophobic and hydration forces under different conditions. The measurements were conducted using both the Surface Forces Apparatus (SFA) and the Atomic Force Microscope (AFM). Mica and Silica were used as substrates, and the effects of dioctylammonium-hydrochloride (DOAHCl), octanol, methanol, ethanol, trifluoroethanol (TFE), pyridine, CaCl2, MgCl2 and sodium oleate were studied. A Mark IV SFA was used to conduct force measurements between mica surfaces in aqueous solutions of DOAHCl, which is a secondary amine. At 7x10-6M DOAHCl, the mica surfaces were rendered electrically neutral, and net attractive hydrophobic forces were observed. The measured forces can be represented by a double-exponential function with the larger decay length (D2) of 5.1 nm. The measured hydrophobic forces are substantially stronger than those reported in literature between self-assembled monolayers of soluble single-chain surfactants such as dodeylammonium hydrochloride (DAHCl) and cetyltrimethylammonium bromide (CTAB). Appearance of the strong hydrophobic forces is due to the likelihood that the double-chain cationic surfactant can create a higher hydrocarbon chain packing density than the single-chain cationic surfactants such as DAHCl and CTAB. Force measurements were also conducted using the AFM between a silica plate and a glass sphere in aqueous solutions of methanol, ethanol, TFE and pyridine to study their effect on the hydration force. It was observed that in Nanopure water, silica surfaces exhibit a strong short-range hydration repulsion, which can be represented by a double-exponential function with its longer decay length (D2) of 2.4 nm. In solutions containing 15% methanol, however, the hydration force disappears completely. This observation can be attributed to the displacement of the water molecules H-bonded to the silanol group by methanol, which in turn destroys the water structure in the vicinity of the silica surface. Methanol can displace water from the silanol group because it is more basic than the water. Ethanol, on the other hand, cannot cause the hydration forces to disappear, suggesting that it is less effective than methanol in displacing the H-bonded water molecules from the silanol groups, possibly due to steric hindrance. In the presence of triflouroethanol (TFE) and pyridine, hydration forces change little, which suggest that they are not effective in disturbing the water structure in the vicinity of silica. Finally, an AFM was used to measure the hydrophobic forces between silica surfaces coated with oleate. Since this surfactant is anionic, and the silica surface is negatively charged in alkaline solutions, it was necessary to reverse the charge of the silica substrate. In the present work, CaCl2 and MgCl2 were used as activators. It was found that hydrophobic forces are observed at pHs where the CaOH+ or MgOH+ ion concentrations reach maximum, suggesting that the singly charged hydroxo-complexes are the activating species. A model developed in the proposed work suggests that a significant part of the free energy of adsorption comes from the lateral interactions between neighboring hydroxo-complexes on the surface. It is also suggested that oleate adsorbs on silica as basic calcium oleate and basic magnesium oleate. These species may be H-bonded to the silanol groups on surface. The force measurements were also conducted between hydrophobic (silanated) silica surfaces in CuCl2 solutions. The results show that the hydrophobic force decreases most significantly at the pH where the concentration of the CuOH+ ions reaches maximum, which suggests that the singly charged hydroxo-complexes are more surface-active than their unhydrolyzed counterpart. The driving forces for the adsorption of the CaOH+ ions may include the electrostatic attraction from the surface and the lateral interaction between neighboring hydroxo-complexes on the surface. / Ph. D.