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Interactions between surfactants and starch: from starch granules to amylose solutions
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

Starch is a mixture of two polysaccharides, amylose (AM) and amylopectin, which occurs naturally in the form of microscopic granules that are abundantly found in tubers, roots, cereal grains and fruits. In order to bring out their functional properties as thickeners and texture enhancers, starch granules are often disrupted by heating in excess water. This process, which is referred to as gelatinisation, causes the granules to swell and exude a fraction of the starch polysaccharides, resulting in a dramatic increase in the viscosity of the starch suspension. Surfactants are known to affect the different aspects of the gelatinisation process and, in particular, the swelling properties of starch. Surfactants are also known to form helical inclusion complexes with AM, the formation of which plays an important role in many of the instances in which starch and surfactants interact. This work was carried out in order to gain insight into how the surfactant structure (head group and chain length) influences the swelling properties of starch and the molecular mechanisms behind these effects. The investigations involved the study of the temperature-induced gelatinisation of starch in the presence of surfactants as well as studies on the association of surfactants to AM in solution and the solubility of the resulting AM-surfactant complexes.

Information on the extent of granule swelling upon heating was indirectly obtained by means of viscometry while insight on the molecular events taking place during gelatinisation was sought by means of differential scanning calorimetry (DSC) and confocal laser scanning microscopy (CLSM). Viscometric studies revealed that, with the exception of the cationic surfactants (alkyl trimethyl ammonium bromides), short-chain (C10, C12) surfactants induce an early swelling (swelling at lower temperatures than the control sample) in normal wheat starch granules, whereas their longer chain counterparts (C14, C16) have the opposite effect. Contrary to this finding, the effect of surfactants on the swelling of waxy wheat starch granules, an AM-free starch variety, is not influenced by the surfactant chain length but by the head group charge of the surfactant. The enhancing/restricting effect of surfactants on the swelling of normal wheat starch is not correlated to their effect on the early aspects of gelatinisation (onset of the gelatinisation transition) but is, in most cases, associated with the dissociation temperature of AM-surfactant complexes formed simultaneously as the granules gelatinise. CLSM studies revealed that, compared to a longer-chain surfactant (C16), a short-chain (C12) surfactant has the ability to penetrate further into the granule matrix during gelatinisation, which may favour its availability for interacting with different starch granule components during gelatinisation.

Studies on the interactions between AM and surfactants with different chain length (C12 vs. C16) and head group (sodium sulphates vs. maltosides) revealed that the presence of a charged head group favours the water solubility of the resulting AM-surfactant complexes. However, this effect can be counteracted by the effect of the surfactant chain length: an increase in the chain length (C12 vs. C16) decreases the solubility of the complex.

Place, publisher, year, edition, pages
Stockholm: KTH , 2006. , vi, 58 p.
Series
Trita-YTK, ISSN 1650-0490 ; 0605
Keyword [en]
food science and technology, polymer chemistry
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4123ISBN: 91-7178-454-3 (print)OAI: oai:DiVA.org:kth-4123DiVA: diva2:10829
Public defence
2006-10-26, F3, KTH, Lindstedsvägen 26, Stockholm, 14:00
Opponent
Supervisors
Note
QC 20100913Available from: 2006-10-03 Created: 2006-10-03 Last updated: 2010-09-13Bibliographically approved
List of papers
1. Effect of surfactant structure on the pasting properties of wheat flour and starch suspensions
Open this publication in new window or tab >>Effect of surfactant structure on the pasting properties of wheat flour and starch suspensions
2005 (English)In: Cereal Chemistry, ISSN 0009-0352, Vol. 82, no 1, 44-52 p.Article in journal (Refereed) Published
Abstract [en]

Systematic studies were performed on the effect of the surfactant alkyl chain length (10-16 carbon atoms) and the head group charge/structure (anionic, cationic, nonionic) on the pasting properties of wheat flour and starch aqueous suspensions by means of a Rapid Visco Analyser (RVA). An excellent agreement was observed between the effect of surfactants on the onset temperature of the pasting process (PT) and the time to reach peak viscosity (t(peak)) of wheat flour and wheat starch suspensions. Moreover, a correlation was found between the effect of different surfactants on these two parameters. With the exception of the cationic surfactants (alkyl trimethyl ammonium bromides), the effect of surfactants (alkyl sulfates, maltosides, monoglycerides, and sucrose esters) was found to be strongly dependent on the surfactant chain length. Shorter chain surfactants (C10-C12) induced an earlier pasting, while longer chain surfactants (C14-C16) had the opposite effect. The effect of surfactants on PT and t(peak) of flour suspensions was enlarged when the surfactant concentration was increased from approximate to1% to 15% (w/w) on a dry starch basis.

Keyword
rheological properties, monoglyceride complexes, amylose, viscosity, lipids, gelatinization, temperature, emulsifiers, gels, potato
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-6185 (URN)10.1094/CC-82-0044 (DOI)000226479200009 ()2-s2.0-12444297540 (Scopus ID)
Note
QC 20100910Available from: 2006-10-03 Created: 2006-10-03 Last updated: 2010-09-10Bibliographically approved
2. On the effect of surface active agents and their structure on the temperature-induced changes of normal and waxy wheat starch in aqueous suspension.: Part I. Pasting and calorimetric studies
Open this publication in new window or tab >>On the effect of surface active agents and their structure on the temperature-induced changes of normal and waxy wheat starch in aqueous suspension.: Part I. Pasting and calorimetric studies
2007 (English)In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Carbohydrate polymers, Vol. 68, no 4, 665-678 p.Article in journal (Refereed) Published
Abstract [en]

Pasting and calorimetric studies of normal and waxy wheat starch were performed in the presence of a series of ionic (sulphates, trimethyl ammonium bromides) and non-ionic (monoglycerides, maltosides) short (12 carbon atoms) and long (16 carbon atoms) n-alkyl chain surfactants. With the exception of the alkyl ammonium bromides, all of the short chain surfactants lower the pasting temperature (PT) in normal wheat starch, while the long chain surfactants have the opposite effect. Contrary, regardless of their chain length, all ionic surfactants lower the PT in waxy wheat starch while the non-ionic surfactants induce small, sometimes almost negligible changes in the PT. Calorimetric studies revealed the absence of a direct connection between the effect of surfactants on the onset of the starch gelatinization transition and the PT. However, in the presence of all surfactants, except the alkyl ammonium bromides, the PT of normal wheat starch was found to lie within or very close the temperature range within which the dissociation of the amylose-surfactant complexes takes place. Waxy wheat starch, in contrast, pasted at temperatures that fell within the temperature range of the starch gelatinization transition. This is taken as evidence of the existence of a correlation between the PT and the dissociation of the amylose-surfactant complexes.

Keyword
surfactants, starch gelatinization, starch pasting, wheat starch, waxy wheat starch
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-6186 (URN)10.1016/j.carbpol.2006.07.032 (DOI)000245846200006 ()2-s2.0-33947156247 (Scopus ID)
Note
Tidigare titel: On the effect of surface active agents and their structure on the : Part I. Pasting and calorimetric studies QC 20100913 Available from: 2006-10-03 Created: 2006-10-03 Last updated: 2010-09-13Bibliographically approved
3. On the effect of surface active agents and their structure on the temperature-induced changes of normal and waxy wheat starch in aqueous suspension.: Part II: A confocal laser scanning microscopy study
Open this publication in new window or tab >>On the effect of surface active agents and their structure on the temperature-induced changes of normal and waxy wheat starch in aqueous suspension.: Part II: A confocal laser scanning microscopy study
2007 (English)In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 68, no 4, 637-646 p.Article in journal (Refereed) Published
Abstract [en]

The location and penetration patterns of two fluorescently labelled, surface active molecules into normal and waxy wheat starch granules prior, during and after the temperature-induced gelatinization were studied by means of confocal laser scanning microscopy (CLSM). Amphiphilic dyes were found to have a tendency to penetrate wheat starch granules in aqueous suspension. The penetration patterns were however found to be dependent on the contact time, type of starch and the chain length (C-12 vs. C-16) of the amphiphilic dye. The penetration of amphiphilic dyes through the starch granule matrix proved to be less restricted in waxy than in normal wheat starch. For a given type of starch, the penetration of the longer chain dye was more constrained than that of the shorter chain one. The extent to which the dye diffuses into the granule matrix as it gelatinizes is also affected by the chain length of the dye, diffusion of the shorter chain dye occurring more profusely and at lower temperatures than for the longer chain one. These differences are suggested to be related to the dissociation temperature of the ANI-amphiphilic dye complexes.

Keyword
starch gelatinization, amphiphilic dyes, CLSM, wheat starch, waxy wheat starch
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-6187 (URN)10.1016/j.carbpol.2006.07.036 (DOI)000245846200003 ()2-s2.0-33947147641 (Scopus ID)
Note
Tidigare titel: On the effect of surface active agents and their structure on the Part II A confocal laser scanning microscopy study QC 20100913Available from: 2006-10-03 Created: 2006-10-03 Last updated: 2010-09-13Bibliographically approved
4. Binding of surfactants to amylose in aqueous solution: Part I Dodecyl and hexadecyl maltosides
Open this publication in new window or tab >>Binding of surfactants to amylose in aqueous solution: Part I Dodecyl and hexadecyl maltosides
(English)Manuscript (Other academic)
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-6188 (URN)
Note
QC 20100913Available from: 2006-10-03 Created: 2006-10-03 Last updated: 2010-09-13Bibliographically approved
5. Binding of surfactants to amylose in aqueous solution: Part II Sodium dodecyl and hexadecyl sulphate
Open this publication in new window or tab >>Binding of surfactants to amylose in aqueous solution: Part II Sodium dodecyl and hexadecyl sulphate
Show others...
(English)Manuscript (Other academic)
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-6189 (URN)
Note
QC 20100913Available from: 2006-10-03 Created: 2006-10-03 Last updated: 2010-09-13Bibliographically approved

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