title: Enthalpy relaxation in binary amorphous mixtures containing sucrose.
abstract: OBJECTIVE
  To compare the enthalpy relaxation of amorphous sucrose and co-lyophilized sucrose-additive mixtures near the calorimetric glass transition temperature, so as to measure the effects of additives on the molecular mobility of sucrose.
  
  
  METHODS
  Amorphous sucrose and sucrose-additive mixtures, containing poly(vinylpyrrolidone) (PVP), poly(vinylpyrrolidone-co-vinyl-acetate) (PVPNA) dextran or trehalose, were prepared by lyophilization. Differential scanning calorimetry (DSC) was used to determine the area of the enthalpy recovery endotherm following aging times of up to 750 hours for the various systems. This technique was also used to compare the enthalpy relaxation of a physical mixture of amorphous sucrose and PVP.
  
  
  RESULTS
  Relative to sucrose alone, the enthalpy relaxation of co-lyophilized sucrose-additive mixtures was reduced when aged for the same length of time at a comparable degree of undercooling in the order: dextran approximately PVP > PVPNA > trehalose. Calculated estimates of the total enthalpy change required for sucrose and the mixtures to relax to an equilibrium supercooled liquid state (deltaHinfinity) were essentially the same and were in agreement with enthalpy changes measured at longer aging times (750 hours).
  
  
  CONCLUSIONS
  The observed decrease in the enthalpy relaxation of the mixtures relative to sucrose alone indicates that the mobility of sucrose is reduced by the presence of additives having a Tg that is greater than that of sucrose. Comparison with a physically mixed amorphous system revealed no such effects on sucrose. The formation of a molecular dispersion of sucrose with a second component, present at a level as low as 10%, thus reduces the mobility of sucrose below Tg, most likely due to the coupling of the molecular motions of sucrose to those of the additive through molecular interactions.
authors.affiliation: University of Connecticut, School of Pharmacy U-92, Storrs 06269, USA.
authors.forename: S L
authors.initials: SL
authors.lastname: Shamblin
authors.forename: G
authors.initials: G
authors.lastname: Zografi
mesh_terms: D001672:Biocompatible Materials / Q000737:chemistry; D002152:Calorimetry, Differential Scanning; D003080:Cold Temperature; D003460:Crystallization; D003911:Dextrans / Q000737:chemistry; D004356:Drug Storage; D005898:Glass / Q000737:chemistry; D008970:Molecular Weight; D010592:Pharmaceutic Aids / Q000737:chemistry; D011145:Polyvinyls / Q000737:chemistry; D011205:Povidone / Q000737:chemistry; D013395:Sucrose / Q000737:chemistry* / Q000378:metabolism*; D013696:Temperature; D013816:Thermodynamics; D013997:Time Factors; D014199:Trehalose / Q000737:chemistry
chemical_list: D001672:Biocompatible Materials; D003911:Dextrans; D010592:Pharmaceutic Aids; D011145:Polyvinyls; D013395:Sucrose; C003080:poly(vinyl chloride)-poly(vinyl acetate) copolymer; D014199:Trehalose; D011205:Povidone