Cross-linking affecting properties and in-vitro digestibility of starch-sucrose ester complexes.

This study investigated the effects of cross-linking on the characteristics and in-vitro digestibility of starch-sucrose ester (SE) complexes. To achieve this, corn starch (CS) was cross-linked with various concentrations of sodium trimetaphosphate /sodium tripolyphosphate (5 %, 10 %, and 15 %). Subsequently, cross-linked starches (CLS) were complexed with SE through hydrothermal treatment. X-ray diffraction analysis revealed that V-type amylose-lipid complexes formed by the interaction between CS and SE. The resultant CS-SE complex significantly reduced CS digestibility, increasing its resistant starch (RS) content from 10.19 % to 22.71 %. The cross-linking modification did not alter the crystalline pattern of the CS-SE complex. Several CLS-SE complexes demonstrated higher enzymatic resistance compared to the CS-SE complex. The CLS10-SE complex exhibited the highest RS content of 39.37 % when the cross-linking agent concentration was 10 %. This phenomenon may be attributable to the cross-linking reaction having enhanced the interaction between starch molecular chains, reducing the solubility and swelling power, thereby hindering the accessibility of starch chains to digestive enzymes. These findings indicate that cross-linking modification is a practical approach to improving the anti-digestion performance of starch-lipid complexes.

From Nucleation to Fat Crystal Network: Effects of Stearic-Palmitic Sucrose Ester on Static Crystallization of Palm Oil.

Palm oil (PO), a semi-solid fat at room temperature, is a popular food ingredient. To steer the fat functionality, sucrose esters (SEs) are often used as food additives. Many SEs exist, varying in their hydrophilic-to-lipophilic balance (HLB), making them suitable for various food and non-food applications. In this study, a stearic-palmitic sucrose ester with a moderate HLB (6) was studied. It was found that the SE exhibited a complex thermal behavior consistent with smectic liquid crystals (type A). Small-angle X-ray scattering revealed that the mono- and poly-esters of the SE have different packings, more specifically, double and single chain-length packing. The polymorphism encountered upon crystallization was repeatable during successive heating and cooling cycles. After studying the pure SE, it was added to palm oil, and the crystallization behavior of the mixture was compared to that of pure palm oil. The crystallization conditions were varied by applying cooling at 20 °C/min (fast) and 1 °C/min (slow) to 0 °C, 20 °C or 25 °C. The samples were followed for one hour of isothermal time. Differential scanning calorimetry (DSC) showed that nucleation and polymorphic transitions were accelerated. Wide-angle X-ray scattering (WAXS) unraveled that the α-to-ß' polymorphic transition remained present upon the addition of the SE. SAXS showed that the addition of the SE at 0.5 wt% did not significantly change the double chain-length packing of palm oil, but it decreased the domain size when cooling in a fast manner. Ultra-small-angle X-ray scattering (USAXS) revealed that the addition of the SE created smaller crystal nanoplatelets (CNPs). The microstructure of the fat crystal network was visualized by means of polarized light microscopy (PLM) and cryo-scanning electron microscopy (cryo-SEM). The addition of the SE created a finer and space-filling network without the visibility of separate floc structures.

Sucrose Esters as Oleogelators in Mono or Binary Structured Oleogels Using Different Oleogelation Routes.

Sucrose esters (SE) have been investigated as structuring agents in oleogels. Due to the low structuration power of SE as single agent, this component has recently been explored in combination with other oleogelators to form multicomponent systems. This study aimed to evaluate binary blends of SEs with different hydrophilic-lipophilic balances (HLBs) with lecithin (LE), monoglycerides (MGs) and hard-fat (HF), according to their physical properties. The following SEs, SP10-HLB2, SP30-HLB6, SP50-HLB11, and SP70-HLB15, were structured using three different routes: "traditional", "ethanol" and "foam-template". All binary blends were made using a 10% oleogelator in 1:1 proportion for binary mixtures; they were then evaluated for their microstructure, melting behavior, mechanical properties, polymorphism and oil-binding capacity. SP10 and SP30 did not form well-structure and self-standing oleogels in any combination. Although SP50 showed some potential blends with HF and MG, their combination with SP70 led to even more well-structured oleogels, with a higher hardness (~0.8 N) and viscoelasticity (160 kPa), and 100% oil-binding capacity. This positive result might be attributed to the reinforcement of the H-bond between the foam and the oil by MG and HF.

Sucrose ester alleviates the agglomeration behavior of bamboo shoot dietary fiber treated via high pressure homogenization: Influence on physicochemical, rheological, and structural properties.

High-pressure homogenization (HPH) is a physical modification method that can rapidly reduce the particle size of bamboo shoot dietary fiber (BSDF), but it can lead to agglomeration. Therefore, the effects of the addition of sucrose ester (SE) to alleviate the agglomeration of BSDF during HPH were investigated. Compared with BSDF without added SE, BSDF obtained the smallest particle size (276.5 nm) and highest ζ-Potential (53.6 mV) when SE was 5 g/L. Water-holding capacity, oil-holding capacity, swelling capacity, and b* increased, whereas L* and a* decreased significantly with the addition of SE. The shear stress and viscoelasticity of BSDF solution were minimized when 5 g/L SE was added. SE reduced relative crystallinity and thermal stability of BSDF. SE could effectively alleviate the aggregation of BSDF through the mechanism of electrostatic repulsion. This study highlights an innovative and promising strategy for alleviating the agglomeration behavior of BSDF during HPH treatment.

Tracing distribution and interface behavior of water droplets in W/O emulsions with fat crystals.

Sucrose palmitate (P170) and sucrose laurate (L195) were used as emulsifiers to control the crystallization behavior of AMF and to stabilize W/O emulsions. In this study, the P170 promoted crystallization and led to strong fat crystal networks with smaller AMF crystals (60-80 µm) in emulsions, retaining flocculation. Water droplets were squeezed into irregular shapes between the strong network but the P170 formed an interface layer with better strength to resist the aggregation. Contrarily, the L195 inhibited crystallization and formed larger AMF spherulites (more than 100 µm) resulting in a low strength of fat crystal networks and unstable emulsions. Meanwhile, the water droplets were easily fixed on the surface of AMF crystals because of the existence of sucrose esters. Protruding crystals on the surface of larger spherulites could pierce the water-oil interface, leading to a greater coalescence and forming larger water droplets. Therefore, a weak crystal network could not prevent the sedimentation and phase separation caused by gravity.

Emulsion Properties during Microencapsulation of Cannabis Oil Based on Protein and Sucrose Esters as Emulsifiers: Stability and Rheological Behavior.

The effects of different emulsifiers, such as soy protein isolate-sucrose ester (SPI-SE) and whey protein isolate-sucrose ester (WPI-SE), on the properties of the emulsion during the microencapsulation of cannabis oil were studied. The influence of SE concentration on the emulsion properties of the two emulsifying systems was analyzed. The results of the adsorption kinetics show that SE can decrease the interfacial tension, particle size and zeta potential of the emulsions. The results of the interfacial protein concentration show that SE could competitively replace the protein at the oil-water interface and change the strength of the interfacial film. The results of the viscoelastic properties show that the emulsion structure of the two emulsion systems results in the maximum value when the concentration of SE is 0.75% (w/v), and the elastic modulus (G') of the emulsion prepared with SPI-SE is high. The viscosity results show that all emulsions show shear-thinning behavior and the curve fits well with the Ostwald-Dewaele model. The addition of SE in the emulsions of the two emulsion systems can effectively stabilize the emulsion and change the composition and strength of the oil-water interface of the emulsion. The cannabis oil microcapsules prepared with protein-SE as an emulsion system exhibit high quality.

Fast and selective synthesis of mono-substituted sucrose methacrylate ester monomer.

Sucrose methacrylate (SM) is a key monomer for synthesizing biocompatible polymers with a carbohydrate core. However, controlled SM synthesis is challenging due to the possible formation of regio-isomers. This study describes SM synthesis that involves ultrasound irradiation of a homogeneous basic medium. The selectivity for mono-substituted SM was 86% within 30 min of reaction. The newly developed methodology is faster and more selective than that of mono-substituted SM synthesis already described in the literature.

A novel strategy to fabricate stable oil foams with sucrose ester surfactant.

HYPOTHESIS: Can a mixture of sucrose ester surfactant in vegetable oil be aerated to yield stable oleofoams? Is foaming achievable from one-phase molecular solutions and/or two-phase crystal dispersions? Does cooling a foam after formation induce surfactant crystallisation and enhance foam stability? EXPERIMENTS: Concentrating on extra virgin olive oil, we first study the effect of aeration temperature and surfactant concentration on foamability and foam stability of mixtures cooled from a one-phase oil solution. Based on this, we introduce a strategy to increase foam stability by rapidly cooling foam prepared at high temperature which induces surfactant crystallisation in situ. Differential scanning calorimetry, X-ray diffraction, infra-red spectroscopy, surface tension and rheology are used to elucidate the mechanisms. FINDINGS: Unlike previous reports, both foamability and foam stability decrease upon decreasing the aeration temperature into the two-phase region containing surfactant crystals. At high temperature in the one-phase region, substantial foaming is achieved (over-run 170%) within minutes of whipping but foams ultimately collapse within a week. We show that surfactant molecules are surface-active at high temperature and that hydrogen bonds form between surfactant and oil molecules. Cooling these foams substantially increases foam stability due to both interfacial and bulk surfactant crystallisation. The generic nature of our findings is demonstrated for a range of vegetable oil foams with a maximum over-run of 330% and the absence of drainage, coalescence and disproportionation being achievable.

New, Biocompatible, Chitosan-Gelled Microemulsions Based on Essential Oils and Sucrose Esters as Nanocarriers for Topical Delivery of Fluconazole.

Biocompatible gel microemulsions containing natural origin excipients are promising nanocarrier systems for the safe and effective topical application of hydrophobic drugs, including antifungals. Recently, to improve fluconazole skin permeation, tolerability and therapeutic efficacy, we developed topical biocompatible microemulsions based on cinnamon, oregano or clove essential oil (CIN, ORG or CLV) as the oil phase and sucrose laurate (D1216) or sucrose palmitate (D1616) as surfactants, excipients also possessing intrinsic antifungal activity. To follow up this research, this study aimed to improve the adhesiveness of respective fluconazole microemulsions using chitosan (a biopolymer with intrinsic antifungal activity) as gellator and to evaluate the formulation variables' effect (composition and concentration of essential oil, sucrose ester structure) on the gel microemulsions' (MEGELs) properties. All MEGELs were evaluated for drug content, pH, rheological behavior, viscosity, spreadability, in vitro drug release and skin permeation and antifungal activity. The results showed that formulation variables determined distinctive changes in the MEGELs' properties, which were nevertheless in accordance with official requirements for semisolid preparations. The highest flux and release rate values and large diameters of the fungal growth inhibition zone were produced by formulations MEGEL-FZ-D1616-CIN 10%, MEGEL-FZ-D1216-CIN 10% and MEGEL-FZ-D1616-ORG 10%. In conclusion, these MEGELs were demonstrated to be effective platforms for fluconazole topical delivery.

The Effect of the HLB Value of Sucrose Ester on Physiochemical Properties of Bigel Systems.

The current research explored the effect of different sucrose esters (SEs), with different hydrophilic-lipophilic balance (HLB) values, on bigel structure and properties. Bigels consisting of a water phase with glycerol and gelatin and an oil phase with glycerol mono-stearate, lecithin, and SEs with different HLB values were prepared. Rheological and thermal analyses revealed similar gelation-melting transitions governed by glycerol-monostearate crystallization (at ≈55 °C) for all bigel samples. The bigel matrix of the H1 and H2 samples (bigels consisting of SEs with HLBs of 1 and 2, respectively) demonstrated physical gel rheological characteristics of higher elastic and solid-like behavior compared with the H6 sample (bigel consisting SE with HLB 6). A similar trend was observed in the mechanical analysis with respect to hardness, firmness, and spreadability values, which were in the order of H1 > H2 > H6. This behavior was attributed to droplet size observed in the microscopy analysis, revealing significantly smaller droplets in the H1 and H2 samples compared with the H6 sample. These differences in droplet size were attributed to the diffusion kinetics of the low-molecular-weight surfactants. More specifically, the ability of mono-esterified SEs to diffuse faster than fully esterified SEs due to lower molar mass leads to a higher SE content at the oil-in-water (O/W) interface as opposed to the bulk oil phase. The results demonstrate the importance of the interface content in O/W bigel systems, providing an effective way to alter and control the bigel bulk properties.

Roles of non-ionic surfactant sucrose ester on the conversion of organic matters and bacterial community structure during composting.

The purpose of this study was to investigate the effect of sucrose ester (SE) addition on the physico-chemical parameters, organic matter (OM) biodegradation and related bacterial communities structure in dairy manure and cassava residuals co-composting. The biodegradation rates of OM, dissolved organic matters (DOM) and lignocellulose in SE (16.34%, 44.11% and 26.73%) group were higher than those in CK (14.71%, 39.11% and 19.90%). In addition, the content of humic substances (HS) (36.34%) in SE was obviously higher than that in CK (17.68%). The relative abundance of bacterial community in SE changed, in which the abundance of Firmicutes and Actinobacteria increased, while the amount of Blastomonas decreased. Redundancy analysis indicated Bacillus and Acinetobacter were positively correlated with the temperature and OM, whereas Azomonas and Luteimonas showed a positive relation with pH. In conclusion, the amendment of SE accelerated the degradation and conversion of organic matters, enhanced the formation of HS and improved the quality of compost.

Regulating water binding capacity and improving porous carbohydrate matrix's humectant and moisture proof functions by mixture of sucrose ester and Polygonatum sibiricum polysaccharide.

The moisture stability of tobacco shred, a typical porous carbohydrate material, is very important during its processing, storage and smoking, moreover, it is sensitive to environmental conditions. Therefore, effect of sucrose esters (SEs) and sucrose ester/Polygonatum sibiricum polysaccharide mixture (SPMs) on the moisture retention and moisture resistance of tobacco shred was assessed. When SEs were added to tobacco shred, moisture resistance was significantly enhanced, whereas moisture holding capacity was attenuated. Contrarily, the addition of SPMs made moisture retention index (MRI) and moisture proof index (MPI) increase from 1.8910 to 2.1612 and from 1.9489 to 2.0665, respectively, revealing that SPMs improved the moisture retention and moisture proof ability of tobacco shred simultaneously. The monolayer moisture content (M0) was decreased by SEs and increased by SPMs. Low-field nuclear magnetic resonance (LF-NMR) analysis showed that during adsorption, SPMs reduced the interaction between tobacco shred and water via hydrophobic property of SEs; during desorption, SPMs promoted the interaction between tobacco shred and water through hydrophilic binding of polysaccharide, leading to the migration of immobilized water to bound state. The modeling of the isotherms and LF-NMR analysis clarified the mechanism why SPMs could improve moisture stability of tobacco.

Effects of emulsifiers on the moisture sorption and crystallization of amorphous sucrose lyophiles.

The crystallization of amorphous sucrose can be problematic in food products. This study explored how emulsifiers (a range of sucrose esters, polysorbates, and soy lecithin) impact the moisture sorption and crystallization of amorphous sucrose lyophiles. Solutions containing sucrose with and without emulsifiers were lyophilized, stored in desiccators, and analyzed by X-ray diffraction, infrared spectroscopy, and polarized light microscopy over time. Moisture sorption techniques, Karl Fischer titration, and differential scanning calorimetry were also used. Different emulsifiers had varying impacts on sucrose crystallization tendencies. Polysorbates enhanced sucrose crystallization, decreasing both the RH and time at which sucrose crystallized. These lyophiles did not collapse upon crystallization, unlike all other samples, indicating the likelihood of variations in nucleation sites and crystal growth. All other emulsifiers stabilized amorphous sucrose by up to a factor of 7x, even in the presence of increased water absorbed and independent of glass transition temperatures, indicating emulsifier structure governed sucrose crystallization tendencies.

Effect of sucrose ester and carboxymethyl cellulose on physical properties of coconut milk.

The influence of sucrose ester (SE) and carboxymethyl cellulose (CMC) on the physical properties of coconut milk was determined using response surface methodology based on central composite design. The R 2 of all response variables was more than 0.80 which indicated a high proportion of variability was explained by the model and showed that increasing the amount of SE decreased the droplet size of coconut milk. The viscosity and creaming index were dependent on the SE and CMC concentration. Increasing the SE and CMC concentration increased viscosity but creaming index was decreased. The results suggested that suitable amount of SE and CMC should be specified in order to obtain a high quality of coconut milk products.

Separation and Analysis of Sucrose Esters in Tobacco by Online Liquid Chromatography-Gas Chromatography/Mass Spectrometry.

In this work, a strategy of in-series combination of ultrasound-assisted extraction and online LC-GC/MS was constructed for effective separation and analysis of sucrose esters in tobacco. Sucrose esters were first extracted by ultrasound-assisted extraction with high efficiency and easyhandling. Online LC-GC/MS was then applied for sucrose ester clean-up and analysis. To better evaluate the effectiveness of this strategy, we limited our focus to five groups of sucrose ester isomers. Each group differed in mass from the next by 14 Da. The obtained coefficient of the calibration curve was 0.9986. Limit of detection (LOD) and limit of quantitation (LOQ) were 0.05 and 0.16 µg/ mL, respectively. The recovery was above 90% and the reproducibility was below 4%. This strategy was subsequently applied to the comparison of relative amounts of five groups of sucrose esters extracted from three different parts of aromatic tobacco. The satisfactory performance indicated that this strategy has great prospect for the rapid and high-throughput analysis of sucrose esters in tobacco.

Study of rabbit erythrocytes membrane solubilization by sucrose monomyristate using laurdan and phasor analysis.

The study of surfactant and bio membranes interaction is particularly complex due to the diversity in lipid composition and the presence of proteins in natural membranes. Even more difficult is the study of this interaction in vivo since cellular damage may complicate the interpretation of the results, therefore for most of the studies in this field either artificial or model systems are used. One of the model system most used to study biomembranes are erythrocytes due to their relatively simple structure (they lack nuclei and organelles having only the plasma membrane), their convenient experimental manipulation and availability. In this context, we used rabbit erythrocytes as a model membrane and Laurdan (6-lauroyl-2-dimethylaminonaphthalene) as the fluorescent probe to study changes promoted in the membrane by the interaction with the sucrose monoester of myristic acid, ß-d-fructofuranosyl-6-O-myristoyl-α-d-glucopyranoside (MMS). Surfactant and erythrocytes interaction was studied by measuring hemoglobin release and the changes in water content in the membrane sensed by Laurdan. Using two-photon excitation, three types of measurements were performed: Generalized Polarization (analyzed as average GP values), Fluorescence Lifetime Imaging, FLIM (analyzed using phasor plots) and Spectral imaging (analyzed using spectral phasor). Our data indicate that at sublytical concentration of surfactant (20µM MMS), there is a decrease of about 35% in erythrocytes size, without changes in Laurdan lifetime or emission spectra. We also demonstrate that as hemolysis progress, Laurdan lifetime increased due to the decrease in hemoglobin (strong quencher of Laurdan emission) content inside the erythrocytes. Under these conditions, Laurdan spectral phasor analyses can extract the information on the water content in the membrane in the presence of hemoglobin. Our results indicate an increase in membrane fluidity in presence of MMS.

Physakengoses K-Q, seven new sucrose esters from Physalis alkekengi var. franchetii.

Seven sucrose esters, physakengoses K-Q (1-7) were isolated from the aerial parts of Physalis alkekengi var. franchetii. Their structures were elucidated on the basis of extensive spectroscopic analyses and chemical methods. These new compounds were tested for their antimicrobial abilities against Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli. Among the isolated sucrose esters, compounds 1-5 showed potent antibacterial activity with MIC values ranging from 2.16 to 12.76 µg/mL.

Lipase-catalyzed synthesis of sucrose monoester: Increased productivity by combining enzyme pretreatment and non-aqueous biphasic medium.

Sucrose monocaprate was synthesized by carrying out a lipase-catalyzed transesterification in a non-aqueous biphasic medium. Vinyl caprate was mechanically dispersed into a solution of sucrose in DMSO. The use of DMSO allowed increasing sucrose concentration up to 0.7M (in DMSO). The denaturing effect of DMSO on lipase was avoided by pretreatment of lipase by pH adjustment in the presence of crown ether. This pretreatment maintained a significant catalytic activity which led to 0.2M sucrose monoester within 1h at 50°C, which represented higher productivity than already reported. Detailed structural characterization revealed that only monoester was recovered and the 2-O-acylated sucrose monocaprate was the major isomer in the final product.

Synthesis of some glucose-fatty acid esters by lipase from Candida antarctica and their emulsion functions.

The synthesis of glucose esters with palmitic acid, lauric acid and hexanoic acid using lipase enzyme was studied and their emulsion functionality in oil-in-water system were compared. Reactions at 3:1M ratio of fatty acids-to-glucose had the highest conversion percentages (over 90% for each of the fatty acid). Initial conversion rate increased as substrate solubility increased. Ester bond formation was confirmed by nuclear magnetic resonance technique that the chemical shifts of glucose H-6 and α-carbon protons of fatty acids in the ester molecules shifted to the higher fields. Contact angle of water on esters' pelleted surface increased as the hydrophobicity increased. Glucose esters' and commercial sucrose esters' functionality as emulsifiers were compared. Glucose esters delayed, but did not prevent coalescence, because the oil droplets diameter doubled during 7days. Sucrose esters prevented coalescence during 7days since the droplets diameter did not have significant change.

Sucrose esters as biocompatible surfactants for penetration enhancement: An insight into the mechanism of penetration enhancement studied using stratumcorneum model lipids and Langmuir monolayers.

Up to now, the molecular mechanism of the penetration enhancing effect of sucrose esters (SEs) on stratumcorneum (SC) has not been explained in details. In this study, variety of surface sensitive techniques, including surface pressure-area (π-A) isotherms, infrared reflection-absorption spectroscopy (IRRAS), and Brewster angle microscopy (BAM), have been used to investigate interactions between SEs and SC intercellular lipids. A monolayer of the mixture of ceramide AS C18:18, stearic acid and cholesterol in the molar ratio of 1:1:0.7 on an aqueous subphase is a good model to mimic a single layer of intercellular SC lipids. The π-A isotherms of mixed monolayers and parameters derived from the curves demonstrated the interaction between nonionic surfactants such as SEs and SC lipids. With increasing SE concentration, the resultant monolayer films became more fluid and better compressible. IRRAS measurements showed that SEs disordered the acyl chains of SC lipids, and the BAM images demonstrated the modification of the domain structures in SC monolayers. Longer chain-SE has a stronger disordering effect and is better miscible with ceramides in comparison to SE with a shorter hydrophobic part. In conclusion, this study demonstrates the disordering effect of SEs on the biomimetic SC model, pointing out that small changes in the structure of surfactant may have a strong influence on a penetration enhancement of lipophilic drugs through intercellular lipids of skin.