Characterisation of normal corn starch using asymmetrical flow field‐flow fractionation

The apparent average molar masses (M_w,app), apparent average radii of gyration (R_g,app), diffusion co‐efficients (D_T), and hydrodynamic radii (R_h) of normal corn (maize) starch and fractions were determined using asymmetrical flow field‐flow fractionation coupled with multi‐angle light scattering and refractive index detectors (AF4/MALS/RI). AM‐type (Fraction A) and AP‐type (Fraction B) were chemically separated from normal corn starch. Normal corn starch and Fractions (A–B) were dissolved in 1 M KSCN using a high pressure microwave vessel. The effect of varying cross flow rates at a fixed channel flow rate upon the M_w,app and R_g,app distributions of normal corn starch and Fractions (A–B) were investigated. The average M_w,app of normal corn starch, Fractions (A) and Fraction (B) were 41 × 10⁶, 1.4 × 10⁶ and 39 × 10⁶ g/mol, respectively, with R_g,app values of 129, 60 and 129 nm, respectively.     

Molecular characteristics of native sago starch and isolated fractions determined using asymmetrical flow field‐flow fractionation

The apparent average molar masses (M_w,app), apparent average radii of gyration (R_g,app), of native sago starch and fractions were determined using asymmetrical flow field‐flow fractionation coupled with multi‐angle light scattering and refractive index detectors (AF4/MALS/RI). Amylose‐type (Fraction A) and amylopectin‐type (Fraction B) were chemically separated from native sago starch. Native sago starch and Fractions (A–B) were dissolved in 1M KSCN using a high pressure microwave vessel. The effect of varying cross flow rates at a fixed channel flow rate upon the M_w,app and R_g,app distributions of native sago starch and Fractions (A–B) were investigated. The average M_w,app values of native sago starch, Fraction (A) and Fraction (B) were 60 × 10⁶, 1.5 × 10⁶ and 60 × 10⁶ g/mol, respectively, with average R_g,app values of 142, 75 and 127 nm, respectively. The sphere‐equivalent hydrodynamic radii (R_h) values for native sago starch and fractions were determined from AF4 experimental parameters.     

Rice Starch Molecular Size and its Relationship with Amylose Content

The composition and starch molecular structure of eight rice varieties were studied. Waxy and non‐waxy (long‐, medium‐, and short‐grain) rice varieties from California and Texas were used. The amylose contents were measured using the Concanavalin A method and were found to be related to the type of rice: waxy ≈ 1.0%, short and medium grain 8.7–15.4%, and long grain 17.1–19.9%. The weight‐average molar masses (M_w) of the starches varied from 0.52 to 1.96×10⁸ g/mol. As would be expected, a higher M_w of rice starch correlated to lower amylose content. The range of M_w of amylopectin was 0.82 to 2.50 ×10⁸ g/mol, and there was also a negative correlation of amylopectin M_w with amylose content. Amylose M_w ranged from 2.20 to 8.31×10⁵ g/mol. After debranching the amylopectin with isoamylase, the weight‐average degree of polymerization (DP_w) for the long‐chain fraction correlated positively with a higher amylose content. California and Texas varieties were significantly different in their amylose content, starch M_w (short‐ and medium‐grain only), and amylopectin M_w (p < 0.05).     

Structural and some nutritional characteristics of Velvet bean (Mucuna pruriens) and Lima bean (Phaseolus lunatus) starches

Velvet bean (Mucuna pruriens) and lima bean (Phaseolus lunatus) starches were isolated from seeds and their structural characteristics evaluated using XRD, size‐exclusion chromatography and light scattering analyzes. Total starch, available starch, RS and in vitro digestibility were also determined. Structural and nutritional characteristics of Velvet bean and Lima bean starches were compared to those of commercial corn starch. The legumes starches presented a C‐type XRD pattern and crystallite sizes of 43.1 Å for velvet bean and 48.3 Å for lima bean. Lima bean starch average molar mass (4.9 × 10⁶ g/mol) was slightly higher than the velvet bean starch (3.04 × 10⁶ g/mol). Size‐exclusion chromatography indicated structural similarity between the lima bean and corn starches which differed from that of the velvet bean starch. Hydrodynamic radius (R_H) for the velvet bean and lima bean starches was 45.5 and 55 nm, respectively, and their radius of gyration (R_G) was 67.7 and 82.5 nm, respectively. Total starch content in all three starches was greater than 98%. Their complex crystalline structure provided the legume starches lower in vitro digestibility values than the corn starch. RS content in both the velvet bean starch (7.72%) and lima bean starch (5.66%) was higher than in the corn starch, essentially qualifying these polysaccharides as natural dietary fiber sources, with the associated physiologic advantages.     

Molecular Background of Technological Properties of Selected Starches

Selected starches, i.e. waxy maize, amaranth, quinoa, wheat, millet and buckwheat starches, were investigated with respect to their technological properties such as gelatinization, stability to mechanical stress, resistance to conditions and stability in continuous freeze/thaw cycles. Technological properties are correlated with molecular features such as branching characteristics in terms of iodine-complexing potential, molar mass, occupied glucan-coil volume, packing density of glucan coils and rheological properties. Waxy maize and amaranth starches were found to be amylopectin-type short-chain branched (scb) glucans with weight average molar masses M_w = 17 × 10⁶ g/mol and 12 × 10⁶ g/mol, respectively. Waxy maize starch had a high gelatinization potential, high viscosity at 95 °C (340 mPas) low stability at acidic conditions, average stability to shearing and good freeze/thaw stability. For amaranth starch a viscosity of 122 mPas at 95 °C, low resistance to acid, but high stability to applied shearing and even high freeze/thaw stability was determined. Investigated quinoa starch was classified as scb-type glucan, however, the branches are significantly longer than those of waxy maize and amaranth. With a M_w = 11 × 10⁶ g/mol and a viscosity of 187 mPas at 95 °C, this sample is comparably resistant to acidic conditions and to shearing, but instable in freeze/thaw experiments. Wheat, millet and buckwheat starches contain significant percentages of amylose-type long-chain branched (lcb) glucans (22.1, 32.1 and 24.3 %, respectively) with M_w values of 5 × 10⁶ g/mol, 12 × 10⁶ g/mol and 15 × 10⁶ g/mol, respectively. Wheat starch, with a viscosity of 107 mPas at 95 °C, shows low stability under acidic conditions, but high stability to shearing. Wheat and millet starches, but not buckwheat starch, form weak gels in the course of subsequent freeze/thaw cycles. Millet starch, with a viscosity of 101 mPas at 95 °C was found to be moderately stable under acidic conditions and to shearing. Buckwheat starch with a viscosity of 230 mPas at 95 °C shows no acid resistance and is instable upon shearing but performs very well in freeze/thaw experiments.     

An SEC−MALLS Study of Molecular Features of Water‐soluble Amylopectin and Amylose of Tef [Eragrostis tef (Zucc.) Trotter] Starches

The molecular features of five tef starches along with those of commercial normal maize starch were investigated by size‐exclusion chromatography with multi‐angle laser light scattering‐differential refractive index detection (SEC/MALLS‐DRI) after solubilization in water by cooking in a household pressure cooker. The weight‐average molar mass ( ) and weight‐average root‐mean square radius of gyration (<R_g>_w) of the amylopectin (AP) of tef starches ranged from 10.1×10⁷ g/mol (156 nm) to 16.5×10⁷ g/mol (205 nm) with a mean of 13.9×10⁷ g/mol (186 nm). The AP of the tef starches was considerably smaller than that of maize starch ( = 19.6×10⁷ g/mol, <R_g>_w = 207 nm). These considerably smaller AP molecules in tef starches were most probably responsible for the low paste viscosity of tef starches as compared to maize starch. In most tef starches, the polydispersity index (PI) of the AP was broader than that of the AP of maize starch. The intermediate fraction (IN) 1.0−1.6, mean = 1.1) of most tef starches were similar to those of the IN of maize starch. The amylose (AM) (range 1.5×10⁶−3.0×10⁶ g/mol, mean = 2.2×10⁶ g/mol) and size (range 176−214 nm, mean = 191 nm) of most tef starches was also apparently similar to that of the maize starch ( = 2.3×10⁶ g/mol, <R_g>_w = 193 nm), but the polymer distribution was narrower. The AM−iodine complex of the tef starches had a λ_max range of 611−679 nm and the absorption shifted toward longer wavelengths by 8−14 nm as compared to the maize starch AM−iodine complex. The blue value (absorption at λ_max) for 1 mg/mL of tef AM had a range of 2.3−2.8 (mean = 2.5), whereas for the maize starch, the mean was 2.2. The branched nature of tef starches was also investigated by debranching with isoamylase and determination of chain lengths (DP_n) of the branches by size exclusion chromatography with refractive index detector (SEC‐RI). The AP in tef starches had a polymodal distribution with a periodicity similar to that of cereal starches. The branches had DP_n values of A = 11, B1 = 16, B2 = 46 (range 46−47), B3 = 70 (range 69−72) and B4 = 118 (range 113−123). The outer (A + B1) chains were shorter than those of maize starch AP with abundance (74%, w/w) only slightly less than that of the maize starch (75%, w/w). The slow rate of retrogradation, the slightly lower percent crystallinity, the lower gelatinization temperatures and the lower gelatinization enthalpy observed for tef starches (as compared to maize starch) are probably related to the shorter outer (A + B1) chain lengths of their amylopectin molecules, and may be the foundation of the comparably good keeping quality of tef injera, the main staple in the Ethiopian diet.     

Characterization of Physical Properties of Flour and Starch Obtained from Gamma‐Irradiated White Rice

Physical and structural characteristics of rice flour and starch obtained from gamma‐irradiated white rice were determined. Pasting viscosities of the rice flour and starch, analyzed by using a Rapid Visco Analyser, decreased continuously with the increase in irradiation dosage. Differential scanning calorimetry showed that gelatinization onset, peak and conclusion temperatures of rice flour and starch changed slightly but the enthalpy change decreased significantly with increase of irradiation dosage. All irradiated starch displayed an A‐type X‐ray diffraction pattern like the native starch. Gel permeation chromatography showed that the blue value ratio of the first peak (amylopectin) to the second one (amylose) decreased with the increase of the irradiation dosage. The weight‐average molecular weight (M_w) and gyration radius (R_z) of amylopectin analyzed by using HPSEC‐MALLS‐RI (high‐performance size‐exclusion chromatography equipped with multiangle laser‐light scattering and refractive index detector) decreased gradually from 1.48×10⁹ (M_w) and 384.1 nm (R_z) of native rice starch to 2.36×10⁸ (M_w) and 236.8 nm of 9 kGy‐irradiated starch. The branch chain‐length distribution of amylopectins determined by HPAEC‐ENZ‐PAD (high‐performance anion‐exchange chromatography with amyloglucosidase post‐column on‐line reactor and pulsed amperometric detector) showed that gamma irradiation had no significant effect on the amylopectin branch chains with 13≤DP≤24 and 37≤DP, but produced more branch chains with 6≤DP≤12 when the irradiation dosage was less than 9 kGy. It might be deduced that gamma irradiation caused the breakage of the amylopectin chains at the amorphous regions, but had little effects on the crystalline regions of starch granules, especially at low dosage irradiation.     

Determination of molar mass distribution of tapioca starch using asymmetrical flow field flow fractionation

The apparent average molar masses (M_w,app) and apparent average radii of gyration (R_g,app) of native tapioca starch and fractions were determined using asymmetrical flow field flow fractionation (AF4) coupled with multi‐angle light scattering and RI detectors (AF4/MALS/RI). AM‐type (Fraction A) and AP‐type (Fraction B) were chemically separated from native tapioca starch. Native tapioca starch and Fractions (A and B) were dissolved in 1 M KSCN using a high pressure microwave vessel. The effect of varying cross flow rates at a fixed channel flow rate upon the M_w,app and R_g,app distributions of native tapioca starch and Fractions (A and B) were investigated. The average M_w,app values for native tapioca starch, Fraction (A) and Fraction (B) were 59 × 10⁶, 2.1 × 10⁶ and 19 × 10⁶ g/mol, respectively, with average R_g,app values of 165, 73 and 87 nm, respectively. Hydrodynamic radii (R_h) values for native tapioca starch and fractions were determined directly from AF4 experimental parameters.     

不同米淀粉精细结构对其回生特性的影响

选用4种不同的淀粉,通过考察回生特性,探究相对分子质量、链长分布、短程有序性、相对结晶度及半结晶层状结构等精细结构影响回生特性的机理。结果表明：与糯米淀粉和粳米淀粉相比,小米淀粉和黑米淀粉回生值、硬度和热焓值较大,糯米淀粉储藏前后硬度和回生后的热焓值均较小,具有较好的抗回生特性。研究发现,这是由于小米淀粉和黑米淀粉的直链质量分数较高(小米淀粉15.55%、黑米淀粉11.22%),支链淀粉峰M_w较大(小米淀粉M_w=2.12×10⁷ g/mol、黑米淀粉M_w=2.25×10⁷ g/mol)、半结晶层厚(小米淀粉d=6.978 4 nm、黑米淀粉d=6.698 6 nm),且中长链占比大(小米淀粉B1链占比40.91%),易形成稳定的双螺旋结构,具有更高的表面有序度(小米淀粉0.76、黑米淀粉0.70),回生后2种淀粉分子重排更有序稳定。     

Effect of Molar Substitution on Rheological Properties of Hydroxypropylated Rice Starch Pastes

The steady and dynamic shear rheological properties of hydroxypropylated rice starch pastes (5%, w/w) were evaluated at different molar substitution (MS, 0.030‐0.142). The swelling power (35.5‐52.8 g/g) and solubility (8.19‐10.7%) values of the hydroxyproylated rice starches were higher than those of native rice starch (26.6 g/g and 7.78%) and increased with an increase in MS. The hydroxypropylated starch pastes at 25°C showed a pronounced shear‐thinning behavior (n = 0.33‐0.40) with Casson yield stress (σ_oc = 15.9‐31.7 Pa). The consistency index (K) and yield stress (σ_oc) values of the hydroxypropylated starch pastes were lower than those of the native starch, and increased progressively with an increase in MS. The apparent viscosity (η_a,500) obeyed the Arrhenius temperature relationship over the temperature range of 10‐55°C; the activation energies (E_a) of the hydroxypropylated starch pastes were in the range of 14.8‐18.5 kJ/mol, i.e. higher than that (14.1 kJ/mol) of the native starch. Storage (G′) and loss moduli (G′′) of hydroxypropylated starch pastes increased with an increase in MS, while tan δ (G′′/G′) values decreased, indicating that G′ rose more strongly than G′′ with increased MS.     

Molar Mass Distribution and Size of Hydroxyethyl Starch Fractions Obtained by Continuous Polymer Fractionation

By the use of continuous polymer fractionation (CPF) the initial polymer can be separated into fractions of different molar masses, which makes it possible to obtain hydroxyethyl starch (HES) fractions tailor‐made for specific application. Two samples of HES (HES A and HES B) were fractionated by means of CPF. By size‐exclusion chromatography‐multi‐angle laser light‐scattering‐differential refractive index (SEC/ MALLS/DRI) measurements it was shown that CPF is able to remove the low‐molarmass components and to adjust the samples to various desired molar masses with lower polydispersities than the original samples. In terms of the weight‐average mean molar mass M_W , the sol fractions have smaller molar masses than the starting sample, whilst the gel fractions have higher molar masses. Furthermore the radius of gyration R_G could be determined for the initial sample HES B with 19.7 and 19.4 nm and also for some of its fractions. However, no general R_G—M_W relationship could be established for the HES samples fractionated using CPF. This is probably due to the complex branched structure of amylopectin. M_W and M_W/M_n of the six fractions obtained from HES A with M_W = 161, 000 g/mol and M_W/M_n = 4.7 ranged from 19, 000 to 362, 000 g/mol with M_W/M_n from 1.8 to 3.1. The molar masses of the four fractions obtained from HES B with M_W = 460, 000 g/mol and M_W/M_n = 6.0 were between 18, 000 and 680, 000 g/mol with M_W/M_n from 1.7 to 4.8 or between 202, 000 and 1, 005, 000 g/mol with M_W/M_n from 2.7 to 4.7 depending on fractionation strategy.     

Physicochemical Properties of Waxy and Normal Maize Starches Irradiated at Various pH and Salt Concentrations

Waxy and normal maize starches of various pH values and salt contents were prepared, irradiated with gamma rays (5–20 kGy) and their molecular structure, pasting viscosity and rheological properties determined. Average molar mass and size of both waxy and normal maize starches decreased considerably by irradiation from >338.0×10⁶ to <39.4×10⁶ g/mol and from >237.5 to <125.2 nm, respectively. Adjustments of pH had little influence on the average molar mass and size of irradiated starch, whereas incorporation of salt greatly reduced the molar mass and size of irradiated waxy and normal maize starches. As the pH increased from 4 to 8, the pasting viscosity of the irradiated starches decreased from 1032 to 279 mPa s in waxy and from 699 to 381 mPa s in normal starches. Pasting viscosity of both irradiated waxy and normal starch decreased from 689 to 358 mPa s and from 327 to 184 mPa s as the salt concentration increased from 1 to 5%. The G′ of gels, determined during cooling from 90 to 10°C or storage for 8 h, decreased in irradiated waxy and normal starches by pre‐conditioning at pH 8 and in irradiated waxy starches by pre‐conditioning at 5% NaCl. With 5% NaCl, G′ of irradiated normal maize starch during cooling increased up to the irradiation level of 10 kGy, and increased during storage for 8 h at all levels of irradiation. Incorporated salt prior to irradiation appears to induce incremental modifications in the molecular structure, rheological and retrogradation properties of starch by boosting the degradation of molecules.     

Comparison between Size Exclusion Chromatography and Micro‐Batch Analyses of Corn Starches in DMSO using Light Scattering Detector

The molecular structure of corn starches different in amylose content (waxy, normal, and high‐amylose) was analyzed in 90% dimethyl sulfoxide (DMSO) solution by refractive index (RI) and multi‐angle laser light scattering (MALLS) detectors. The starch sample solutions were measured either by medium‐pressure size exclusion chromatography (MPSEC) or by the micro‐batch mode. For waxy corn starch, the average molar mass (M_w) and radius of gyration (R_g) values were similar in both methods. However, for normal and high‐amylose corn starches, M_w measured by the micro‐batch mode was 2–4 times greater than that by the chromatographic method, although R_g values obtained from both methods were not very different. The M_w difference was the greater the higher the amylose content of starch.     

Characterization of Acetyl Starch by Means of NMR Spectroscopy and SEC/MALLS in Comparison with Hydroxyethyl Starch

The properties of starch derivatives which may be used as plasma substitutes, are dependent upon the molecular structure. Seven acetyl starch (AS) samples were determined and compared with results from hydroxyethyl starch (HES) samples. The molar masses and their distributions were determined with the combination of size exclusion chromatography and light scattering. Slightly asymmetric distributions were determined with a polydispersity M_w/M_n = 2.4 and weight-average molar masses of M_w = 250,000–300,000 g/mol for six AS samples and M_w/M_n = 3.6 and a weight-average molar mass of 766,000 g/mol for one AS sample. The average degrees of substitution (DS) and the substitution pattern were determined by high resolution NMR spectroscopy. The AS samples investigated had a DS of 0.42 to 0.81, comparable to HES, but the regioselective substitution pattern revealed differences. While for HES the position C-2 is preferred and the position C-3 has nearly no substituent, for AS both positions, C-2 and C-3, are substituted likewise. Degradability by α-amylase was tested in the laboratory for AS as well as for HES having nearly the same degree of substitution and molar mass, but C-2/C-6 = 2 for AS and C-2/C-6 = 1.4 for HES. An exponential decrease in the molar mass was observed over time, down to a limiting molar mass M_w = 50,000 g/mol for AS and M_w = 30,000 g/mol for HES, the degradation of AS occurred more slowly.     

Influence of Jet‐Cooking Temperature and Ionic Strength on Size and Structure of Cationic Potato Amylopectin Starch as Measured by Asymmetrical Flow Field‐Flow Fractionation Multi‐Angle Light Scattering

Asymmetrical flow field‐flow fractionation (AsFlFFF) in combination with multi‐angle light scattering (MALS) was applied to cationic potato amylopectin (CPAP) to investigate how molar mass, root‐mean‐square (r.m.s.) radius and shape was influenced by different conditions of jet‐cooking. The effect of different jet‐cooking temperatures in the range 110°C – 140°C was studied in an excess steam jet‐cooker. This equipment is used in the industry for dissolution of starch and starch derivatives before technical application. The effect of different ionic strengths conditions was examined in the range of 10–200 mM. The weight‐average molar mass decreased from about 34×10⁷ g/mol to 2.6×10⁷ g/mol when the jet‐cooking temperature was increased from 110°C to 140°C. Concurrently the root‐mean‐square radius decreased from ca 380 nm to 90 nm. The decrease in size was reflected by a decrease in viscosity with increasing temperature. The root‐mean‐square radius was reduced when increasing the ionic strength. This decrease in size was correlated with a decrease in viscosity. Conformation and Kratky plots showed that at low ionic strength (≤ 10 mM) CPAP behaved as a flexible chain with high degree of branching, close to hyperbranching. Increase of the ionic strength gave a more compact structure and changes in the internal structure were observed as well. Consequently, by using AsFlFFF – MALS the effect of technical processing on the molar mass, molecular radius, conformational structure, and shape could be determined in a size region where standard methodology commonly fails.     

Isolation and Molecular Characterization of Makal (Xanthosoma yucatanensis) Starch

Starch was isolated from a non‐conventional source: makal (Xanthosoma yucatanensis) and molecular characteristics were determined using X‐ray diffraction, light scattering and chain length determination. The granules had an oval shape with sizes between 8 and 20 μm, with an average size of 12.4 μm. Amylose content was 22.4% and amylopectin content 77.6%. The granules presented a C‐type X‐ray diffraction pattern, with a degree of polymerization (DP) of 5–19 for branch chain lengths and an average molar mass of 5.4×10⁶ g/mol. The R_H and the R_G was 61.7 and 92.7 nm, respectively. Gelatinization temperature was 72.6 to 84.2°C and transition enthalpy was 15 J/g, which may be related to the X‐ray diffraction pattern and to the small granule size of makal starch. The retrogradation of makal starch increased during storage.     

Steady and Dynamic Shear Rheology of Rice Starch‐Galactomannan Mixtures

Rheological properties of rice starch‐galactomannan mixtures (5%, w/w) at different concentrations (0, 0.2, 0.4, 0.6 and 0.8%, w/w) of guar gum and locust bean gum (LBG) were investigated in steady and dynamic shear. Rice starch‐galactomannan mixtures showed high shear‐thinning flow behaviors with high Casson yield stress. Consistency index (K), apparent viscosity (η_a,100) and yield stress (σ_oc) increased with the increase in gum concentration. Over the temperature range of 20–65°C, the effect of temperature on apparent viscosity (η_a,100) was described by the Arrhenius equation. The activation energy values (E_a = 4.82–9.48 kJ/mol) of rice starch‐galactomannan mixtures (0.2–0.8% gum concentration) were much lower than that (E_a = 12.8 kJ/mol) of rice starch dispersion with no added gum. E_a values of rice starch‐LBG mixtures were lower in comparison to rice starch‐guar gum mixtures. Storage (G′) and loss (G′′) moduli of rice starch‐galactomannan mixtures increased with the increase in frequency (ω), while complex viscosity (η*) decreased. The magnitudes of G′ and G′′ increased with the increase in gum concentration. Dynamic rheological data of ln (G′, G′′) versus ln frequency (ω) of rice starch‐galactomannan mixtures have positive slopes with G′ greater than G′′ over most of the frequency range, indicating that their dynamic rheological behavior seems to be a weak gel‐like behavior.     

Influence of the Cross‐linking Agent on the Gel Structure of Starch Derivatives

Hydrogels were synthesized through cross‐linking of carboxymethyl starch (CMS; Degree of Substitution DS = 0.45) using polyfunctional carboxylic acids (malic, tartaric, citric, malonic, succinic, glutaric and adipic acid). The syntheses used a cross‐linking agent ratio (ratio of the number of cross‐linking agent molecules to the number of monomer units constituting the polymer) of F_Z = 0.05. After cross‐linking the gels were dried, ground and then hydrogels of a polymer concentration of 4 mass‐% were produced. These CMS‐hydrogels were then rheologically characterized using dynamic oscillatory measurements. From measurements of the plateau region storage modulus G'_P, the network parameters molar mass between two entanglement points M_e (M_e ranging from 9.318 (citric acid) to 281.397 g/mol (tartaric acid)), the cross‐link density ν_e and the distance between two entanglement points ξ were calculated. Using carboxylic acids without other functional groups, a maximum in gel sturdiness is found at a spacer length of two CH₂‐groups. The evaluation of the loss factor tan δ for the CMS‐hydrogels showed that values of tan δ = 0.2 varied only slightly with the frequency ω. Flow curves showed a pseudopIastic flow behavior for all CMS‐hydrogels (the shear viscosity η declining over five decades in the range of the shear rate γ of 10⁻³ to 10³ s⁻¹) The different polyfunctional carboxylic acids have a strong influence on the sturdiness of the synthesized CMS‐hydrogels.     

Determination of the mass‐specific distribution of the substituents in cationic starch derivatives

The mass‐specific charge distribution in molar mass fractions of cationic starch derivatives was investigated. The molar mass fractions were produced by semi‐preparative SEC (SP‐SEC). The derivatives were cut into an amylopectin‐rich fraction F1, an intermediate fraction F2, containing low molar mass amylopectin and high molar mass amylose, and an amylose‐rich fraction F3. The weight‐average molar mass (M_w) and molar mass distribution (MMD) of the fractions were determined by SEC with multi‐angle laser light scattering (SEC‐MALLS). The mass‐specific charge of each fraction was calculated from the consumption of anionic titrant solution using polyelectrolyte titration (PET) in combination with particle charge detection (PCD). The difference in substituent distribution between the fractions was tested by the Student's t‐test. The weight‐average molar mass of the starch derivatives was not dependent on the degree of substitution (DS) or the derivatization process. Depending on the DS value or derivatization process, different substituent distributions were observed. The results for the mass‐specific charge distribution in different molar mass fractions of cationic starch derivatives with graded DS between 0.015 and 0.130 from the slurry process were discussed. The heterogeneity of substituent distribution decreased with increasing DS of the starch derivative. This was the case for samples from both the slurry and semi‐dry processes. The heterogeneity of derivatization was highest for low DS samples up to DS 0.03, with the amylopectin‐rich fraction incorporating more charges than the amylose‐rich fraction. This was more pronounced for the sample from the slurry process than from the semi‐dry process.     

Use of High-Performance Size-Exclusion Chromatography for Characterization of Amylose Isolated from Diverse Botanical Sources

Amyloses were isolated from diverse botanical sources (apple, mango, maize, and potato), and they were studied in their molecular characteristics (amylose content, molar mass, and molecular weight) using high-performance size-exclusion chromatography as a repetitive and faster protocol. The amylose purity ranged between 85.6–92.6 %, in agreement with the λ_max values (601–610 nm), showing that some impurities with molecules of higher molar mass (amylopectin) were present. The standard curve of pullulan showed a high regression coefficient (0.998) inside of the limits of molar mass of amylose. Chromatograms of amylose showed the presence of components of high molar mass with a principal peak that corresponds to amylose. Molar mass of amylose ranged between 1.2 and 8.5 × 10⁵ g/mol with polydispersity values between 1.3–4.1, indicating a narrow range of molar mass distribution of the amyloses analyzed. The high-performance size-exclusion chromatography coupled with a refractive index methodology used in this study may be considered simple and rapid for molecular studies of amylose.