Search Results (20)

The tetrahydroisoquinoline skeleton is a pharmacologically significant core structure containing chiral centers, making enantiomeric separation crucial due to the potentially distinct biological effects of each enantiomer. In this study, laudanosine (N-methyl-tetrahydropapaverine) and its three derivatives (6′-bromo-laudanosine, norlaudanosine, and N-propyl-norlaudanosine) were synthesized and used as model compounds to investigate chiral recognition mechanisms. Screening over twenty cyclodextrins (CyDs) as chiral selectors in capillary electrophoresis (CE), we found anionic CyDs to be the most effective, with sulfated-γ-CyD (S-γ-CyD) achieving a maximum R_s of 10.5 for laudanosine. Notably, octakis-(6-deoxy-6-(2-carboxyethyl)-thio)-γ-CyD (sugammadex, SGX), heptakis-(2,3-O-diacetyl-6-O-sulfo)-β-CD (HDAS), heptakis-(2,3-O-dimethyl-6-O-sulfo)-β-CD (HDMS), and octakis-(2,3-O-dimethyl-6-O-sulfo)-γ-CD (ODMS) provided excellent enantioseparation for all four analytes. Following HPLC screening on CyD-based and polysaccharide-based chiral stationary phases, semi-preparative HPLC methods using amylose and cellulose-based columns were optimized to isolate enantiomers. The purity of the isolated enantiomers was evaluated by HPLC, and their configurations were confirmed via circular dichroism spectroscopy. The isolated enantiomers allowed us to explore enantiomer migration order reversals in CE and enantiomer elution order reversal in HPLC. Further ¹H and 2D ROESY NMR experiments provided atomic-level insights into enantioselective complex formation, confirming enantiomer differentiation by SGX and elucidating the inclusion complex structure, where the ring C immersion into the CyD cavity is prevalent. Full article

This study delved into the interaction between corn starch and ethyl maltol during innovative repeated continuous heat-moisture treatment (RCHMT) and its impact on the quality of fried chicken nuggets. The results reveal that the complexation ratio of ethyl maltol is about 31.6%, and the complex creates dense microporous structures. Native starch and complex samples exhibited an A-type crystal structure, while the physical mixture sample showed superposition peaks of starch and ethyl maltol. Additionally, the peak of C-O-H def., CH₂ of the complex sample was blue-shifted to the larger wave number, and the hydrogen bond structure was enhanced. Moreover, the complex exhibited a higher resistant starch content and lower hydrolysis rate and amylose content than the physical mixture sample. The starch–ethyl maltol complex has been demonstrated to be a non-inclusion compound. It has been shown to reduce oil absorption and enhance the crispness of fried chicken nuggets, matching that of commercial products. This finding provides a direction for the development of innovative coating powders. Full article

Starch, conformed by amylose and amylopectin, represents the major carbohydrate macromolecule consumed globally as a major component of staple foods. Phenolic compounds are ubiquitous secondary metabolites in plants with strong antioxidant capacities and have attracted a great deal of attention in recent decades. Besides these capabilities, polyphenols are known to interact through different bonds with polysaccharides, lipids or proteins, which impact the formed complex structure and its digestibility. Due to their hydroxyl groups, it appears as if lower MW polyphenols tend to display fewer H-bonds due to their fewer hydroxyl groups and thus weaker interactions and affinity, whereas higher MW polyphenols, such as polymerized tannins and especially proanthocyanidins, display a higher number of available H-bonds and a generally higher affinity. Native starch is usually present in two main forms: V-type inclusion complexes with hydrophobic bonds or non-inclusion crystal complexes (A- or B-type) prone to H-bonds and ionic/electrostatic interactions. The formation of the complexes depends on the starch microstructure, and also depends on the amylose/amylopectin ratio, and the ratio of crystalline and amorphous structures, with polyphenols showing higher affinity towards amylose and the hydrophobic interior of helix structures in starch. At the microstructural level, starch–polyphenol complexation leads to increased porosity and denser granules. At the rheological level, this translates into the starch showing reduced viscosity and elasticity. Moreover, this greatly impairs starch’s gelatinization and retrogradation during cooking, providing a final structure more akin to resistant starch, with a final reduced hardness and adhesiveness. These changes affect the digestibility of starch by amylolytic enzymes (i.e., α-amylase) and lead to lowered glucose release from it and absorption. This review aims to present a comprehensive and summarized overview of updated knowledge on this and the remaining gaps in knowledge. Full article

This review article presents the biomimetic helical inclusion of amylose toward hydrophobic polyesters as guests through a vine-twining polymerization process, which has been performed in the glucan phosphorylase (GP)-catalyzed enzymatic polymerization field to fabricate supramolecules and other nanostructured materials. Amylose, which is a representative abundant glucose polymer (polysaccharide) with left-handed helical conformation, is well known to include a number of hydrophobic guest molecules with suitable geometry and size in its cavity to construct helical inclusion complexes. Pure amylose is prepared through enzymatic polymerization of α-d-glucose 1-phosphate as a monomer using a maltooligosaccharide as a primer, catalyzed by GP. It is reported that the elongated amylosic chain at the nonreducing end in enzymatic polymerization twines around guest polymers with suitable structures and moderate hydrophobicity, which is dispersed in aqueous polymerization media, to form amylosic nanostructured inclusion complexes. As the image of this system is similar to how vines of a plant grow around a support rod, this polymerization has been named ‘vine-twining polymerization’. In particular, the helical inclusion behavior of the enzymatically produced amylose toward hydrophobic polyesters depending on their structures, e.g., chain lengths and substituents, has been systematically investigated in the vine-twining polymerization field. Furthermore, amylosic supramolecular network materials, such as hydrogels, are fabricated through vine-twining polymerization by using copolymers, where hydrophobic polyester guests or maltooligosaccharide primers are covalently modified on hydrophilic main-chain polymers. The vine-twining polymerization using such copolymers in the appropriate systems induces the formation of amylosic nanostructured inclusion complexes among them, which act as cross-linking points, giving rise to supramolecular networks at the nanoscale. The resulting materials form supramolecular hydrogels, films, and microparticles. Full article

Chia oil is a source of α-linolenic (omega-3) fatty acid, which is known to promote human health but is highly prone to oxidation. Amylose (a polymer of α-1,4 D-glucose units) can molecularly encapsulate hydrophobic molecules, forming inclusion complexes that could potentially allow the incorporation of sensitive bioactive substances into functional foods. The evaluation of their oxidative stability is relevant to understand their behavior as delivery systems, but monitoring this parameter under real storage conditions requires long periods. In the present work, the oxidative stability of amylose-hydrolyzed chia oil inclusion complexes at 25 °C was estimated from the extrapolation of the exponential dependence of the Rancimat induction times determined at different temperatures (70–98 °C). The complexes were formed with high amylose corn starch and enzymatically hydrolyzed chia oil (10% or 20% hydrolysate/starch), with and without crystallization, using the KOH/HCl method followed by freeze-drying. The spectra of attenuated total reflectance Fourier-transform infrared spectroscopy revealed typical bands that confirmed the effective retention of chia oil fatty acids by the starch structure. The scanning electron micrographs showed that these samples were formed by irregular and porous solid particles. The induction time at 25 °C of crystallized complexes decreased with an increasing hydrolysate content, while the opposite was observed in non-crystallized complexes, as those formed with 20% hydrolysate were the ones that showed the highest stability. Although these findings should be confirmed under real storage conditions, the Rancimat results could be considered as a preliminary quick prediction of the behavior of inclusion complexes as carriers of omega-3 fatty acids. Full article

Vitamin D plays a significant role in the physiological functions of the human body. However, the application of vitamin D in functional foods is limited due to its sensitivity to light and oxygen. Therefore, in this study, we developed an effective method to protect vitamin D by encapsulating it in amylose. In detail, vitamin D was encapsulated by amylose inclusion complex, followed by structural characterization and evaluation of its stability and release properties. The results of X−ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopy showed that vitamin D was successfully encapsulated in the amylose inclusion complex, and the loading capacity was 1.96% ± 0.02%. The photostability and thermal stability of vitamin D after encapsulation was increased by 59% and 28%, respectively. In addition, in vitro simulated digestion showed that vitamin D was protected through the simulated gastric environment and can be released gradually in the simulated intestinal fluid, implying its improved bioaccessibility. Our findings provide a practical strategy for the development of functional foods based on vitamin D. Full article

This study investigates inclusion behavior of amylose towards, poly(β-propiolactone) (PPL), that is a hydrophobic polyester, via the vine-twining process in glucan phosphorylase (GP, isolated from thermophilic bacteria, Aquifex aeolicus VF5)-catalyzed enzymatic polymerization. As a result of poor dispersibility of PPL in sodium acetate buffer, the enzymatically produced amylose by GP catalysis incompletely included PPL in the buffer media under the general vine-twining polymerization conditions. Alternatively, we employed an ethyl acetate–sodium acetate buffer emulsion system with dispersing PPL as the media for vine-twining polymerization. Accordingly, the GP (from thermophilic bacteria)-catalyzed enzymatic polymerization of an α-d-glucose 1-phosphate monomer from a maltoheptaose primer was performed at 50 °C for 48 h in the prepared emulsion to efficiently form the inclusion complex. The powder X-ray diffraction profile of the precipitated product suggested that the amylose-PPL inclusion complex was mostly produced in the above system. The ¹H NMR spectrum of the product also supported the inclusion complex structure, where a calculation based on an integrated ratio of signals indicated an almost perfect inclusion of PPL in the amylosic cavity. The prevention of crystallization of PPL in the product was suggested by IR analysis, because it was surrounded by the amylosic chains due to the inclusion complex structure. Full article

Chia (Salvia hispanica L.) seed oil is a naturally rich source of α-linolenic (~65%) and linoleic (~20%) essential fatty acids, which are known for their beneficial effects on health. However, they are highly susceptible to oxidative deterioration. Amylose, the linear component of starch, has the ability to form inclusion complexes with hydrophobic molecules (ligand), which may act as delivery systems of sensitive bioactive compounds, including essential omega-3 and omega-6 fatty acids. In the present work, the hydrolytic effectiveness of Candida rugosa and porcine pancreatic lipases to obtain chia seed oil-free fatty acids was compared, which were complexed with high-amylose starch through the alkaline method with and without the incorporation of ultrasonic treatment. The highest level of free fatty acids released (>80%) was reached with Candida rugosa lipase. The inclusion complexes formed with this hydrolysate displayed a typical V-type X-ray diffraction pattern (peaks at ~7.5, 13, and 20° (2θ)), which confirmed an effective complexation. Moreover, ultrasonically treated complexes displayed a small peak at ~21°, from crystallized saturated fatty acids. Through attenuated total reflectance Fourier-transform infrared spectroscopy, the presence of typical bands of fatty acids in the complexes was verified, whose intensity increased after the application of ultrasonic treatment. The dissociation temperature determined using differential scanning calorimetry was >90 °C. According to this, Candida rugosa lipase showed better hydrolytic effectiveness on chia seed oil, and the fatty acids released were able to form amylose inclusion complexes with high thermal stability, whose properties varied after ultrasonic treatment. Full article

Due to the potential reduction in starch availability, as well as the production of the distinct physico-chemical characteristics of starch in order to improve health benefits, the formation of starch–lipid complexes has attracted significant attention for improving the quantity of resistant starch (RS) content in starchy-based foods. The purpose of this research was to apply ultrasonication to produce intermediate amylose rice (Oryza sativa L.) cv. Noui Khuea (NK) starch–fatty acid (FA) complexes. The effects of ultrasonically synthesized conditions (ultrasonic time, ultrasonic amplitude, FA chain length) on the complexing index (CI) and in vitro digestibility of the starch–FA complex were highlighted. The optimum conditions were 7.5% butyric acid with 20% amplitude for 30 min, as indicated by a high CI and RS contents. The ultrasonically treated starch–butyric complex had the highest RS content of 80.78% with a V-type XRD pattern and an additional FTIR peak at 1709 cm⁻¹. The increase in the water/oil absorption capacity and swelling index were observed in the starch–lipid complex. The pasting viscosity and pasting/melting temperatures were lower than those of native starch, despite the fact that it had a distinct morphological structure with a high proportion of flaky and grooved forms. The complexes were capable of binding bile acid, scavenging the DPPH radical, and stimulating the bifidobacterial proliferation better than native starch, which differed depending on the FA inclusion. Therefore, developing a rice starch–lipid complex can be achieved via ultrasonication. Full article

Starch is the most abundant carbohydrate in legumes (22–45 g/100 g), with distinctive properties such as high amylose and resistant starch content, longer branch chains of amylopectin, and a C-type pattern arrangement in the granules. The present study concentrated on the investigation of hydrolyzed faba bean starch using acid, assisted by microwave energy, to obtain a possible food-grade coating material. For evaluation, the physicochemical, morphological, pasting, and structural properties were analyzed. Hydrolyzed starches developed by microwave energy in an acid medium had low viscosity, high solubility indexes, diverse amylose contents, resistant starch, and desirable thermal and structural properties to be used as a coating material. The severe conditions (moisture, 40%; pure hydrochloric acid, 4 mL/100 mL; time, 60 s; and power level, 6) of microwave-treated starches resulted in low viscosity values, high amylose content and high solubility, as well as high absorption indexes, and reducing sugars. These hydrolyzed starches have the potential to produce matrices with thermo-protectants to formulate prebiotic/probiotic (symbiotic) combinations and amylose-based inclusion complexes for functional compound delivery. This emergent technology, a dry hydrolysis route, uses much less energy consumption in a shorter reaction time and without effluents to the environment compared to conventional hydrolysis. Full article

An emulsifier with a targeted antioxidant effect was prepared using the inclusion complexes of octenyl succinic anhydride (OSA)-modified cassava amylose (CA) and quercetin (Q). The designed emulsifier, a carbohydrate polymer-flavonoid complex, exhibited both amphiphilic and antioxidant properties. To investigate the physical and oxidation stabilities of the prepared emulsion, three types of emulsions were prepared: primary emulsions stabilized by enzyme-modified starch, secondary emulsions stabilized by OSA-CA, and tertiary emulsions stabilized by Q-encapsulated complexes (OSA-CA/Q). The structural characteristics of CA, OSA-CA, and OSA-CA/Q were investigated by scanning electron microscopy, Fourier transform infrared spectrometry, and small-angle X-ray scattering analysis. The stabilities of the emulsions were evaluated based on their particle size distribution, zeta potential, creaming stability, and peroxide value. The results showed that the secondary and tertiary emulsions exhibited a relatively narrower particle size distribution than the primary emulsions, but the particle size distribution of the tertiary emulsions was the narrowest (10.42 μm). Moreover, the secondary and tertiary emulsions had lower delamination indices than the primary emulsions after 7 days of storage. The results obtained from the antioxidant experiments indicated that OSA-CA/Q exhibited good oxidation stability for application in emulsion systems. Full article

In this study, we attempted to prepare an amylose-oligo[(R)-3-hydroxybutyrate] (ORHB) inclusion complex using a vine-twining polymerization approach. Our previous studies indicated that glucan phosphorylase (GP)-catalyzed enzymatic polymerization in the presence of appropriate hydrophobic guest polymers produces the corresponding amylose–polymer inclusion complexes, a process named vine-twining polymerization. When vine-twining polymerization was conducted in the presence of ORHB under general enzymatic polymerization conditions (45 °C), the enzymatically produced amylose did not undergo complexation with ORHB. However, using a maltotriose primer in the same polymerization system at 70 °C for 48 h to obtain water-soluble amylose, called single amylose, followed by cooling the system over 7 h to 45 °C, successfully induced the formation of the inclusion complex. Furthermore, enzymatic polymerization initiated from a longer primer under the same conditions induced the partial formation of the inclusion complex. The structures of the different products were analyzed by X-ray diffraction, ¹H-NMR, and IR measurements. The mechanism of formation of the inclusion complexes discussed in the study is proposed based on the additional experimental results. Full article

Although the insecticidal properties of some plant essential oils are well-documented, their use in integrated pest and vector management is complicated by their high volatility, low thermal stability, high sensitivity to oxidation, and low solubility in water. We investigated the use of bio-based N-1-hexadecylammonium chloride and sodium palmitate amylose inclusion complexes as emulsifiers for two essential oils, garlic and asafoetida, known to be highly toxic to mosquito larvae. Four emulsions of each essential oil based on amylose hexadecylammonium chloride and amylose sodium palmitate inclusion complexes were evaluated for their toxicity against Aedes aegypti L. larvae relative to bulk essential oils. All emulsions were significantly more toxic than the bulk essential oil with the lethal dosage ratios ranging from 1.09–1.30 relative to bulk essential oil. Droplet numbers ranged from 1.11 × 10⁹ to 9.55 × 10⁹ per mL and did not change significantly after a 6-month storage period. These findings demonstrated that amylose inclusion complexes enhanced the toxicity of essential oils and could be used to develop new essential oil based larvicides for use in integrated vector management. Full article

Enzymatic polymerization has been noted as a powerful method to precisely synthesize polymers with complicated structures, such as polysaccharides, which are not commonly prepared by conventional polymerization. Phosphorylase is one of the enzymes which have been used to practically synthesize well-defined polysaccharides. The phosphorylase-catalyzed enzymatic polymerization is conducted using α-d-glucose 1-phosphate as a monomer, and maltooligosaccharide as a primer, respectively, to obtain amylose. Amylose is known to form supramolecules owing to its helical conformation, that is, inclusion complex and double helix, in which the formation is depended on whether a guest molecule is present or not. In this paper, we would like to report the preparation of amylose-carboxymethyl cellulose (CMC) conjugated supramolecular networks, by the phosphorylase-catalyzed enzymatic polymerization, using maltoheptaose primer-grafted CMC. When the enzymatic polymerization was carried out using the graft copolymer, either in the presence or in the absence of a guest polymer poly (ε-caprolactone) (PCL), the enzymatically elongated amylose chains from the primers on the CMC main-chain formed double helixes or inclusion complexes, depending on the amounts of PCL, which acted as cross-linking points for the construction of network structures. Accordingly, the reaction mixtures totally turned into hydrogels, regardless of the structures of supramolecular cross-linking points. Full article

Amylose, a natural polysaccharide, acts as a host molecule to form supramolecular inclusion complexes in its enzymatically formation process, that is, phosphorylase-catalyzed enzymatic polymerization using the α-d-glucose 1-phosphate monomer and the maltooligosaccharide primer, in the presence of appropriate guest polymers (vine-twining polymerization). Furthermore, in the vine-twining polymerization using maltooligosaccharide primer-grafted polymers, such as maltoheptaose (G₇)-grafted poly(γ-glutamic acid) (PGA), in the presence of poly(ε-caprolactone) (PCL), the enzymatically elongated amylose graft chains have formed inclusion complexes with PCL among the PGA main-chains to construct supramolecular networks. Either hydrogelation or aggregation as a macroscopic morphology from the products was observed in accordance with PCL/primer feed ratios. In this study, we evaluated macroscopic morphologies from such amylosic supramolecular networks with different guest polymers in the vine-twining polymerization using G₇-grafted PGA in the presence of polytetrahydrofuran (PTHF), PCL, and poly(l-lactide) (PLLA). Consequently, we found that the reaction mixture using PTHF totally turned into a hydrogel form, whereas the products using PCL and PLLA were aggregated in the reaction mixtures. The produced networks were characterized by powder X-ray diffraction and scanning electron microscopic measurements. The difference in the macroscopic morphologies was reasonably explained by stabilities of the complexes depending on the guest polymers. Full article