Starch Esters Research Articles

Synthesis and properties of fatty acid starch esters

Being completely bio-based, fatty acid starch esters (FASEs) are attractive materials that represent an alternative to crude oil-based plastics. In this study, two synthesis methods were compared in terms of their efficiency, toxicity and, especially, product solubility with starch laurate (C12) as model compound. Laurates (DS>2) were obtained through transesterification of fatty acid vinylesters in DMSO or reaction with fatty acid chlorides in pyridine. The latter lead to higher DS-values in a shorter reaction time. But due to the much better solubility of the products compared to lauroyl chloride esterified ones, vinylester-transesterification was preferred to optimize reaction parameters, where reaction time could be shortened to 2h. FASEs C6–C18 were also successfully prepared via transesterification. To determine the DS of the resulting starch laurates, the efficient ATR-IR method was compared with common methods (elementary analysis, 1H NMR). Molar masses (Mw) of the highly soluble starch laurates were analyzed using SEC-MALLS (THF). High recovery rates (>80%) attest to the outstanding solubility of products obtained through transesterification, caused by a slight disintegration during synthesis. Particle size distributions (DLS) demonstrated stable dissolutions in CHCl3 of vinyl laurate esterified – contrary to lauroyl chloride esterified starch. For all highly soluble FASEs (C6–C18), formation of concentrated solutions (10wt%) is feasible.

The identification of organic additives in traditional lime mortar

Abstract Organic-inorganic lime mortars were widely used in many ancient buildings due to their good performance in some fields (such as caking property, water repellency, weatherability, etc.). However, many ancient buildings and sites are suffering from various degrees of damage with the development of the economy and society and appropriate conservation and restoration are needed. The application of traditional construction materials, such as organic-inorganic lime mortars, attracts more and more attention in the conservation and restoration of ancient buildings in the recent years. So, the understanding of the components of original lime mortar which remained in ancient sites is of fundamental significance. In this work a set of analytical procedures to identify the organic additives in lime mortars by classical chemical analysis is proposed. The results show that using iodine-potassium iodide reagent, Benedict's reagent, reduction phenolphthalein reagent, Coomassie brilliant blue and sodium periodate oxidation glycerin acetyl acetone method could effectively detect a small amount of starch, reducing sugar, blood, protein and fatty acid ester that remained in ancient buildings’ lime mortars, respectively. These analytical methods are easy to operate with low detection limit, high accuracy and some other advantages.

Properties of retrograded and acetylated starch produced via starch extrusion or starch hydrolysis with pullulanase

The aim of the present study was to determine the impact of serial modifications of starch, including firstly starch extrusion or hydrolysis with pullulanase, followed by retrogradation (through freezing and defrosting of pastes) and acetylation (under industrial conditions), on its susceptibility to amylolysis. The method of production had a significant effect on properties of the resultant preparations, whilst the direction and extent of changes depended on the type of modification applied. In the produced starch esters, the degree of substitution, expressed by the per cent of acetylation, ranged from 3.1 to 4.4g/100g. The acetylation had a significant impact on contents of elements determined with the atomic emission spectrometry, as it contributed to an increased Na content and decreased contents of Ca and K. The DSC thermal characteristics enabled concluding that the modifications caused an increase in temperatures and a decrease in heat of transition (or its lack). The acetylation of retrograded starch preparations increased their solubility in water and water absorbability. The modifications were found to exert various effects on the rheological properties of pastes determined based on the Brabender's pasting characteristics and flow curves determined with the use of an oscillatory-rotating viscosimeter. All starch acetates produced were characterized by ca. 40% resistance to amylolysis.

Plasticization effect of triacetin on structure and properties of starch ester film

The aim of this work was to evaluate the plasticizing effect of triacetin on the structure and properties of starch ester film and further establish the structure–property relationships. The presence of triacetin resulted in multiple structure changes of the film. The mobility of macromolecular chain was increased to form scattered crystallite during the film formation process. The amorphous region was enlarged to contain more triacetin squeezed from crystalline region. The plasticization of triacetin and restriction of crystallite oppositely influenced the mobility of macromolecular chains in different regions. The thermal stability of triacetin changed along with its fluctuant interaction with macromolecules. Comparatively, the enhanced ether bond and the restriction from crystalline regions on the mobility of the amorphous chain consequently improved the thermal stability of the film matrix. The interaction between triacetin and starch ester was essential to film forming but unexpectedly lowered the triacetin stability.

Effects of amylose content on the paste properties and emulsification of octenyl succinic starch esters

AbstractOctenyl succinic starch esters were prepared from 12 strains of native indica rice starches with AM contents (AC) of 1.65–27.15%. The paste properties and emulsification were also investigated to evaluate the effect of ACs on starch properties. Results indicated that the degree of substitution for octenyl succinic starch ester were 0.0212–0.0252. Rapid visco analyzer (RVA) parameters demonstrated that octenyl succinic starch esters had higher relative viscosities than the native counterparts. Moreover, AC correlated negatively with the major RVA parameters (e.g. peak viscosity and breakdown viscosity). Compared with the native starches, octenyl succinic starch esters had higher paste clarity, decreased retrogradation, better freeze–thaw stability, and excellent gel texture, depending on ACs of the native starches. SEM showed that the gels from octenyl succinic starch esters had less and smaller pores, however, the gels from native starches changed to sponge‐like structure after three freezing/thawing cycles. Fluorescence photomicrographs and droplet size distribution indicated that octenyl succinic starch ester was an effective emulsifier for oil‐in‐water emulsions. This type of modified rice starch can potentially be employed as a thickener and emulsifier in frozen foods.

Lipase-catalyzed Synthesis of Starch Palmitate in Mixed Ionic Liquids

Lipase-catalyzed synthesis of starch palmitate was investigated in ionic liquid mixtures consisting of 1-butyl-3-methyl-imidazolium acetic ([BMIm]Ac) and 1-butyl-3-methyl-imidazolium tetraflouroborate ([BMIm][BF(4)]). The effect of reaction parameters such as the amount of enzyme used, the reaction temperature, the mass ratio of [BMIm][BF(4)]/[BMIm]Ac, the molar ratio of methyl palmitate/anhydroglucose unit in starch, and the reaction time on the degree of substitution was studied. The formation of starch esters was confirmed by the presence of the carbonyl signal in the FT-IR and NMR spectra. Scanning electron microscopy and X-ray diffraction data showed that the morphology and crystallinity of starch esters were largely disrupted. Thermogravimetric analysis suggested thermal stability of starch palmitate decreased compared to native starch. Water contact angle measurements revealed that the hydrophobicity of starch esters was improved after modification. The successful lipase-catalyzed synthesis of starch palmitate in ionic liquids suggested that ionic liquids could be used as a potentially attractive green alternative to harmful organic solvents for synthesis of high fatty acid starch ester.

Biosysthesis of Corn Starch Palmitate by Lipase Novozym 435

Esterification of starch was carried out to expand the usefulness of starch for a myriad of industrial applications. Lipase B from Candida antarctica, immobilized on macroporous acrylic resin (Novozym 435), was used for starch esterification in two reaction systems: micro-solvent system and solvent-free system. The esterification of corn starch with palmitic acid in the solvent-free system and micro-solvent system gave a degree of substitution (DS) of 1.04 and 0.0072 respectively. Esterification of corn starch with palmitic acid was confirmed by UV spectroscopy and IR spectroscopy. The results of emulsifying property analysis showed that the starch palmitate with higher DS contributes to the higher emulsifying property (67.6%) and emulsion stability (79.6%) than the native starch (5.3% and 3.9%). Modified starch obtained by esterification that possesses emulsifying properties and has long chain fatty acids, like palmitic acid, has been widely used in the food, pharmaceutical and biomedical applications industries.

The plastidial glucan, water dikinase (GWD) catalyses multiple phosphotransfer reactions

The plant genome encodes at least two distinct and evolutionary conserved plastidial starch-related dikinases that phosphorylate a low percentage of glucosyl residues at the starch granule surface. Esterification of starch favours the transition of highly ordered α-glucans to a less ordered state and thereby facilitates the cleavage of interglucose bonds by hydrolases. Metabolically most important is the phosphorylation at position C6, which is catalysed by the glucan, water dikinase (GWD). The reactions mediated by recombinant wild-type GWD from Arabidopsis thaliana (AtGWD) and from Solanum tuberosum (StGWD) were studied. Two mutated proteins lacking the conserved histidine residue that is indispensible for glucan phosphorylation were also included. The wild-type GWDs consume approximately 20% more ATP than is required for glucan phosphorylation. Similarly, although incapable of phosphorylating α-glucans, the two mutated dikinase proteins are capable of degrading ATP. Thus, consumption of ATP and phosphorylation of α-glucans are not strictly coupled processes but, to some extent, occur as independent phosphotransfer reactions. As revealed by incubation of the GWDs with [γ-(33) P]ATP, the consumption of ATP includes the transfer of the γ-phosphate group to the GWD protein but this autophosphorylation does not require the conserved histidine residue. Thus, the GWD proteins possess two vicinal phosphorylation sites, both of which are transiently phosphorylated. Following autophosphorylation at both sites, native dikinases flexibly use various terminal phosphate acceptors, such as water, α-glucans, AMP and ADP. A model is presented describing the complex phosphotransfer reactions of GWDs as affected by the availability of the various acceptors.

Facile preparation of sago starch esters using full factorial design of experiment

AbstractA facile solvent‐free method to acetylate sago starch (Metroxylon sagu) is reported. Microwave (100 W) was used as the heating source and the heating time was varied from 2 to 10 min with the temperature of acetylation maintained at 100°C under continuous stirring. Using a 24 full factorial design of experiment, it was found that the degree of substitution (DS) of acetylated sago starch was strongly affected by the ratio of starch to acylating reagents, the ratio of acetic anhydride to acetic acid as the acylating reagents, the concentration of iodine as catalyst and reaction time. The physicochemical characteristics of the acetylated sago starch were assessed based on the FTIR spectra, the XRD spectra, the water absorption index (WAI), and the water solubility index (WSI). SEM was used to study the surface morphology of the acetylated sago starch at different DS.

Ionic liquids as solvents for dissolution of corn starch and homogeneous synthesis of fatty-acid starch esters without catalysts

Ionic liquids (ILs) utilized for dispersing cellulose have gained increasing attention in recent years, but the number of the reports using ILs for starch is still limited. In this study, 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) and 1-ethyl-3-methlyimidazolium acetate ([EMIM]AC) were used to dispersing corn starch. Dimethyl sulfoxide (DMSO), a traditional organic solvent for starch, was added into [BMIM]Cl, and the mixture of [BMIM]Cl/DMSO was utilized for dispersing corn starch as well. Results showed that the starch granules dispersed in ILs was much smaller than native starch granules, and large starch aggregates were partially formed. Starch granules dispersed in [BMIM]Cl at 100°C for 60min remained less crystallinity than native starch granules, while it was disappeared when starch granules were dispersed in [EMIM]AC at 100°C for 60min. Homogenous synthesis of fatty-acid starch esters without catalysts in these ILs was also studied. The degree of substitution (DS) value of starch laurate was reached to 0.053, 0.068 and 0.100 in [BMIM]Cl, [EMIM]AC and the mixture of [BMIM]Cl/DMSO, respectively, at the reaction conditions of lauric acid/AGU molar ratio 1:5, temperature 120°C at a reaction time of 3h.

Mechanical, thermal, and biodegradation studies of polystyrene-phthalated starch blends using epoxy functionalized compatibilizer

Blends of polystyrene (PS) and esterified starch has been prepared using an epoxy functionalized PS as compatibilizer along with zinc stearate as prooxidant. The starch phthalate (Stph) loading was varied from 20 to 60%. The mechanical, thermal, and biodegradability studies of the blends were carried out as per the ASTM standards and the results were compared with that of neat PS. The blends exhibited enhanced mechanical properties with the addition of compatibilizer although the biodegradation rate slows down. The blend containing 40% starch ester with 12% compatibilizer showed maximum tensile strength. Thermogravimetric and differential scanning colorimetric analyses has been done for the blends, and the neat PS and the glass transition temperature of the blend has been obtained at 327 K. The water absorbency of the blends showed an increase with the increase in loading of Stph and a reduction with the addition of compatibilizer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Low power microwave‐assisted enzymatic esterification of starch

AbstractA series of starch esters was obtained using microwave‐assisted enzymatic transformation of starch. For the reaction hog pancreas lipase was used as a biocatalyst as well as followed acyl donors: acetic, lauric, and stearic acid. DMF and DMSO were applied as a reaction media. Experiments focused on low level microwave irradiation were compared with conventional heating of the reaction mixture. The structure of obtained starch esters was investigated by means of FTIR, analysis of substitution degree, changes in molecular parameters (MWs and MWs distributions), and microscopic studies (SEM). The spectroscopic analysis confirmed the ester bond formation. The microwave‐assisted reaction in DMF and lauric acid as an acyl donor, gave the highest degree of substitution (0.513) what followed the lowest polysaccharide degradation and maintaining the granular structure of starch. According to all the results the significant shortening in the reaction time (about 2.5 times) for microwave‐assisted reactions were observed. The influence of microwaves on esterification of starch was discussed focusing on reaction media and acyl donor type. The investigated reaction systems were demonstrated as new protocols for obtaining starch ester with higher efficiency in comparison to those known as conventional. Replacement of sophisticated derivatives including vinyl esters or acyl chlorides by simple acyl donors were shown as an additional benefit of proposed starch esterification method.

Lipase-coupling esterification of starch with octenyl succinic anhydride

Abstract Enzymatic modification of starch was conducted by lipase-coupling esterification with octenyl succinic anhydride (OSA). Parameters affecting the esterification were systematically studied. Products were characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction, differential scanning calorimetry (DSC) and viscosity analysis (VA). Optimum condition for lipase-coupling OSA starch preparation was as follows: starch pretreatment at 65 °C for 15 min, starch concentration 35%, amount of lipase and OSA, 0.6% and 3%, reaction pH, temperature and time, 8.0, 40 °C and 30 min respectively, which resulted in 0.0195 of the degree of substitution and 84.05 ± 2.07% of the reaction efficiency. FT-IR spectroscopy confirmed the formation of OSA starch. SEM and X-ray diffraction showed apparent surface change, but no crystalline change. DSC and VA results indicated the synthesized OSA starch gelatinized rapidly with high viscosity. Attractively, reaction time drastically reduced to 30 min, showing vast potential for scale production of OSA starch.

Pure, Transparent‐Melting Starch Esters: Synthesis and Characterization

Long chain starch esters were prepared by a new method using molten imidazole as solvent for the biopolymer. The advantage is the simplicity of the reaction mixture. Imidazole is acting not only as solvent, but also as reagent and base. The reaction succeeds via the imidazolide, which is formed in situ with an acid chloride. It yields highly pure derivatives, as could be shown by NMR spectroscopy and elemental analysis. No hints for desoxychloro substituents or other impurities could be found. The high quality of the products prepared is responsible for the occurrence of colorless melts. Although DSC measurements show a variety of thermal transitions, the formation of melts in the range of 40 to 255 °C could be observed with a hot stage microscope. The melting behavior can be adjusted by the type of ester moiety and the amount of ester functions introduced. In case of starch palmitates completely transparent melts are obtained within two distinct DS regions namely around 1.5 and 2.2 to 3.0. Upon cooling the melts form homogeneous films on different supports including glass. They show good adhesion and should therefore be a suitable basic material for the preparation of composites like laminated glass.

A novel starch-based adsorbent for removing toxic Hg(II) and Pb(II) ions from aqueous solution

A novel effective starch-based adsorbent was prepared through two common reactions, which included the esterification of starch with excess maleic anhydride in the presence of pyridine and the cross-linking reaction of the obtained macromonomer with acrylic acid by using potassium persulphate as initiator. The percentage of carboxylic groups of the macromonomer ranged from 14% to 33.4%. The cross-linking degree of the adsorbent was tailored with the amount of acrylic acid which varied from 10 wt% to 80 wt%. Both Fourier transform infrared spectra and thermogravimetric analysis results verified the structure of the adsorbent. The maximum gel fraction and swelling ratio of the adsorbent were about 72% and 6.25, respectively, and they were able to be adjusted with the amount of monomers. The weight loss percentage of the adsorbent could reach 96.9% after immersing in the buffer solution that contained α-amylase for 14 h. It was found that the adsorption capacities of the adsorbent for lead and mercury ions could be 123.2 and 131.2 mg/g, respectively. In addition, the adsorbent was able to remove ca. 51–90% Pb(II) and Hg(II) ions that existed in the decoctions of four medicinal herbals.

Thermally Induced Multimicellar‐Aggregate‐to‐Vesicle Transition for a Dentritic Starch Ester

What a transition! A fast, temperature-induced transition from multimicellar aggregates to vesicles has been presented for a dentritic starch ester decorated with a temperature-sensitive group. The large micelles are multimicellar aggregates composed of unimolecular micelle units. The morphology transition is due to the reorganization of unimolecular micelles during a long-term heating process. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Hydrophobically modified starch using long-chain fatty acids for preparation of nanosized starch particles

An efficient method for synthesis of hydrophobically modified starch without using organic solvents is described. The esterification of starch was performed with long chain fatty acid chlorides (C8, C12, C16), in two steps. In the first step, native starch was dispersed in an alkali reaction medium, and in the second step, it was treated for esterification. Finally, hydrophobic starch esters were obtained with moderate degrees of substitution (DS-values < 0.45). The reactivity of corn and potato starches under the same reaction conditions was also studied. The chemical structural determinations of the obtained products were investigated using common spectroscopy methods, such as FTIR and 1H NMR spectra. Starch nanoparticles and nanodispersion solutions were prepared via a dialysis method. The particle size distribution of the nanoparticles was determined using a laser diffraction particle size analyzer in an aqueous dispersion. The morphology investigation of the starch and the grafted starch nanoparticles was performed using SEM after freeze drying.

Research on Synthesis Processing of Microcapsule Wall Material with Emulsion Crosslinking Method

In this study, the microcapsule was prepared by emulsion crosslinking method, using trisodium trimetaphosphate (TSTP) as crosslinking agent. The microcapsule was named OMA-MPs because the mixture of Octenyl succinic starch ester(OSA-starch)，maltodextrin starch and arabic gum were used as raw material. Orthogonal experiment was used in this work to find the relationship between the small diameter of OMA - MPs and preparation factors. The better condition is that the small diameter of OMA-MPs technique was that the stirring rate 400 rpm, the materials concentration 15%, the crosslinking agent concentration 1%, and the volume ratios(w2/w1) 120:100. Due to the processing route without the use of toxic organic solvents, it is expected that these microparticles can be used as delivery vehicles for controlled release of food and drug.

Synthesis of high fatty acid starch esters with 1‐butyl‐3‐methylimidazolium chloride as a reaction medium

AbstractIn this work, high fatty acid esters of corn starch were synthesized by reacting the starch with fatty acid methyl ester using 1‐butyl‐3‐methylimidazolium chloride (BMIMCl) ionic liquid (IL) as reaction media. The effect of reaction variables such as the catalyst amount, molar ratio of fatty acid methyl ester/anhydroglucose unit (AGU) in starch, pyridine/AGU molar ratio, reaction temperature, as well as reaction time on the degree of substitution (DS) of starch esters was investigated. The experimental results showed that the DS value of the obtained starch esters could be varied depending on the process conditions. In the optimum reaction condition, the achieved maximum DS of starch laurate and starch stearate was 0.37 and 0.28, respectively, at a reaction temperature of 110°C for starch laurate and 120°C for starch stearate for a reaction duration of 2 h. Furthermore, the starch esters were characterized by FTIR, SEM, and X‐ray diffractometry (XRD) techniques, respectively. Results from FT‐IR spectroscopy suggested that the hydroxyl groups in the starch molecules were converted into ester groups. SEM and XRD studies showed that the morphology and crystallinity of starch esters were disrupted largely in the IL medium under the reaction conditions.

Biocompatible functionalisation of starch

The enzyme catalysed esterification of starch and fatty acids with terminal triple bonds is described. This material can be used as an acceptor for azide containing molecules, through azide/alkyne cycloaddition. The potential is illustrated by the production of fluorescently-labelled starch, and a biotinylated derivative which can bind streptavidin.