Near-infrared analysis of hydrogen-bonding in glass- and rubber-state amorphous saccharide solids.
Near-infrared (NIR) spectroscopic analysis of noncrystalline polyols and saccharides (e.g., glycerol, sorbitol, maltitol, glucose, sucrose, maltose) was performed at different temperatures (30-80 degrees C) to elucidate the effect of glass transition on molecular interaction. Transmission NIR spectra (4,000-12,000 cm(-1)) of the liquids and cooled-melt amorphous solids showed broad absorption bands that indicate random configuration of molecules. Heating of the samples decreased an intermolecular hydrogen-bonding OH vibration band intensity (6,200-6,500 cm(-1)) with a concomitant increase in a free and intramolecular hydrogen-bonding OH group band (6,600-7,100 cm(-1)). Large reduction of the intermolecular hydrogen-bonding band intensity at temperatures above the glass transition (T(g)) of the individual solids should explain the higher molecular mobility and lower viscosity in the rubber state. Mixing of the polyols with a high T(g) saccharide (maltose) or an inorganic salt (sodium tetraborate) shifted both the glass transition and the inflection point of the hydrogen-bonding band intensity to higher temperatures. The implications of these results for pharmaceutical formulation design and process monitoring (PAT) are discussed.
Izutsu
Ken-ichi
K
National Institute of Health Sciences, Kamiyoga 1-18-1, Setagaya, Tokyo, 158-8501, Japan. izutsu@nihs.go.jp
Hiyama
Yukio
Y
Yomota
Chikako
C
Kawanishi
Toru
T
D002241:Carbohydrates / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry; D006860:Hydrogen Bonding; D008320:Maltose / Q000031:analogs & derivatives / Q000737:chemistry; D019265:Spectroscopy, Near-Infrared; D013395:Sucrose / Q000737:chemistry; D013402:Sugar Alcohols / Q000737:chemistry; D013696:Temperature
D002241:Carbohydrates; D013402:Sugar Alcohols; D013395:Sucrose; D008320:Maltose; C010745:maltitol; D005947:Glucose