Kinetic studies of the photopolymerisation of acrylamide in aqueous solution:effects of bromoform as a Chain transfer agent

The effects of adding bromoform (CHBr3) as a potential chain transfer agent in the photopolymerisation of acrylamide (AM) in aqueous solution have been studied both in terms of influencing the rate of polymerisation and the molecular weight of the polyacrylamide (PAM) formed. Using 4,4′-azo-bis(4-cyanopentanoic acid) (ACPA) as photoinitiator, two different CHBr3 concentrations as chain transfer agent were compared: 0.5 and 2.0 mol % (relative to AM), the higher of which was determined by the limit of CHBr3 water solubility. The results showed that CHBr3 was an effective chain transfer agent that could regulate the molecular weight of the PAM formed without seriously affecting the polymerisation rate. It is concluded that chain transfer to CHBr3occurs by both Br and H atom transfer although Br transfer is the more favoured due to the weaker C-Br bond. Furthermore, Br transfer leads to Br-terminated chains in which the terminal C-Br bond can re-dissociate leading to re-initiation and re-propagation of the same chain, thereby maintaining the polymerisation rate. Continuing studies into how this mechanism can be exploited in order to synthesize water-soluble block copolymers of potential biomedical importance are currently in progress

Encapsulation of propolis extracts in aqueous formulations by using nanovesicles of lipid and poly(styrene-alt-maleic acid)

Bee propolis has been used in alternative medicine to treat various diseases. Due to its limited water solubility, it is often used in combination with alcohol solvents, causing skin irritation and immune response. To solve this, the new drug delivery system, based on the lipid nanodiscs of 1,2-dimyristoyl-sn-glycero-3-phosphochline (DMPC) and poly(styrene-alt-maleic acid) (PSMA), were created in an aqueous media. At the excess polymer concentrations, the PSMA/DMPC complexation produced the very fine nanoparticles (18 nm). With the increased molar ratio of styrene to maleic acid (St/MA) in the copolymer structure, the lipid nanodisc showed the improved encapsulation efficiency (EE%), comparing to their corresponding aqueous formulations. The maximum value had reached to around 20% when using the 2:1 PSMA precursor. Based on the cytotoxicity test, these nanoparticles were considered to be non-toxic over the low dose administration region

Synthesis and Characterization of Block Copolymers of Styrene-maleic Acid with Acrylamide and N,N-dimethylacrylamide

Styrene-maleic acid (SMA) block copolymers with either acrylamide (AM) or N,N-dimethylacrylamide (DMA) have been synthesized via a 3-step process comprising: (1) photopolymerization of styrene and maleic anhydride in solution to yield an alternating styrene maleic anhydride (SMAnh) copolymer, (2) copolymerization of SMAnh with either AM or DMA to yield SMAnh-b-AM and SMAnh-b-DMA block copolymers and (3) hydrolysis of the anhydride groups to yield water-soluble SMA-b-AM and SMA-b-DMA block copolymers as the final products. With a view to their intended application in membrane protein solubilization, molecular weights are controlled to below 10,000 by the synthesis conditions employed in step (1), including using carbon tetrabromide (CBr4) as a chain transfer agent. The CBr4 also plays an important role in step (2). By terminating the SMAnh chain radicals from step (1) with C-Br bonds that are photolytically active, SMAnh chain radicals can be regenerated to act as macroinitiators for the polymerization of AM or DMA in step (2). Finally, following step (3) and due to the pH-dependency of the SMA chain conformation in solution, a pH of 7-8 is found to be optimal for enabling the final products to be precipitated in a solid form that is completely soluble in water

Polymer-lipid interactions:biomimetic self-assembly behaviour and surface properties of poly(styrene-alt-maleic acid) with diacylphosphatidylcholines

Abstract Various lubricating body fluids at tissue interfaces are composed mainly of combinations of phospholipids and amphipathic apoproteins. The challenge in producing synthetic replacements for them is not replacing the phospholipid, which is readily available in synthetic form, but replacing the apoprotein component, more specifically, its unique biophysical properties rather than its chemistry. The potential of amphiphilic reactive hypercoiling behaviour of poly(styrene-alt-maleic acid) (PSMA) was studied in combination with two diacylphosphatidylcholines (PC) of different chain lengths in aqueous solution. The surface properties of the mixtures were characterized by conventional Langmuir-Wilhelmy balance (surface pressure under compression) and the du Noüy tensiometer (surface tension of the non-compressed mixtures). Surface tension values and 31P NMR demonstrated that self-assembly of polymer-phospholipid mixtures were pH and concentration-dependent. Finally, the particle size and zeta potential measurements of this self-assembly showed that it can form negatively charged nanosized structures that might find use as drug or lipids release systems on interfaces such as the tear film or lung interfacial layers. The structural reorganization was sensitive to the alkyl chain length of the PC

Synthetic analogues of protein-lipid complexes

Hypercoiling poly(styrene-alt-maleic anhydride) (PSMA) is known to undergo conformational transition in response to environmental stimuli. The association of PSMA with lipid 2-dilauryl-sn-glycero-3-phosphocholine (DLPC) produces polymer-lipid complex analogues to lipoprotein assemblies found in lung surfactant. These complexes represent a new bio-mimetic delivery vehicle with applications in the cosmetic and pharmaceutical industries. The primary aim of this study was to develop a better understanding of PSMA-DLPC association by using physical and spectroscopic techniques. Ternary phase diagrams were constructed to examine the effects of various factors, such as molecular weight, pH and temperature on PSMA-DLPC association. 31P-NMR spectroscopy was used to investigate the polymorphic changes of DLPC upon associating with PSMA. The Langmuir Trough technique and surface tension measurement were used to explore the association behaviour of PSMA both at the interface and in the bulk of solution, as well as its interaction with DLPC membranes. The ultimate aim of this study was to investigate the potential use of PSMA-DLPC complexes to improve the bioavailability and therapeutic efficacy of a range of drugs. Typical compounds of ophthalmic interest range from new drugs such as Pirenzepine, which has attracted clinical interest for the control of myopia progression, to the well-established family of non-steroid anti-inflammatory drugs. These drugs have widely differing structures, sizes, solubility profiles and pH-sensitivities. In order to understand the ways in which these characteristics influence incorporation and release behaviour, the marker molecules Rhodamine B and Oil Red O were chosen. PSMA-DLPC complexes, incorporated with marker molecules and Pirenzepine, were encapsulated in hydrogels of the types used for soft contact lenses. Release studies were conducted to examine if this smart drug delivery system can retain such compounds and deliver them at a slow rate over a prolonged period of time

Synthetic analogues of protein-lipid complexes

Hypercoiling poly(styrene-alt-maleic anhydride) (PSMA) is known to undergo conformational transition in response to environmental stimuli. The association of PSMA with lipid 2-dilauryl-sn-glycero-3-phosphocholine (DLPC) produces polymer-lipid complex analogues to lipoprotein assemblies found in lung surfactant. These complexes represent a new bio-mimetic delivery vehicle with applications in the cosmetic and pharmaceutical industries. The primary aim of this study was to develop a better understanding of PSMA-DLPC association by using physical and spectroscopic techniques. Ternary phase diagrams were constructed to examine the effects of various factors, such as molecular weight, pH and temperature on PSMA-DLPC association. 31P-NMR spectroscopy was used to investigate the polymorphic changes of DLPC upon associating with PSMA. The Langmuir Trough technique and surface tension measurement were used to explore the association behaviour of PSMA both at the interface and in the bulk of solution, as well as its interaction with DLPC membranes. The ultimate aim of this study was to investigate the potential use of PSMA-DLPC complexes to improve the bioavailability and therapeutic efficacy of a range of drugs. Typical compounds of ophthalmic interest range from new drugs such as Pirenzepine, which has attracted clinical interest for the control of myopia progression, to the well-established family of non-steroid anti-inflammatory drugs. These drugs have widely differing structures, sizes, solubility profiles and pH-sensitivities. In order to understand the ways in which these characteristics influence incorporation and release behaviour, the marker molecules Rhodamine B and Oil Red O were chosen. PSMA-DLPC complexes, incorporated with marker molecules and Pirenzepine, were encapsulated in hydrogels of the types used for soft contact lenses. Release studies were conducted to examine if this smart drug delivery system can retain such compounds and deliver them at a slow rate over a prolonged period of time.EThOS - Electronic Theses Online ServiceGBUnited Kingdo