During the past decade, the importance of amorphous water-soluble substances has been increasingly recognised within the food and pharmaceutical industries. In response, Amorphous Food and Pharmaceutical Systems brings together current leading experts to contribute to this unique cross-disciplinary account of the subject. Coverage includes: water-compatible amorphous solids (physical, chemical behaviour), low water content systems (water as plasticizer); applications in food and pharmaceutical sciences and industries (processing and stability) along with state-of-the-art technology in food and pharmaceutical systems. This timely publication will be welcomed by academic and industrial researchers and professionals in the pharmaceuticals, food, materials and polymer sciences.
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Introduction – Progress in Amorphous Food and Pharmaceutical Systems H. Levine, 1,
Structure and its Significance in the Application Technology of Amorphous Materials,
The Concept of 'Structure' in Amorphous Solids from the Perspective of the Pharmaceutical Sciences E. Shalaev and G. Zografi, 11,
Analytical Model for the Prediction of Glass Transition Temperature of Food Systems V. Truong, B.R. Bhandari, T. Howes and B. Adhikari, 31,
Microstructural Domains in Foods: Effect of Constituents on the Dynamics of Water in Dough, as Studied by Magnetic Resonance Spectroscopy Y. Kou, E. W. Ross and I.A. Taub, 48,
Supplemented State Diagram for Sucrose from Dynamic Mechanical Thermal Analysis I. Braga da Cruz, W.M. MacInnes, J.C. Oliveira and F.X. Malcata, 59,
Glassy State Dynamics and its Significance for Stabilization of Labile Bioproducts,
Glassy State Dynamics, its Significance for Biostabilisation and the Role of Carbohydrates R. Parker, Y.M. Gunning, B. Lalloué, T.R. Noel and S.G. Ring, 73,
Influence of Physical Ageing on Physical Properties of Starchy Materials D. Lourdin, P. Colonna, G. Brownsey and S. Ring, 88,
Uptake and Transport of Gas in Microstructured Amorphous Matrices A. Schoonman, J.B. Ubbink, W.M. MacInnes and H.J. Watzke, 98,
Theories of Unstable Aqueous Systems: How Can They Help the Technologist?,
Recent Developments in the Theory of Amorphous Aqueous Systems P.G. Debenedetti and J.R. Errington, 115,
Studies on Raffinose Hydrates K. Kajiwara, A. Motegi, M. Sugie, F. Franks, S. Munekawa, T. Igarashi and A. Kishi, 121,
Comparison between WLF and VTF Expressions and Related Physical Meaning A. Schiraldi, 131,
Progress in Food Processing and Storage,
Progress in Food Processing and Storage, Based on Amorphous Product Technology L. Slade and H. Levine, 139,
The Effect of Microstructure on the Complex Glass Transition Occurring in Frozen Sucrose Model Systems and Foods H.D. Goff, K. Montoya and M.E. Sahagian, 145,
Relationship between the Glass Transition, Molecular Structure and Functional Stability of Hydrolyzed Soy Proteins V. Zylberman and A.M.R. Pilosof, 158,
A Study of Vitrification of Australian Honeys at Different Moisture Contents P.A. Sopade, B. Bhandari, B. D'Arcy, P. Halley and N. Caffin, 169,
Rational Pharmaceutical Formulation of Amorphous Products,
Rational Formulation Design – Can the Regulators be Educated? T. Auffret, 187,
Solid–Liquid State Diagrams in Pharmaceutical Lyophilisation: Crystallization of Solutes E. Shalaev and F. Franks, 200,
Miscibility of Components in Frozen Solutions and Amorphous Freeze-dried Protein Formulations K.-I. Izutsu and S. Kojima, 216,
Investigations into the Amorphous and Crystalline Forms of a Development Compound D. O'Sullivan, G. Steele and T.K. Austin, 220,
Thermophysical Properties of Amorphous Dehydrated and Frozen Sugar Systems, as Affected by Salts M.F. Mazzobre, M.P. Longinotti, H.R. Corti and M.P. Buera, 231,
Glass-forming Ability of Polyphosphate Compounds and Their Stability K. Kawai, T. Suzuki, T. Hagiwara and R. Takai, 244,
Chemistry in Solid Amorphous Matrices,
Chemistry in Solid Amorphous Matrices: Implication for Biostabilization M.J. Pikal, 257,
Residual Water, its Measurement, and its Effects on Product Stability,
Residual Water in Amorphous Solids: Measurement and Effects on Stability D. Lechuga-Ballesteros, D.P. Miller and J. Zhang, 275,
A Decrease in Water Adsorption Ability of Amorphous Starch Subjected to Prolonged Ball-milling is Accompanied by Enthalpy Relaxation T. Suzuki, Y.J. Kim, C. Pradistsuwana and R. Takai, 317,
Novel Experimental Approaches to Studies of Amorphous Aqueous Systems,
Use, Misuse and Abuse of Experimental Approaches to Studies of Amorphous Aqueous Systems D.S. Reid, 325,
Glass Transition and Ice Crystallisation of Water in Polymer Gels, Studied by Oscillation DSC, XRD–DSC Simultaneous Measurements, and Raman Spectroscopy N. Murase, M. Ruike, S. Yoshioka, C. Katagiri and H. Takahashi, 339,
Subject Index, 347,
The Concept of 'Structure' in Amorphous Solids from the Perspective of the Pharmaceutical Sciences
Evgenyi Shalaev and George Zografi
1 Introduction
Partially or completely amorphous pharmaceutical materials are often created during the manufacture of dosage forms, when an initially highly crystalline bulk drug is processed by standard methods, such as milling, compaction, wet granulation, freeze-drying and spray-drying. The importance of amorphous materials in pharmaceutical research and development has been highlighted in a number of reviews. Formation of a disordered solid may be intentional, when higher solubility and bioavailability are desired, or it may be accidental, during the processing of crystalline materials. In both cases, the physical and chemical stability of such a disordered solid drug must be considered to have possibly been compromised. Because of the very strict regulatory requirements for maintaining the stability of pharmaceuticals, an understanding of amorphous/crystal relationships is an essential part of the drug development process.
In the pharmaceutically related literature on amorphous solids, the main focus has been on studies of the relationships between molecular mobility and chemical and physical stability. In particular, many efforts have been devoted to identifying a 'critical' temperature, below which an amorphous material will be completely stable on practical time scales. Candidates for such a critical stability temperature include the glass transition temperature (Tg) a 'chemical reaction glass transition temperature' and the Kauzmann temperature (TK or T0) (see refs. 4–7 for examples). It has been recognized, however, that although molecular mobility is important, it is not the only factor that determines the stability of amorphous solids. For example, it has been suggested recently that effects (e.g. polarity) of the medium can be important in controlling the chemical stability of amorphous solids. In particular, the role of 'solid-state pH' in amorphous systems is attracting increasing attention in the pharmaceutical literature.
Another critical factor that is expected to have a significant impact on the stability of amorphous solids is the structural nature of molecules in the solid state. Indeed, there are well-established relationships between crystal structure and chemical reactivity in crystalline solids. However, studies on amorphous structure/stability relationships are still under-represented in the pharmaceutical literature. In the present paper, we review different aspects of the structural features of amorphous solids, in relation to their chemical and physical stability. The paper includes five following sections. In the first, we ask the following question, 'is there more than one amorphous state of the same material?' In particular, the issue of 'polyamorphism' is considered. Both true polyamorphism (i.e. involving a phase transition between two amorphous phases) and relaxation 'polyamorphism', where there is a continuous space of dynamic amorphous states, are discussed. The second section is devoted to the microscopic heterogeneity of amorphous materials, and in...
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