Carolin Menzel

Molecular structure of citric acid cross-linked starch films

The effect of citric acid (CA) on starch films has been examined. A new method to detect cross-linking of starch by CA in solution-cast films by molecular weight measurements is described. Furthermore, we managed to distinguished between free, mono- and di-esterified CA and quantify di-ester content within starch films by using a modification in the method of complexometric titration with copper(II)-sulfate. Cross-linking of starch by CA occurred at low temperature, 70°C, which we assumed is so far the lowest temperature reported where cross-linking reaction occurred. This is essential for starch coating applications within paper industry since no high temperatures for curing will be required. However, curing at 150°C and high CA concentrations, 30 pph, increased cross-linking reaction. Furthermore, the physical properties like water solubility, gel content and glass transition temperature, were highly reflected by changes in the molecular structure i.e. cross-linking and hydrolysis, as well as CA content and curing temperature.

The effect of pH on hydrolysis, cross-linking and barrier properties of starch barriers containing citric acid.

Citric acid cross-linking of starch for e.g. food packaging applications has been intensely studied during the last decade as a method of producing water-insensitive renewable barrier coatings. We managed to improve a starch formulation containing citric acid as cross-linking agent for industrial paper coating applications by adjusting the pH of the starch solution. The described starch formulations exhibited both cross-linking of starch by citric acid as well as satisfactory barrier properties, e.g. fairly low OTR values at 50% RH that are comparable with EVOH. Furthermore, it has been shown that barrier properties of coated papers with different solution pH were correlated to molecular changes in starch showing both hydrolysis and cross-linking of starch molecules in the presence of citric acid. Hydrolysis was shown to be almost completely hindered at solution pH≥4 at curing temperatures≤105 °C and at pH≥5 at curing temperatures≤150 °C, whereas cross-linking still occurred to some extent at pH≤6.5 and drying temperatures as low as 70 °C. Coated papers showed a minimum in water vapor transmission rate at pH 4 of the starch coating solution, corresponding to the point where hydrolysis was effectively hindered but where a significant degree of cross-linking still occurred.

Improved material properties of solution-cast starch films: Effect of varying amylopectin structure and amylose content of starch from genetically modified potatoes

High-amylose potato starches were produced through genetic modification resulting in changed granule morphology and composition, with higher amylose content and increased chain length of amylopectin. The increased amylose content and structural changes in amylopectin enhanced film-forming behavior and improved barrier and tensile properties in starch films. The molecular structure in these starches was related to film-forming properties. Solution-cast films of high-amylose starch revealed a homogeneous structure with increasing surface roughness at higher amylose content, possibly due to amylose aggregation. Films exhibited significantly higher stress and strain at break compared with films of wild-type starch, which could be attributable to the longer chains of amylopectin being involved in the interconnected network and more interaction between chains, as shown using transmission electron microscopy. The oxygen permeability of high-amylose starch films was significantly decreased compared with wild-type starch. The nature of the modified starches makes them an interesting candidate for replacement of non-renewable oxygen and grease barrier polymers used today.

Nanostructural Morphology of Plasticized Wheat Gluten and Modified Potato Starch Composites: Relationship to Mechanical and Barrier Properties

In the present study, we were able to produce composites of wheat gluten (WG) protein and a novel genetically modified potato starch (MPS) with attractive mechanical and gas barrier properties using extrusion. Characterization of the MPS revealed an altered chain length distribution of the amylopectin fraction and slightly increased amylose content compared to wild type potato starch. WG and MPS of different ratios plasticized with either glycerol or glycerol and water were extruded at 110 and 130 °C. The nanomorphology of the composites showed the MPS having semicrystalline structure of a characteristic lamellar arrangement with an approximately 100 Å period observed by small-angle X-ray scattering and a B-type crystal structure observed by wide-angle X-ray scattering analysis. WG has a structure resembling the hexagonal macromolecular arrangement as reported previously in WG films. A larger amount of β-sheets was observed in the samples 70/30 and 30/70 WG-MPS processed at 130 °C with 45% glycerol. Highly polymerized WG protein was found in the samples processed at 130 °C versus 110 °C. Also, greater amounts of WG protein in the blend resulted in greater extensibility (110 °C) and a decrease in both E-modulus and maximum stress at 110 and 130 °C, respectively. Under ambient conditions the WG-MPS composite (70/30) with 45% glycerol showed excellent gas barrier properties to be further explored in multilayer film packaging applications.

Amylose and amylopectin molecular fractions and chain length distribution of amylopectin in 12 varieties of Ghanaian sweet potato (Ipomoea batatas) flours

ABSTRACT Sweet potato (Ipomoea batatas) is a commonly cultivated root crop in tropical and subtropical regions, including Ghana. Different varieties of sweet potato have been bred, in order to expand its utilisation within the food and industrial sector. This study analysed flours made from 12 recently developed Ghanaian sweet potato varieties in terms of their amylose and amylopectin molecular fractions and amylopectin chain length distribution. Starch content of the sweet potato flours ranged from 49 to 77 g/100 g dry matter, with 11 of the varieties containing above 60 g/100 g dry matter. An orange-fleshed variety, Apomuden, had the lowest amount of starch (48.9 g/100 g dry matter), while the cream-fleshed variety Histarch had the highest (77.3 g/100 g dry matter). The flours from the 12 sweet potato varieties had intermediate amounts of amylose, within the range 10–30 g/100 g dry matter, and showed typical molecular distribution according to size-exclusion chromatography (SEC). The fine structures of amylopectin, as revealed by anion-exchange chromatography, contained features common for starches of C-type X-ray pattern, but some structural differences were also observed.

Wheat starch carbamate: Production, molecular characterization, and film forming properties

Wheat starch carbamates of different degrees of substitution were produced in laboratory experiments and for the first time their film forming performance were investigated. The carbamation reaction between urea and starch was investigated using a factorial design. Long reaction time, 2h, and high urea content, 10 and 25%, resulted in a high degree of substitution, 0.07 and 0.15, respectively. These starch carbamates were assumed to be cross-linked and showed best film forming properties resulting in continuous and firm films. Furthermore, a high degree of carbamate substitution favored a decrease in glass transition temperature (Tg) in cast films. The addition of acid as a catalyst for carbamation of starch produced inconsistent results and mainly lead to degradation of starch molecules that caused brittle films. FTIR and 13C NMR analyses confirmed the covalent bonding between urea and starch in starch carbamates. In a final step, production of starch carbamates was successfully scaled up. A potential industrial use of these starches is as oxygen barrier in multilayer food packaging.