title: Molecular dynamics simulation study of the effect of glycerol dialkyl glycerol tetraether hydroxylation on membrane thermostability.
abstract: Archaeal tetraether membrane lipids span the whole membrane width and present two C40isoprenoid chains bound by two glycerol groups (or one glycerol and calditol). These lipids confer stability and maintain the membrane fluidity in mesophile to extremophile environments, making them very attractive for biotechnological applications. The isoprenoid lipid composition in archaeal membranes varies with temperature, which has placed these lipids in the focus of paleo-climatological studies for over a decade. Non-hydroxylated isoprenoid archaeal lipids are typically used as paleo-thermometry proxies, but recently identified hydroxylated (OH) derivatives have also been proposed as temperature proxies. The relative abundance of hydroxylated lipids increases at lower temperatures, but the physiological function of the OH moiety remains unknown. Here we present molecular dynamics simulations of membranes formed by the acyclic glycerol-dialkyl-glycerol-tetraether caldarchaeol (GDGT-0), the most widespread archaeal core lipid, and its mono-hydroxylated variant (OH-GDGT-0) to better understand the physico-chemical properties conferred to the membrane by this additional moiety. The molecular dynamics simulations indicate that the additional OH group forms hydrogen bonds mainly with the sugar moieties of neighbouring lipids and with water molecules, effectively increasing the size of the polar headgroups. The hydroxylation also introduces local disorder that propagates along the entire alkyl chains, resulting in a slightly more fluid membrane. These changes would help to maintain trans-membrane transport in cold environments, explaining why the relative abundance of hydroxylated Archaea lipids increases at lower temperatures. The in silico approach aids to understand the underlying physiological mechanisms behind the hydroxylated lipid based paleo-thermometer recently proposed.
authors.affiliation: Departamento de Geociencias, Universidad de los Andes, A.A. 4976 Bogotá, Colombia.
authors.forename: Carme
authors.initials: C
authors.lastname: Huguet
authors.affiliation: Department of Earth Sciences, Stellenbosch University, 7602 Matieland, South Africa.
authors.forename: Susanne
authors.initials: S
authors.lastname: Fietz
authors.affiliation: Institució Catalana de Recerca i Estudis Avançats (ICREA), 08010 Barcelona, Spain; Institut de Ciencia i Tecnologia Ambientals (ICTA), Universitat Autònoma de Barcelona (UAB), 08193 Bellaterra, Spain.
authors.forename: Antoni
authors.initials: A
authors.lastname: Rosell-Melé
authors.affiliation: Institució Catalana de Recerca i Estudis Avançats (ICREA), 08010 Barcelona, Spain; Institute of Biotechnology and Biomedicine, UAB, Bellaterra, 08193, Spain. Electronic address: xavier.daura@uab.cat.
authors.forename: Xavier
authors.initials: X
authors.lastname: Daura
authors.affiliation: Institute of Biotechnology and Biomedicine, UAB, Bellaterra, 08193, Spain. Electronic address: lionel.costenaro@bioinf.uab.es.
authors.forename: Lionel
authors.initials: L
authors.lastname: Costenaro
mesh_terms: D005995:Glyceryl Ethers / Q000737:chemistry*; D006900:Hydroxylation; D008051:Lipid Bilayers / Q000737:chemistry*; D008560:Membrane Fluidity; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D013696:Temperature
chemical_list: D005995:Glyceryl Ethers; D008051:Lipid Bilayers
keywords: Archaea; Caldarchaeol; Isoprenoid lipid; Molecular dynamics; OH-GDGT; Temperature adaptation