Degree Of Substitution Research Articles

Correlation between emulsification and butyryl group distribution in various butyrylated starches

Butyrylated starch, a modified starch with significant applications in the food and pharmaceutical industries, lacks sufficient research on its emulsification. In this study, butyrylation was performed using waxy corn starch, tapioca starch and corn starch as raw materials, and their group distribution were determined. X-ray photoelectron spectroscopy (XPS), Raman microscopy and water contact angle measurements showed that the distribution of butyryl group in B-WCS was highly uniform. The results of the emulsification assay illustrated that B-WCS exhibited significant emulsifying potential at similar degrees of substitution. Analysis of the interface behavior demonstrated that B-WCS reduced the oil-water interfacial tension and formed a rigid interface film that resisted external deformation, thereby maintaining emulsion stability. This indicates that B-WCS exhibiting a highly uniform group distribution has significant emulsification potential. This study revealed the emulsification mechanism of butyrylated starch from an interface perspective and analyzed the relationship between the butyryl group distribution and emulsifiability.

Physicochemical and functional properties of short-chain fatty acid starch modified with different acyl groups and levels of modification

Rice and quinoa starches are modified with short-chain fatty acids (SCFA) with different SCFA acyl chain lengths and levels of modification. This work is aimed to investigate the impact of modifying rice and quinoa starches with short-chain fatty acids (SCFAs) on various physicochemical properties, including particle size, protein and amylose content, thermal behavior, pasting characteristics, and in vitro digestibility. Both native and SCFA-starches showed comparable particle sizes, with rice starches ranging from 1.58 to 2.22 μm and quinoa starches from 5.18 to 5.72 μm. SCFA modification led to lower protein content in both rice (0.218–0.255 %) and quinoa starches (0.537–0.619 %) compared to their native counterparts. Esterification led to the reduction of gelatinization and pasting temperatures as well as the hardness of the paste of SCFA-starches were reduced while paste clarity increased. The highest level of modification in SCFA-starch was associated with the highest amount of resistant starch fraction. Principal component analysis revealed that modification levels exerted a greater influence on starch properties than the types of SCFA used (acetyl, propionyl, and butyryl). These findings is importance in considering the degree of substitution or level of modification when tailoring starch properties through SCFA modification, with implications for various applications in food applications.

Synthesis and unambiguous NMR characterization of linear and branched N-alkyl chitosan derivatives

Chitosan, sourced from abundant chitin-rich waste streams, emerges as a promising candidate in the realm of future functional materials and chemicals. While showing numerous advantageous properties, chitosan sometimes falls short of competing with today's non-renewable alternatives. Chemical derivatization, particularly through N-alkylation, proves promising in enhancing hydrophobic functionalities. This study synthesizes fifteen chitosan derivatives (degree of substitution = 2–10 %) using an improved reductive amination method. Next, selective depolymerization through acid hydrolysis reduced the chain rigidity imposed by the polymer backbone. This facilitated unambiguous structural characterization of the synthesized compounds using a combination of common NMR techniques. Two potential side reactions are identified for the first time, emphasizing the need for detailed structural information to unlock the true potential of these derivatives in future applications. HypothesisThe increase in chain mobility induced by the selective depolymerization of aliphatic N-alkyl chitosan derivatives allows for an unambiguous NMR characterization.

The welfare effect of release timing of relative performance evaluation under quantity competition and asymmetric costs

AbstractWe examine the welfare effects of the endogenous decision and release timing of weight placed on the rival's profits under relative performance evaluation with quantity competition and asymmetric marginal costs. We find that when the advantaged firm decides and releases the weight as the leader, it always chooses a negative weight on relative performance evaluation, whereas the disadvantaged firm may choose a positive or negative weight depending on the degree of product substitution. Furthermore, we demonstrate that while all firms prefer to release weights early, this situation does not improve social welfare in several economic environments.

Gas-Phase Functionalization of Phytoglycogen Nanoparticles and the Role of Reagent Structure in the Formation of Self-Limiting Hydrophobic Shells.

A suite of acyl chloride structural isomers (C6H11OCl) was used to effect gas-phase esterification of starch-based phytoglycogen nanoparticles (PhG NPs). The surface degree of substitution (DS) was quantified using X-ray photoelectron spectroscopy, while the overall DS was quantified using 1H NMR spectroscopy. Gas-phase modification initiates at the NP surface, with the extent of surface and overall esterification determined by both the reaction time and the steric footprint of the acyl chloride reagent. The less sterically hindered acyl chlorides diffuse fully into the NP interior, while the branched isomers are restricted to the near-surface region and form self-limiting hydrophobic shells, with shell thicknesses decreasing with increasing steric footprint. These differences in substitution were also reflected in the solubility of the NPs, with water solubility systematically decreasing with increasing DS. The ability to separately control both the surface and overall degree of functionalization and thereby form thin hydrophobic shells has significant implications for the development of polysaccharide-based biopolymers as nanocarrier delivery systems.

Preparation and Characterization of Cellulose Derivatives from Agricultural Wastes

Background: Rice straw was pretreated with dilute alkaline and acid solutions to extract cellulose, which was then converted into cellulose acetate with acetic anhydride and phosphotungstic acid (H3PW12O40·6H2O). The concentration of KOH and the duration of immersion in acetic acid solution affected the removal of hemicellulose and lignin, and after pretreatment with 4% KOH and immersion in acetic acid for 5 hours, the treated rice straw contained 83wt.% cellulose. Phosphotungstic acid has been shown to be an excellent catalyst for the acetylation of rice straw cellulose. The degree of substitution (DS) values had a substantial effect on the solubility of cellulose acetate, and acetone-soluble cellulose acetate with DS values about 2.2 can be generated by varying the amount of phosphotungstic acid and acetylation duration. Objectives: The aim of the study was to evaluate the preparation and characterization of cellulose derivatives from agricultural wastes. Methods: This cross-sectional study was carried out in the Department of Communicable Diseases Control, Director General of Health Services, Dhaka, Bangladesh. For this investigation the rice plant straw was collected from Magura district region. The collected straws were then treated with 3 wt% nitric acid and 1.5 wt% NaOH solution separately. Statistical analyses of the results were be obtained by using window-based Microsoft Excel and Statistical Packages for Social Sciences (SPSS-24). Results: This study observed that the rice straw contained about 35.67% cellulose, 5.50% hemicellulose and 30.18 % α-cellulose. And the wheat straw contained about 43.99% cellulose, 7.30% hemicellulose and 36.70% α-cellulose. The degree of acetylation and degree of substitution of the synthesized cellulose acetate from rice straw were 39.046% and 2.413 respectively. On the other hand, the degree of acetylation and degree of substitution of the synthesized cellulose acetate from wheat straw were 40.79% and 2.59 respectively. ....

Interplay between cation composition and charge transport characteristics in GAxFAyMA1-x-yPbI3 halide perovskites

Halide perovskites (HPs) are a well-known class of mixed electronic and ionic conductors with diverse applications in optoelectronic devices. The simultaneous transport of ionic and electronic carriers has beneficial and detrimental effects depending on the intended applications. There is an extensive understanding of the charge transport characteristics in HPs since the phenomenon is of applied relevance. However, considering that several applications use compositions containing mixed cations, a deeper understanding of how the degree of substitution and the characteristics of the substituent cations affect the charge transport characteristics is needed. To this end, we experimentally studied the ionic conductivity (σion), current–voltage hysteresis (J–E hysteresis), mobility (μe) and density (ne) of electronic carriers, and bandgap energies (Eg) of up to 24 compositions of methylammonium lead iodide partially substituted with guanidinium and formamidinium. The results indicate that σion, J–E hysteresis, and μe decrease with the degree of substitution, with the J–E hysteresis being smaller the larger size of the substituent cation. At the same time, σion appears to be lower in compositions with equimolar substituents, in which the entropy of mixing is maximum. On the other hand, a slight increase in ne was observed with the substitution degree, showing highest values for FA+-rich compositions, where Eg is the lowest. The results advance the understanding of how it is possible to customize charge transport properties through the rational design of compositions in HPs.

Comparative Study on the Emulsification of Octenyl Succinic Anhydride Modified Sweet Potato Starch: As Macromolecular and Particulate Stabilizers

AbstractSweet potato is one of the essential starch materials for food and feed world widely. However, its application is limited by the low viscosity and poor stability of native starches. Herein, sweet potato starch is modified by octenyl succinic anhydride (OSA) in the aqueous system. The optimization for esterification is studied using response surface methodology. The characteristics of OSA‐modified sweet potato starch are investigated, and its emulsifying properties as macromolecular and particulate stabilizers in the oil‐in‐water systems are compared. The optimal process conditions for OSA modification are: reaction time 4.0 h, temperature 38.8 °C, pH of the reaction system 8.2, starch concentration 32.2%, OSA amount 3.0%. The degree of substitution is 0.0185, and reaction efficiency is 79.7% under the optimum conditions. The new peaks at 1725 and 1573 cm−1 are observed by Fourier transform infrared spectroscopy. Compared with native starch, OSA‐modified sweet potato starch exhibits higher viscosities, improved paste clarity, and decreased retrogradation. The confocal laser scanning microscope results show that the gelatinized starch macromolecule and ungelatinized starch particles can arrange at the water–oil interface. The OSA‐modified sweet potato starch is both an effective macromolecular emulsifier and a particulate stabilizer, effectively stabilizing oil‐in‐water emulsions.

Fingerprinting of hydroxy propyl methyl cellulose by comprehensive two-dimensional liquid chromatography-mass spectrometry of monomers resulting from acid hydrolysis

Hydroxypropyl methyl cellulose (HPMC) is a type of cellulose derivative with properties that render it useful in e.g. food, cosmetics, and pharmaceutical industry. The substitution degree and composition of the β-glucose subunits of HPMC affect its physical and functional properties, but HPMC characterization is challenging due to its high structural heterogeneity, including many isomers. In this study, comprehensive two-dimensional liquid chromatography-mass spectrometry was used to examine substituted glucose monomers originating from complete acid hydrolysis of HPMC. Resolution between the different monomers was achieved using a C18 and cyano column in the first and second LC dimension, respectively. The data analysis process was structured to obtain fingerprints of the monomers of interest. The results revealed that isomers of the respective monomers could be selectively separated based on the position of substituents. The examination of two industrial HPMC products revealed differences in overall monomer composition. While both products contained monomers with a similar degree of substitution, they exhibited distinct regioselectivity.

Effect of ionic liquid-surfactant compound solutions on the wettability and functional groups of coal

In order to investigate the feasibility of ionic liquid-surfactant compound solutions for coal dust suppression, three ionic liquids and sodium alpha-olefin sulfonate (AOS) were selected to be compounded respectively. The compound solutions were optimized by surface tension tests and coal dust settling experiments, and FTIR and SEM tests were carried out on coal samples treated with the optimum wetting agent. The results show that when the concentration is 0.3 wt%, and the ratio of [Bmim][Cl]/AOS is 4:6, the wetting rate of compound solution is the maximum. The content of hydrophilic functional groups OH…O and C-O in the coal samples increases significantly, and the degree of benzene ring substitutions is elevated; while hydrophobic functional groups –CH, aromatic ring C = C, and benzene ring 3 substitutions (3H) are destroyed by dissolution. The micromorphology of the coal surface changes with the appearance of many cracks and pores and an increase in surface roughness. [Bmim]+ can adsorb on the drain absorption points on the coal surface by electrostatic effect, turning them into water absorption sites and attracting the surrounding AOS molecules to arrange the composite adsorption layer more closely. These results can contribute to the development of novel wetting agents with specific structures and provide theoretical guidance for the reduction of coal dust concentrations.

Prebiotic effects of dietary xylooligosaccharides on fish gut microbiota, growth, and immunological parameters – A review

Abstract Xylooligosaccharides (XOSs) are being explored as prebiotics in fish diets; however, their effects and modes of action have not been well evaluated. Reports have shown that dietary XOS has the potential to improve the proliferation of beneficial gut microbes, and their metabolites, and enhance disease resistance in several fish species. In contrast, other studies report no substantial changes in immune and growth parameters compared to control groups. Like all prebiotics, the mode of action of XOS is based on their selective stimulation of beneficial gut microbiota, which will outcompete and prevent pathogen proliferation in the gut, and produce metabolites that modulate host immune responses. The reports of improved growth performance of XOS fed fish may be due to improved intestinal microbiome, enhanced glycolysis activity and elevated gastrointestinal enzymatic activities. Dietary XOSs have different effects on fish performance depending on the fish species and the structure of XOSs (degree of XOS polymerization and substitution). Nevertheless, further research is essential to determine the optimal dosage, degree of polymerization, and substitution levels required to improve each fish species’ gut health and growth performance. This review highlights the prebiotic effects of XOSs, their mechanism of action, and knowledge gaps.

Optimizing filtration properties of water based drilling mud systems using dually modified starch

This research explores the efficacy of dually modified starch as a fluid loss controlling agent in drilling mud systems, aiming to optimize filtration properties for improved borehole stability and reservoir productivity. Filtrate loss and filter cake thickness (API and HPHT) were examined under varying conditions, focusing on the influence of degree of substitution (DS) of the starch, CMITS concentration, salt concentration, and temperature. The current findings reveal that DS 0.66 starch exhibited the highest reduction in filtrate volume and cake thickness, achieving an 81% decrease at 8 ppb concentration. Regression models accurately predicted filtration properties and were confirmed through additional experiments. Comparison with previous studies underscores the potential of modified starch as a cost-effective alternative for drilling mud additives. Furthermore, the correlation between viscosity and filtration properties was explored, highlighting its impact on improved filtration characteristics. Overall, this research contributes valuable insights into enhancing drilling efficiency and borehole stability, minimizing dependence on costly chemical additives.

Thermodynamic analysis of cellulose nitration

In this study, the standard formation enthalpies and entropies of cellulose and nitrocellulose samples were determined. These characteristics were used for thermodynamic analysis of bulk nitration of the entire cellulose sample and local nitration only of amorphous domains (ADs) of cellulose. It was found that the reaction of bulk nitration of cellulose up to a substitution degree (DS) of 1.5 is endothermic and determined primarily by the contribution of the temperature-entropy component to the negative Gibbs potential. However, if DS is higher than 1.5, the bulk nitration becomes exothermic and its feasibility is determined by the impact of enthalpy on the Gibbs potential. In the case of local nitration of cellulose ADs, the main contribution to the Gibbs potential is made by the reaction enthalpy that determines the feasibility of this process. It was shown that with the enhancement in DS of nitrocellulose, the negative value of the Gibbs potential of the reaction increases. Thus, the cellulose nitration to higher DS is thermodynamically favorable. Since the locally nitrated samples are copolymers of amorphous nitrocellulose and crystalline cellulose, they should be significantly less hydrophilic than cellulose. Therefore, it can be expected that the local nitration method will find a wide practical application for inexpensive hydrophobization of cellulose materials.

Influence of degree of substitution on the hydroxypropyl-β-cyclodextrin complexation with rifampicin in water solution: a molecular simulation.

Hydroxypropyl-β-cyclodextrin (HPβCD) is one of the derivatized cyclodextrins most widely used as an excipient in the pharmaceutical industry, for its capacity to improve certain drugs properties. Different configurations of HPβCD are possible depending on the number and location of the 2-hydroxypropyl groups substituted on the glucose rings. Rifampicin has become the most commonly clinically used antibiotic against tuberculosis in recent years, despite its low solubility and variable bioavailability. Different techniques and materials have been proposed to enhance the properties of rifampicin: cyclodextrin complexation is one of them. The van der Waals term was the main contribution to the interaction energy, which then decisively conditioned the complex configurations. The size of rifampicin did not allow the whole molecule to fit into the host. Moreover, interaction energy was much greater when the guest was located near each rim of HPβCD, where rifampicin was partially included in the cavity and formed inclusion complexes. The piperazine tail of rifampicin was included inside the host in minimum energy structures and the guest was situated near the primary rim of HPβCD in most cases, although the complex configurations depended on the degree of substitution. A molecular mechanics simulation based on the GROMOS 53A6 force field was applied in this work to study the inclusion complexes formed by twelve configurations of HPβCD, with different degrees of substitution and rifampicin in water solution. We determined the penetration potential, the complex structures with minimum energies, the possibility of forming inclusion complexes other than those of minimum energies and potential energy surfaces.

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.

Measuring the impact of scheduling overlap and market structure on prices: Evidence from the airline industry

Measuring the degree of competition in markets is important for setting competition and regulatory policies as well as developing management strategies. Commonly used structural indices, such as the HHI, overlook the way in which firms compete and, hence, set their prices in markets. We propose a family of horizontal differentiation measures, which encapsulates firms’ portfolio of products as well as the degree of overlap and substitution between competing services. We term this family of measures Schedule Differentiation Metric or SDM. Applied to aviation markets, we illustrate one instance of SDM and demonstrate the significant importance of SDM in explaining price levels and structure. The information captured by SDM also explains fares across fare percentiles depending on the competing airlines’ business models.

Acetylation of cotton knitted fabrics for improved quick drying after water absorption

Quick drying after water or sweat absorption is an important function of underwear. In this study, the hydroxy groups of cotton knitted fabrics (CFs) were partially acetylated, maintaining the original fabric structure. The following three heterogeneous acetylation processes were used: Ac-I (Ac2O/H2SO4/toluene), Ac-II (Ac2O/H2SO4/AcOH/water), and Ac-III (Ac2O/AcONa) systems (Ac2O, acetic anhydride; AcOH, acetic acid; AcONa, sodium acetate). Acetylated cotton knitted fabrics (AcCFs) with degree of substitution (DS) ≤ 0.5 and yields of > 80% were prepared. AcCFs prepared with the Ac-III system gave high degree of polymerization (DP) values of > 1500, whereas those prepared with the Ac-II system exhibited low DP values of ≤ 400. The moisture contents of AcCFs at 20 °C and 65% relative humidity decreased from 7.1 to 4.7% with increasing DS value up to 0.46; introducing hydrophobic acetyl groups into the CFs decreased their hydrophilic nature. Quick drying similar to that of a polyester fabric was achieved for some of the AcCFs with DS values of < 0.2. When the acetyl groups in the AcCFs were homogeneously distributed across each fiber width (achieved for AcCFs prepared with the Ac-II system), quick drying was evident in the AcCFs. The crystallinities and crystal widths of cellulose I for the AcCFs with DS values of ≤ 0.28 were almost unchanged compared with those of the original CFs. However, neither the crystallinities nor crystal widths of cellulose I were directly related to quick drying after water absorption. Thermal degradation of the AcCFs varied between the acetylation systems, and depended on the DP values and/or the presence of sulfate ester groups in the AcCFs.Graphical

Quaternization of cassava starch and determination of antimicrobial activity against bacteria and coronavirus

This study describes the novel development of quaternized cassava starch (Q-CS) with antimicrobial and antiviral properties, particularly effective against the MHV-3 coronavirus. The preparation of Q-CS involved the reaction of cassava starch (CS) with glycidyltrimethylammonium chloride (GTMAC) in an alkaline solution. Q-CS physicochemical properties were determined by FTIR, NMR, elemental analysis, zeta potential, TGA, and moisture sorption. FTIR and NMR spectra confirmed the introduction of cationic groups in the CS structure. The elemental analysis revealed a degree of substitution (DS) of 0.552 of the cationic reagent on the hydroxyl groups of CS. Furthermore, Q-CS exhibited a positive zeta potential value (+28.6 ± 0.60 mV) attributed to the high positive charge density shown by the quaternary ammonium groups. Q-CS demonstrated lower thermal stability and higher moisture sorption compared to CS. The antimicrobial activity of Q-CS was confirmed against Escherichia coli (MIC = 0.156 mg mL−1) and Staphylococcus aureus (MIC = 0.312 mg mL−1), along with a remarkable ability to inactivate 99% of MHV-3 coronavirus after only 1 min of direct contact. Additionally, Q-CS showed high cell viability (close to 100%) and minimal cytotoxicity effects, guaranteeing its safe use. Therefore, these findings indicate the potential use of Q-CS as a raw material for antiseptic biomaterials.

Ozonation effects on structural and functional characteristics of starch

Ozone oxidation leads to the substitution of hydroxyl groups in the starch molecules with carboxyl or carbonyl groups, thereby increasing the degree of substitution. A thorough examination of how ozone treatment impacts the composition of various cereal crops, including wheat, rice, and maize, is provided. This review explores the repercussions of ozone on starch rheology, germination ability, and storage stability.The present review also explores the textural qualities of food products such as bread, noodles, and cakes prepared with ozonized grains. Ozone treatment is found to significantly reduce swelling capacity and solubility of natural starch, and differential scanning calorimetry reveals that the gelatinization and retrogradation temperature profiles of oxidized starches remain comparable to those of native starch. The evidence that ozone treatment holds substantial promise for enhancing the functionality of starch in various applications while simultaneously upholding the essential standards of food safety has also been explained in detail. The findings synthesized in this review shed light on the intricate interplay between ozone and starch, providing valuable insights for both the scientific community and the food industry.

Drug delivery using reduction-responsive hydrogel based on carboxyethyl-succinoglycan with highly improved rheological, antibacterial, and antioxidant properties

The development of exopolysaccharide-based polymers is gaining increasing attention in various industrial biotechnology fields for materials such as thickeners, texture modifiers, anti-freeze agents, antioxidants, and antibacterial agents. High-viscosity carboxyethyl-succinoglycan (CE-SG) was directly synthesized from succinoglycan (SG) isolated from Sinorhizobium meliloti Rm 1021, and its structural, rheological, and physiological properties were investigated. The viscosity of CE-SG gradually increased in proportion to the degree of carboxyethylation substitution. In particular, when the molar ratio of SG and 3-chloropropionic acid was 1:100, the viscosity was significantly improved by 21.18 times at a shear rate of 10 s−1. Increased carboxyethylation of SG also improved the thermal stability of CE-SG. Furthermore, the CE-SG solution showed 90.18 and 91.78 % antibacterial effects against Escherichia coli and Staphylococcus aureus and effective antioxidant activity against DPPH and hydroxyl radicals. In particular, CE-SG hydrogels coordinated with Fe3+ ions, which improved both viscosity and rheological properties, while also exhibiting reduction-responsive drug release through 1,4-dithiothreitol. The results of this study suggest that SG derivatives, such as CE-SG, can be used as functional biomaterials in various fields such as food, cosmetics, and pharmaceutical industries.