Starch Esters Research Articles

Characteristics of sweet potato starch particles modified by various methods for use in food-grade Pickering emulsion

The objective of the current work was to formulate Pickering emulsions prepared solely of sweet potato starch that were renewable and surfactant-free. Native starch has a low capacity for emulsification, for this reason, three different modification techniques including anti-solvent precipitation, esterification with octenyl succinic anhydride (OSA), and hydrothermal treatment were applied to modify native sweet potato starch particles (NSPSP). The outcomes demonstrated that the characteristics of the particles, such as size, wettability, surface morphology, crystallinity, thermal behavior, and interfacial tension, were significantly impacted by modification. The amylose content and roughness of NSPSP were reduced by applying OSA, and OSA-modified samples had the highest contact angle and crystalline region. Conversely, ethanol-induced starch granules showed increased amorphous area, higher surface roughness, and agglomeration. From an interfacial perspective, esterification of starch with OSA could decrease the interfacial tension, whereas the anti-solvent approach caused an increase in this parameter. Droplet size, surface charge, microstructure, and emulsification index were used to describe O/W Pickering emulsions stabilized by native and modified particles. This investigation suggested that, in contrast to the other two techniques, modifying NSPSP with OSA had a favorable effect on the emulsifying capacity of the resulting Pickering emulsion. The findings suggested that modified NSPSP could be a promising candidate to stabilize Pickering emulsion with demanding characteristics, which could be applied for carrying the bioactive compounds.

Study on the Enhanced Calcium Ion Adsorption Capacity of Magnetic Materials Modified by the Enzymatic and Activated Comodification Esterification of Starch (Fe3O4@EES)

Study on the Enhanced Calcium Ion Adsorption Capacity of Magnetic Materials Modified by the Enzymatic and Activated Comodification Esterification of Starch (Fe3O4@EES)

Hydrophobic bio-composites of stearic acid starch esters and micro fibrillated cellulose processed by extrusion

Fatty acid starch esters are potential candidates for obtaining hydrophobic starch-based materials. The objective was to evaluate thermoplastic bio-composites with stearic acid cassava starch esters (SAE) as matrices reinforced with micro fibrillated cellulose (MFC). SAE with 0.11 and 0.14 of DS and native cassava starch were processed with 5 % and 10 % MFC by extrusion and then thermo-compression to obtain bio-composite films. Performance of bio-composites as a function of the degree of substitution (DS) of starch esters and the content of MFC, was evaluated. Starch esterification reduced the crystalline phase and glass transition temperature of bio-composites, as confirmed by structural and thermal analysis. The increase of DS reduced the degradation temperature, which was compensated by adding MFC, favoring thermal stability. The hydrophobicity of films increased with the degree of starch esterification. Treatments with 0.14 DS formed stiffer and less tensile strength films. There was an increase in the modulus of elasticity and a reduction in elongation by increasing MFC. Fracture microscopy of films showed defects by incomplete starch melting and lack of interfacial adhesion with MFC caused by starch esterification. Starch esterification and MFC dispersion were determinants in the performance of bio-composites. In consequence, starch esterification with stearic acid reduces the compatibility with the MFC and, consequently, the performance of composites.

Effects of different pretreatment methods on the degree of substitution, structure, and physicochemical properties of synthesized malic acid sweet potato starch ester.

The preparation of malic acid starch ester (MSE) is mostly carried out using a high temperature method, but there are problems such as high energy consumption, long preparation time, and uneven heating. Microwave technology can be used to overcome these limitations. The semi-crystalline structure of starch granules hinders the modifier's access to the matrix, thus limiting the esterification reaction. Physical techniques can act on the interior of the starch to create a number of active sites, thereby facilitating the reaction of the starch with esterification reagents. Therefore, this study investigated the effect of starch pretreatment by microwave, heat-moisture, and ultrasonic techniques on the degree of substitution (DS), structure, and physicochemical properties of MSE synthesized by the microwave method. The DS of MSE was increased after pretreatments. The modified starch obtained by different pretreatment methods did not show new characteristic peaks, while the MSE synthesized showed new absorption peaks near 1735 cm-1. The granular structure and morphology of the modified starch obtained by microwave and heat-moisture pretreatment were gelatinized and aggregated, while some of the starch particles of the modified starch obtained by ultrasonic pretreatment appeared pore-sized. The relative crystallinity and gelatinization enthalpy of the MSE were reduced, but the crystallization pattern remained as A-type. Overall, the results suggest that various pretreatment methods can enhance the DS of MSE by disrupting the structure of starch. The findings of this study provide theoretical support for improving the DS of esterified starch. © 2024 Society of Chemical Industry.

The inhibition mechanism of esterified starch on flotation separation of fluorite and calcite

Herein, the flotation behavior of fluorite and calcite was examined before and after starch esterification through mineral flotation experiments. Moreover, the adsorption action mechanisms on minerals before and after starch esterification were investigated using methods such as solution surface tension measurement, infrared spectroscopy, and extended Derjaguin–Landau–Verwey–Overbeek theory. The results showed that after starch esterification (esterified starch), there was a greater difference in the mineral recovery rate compared to before starch esterification (ordinary starch), with a better inhibition effect on calcite. The interaction between mineral surfaces and ordinary starch was weaker than the interaction between minerals and esterified starch. In particular, after starch esterification, the surface tension increased, two minerals contact angle decreased, the surface potential became more negative, and the difference in the mineral recovery rate was greater than before starch esterification. After the interaction between minerals and esterified starch, calcite particles displayed good dispersibility, while the cohesion between calcite particles and sodium oleate particles decreased; notably, the effect on fluorite was opposite. Calcite and esterified starch exhibited chemical adsorption, impeding the adsorption of sodium oleate onto calcite and resulting in calcite inhibition. The interaction between fluorite surface and esterified starch involved electrostatic adsorption, with sodium oleate chemically adsorbed onto the fluorite surface. Chemical adsorption proved stronger than electrostatic adsorption, enabling sodium oleate to capture fluorite.

An Attempt to Replace Pure Citric Acid with Natural Lemon Juice during Potato Starch Esterification.

The application of chemical operations in food processing, in which pure chemical compounds are used to modify food ingredients, often raises social concerns. One of the most frequently modified dietary substances is starch, e.g., E1401-E1404, E1412-E1414, E1420, E1422, E1440, E1442, and E1450-E1452. An alternative solution to chemical treatments seems to be the use of raw materials naturally containing substrates applied for starch modification. Heating starch with a lemon juice concentrate can be considered a novel and effective method for producing starch citrate, which is part of the so-called "green chemistry". The modified preparations obtained as a result of potato starch esterification with natural lemon juice had a comparable degree of esterification to that of the esters produced with pure citric acid. In addition, the use of the juice doubled their resistance to amylolytic enzymes compared to the preparations made with pure acid. Replacing citric acid with lemon juice can facilitate the esterification process, and the analyzed properties of both types of modified preparations indicate that starch esters produced with pure citric acid can be successfully replaced by those produced using natural lemon juice, which may increase the social acceptance of these modified preparations.

Effect of amylose partial extraction on citrate esterification of potato starch and its role in structure and physicochemical modification

This study examines the impact and influence of amylose on the starch esterification reaction through partial extraction of amylose. Citric acid was added for the esterification reaction, and then the esterified starches' multiscale structure, physicochemical, and functional properties were evaluated. As the extraction time of amylose increased, the amylose content in the starch decreased. Higher concentrations of citric acid will lead to samples with a higher degree of substitution, with DS rising from 0.203 % (0 h) to 0.231 % (3.5 h) at CA3 treatment. While removing amylose had minimal effects on the crystal structure of starch granules, it did decrease the ratio of A and B1 chains and the molecular weight of amylose. Acid hydrolysis exacerbated these changes upon the addition of citric acid. Furthermore, removing amylose followed by citrate esterification resulted in lower pasting viscosity, enthalpy of gelatinization (from 13.37 J to 2.83 J), and degree of short-range ordering. Also, digestion shows a decrease caused by the increasing content of slow-digesting starch. The presence of amylose in starch granules does affect the formation of starch esters, and removing it before esterification modification may improve production efficiency and reduce costs to some extent.

Cassava starch esterification with formic acid for fabrication of electrospun fibers

Formic acid is utilized to induce esterification and chemical gelatinization in starch, particularly in the fabrication of electrospun fibers for nanomaterial production. This study investigated the impact of different concentrations (15, 20, 25, and 30 %) of cassava starch and formic acid as a solvent on the characteristics of the resultant polymeric solutions and electrospun fibers. Morphology, size distribution, thermogravimetric properties, diffraction patterns, and relative crystallinity were evaluated for the electrospun fibers. The amylose content of starch varied from 16.5 to 23.7 %, decreasing with esterification, achieving a degree of substitution of approximately 0.93. The solution-rheology exhibited elastic behavior, with viscosity increasing as starch concentration increased, hindering the fabrication of fibers at 25 and 30 % starch. Successful electrospun fibers were formed using 15 % and 20 % starch, displaying homogeneous morphologies with mean diameters of 165 nm and 301 nm, respectively. Esterification influenced thermogravimetric properties, leading to fibers with reduced degradation temperatures and mass loss compared to native starches. The electrospun fibers presented an amorphous structure, indicating a drastic reduction in relative crystallinity from 35.2 % in native starch to 8.5 % for esterified starches. This study highlights the intricate relationship between starch concentration, esterification, and solution viscosity, affecting the electrospinnability and properties of starch-polymeric solutions.

Effects of microwave radiation on the physicochemical properties, structure, and digestibility of the synthesized different crystal forms of malic acid starch ester

The effects of microwave combined with L-malic acid treatment on the degree of substitution (DS), structure, physicochemical properties, and digestibility of sweet potato starch (A-type), potato starch (B-type), and pea starch (C-type) were evaluated. The order of DS obtained was: DSM-POS > DSM-SPS > DSM-PES. Fourier transform-infrared spectroscopy (FT-IR) showed that the obtained modified starch produced a new absorption band at 1735 cm−1. Scanning electron microscopy (SEM) and polarized light microscopy indicated that different types of native starches exhibited different granular morphologies and appeared to have different degrees of damage, but still had polarized crosses after modification. Sweet potato starch had the smallest particle size, while potato starch had the largest. X-ray diffractometry (XRD) showed that the modified starches still retained the same crystal structure as the native starches, but the relative crystallinity decreased. The apparent viscosity and swelling power of modified starches dropped, but their water/oil holding capacity, amylose content, and resistant starch content all increased. The results demonstrate that the degree of influence on the structure, physicochemical properties, and digestibility of different starches varies under the same modification conditions.

Starch esterification using deep eutectic solvents as chaotropic agents and reaction promoters

Choline chloride (ChCl):urea and acetic anhydride represents a homogeneous, efficient and sustainable reaction system for starch esterification.

Fabrication of biodegradable and cold-water-soluble starch/polyvinyl alcohol films as inner packaging materials of pesticides: Enhanced emulsification, dispersibility, and efficacy

Developing environmentally friendly film materials for packaging pesticides is significant yet challenging. The use of native starch for preparing inner packaging materials of pesticides is limited by its physicochemical properties. In this study, a novel strategy of synergetic mechanical activation (MA)-enhanced solid-phase esterification of starch and cooperative combination of starch and polyvinyl alcohol (PVA) was proposed to fabricate biodegradable and cold-water-soluble starch (St)/PVA films. The appropriate esterification of starch and favorable compatibility between starch and PVA contributed to the production of St/PVA films by the extrusion-blowing method. The as-prepared film with St/PVA ratio of 4:6 exhibited outstanding mechanical properties (tensile strengths of 21.0 MPa; elongation at break of 213.9 %), cold-water solubility (dissolution time of 90 s), and oxygen barrier performance (oxygen transmission rate of 1.41 cm3/(m2·day·bar)). The dissolved St/PVA films with amphiphilic groups were conducive to the emulsification of butachlor (a fat-soluble liquid pesticide) and the dispersibility of oxyfluorfen (a fat-soluble solid pesticide). Furthermore, a mechanism of the interaction between pesticides and the surface of weed leaves was proposed to reveal the enhanced efficacy of St/PVA films-packaged pesticides. The strategy based on MA-enhanced esterification and PVA blending is efficient to produce starch-based films suitable for inner packaging materials of pesticides.

Revisiting the Formation of Starch-Monoglyceride-Protein Complexes: Effects of Octenyl Succinic Anhydride Modification.

Starch-lipid-protein complexes are attracting increasing attention due to their unique structure and low enzymatic digestibility. However, the mechanisms underlying the formation of these ternary complexes, especially those with monoglycerides as the lipid component, remain unclear. In the present study, potato starch or octenyl succinic anhydride (OSA)-modified potato starch (OSAPS), various monoglycerides (MGs), and beta-lactoglobulin (βLG) were used in model systems to characterize the formation, structure, and in vitro digestibility of the respective ternary complexes. Colorimetry and live/dead staining assays demonstrated that the OSAPS had good biocompatibility. Experimental data and molecular dynamics simulations showed that both unmodified potato starch and OSAPS formed starch-lipid-protein complexes with MGs and βLG. Of the two types of starch, OSA formed a greater amount of the more stable type II V-crystallites in complexes, which had greater resistance to in vitro enzymic digestion. This study demonstrated for the first time that starch can interact with MGs and βLG to form ternary complexes and that OSA esterification of starch promoted the formation of more complexes than unmodified starch.

Insight into structure-activity relationships of hydroxycinnamic acids modified porous starch: The effect of phenolic hydroxy groups.

Antioxidant capacity of hydroxycinnamic acids-modified starch mainly depends on their chemical structure. Herein, cinnamic acid as well as meta-substituted and para-substituted cinnamic acid were selected for esterification with porous starch (labelled as CA@PS, m-CA@PS and p-CA@PS), with the successful formation of porous starch (labelled as PS) esters then confirmed by 1H NMR, 13C solid-state NMR and FT-IR spectroscopy. Three PS esters with almost same degrees of substitution (DS) were obtained, and antioxidant assays, including DPPH radical scavenging, reducing power and hydroxyl radical scavenging tests, were subsequently used to evaluate the antioxidant activity of the esterified PS. Overall, CA@PS showed weak antioxidant activity because of the absence of phenolic hydroxy, while p-CA@PS displayed better antioxidant capacity. Because its conjugated structure offered the stronger electron-donating effect, that could enhance antioxidant capacity. Therefore, antioxidant capacity depended significantly on overall chemical structure, including numbers and substitution positions of phenolic hydroxy groups.

Adsorptive removal of ciprofloxacin from simulated wastewater using crosslinked starch ester: Isotherms, kinetics, thermodynamics, modeling, and simulation for continuous operation

The rise in fluoroquinolone concentrations in wastewater caused significant concern due to their potential acute toxicity to living organisms. A novel eco-friendly adsorbent, crosslinked potato starch ester, was used to remove ciprofloxacin from a simulated aqueous solution by a batch adsorption process and used its obtained parameters to solve mathematical modeling. With a maximum adsorption capacity of 243.90 mg/g, the ciprofloxacin adsorption on crosslinked potato starch ester was suitable for the Langmuir isotherm model. The kinetics of ciprofloxacin adsorption showed that the pseudo-first-order kinetic model was a good fit for the adsorption process. Thermodynamic parameters exhibited that ciprofloxacin adsorption onto crosslinked potato starch ester was exothermic, achievable, and spontaneous. Finally, the process is simulated under various operating conditions using the mathematical model of a fixed bed continuous adsorption column. According to the results, under optimal operation conditions of inlet fluid velocity, particle size, bed height, and initial ciprofloxacin concentration with values 0.002 m/s, 1.2 mm, 0.2 m, and 143.4 mg/L, respectively, the highest dynamic adsorption capacity was 18.75 mg/g.

A synthesis of post‐esterified oxidized starch accompanied with physicochemical property analysis and esterification reaction condition optimization

AbstractEsterification is a normal method for starch modification while reaction condition is not clear. Here, pure corn starch and vinyl acetate were chosen for starch esterification. Reaction conditions involving esterifying agent content, pH, reaction time and temperature were explored. Dess‐Martin periodinane (DMP) pretreatment was adopted to accelerate esterification. Main results reveal that a content of 30 wt% vinyl acetate, pH = 9, time as 1 h and temperature as 45°C is an optimized condition for vinyl acetate esterification and DMP oxidization can enhance it. After modification, variations in microstructure, surface morphology and macroscopic properties such as viscosity, transparency, adhesion property were explored by FT‐IR, XRD, SEM, TGA, UV–Vis, viscosity, and slushing experiments. Main results reveal that after esterification carbonyl groups were introduced, lattice plane occurred expansion, surface morphology was destroyed, water absorption capacity, viscosity, and gelatinization temperature decreased while transparency, thermal‐stability and adhesion property increased. DMP treatment enhanced the previous variations. It seems via a middle‐level DMP pretreatment and vinyl acetate esterification starch solution viscosity and gelatinization temperature decreased greatly while transparency and adhesion force increased greatly, possibly having a potential use in textile industry. For instance, using as slurry its manufacture cost can be decreased with decreased energy consumption, economical.

Unveiling Optimal Synthesis and Structural Insights of Starch Ferulate via the Mechanoenzymatic Method.

In this study, starch ferulate was synthesized employing a mechanoenzymatic method, specifically based on the twin screw extrusion technique and lipase catalysis. The research then primarily centered on optimizing process parameters and conducting structural analysis. Optimal conditions were determined to be 8.2% ferulic acid addition, 66 °C extrusion temperature, and 3.2% lipase (N435) addition. The enzyme-catalyzed time was 30 s. The degree of substitution for starch ferulate was quantified at 0.005581 under these specific conditions. The presence of C=O bonds in the synthesized starch ferulate proved that the synthesis process was efficient. Additionally, the crystal structure underwent reconstruction. Observations through Scanning Electron Microscopy (SEM) and Confocal Laser Scanning Microscopy (CLSM) demonstrated that the mechanoenzymatic method led to an augmentation in the specific surface area of starch molecules, thereby facilitating the exposure of active sites. This breakthrough underscores the vast potential of mechanoenzymatic techniques to revolutionize the rapid and sustainable synthesis of starch ferulate, marking a pioneering stride in ester synthesis. The insights garnered from this study transcend theory, offering a visionary roadmap for the development and real-world deployment of advanced modified starch esters.

Structure and Mechanical Behavior of Fully Substituted Acid Starch Esters

AbstractThis study deals with the evolution of structural, thermal, and mechanical properties of a series of fully substituted fatty acid starch esters (FASEs) according to side chain length (from 2 (C2) up to 16 (C16) Carbons). FASEs with C2 to C12 side chains are fully amorphous with a glass transition temperature depending on chain length while in the case of FASE with C16 side chains, a part of side chains is able to crystallize. Thermomechanical behavior depends strongly on both the alkyl chain length and crystallinity of samples. In particular, for FASE‐C16, the presence of crystals leads to a brittle behavior. During stretching, no macromolecular orientation is evidenced for short‐chain FASEs (<C8), whereas, for long‐chain starch ester from C8 to C16 length, an orientation of starch backbone in the drawing direction is observed.

Fabrication and study on dually modified starch embedded in alginate hydrogel as an encapsulation system for Satureja essential oil

This study aimed to investigate how the types and order of modifications influence the structure and physicochemical characteristics of modified porous starch. The work focuses on the encapsulation of essential oil in hydrophobic microcapsules embedded in sodium alginate hydrogels. FTIR spectra indicated successful esterification of starch with OSA. 1047:1022 cm−1 and 1022:995 cm−1 band ratios of FTIR spectra revealed increased crystallinity due to enzymatic modification, supported by XRD patterns. Porous-OSA (PO) starch had 1.5 times higher degree of substitution (DS) than OSA-porous (OP) starch, confirmed by the intense peak at 0.85 ppm in 1H NMR spectra. SEM images displayed larger particles and smaller pore diameter in OP compared to PO and porous starch, indicating amylolytic enzyme inhibition by OSA. Loading efficiency (LE) showed no significant difference between OP and PO microcapsules (≈70 %), both significantly higher other starch microcapsules. OP and PO microcapsules exhibited sustained release, with enhanced antibacterial activity. Alginate hydrogels preserved about 60 % antioxidant and 90 % antibacterial activities of SEO against 2 h of UV radiation. These findings suggest that the order of modification could not affect the functional properties of final microcapsules. Additionally, the importance of alginate hydrogels as the protective and second wall material was disclosed.

Starch ester film properties: The role of the casting temperature and starch its molecular weight and amylose content

Oleic acid and 10-undecenoic acid were used to esterify corn, tapioca, potato and a waxy potato starch, with a maximum degree of substitution of 2.4 and 1.9 respectively. The thermal and mechanical properties were investigated as a function of the amylopectin content and Mw of starch, and by the fatty acid type. All starch esters had an improved degradation temperature regardless of their botanical origin. While the Tg did increase with increasing amylopectin content and Mw, it decreased with increasing fatty acid chain length. Moreover, films with different optical appearances were obtained by varying the casting temperature. SEM and polarized light microscopy showed that films cast at 20 °C had porous open structures with internal stress, which was absent when cast at higher temperatures. Tensile test measurements revealed that films had a higher Young's modulus when containing starch with a higher Mw and amylopectin content. Besides that, starch oleate films were more ductile than starch 10-undecenoate films. In addition, all films were resistant to water at least up to one month, while some light-induced crosslinking took place. Finally, starch oleate films showed antibacterial properties against Escherichia coli, whereas native starch and starch 10-undecenoate did not.

Comparative Assessment of Compression Strength of Solid Biobriquette using Different Binding Materials

Charcoal and firewood are the most common cooking fuels, despite the fact that they represent a variety of social and economic environmental difficulties in many affluent countries. Apart from the environmental implications of deforestation and resource loss, indoor air pollution caused by cooking with solid fuels causes 2 million fatalities each year. Biobriquettes are then utilized as a substitute for oils. Briquettes are also employed as carbon sources for cooking in various industries such as power plants, brick factories, and bakeries. Five specific binding materials were tested in this study for manual densification of cabbage waste, including beef tallow oil, starch, cassava binder, sodium silicate, and vinyl ester resin. The briquettes are made from a combination of 80% densified biological waste and 20% binder material. The sample density ranges from 545.564 to 591.278 kg/m3. The samples with the highest calorific value were beef tallow oil and vinyl ester resin, which had 5,357.26 and 5,800.79 kcal/kg respectively. The content of the samples were ashes, fixed carbon content, volatile material, and total humidity is 6.47% ± 1.13%, 18.43% ± 6%, 70.68% ± 6%, and 4.42% ± 4%, respectively. The sample with the most calorific value and densification is the one with the inorganic binder mixture.