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#transition temperature

2 public questions tagged with this topic.

Which molecule has the lowest transition temperature (Tm)?

Transition temperature dependence reflects chain packing efficiency influenced by length unsaturation. DOPC dioleoyl phosphatidylcholine contains two eighteen carbon chains each with cis delta nine double bond bending chain thirty degrees creating double kinks and large cross sectional volume reducing van der Waals contacts. Its Tm about minus seventeen to minus twenty Celsius lowest among common PCs. POPC one palmitoyl saturated sixteen plus one oleoyl unsaturated Tm minus two, DPPC dipalmitoyl two saturated sixteen packs tightly all trans Tm forty one due to high cooperative enthalpy, DMPC dimyristoyl two saturated fourteen shorter fewer contacts Tm twenty four despite saturation. Therefore degree of unsaturation dominates over length lowering Tm within this series. Psychrophilic bacteria enrich DOPC like lipids maintaining fluidity at zero degrees. Differential scanning calorimetry endotherm width also broadens with unsaturation. This ranking underpins liposome formulation for temperature sensitive drug delivery and calibration fluorescence anisotropy probes DPH TMA DPH used measuring fluidity in laboratory assessments and examination questions about membrane biophysics quantitative aspects and thermodynamic principles.

Ref: Lewis et al., Biochemistry 1987, Phosphatidylcholine Tm table DOPC lowest.

Which of the following affects the transition temperature (Tm) of membranes?

Phase transition of lipid bilayers from lamellar gel L beta where acyl chains fully extended ordered tight orthorhombic packing low mobility to liquid crystalline L alpha where chains disordered gauche isomers high mobility monitored by differential scanning calorimetry DSC exhibiting endothermic peak at Tm and by fluorescence anisotropy probes DPH TMA-DPH showing sharp decrease. Factors affecting Tm: chain length longer sixteen to eighteen carbons increases van der Waals interactions raising Tm dipalmitoyl phosphatidylcholine sixteen zero Tm forty one degrees centigrade distearoyl eighteen zero Tm fifty five degrees, unsaturation one cis double bond drastically lowers Tm dioleoyl eighteen one Tm minus twenty degrees due kink disruption, cholesterol broadens transition forming liquid-ordered phase no cooperative melting, headgroup type minor. Transmembrane proteins broadens but not set intrinsic lipid Tm, ATP hydrolysis fuels pumps not lipid melting, lipopolysaccharides outer membrane Gram-negative influences permeability distinct. Organisms regulate fatty acid synthase and desaturases homeoviscous adaptation keeping membrane above Tm fluid at growth temperature. Hence fatty acid chain length primary determinant affecting Tm together with unsaturation, illustrating hydrocarbon packing energetics governing membrane phase behavior and adaptation.

Ref: McElhaney, Lipid Phase Transition and Chain Length Effect, Biochim Biophys Acta 1984.