title: Infrared spectroscopic study of thermotropic phase behavior of newly developed synthetic biopolymers.
abstract: The thermotropic phase behavior of a suite of newly developed self-forming synthetic biopolymers has been investigated by variable-temperature Fourier transform infrared (FT-IR) absorption spectroscopy. The temperature-induced infrared spectra of these artificial biopolymers (lipids) composed of 1,2-dimyristoyl-rac-glycerol-3-dodecaethylene glycol (GDM-12), 1,2-dioleoyl-rac-glycerol-3-dodecaethylene glycol (GDO-12) and 1,2-distearoyl-rac-glycerol-3-triicosaethylene glycol (GDS-23) in the spectral range of 4000-500 cm(-1) have been acquired by using a thin layered FT-IR spectrometer in conjunction with a custom built temperature-controlled demountable liquid cell having a pathlength of ∼15 μm. The lipids under consideration have long hydrophobic acyl chains and contain various units of hydrophilic polyethylene glycol (PEG) headgroups. In contrast to conventional phospholipids, this new kind of lipids forms liposomes or nanovesicles spontaneously upon hydration, without requiring external activation energy. We have found that the thermal stability of the PEGylated lipids differs greatly depending upon the acyl chain-lengths as well as the nature of the associated bonds and the number of PEG headgroup units. In particular, GDM-12 (saturated 14 hydrocarbon chains with 12 units of PEG headgroup) exhibits one sharp order-disorder phase transition over a temperature range increasing from 3°C to 5°C. Similarly, GDS-23 (saturated 18 hydrocarbon chains with 23 units of PEG headgroup) displays comparatively broad order-disorder phase transition profiles between temperature 17°C and 22°C. In contrast, GDO-12 (monounsaturated 18 hydrocarbon chains with 12 units of PEG headgroup) does not reveal any order-disorder transition phenomena demonstrating a highly disordered behavior for the entire temperature range. To confirm these observations, differential scanning calorimetry (DSC) was applied to the samples and revealed good agreement with the infrared spectroscopy results. Finally, the investigation of thermal properties of lipids is extremely critical for numerous purposes and the result obtained in this work may find application in various studies including the development of PEGylated lipid based novel drug and substances delivery vehicles.
authors.affiliation: Department of Physics, University of Nevada, Reno, NV 89557, USA. rab125@pitt.edu
authors.forename: Rajan K
authors.initials: RK
authors.lastname: Bista
authors.forename: Reinhard F
authors.initials: RF
authors.lastname: Bruch
authors.forename: Aaron M
authors.initials: AM
authors.lastname: Covington
mesh_terms: D001704:Biopolymers / Q000096:biosynthesis / Q000737:chemistry*; D002152:Calorimetry, Differential Scanning; D008055:Lipids / Q000737:chemistry; D008954:Models, Biological; D044367:Phase Transition; D011092:Polyethylene Glycols / Q000737:chemistry; D013055:Spectrophotometry, Infrared / Q000295:instrumentation / Q000379:methods; D017550:Spectroscopy, Fourier Transform Infrared; D013696:Temperature; D013816:Thermodynamics
chemical_list: D001704:Biopolymers; D008055:Lipids; D011092:Polyethylene Glycols