Molecular Weight Distribution Research Articles

Development and attestation of a standard sample of calcium nadroparin

Introduction. The widespread use of heparin preparations for the treatment and prevention of venous thromboembolic complications is known. One of the low molecular weight heparin drugs successfully used in clinical practice is calcium nadroparin. The modern approach to assessing the quality of medicines involves the use of standards, in comparison with which the quality control of the drug is carried out – standard samples (SS). The most important specific parameter in assessing the authenticity of low molecular weight heparins is the characteristic of the fractional composition.Aim. The aim of the work was to develop, attestation and determine the stability during the shelf life of a secondary standard sample to determine the authenticity of calcium nadroparin as part of improving the quality control system of the enterprise with the prospect of creating a domestic pharmacopoeia standard sample.Materials and methods. The object of development and attestation was the standard sample of the enterprise – low molecular weight heparin, obtained on the basis of the Technology implementation center of Siberian state medical university. The certified standard sample was obtained by purification of calcium nadroparin by solid-phase extraction. The completeness of the purification was confirmed by comparing the chromatograms of the purified samples with the chromatograms of the international standard sample. The characteristics of the molecular weight distribution were determined chromatographically. The stability of the certified SSE (the standard sample of the enterprise) was studied under two storage conditions – at a temperature below 8 °C in a dry state for 16 months and in solution at –40 °C for 6 months by evaluating trends in molecular weight distribution.Results and discussion. For each batch of the certified standard sample, the molecular weight and molecular weight characteristics are calculated in 2 parallel definitions, and a representative chromatogram is presented. The values of the relative standard deviation of the molecular weight of the samples and the content of the controlled fractions did not exceed 2.5 %. A detailed analysis of the molecular weight distribution showed the "classical" dependence of RSD (relative standard deviation) from the average value with a significant increase up to 30 % for small fraction values (less than 0.5 %). It was found that during 16 months at a storage temperature below 8 ºC, the molecular weight and molecular weight characteristics of standard samples of low molecular weight heparin did not significantly change. However, in the SSE solution at a storage temperature of minus 40 °C for 6 months, they degraded by more than 10 %.Conclusion. According to the results of the study, a protocol has been developed for obtaining a standard sample of low-molecular-weight heparin for the standardization of the calcium nadroparin substance according to the indicator "molecular weight distribution". The established shelf life of the sample is at least 16 months at temperatures below 8 °C. The stability of solutions of the standard sample at a storage temperature of –40 °C for 3 months is shown.

Electric Field Effect of the Plasma-Initiated Polymerization of Methyl Methacrylate: A Negatively Charged Long-Lived Radical.

Plasma-initiated polymerization (PIP) is generally attributed to a radical process due to its inhibiting property. However, its unique polymerization behaviors like long-lived radical and solvent effect do not comply well with the traditional radical mechanism. Herein, the PIP of methyl methacrylate (MMA) was conducted in a high-voltage DC electric field to investigate the charged nature of its radicals. Consequently, the polymerization presented a preferential distribution of polymers at the anode but not the cathode, revealing the negatively charged nature of the growing radicals. An acceleration phenomenon, accompanied by the growth in molecular weights and the reduction in molecular weight distributions (Ð), was observed at the voltages above 16 kV, suggesting the dissociation of ion pairs of growing radicals. The PIP yielded PMMA with analogous chemical and steric structures to those of PMMA from traditional radical initiation, whether in the presence or absence of the external electric field. This work offers new insights into the PIP of vinyl monomers, wherein a one-electron transfer reaction is inferred to be involved in the monomer activation.

Linking Chemical Structure to the Linear and Nonlinear Properties of Asphalt Binders

The study described in this paper aims to establish the relationship between the chemical composition and rheological properties of asphalt binders in both the linear viscoelastic (LVE) and nonlinear viscoelastic (NLVE) domains. Two asphalt binders with different penetration grades were subjected to four distinct aging treatments of varying severity, resulting in changes in their chemical fingerprints. Chemical characteristics of the asphalt binders were analyzed using thin-layer chromatography (TLC), Fourier Transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Frequency sweep tests were conducted to evaluate the LVE behavior of the asphalt binders, while multiple stress creep recovery (MSCR) tests were employed to assess their NLVE properties. With regard to the LVE properties, rheological index ( R) and zero shear viscosity (ZSV) derived from the Christensen-Anderson-Marasteanu (CAM) model exhibited high correlations with FTIR and molecular weight distribution (MWD) parameters. Additionally, the polydispersity index (PDI) displayed a stronger correlation with LVE-based parameters. Findings from the MSCR tests revealed that the sensitivity of the percentage recovery ( %R) to chemical composition, as opposed to nonrecoverable creep compliance ( Jnr), can be largely attributed to the degree of nonlinearity. Furthermore, it was observed that lower molecular weight molecules exert a greater influence on %R in the nonlinear domain. Finally, it was found that Jnrslope is a more reliable parameter than Jnrdiff for assessing the effects of chemical makeup on stress and temperature sensitivity.

Micronization induced gelatinization of tapioca starch and its effects on starch physicochemical and structural properties.

The vibrating superfine mill (VSM) is a machine that belongs to the micronization technique. In this study, VSM was employed to produce micronized tapioca starch by varying micronization times (15, 30, 45, and 60min). The structural and physicochemical properties of the micronized starch were then examined. Scanning electron microscopy studies revealed that micronized starch was partially gelatinized, and the granule size dramatically increased when micronization time increased. X-ray diffraction patterns showed that the relative crystallinity was decreased from 24.67% (native) to 4.13% after micronization treatment for 15min and slightly decreased after that. The solubility of micronized starch significantly increased as the micronization time increased, which was associated with the destruction of the starch crystalline structure. Differential scanning calorimetry investigations confirmed that micronized starch was "partly gelatinized," and the degree of gelatinization increased to 81.27% when the micronization time was 60min. The weight-average molar mass was reduced by 15.0% (15min), 30.9% (30min), 55.7% (45min), and 70.5% (60min), respectively, indicating that the molecular structure was seriously degraded. The results demonstrated that the physicochemical changes of micronized starch granules were related to the destruction of the starch structure. These observations would provide details on micronized starch and its potential applications. PRACTICAL APPLICATION: These observations would provide details on micronized starch and its potential applications. Moreover, we believe that when the structures of starches were known, it is probable that the effect of VSM on the structural and physicochemical properties change of other starches might be predicted by adjusting the processing time.

Scaling of the linear viscoelasticity of entangled poly(ethylene oxide) aqueous solutions

The dynamic modulus of polymer solutions and melts can be expressed as a universal function of reduced frequency when the modulus is scaled by a characteristic value according to the scaling theory of polymer physics. Although the plot of the scaled modulus as a function of the scaled frequency supports the theory, it suffers from considerable scattered distribution of data points around the hypothetical master curve. Compared with the master curve of the time–temperature superposition (TTS) of polymer melts, the master curve of polymer solutions has poor quality. Furthermore, the scale factors of polymer solutions may not show a clear dependency on molecular weight and concentrations. Experimental errors and molecular weight distribution appear to enhance the inaccuracy of the master curve. Therefore, we apply a global optimization for the superposition of the viscoelastic data of polymer solutions with various molecular weights and concentrations. The global optimization resulted in the superposition of data as accurate as that of TTS. Furthermore, the numerically determined shift factors, which were relative scale factors, showed clear dependences on molecular weight and concentrations. We compared our global optimization with previous scaling methodologies.

Preparation and Characterization of H-Shaped Polylactide.

An H-polymer has an architecture that consists of four branches symmetrically attached to the ends of a polymer backbone, similar in shape to the letter "H". Here, a renewable H-polymer efficiently synthesized using only ring-opening transesterification is demonstrated. The strategy relies on a tetrafunctional poly(±-lactide) macroinitiator, from which four poly(±-lactide) branches are grown simultaneously. 1H NMR spectroscopy, size exclusion chromatography (SEC), and matrix-assisted laser desorption/ionization (MALDI) spectrometry were used to verify the macroinitiator purity. Branch growth was probed using 1H NMR spectroscopy and SEC to reveal unique transesterification phenomena that can be controlled to yield architecturally pure or more complex materials. H-shaped PLA was prepared at the multigram scale with a weight-average molar mass Mw > 100 kg/mol and low dispersity Đ < 1.15. Purification involved routine precipitations steps, which yielded products that were architecturally relatively pure (∼93%). Small-amplitude oscillatory shear and extensional rheology measurements demonstrate the unique viscoelastic behavior associated with the H-shaped architecture.

Physicochemical Properties and Fine Structure of Starch in Jinong Xiangruan 1 and DGR1 Soft Rice Varieties Cultivated in Different Regions of China

Rice, a staple food for billions around the globe, is cultivated in numerous forms. Among them, soft rice is well known, which is characterized by its tender, creamy consistency and desirable texture. In this study, we examined the physicochemical properties and fine structure of starch from two soft rice varieties, Jinong Xiangruan 1 and DGR1, cultivated in different regions in China (Baodi District, Tianjin City; Liaoning Province; and Fengyang City, Anhui Province). The aim was to understand how amylopectin content (AC) influences rice quality. This research aims to bridge the knowledge gap regarding the role of amylopectin in determining rice’s adhesive consistency and viscosity. Significant regional differences were observed in yield components such as the number of grains per panicle, seed setting rates and 1000-grain weight, with Liaoning generally showing higher performance metrics compared to other regions. Physicochemical analysis highlighted that though glue consistency and taste values showed little regional variation, AC significantly influenced rice hardness and viscosity. Rapid Visco Analyzer (RVA) profile analysis further demonstrated distinct differences in viscosity characteristics, underscoring the regional impacts on starch behavior. Additionally, molecular weight distribution and amylopectin chain length analysis, conducted via SEC-MALLS-RI and ICS ion chromatography, revealed notable differences in starch composition across varieties and locations. The findings suggest that environmental conditions play a crucial role in defining starch characteristics and, consequently, the eating quality of rice. This provides valuable insights for breeding high-quality japonica rice with broad adaptability.

Preparation and luminescence properties of polypyrrole-thiophene derivatives

Four kinds of polypyrrole-thiophene derivatives (PPy-Th) are prepared via solution polycondensation using pyrrole, 3-acylpyrrole, and 2-thenaldehyde as monomers. The structure, molecular weight, micromorphology, thermal degradation, ultraviolet-visible absorption, and luminescence performance of the derivatives are investigated by fourier transform infrared (FTIR), hydrogen nuclear magnetic resonance (1HNMR) spectroscopy, gel permeation chromatography (GPC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), ultraviolet-visible (UV-Vis), and fluorescence spectra. FTIR and 1HNMR confirm that the derivatives have been successfully fabricated, and GPC indicates that the derivatives belong to oligomers with narrow molecular weight distribution. For acyl-substituted derivatives, the microstructures are mainly lamellar accumulation. Furthermore, under ultraviolet excitation, the derivatives can produce blue or green light emission, corresponding to the transitions of large π electrons in the conjugated structure of the molecular chains. Especially, the maximum emission wavelengths and Stokes shifts of the acyl-substituted derivatives are markedly larger than that of the non-acyl-substituted derivatives. The fluorescence quantum yield and band gap of the PVT are 4.46% and 2.01 eV, respectively. The fabricated PPy-Th can be used as luminescent materials in the development and application of polymer light-emitting diodes.

Synergy of metallic Co and oxygen vacancy sites in Co/Ce-MOF catalysts for efficiently promoting lignin derived phenols and macromolecular lignin hydrodeoxygenation

The enhanced utilization of biomass-derived chemicals for the generation of high value aromatics through an advanced catalytic strategy has captured considerable attention within the realm of eco-friendly manufacturing. This work presented four innovative three-dimensional rod-shaped mesoporous Ce-based MOF materials, which were coupled with a H-donor solvent to facilitate vanillin hydrodeoxygenation and macromolecular lignin. Under the optimized conditions (30 mg CoCe@C catalyst, 2 MPa N2 pressure, 15 mL isopropanol, 190 °C, and 5 h), the CoCe@C catalyst achieved nearly complete conversion of vanillin and demonstrated 87.8 % selectivity in the hydrogen-donor solvent. The characterization findings suggested that the synergy between metallic Co and oxygen vacancy sites enabled the effective activation of CHO group in vanillin, leading to formation of reactive product MMP. In addition, the optimal CoCe@C catalyst could also achieve macromolecular lignin hydrodeoxygenation to obtain high yield of lignin oil products with narrower molecular weight distribution. This study presented a viable approach for the concurrent utilization of lignin derivatives in the generation of high value fuels and chemicals.

Experimental Tensile Strength Analysis of Different Manufacturer Oring

Importance and Purpose of Tensile Testing on ORings The tensile test on rings and especially on O-rings is primarily carried out for quality assurance reasons. The tensile test provides information about the formulation quality (evaluation of the absolute values, strength of the material, and determination of formulation changes). For example, it is not possible to detect an exchange of the polymer of compounds with different molecular weights and/or a different molecular weight distribution (e.g. highviscosity press mix by low-viscosity spray mix) by infrared spectroscopy (IR), but only by tensile testing and possibly by long-term compression set tests. Furthermore, the tensile test provides information on subsequent changes compared to the prototype condition. The Influence of Processing In the case of some O-rings, due to poor processing, it is not the strength value of the material that is determined, but the lower strength of the joining line (= confluence point of the rubber compound in the production of the O-ring in the injection mold) at which the O-ring tears. This problem depends on the material (e.g. certain acrylate rubbers), the tool and the process parameters. The joining line can usually be detected in advance by a visual and strain test or by relatively large scatter in a tensile test. Typical for the scatter in tensile tests of O-rings are 5-10%-points standard deviation related to the mean value of the elongation at break or the tensile strength. An important characteristic of good processing is the achievement of the optimum degree of vulcanization. However, there is no generally valid optimum, but this must be determined depending on the intended application of the elastomeric component. If, for example, the tear resistance is the most important material parameter for the finished product, a different degree of crosslinking or a different cross linking density must be aimed for than if, for example, a low

Effects of different extraction methods on the structure and function of blackberry seed polysaccharides

SummaryThe different extraction methods including hot‐water extraction, ultrasound‐assisted extraction, and microwave‐assisted extraction, enzyme‐assisted extraction, ultrasound and microwave‐assisted extraction, and ultrasound and enzyme‐assisted extraction (UEE) methods were carried out to extract blackberry seed polysaccharides (BSPs). The extraction yield, structure, antioxidant capacity, and glucometabolic enzyme inhibition activities of BSPs were determined in this work. Extraction methods have no influence on the monosaccharide composition of BSPs but affected the molar ratio of monosaccharides. Fourier transform infrared spectroscopy and X‐ray diffraction results showed that the extraction method cannot effect on the functional groups and crystal forms of BSPs. The findings also revealed that UEE led to the highest BSP extraction yield (4.56%), highest antioxidant capacities, and highest α‐amylase (48.49%) and α‐glucosidase (67.33%) inhibitory rates, which may because of the dispersed molecular weight distribution and loose microstructure of BSPs. These results suggest that UEE may be used in the industry to obtain BSPs with high functional activities.

Using Capillary Electrophoresis to Investigate Protein Conformational and Compositional Heterogeneity.

Detailed insights into protein structure/function relationships require robust characterization methodologies. Free-solution capillary electrophoresis (CE) is a unique separation technique which is sensitive to the conformation and/or composition of proteins, and therefore provides information on the heterogeneity of these properties. Three unrelated, conformationally/compositionally-altered proteins were separated by CE. An electrophoretic mobility distribution was determined for each protein along with its conformational and/or compositional heterogeneity. The CE results were compared with molar mass distributions obtained from size-exclusion chromatography coupled to light scattering (SEC-MALS). Bovine serum albumin multimers and two monomeric species were separated, highlighting variations in conformational/compositional heterogeneity among the multimers. Analysis of yeast alcohol dehydrogenase resolved two monomeric conformers and various tetrameric species, illustrating the impact of zinc ion removal and disulfide bond reduction on the protein's heterogeneity. The apo (calcium-free) and holo forms of bovine α-lactalbumin were separated and differences in the species' heterogeneity were measured; by contrast, the SEC-MALS profiles were identical. Comparative analysis of these structurally unrelated proteins provided novel insights into the interplay between molar mass and conformational/compositional heterogeneity. Overall, this study expands the utility of CE by demonstrating its capacity to discern protein species and their heterogeneity, properties which are not readily accessible by other analytical techniques.

Efficient degradation of vulcanized natural rubber into liquid rubber by catalytic oxidation

Waste tire rubber based on natural rubber (NR) represents an abundant feedstock for the production of valuable products. This study investigated an efficient approach to convert NR vulcanizates into liquid rubber with the number-average molar masses of 1.3 × 104 g/mol. Compared to the anaerobic liquefaction at 300 °C for 3 min, NR vulcanizates were liquefied efficiently at 210 °C for 3 min by thermo-oxidative degradation catalyzed by manganese (II) stearate. The apparent activation energy of the NR degradation reaction decreased from 470.8 kJ/mol to 208.2 kJ/mol with catalysis, which was attributed to the formation of a coordination complex between catalysts and peroxides via the single-electron transfer redox reaction, leading to the catalytic oxidative degradation of NR vulcanizates. The main chain scission and crosslink scission occurred simultaneously during the degradation process, and the main chain scission was the primary catalytic oxidation reaction according to the Horikx theory. In addition, the obtained liquid rubber contained carbonyls, ether linkages, and sulfoxide groups, as proved by FTIR and 13CNMR . The catalytic oxidative degradation mechanism of NR vulcanizates was proposed based on the chemical structure of products and simulation results. The efficient method was proposed to highly facilitate the recycling and valorization of NR-based waste tire rubber.

BaTiO3 catalyzed ultrasonic driven piezoelectric induced miniemulsion atom transfer radical polymerization (Piezo-miniATRP)

Compared with other stimulus such as light and heat, ultrasonic possesses much deeper penetration into tissues and organs and has lower scattering in heterogeneous systems as a noninvasive stimulus, and has already been used as the external stimulus to initiate reversible-deactivation radical polymerization (RDRP). However, the development of efficient ultrasonic drive RDRP in aqueous dispersed media remains a challenge. Here in this work, ultrasonic driven piezoelectric induced miniemulsion atom transfer radical polymerization (Piezo-miniATRP) was performed, with tetragonal BaTiO3 (BTO) nanoparticles as the piezoelectric catalyst. The Piezo-miniATRP exhibited features of controllable and livingness, such as linear increase of molar mass and narrow molar mass distributions (Mw/Mn < 1.30). The effect of different polymerization parameters on the polymerization reaction was investigated, including the amounts of surfactant, CuBr2 and BTO dosages. Excellent temporal control of the polymerization and the chain fidelity of polymers were illustrated by “ON and OFF” experiment and chain extension, separately. This novel BTO catalyzed Piezo-miniATRP process could also be extended to other aqueous dispersion RDRP systems.

Crystallographic Texture Evolution in 3D Printed Polyethylene Reactor Blends.

In this work, crystallographic texture evolution in 3D printed trimodal polyethylene (PE) blends and high-density PE (HDPE) benchmark material were investigated to quantify the resulting material anisotropy, and the results were compared to materials made from conventional injection molded (IM) samples. Trimodal PE reactor blends consisting of HDPE, ultrahigh molecular weight PE (UHMWPE), and HDPE_wax have been used for 3D printing and injection molding. Changes in the preferred orientation and distribution of crystallites, i.e., texture evolution, were quantified utilizing the wide angle X-ray diffraction through pole figures and orientation distribution functions (ODFs) for 3D printed and IM samples. Since the change in weight-average molecular weight (Mw) of the blend was expected to significantly affect the resulting crystallinity and orientation, the overall Mw of the trimodal PE blend was varied while keeping the UHMWPE component weight fraction to 10% in the blend. The resulting texture was analyzed by varying the overall Mw of the trimodal blend and the process parameters in 3D printing and compared to the texture of conventional IM samples. The printing speed and orientation (defined with respect to the axis along the length of the samples) were used as the variable process parameters for 3D printing. The degree of anisotropy increases with an increase in the nonuniform distribution of intensities in pole figures and ODFs. All the highest intensity major texture components in IM and 3D printed samples (0° printing orientation) of reactor blends are observed to have crystals oriented in [001] or [001̅]. Overall, for the same throughput, 3D printed samples in the 0° orientation showed greater texture evolution and higher anisotropy compared to IM samples. Most notably, an increase in 3D printing speed increased the crystalline distribution closer to the 0° direction, increasing the anisotropy, while deviation from this printing orientation reduced crystalline distribution closer to the 0° direction, thus increasing isotropy. This demonstrates that tailoring material properties in specific directions can be achieved more effectively with 3D printing than with the injection molding process. Change in the overall Mw of the trimodal PE blend changed the preferential orientation distribution of the crystal planes to some degree. However, the degree of anisotropy remained the same in almost all cases, indicating that the effect of molecular weight distribution is not as significant as the printing speed and printing orientation in tailoring the resulting properties. The 3D printing process parameters (speed and orientation) were shown to have more influence on the texture than the material parameters associated with the blend.

Enhancing starch functionality through synergistic modification via sequential treatments with cold plasma and electron beam irradiation

The impact of dual sequential modifications using radio-frequency (RF) plasma and electron beam irradiation (EBI) on starch properties was investigated and compared with single treatments within an irradiation dose range of 5–20 kGy. Regardless of sequence, dual treatments synergistically affected starch properties, increasing acidity, solubility, and paste clarity, while decreasing rheological features with increasing irradiation dose. The molecular weight distribution was also synergistically influenced. Amylopectin distribution broadened particularly below 10 kGy. Amylose narrowed its distribution across all irradiation doses. This was due to dominating EBI-induced degradation and molecular rearrangements from RF plasma. With the highest average radiation-chemical yield (G) and degradation rate constant (k) of (2.12 ± 0.14) × 10−6 mol·J−1 and (3.43 ± 0.23) × 10−4 kGy−1, respectively, upon RF plasma pre-treatment, amylose underwent random chain scission. In comparison to single treatments, dual modification caused minor alterations in spectral characteristics and crystal short-range order structure, along with increased granule aggregation and surface irregularities. The synergistic effect was dose-dependent, significant up to 10 kGy, irrespective of treatment sequence. The highest synergistic ratio was observed when RF plasma preceded irradiation, demonstrating the superior efficiency of plasma pre-treatment in combination with EBI. This synergy has the potential to lower costs and extend starch's technological uses by enhancing radiation sensitivity and reducing the irradiation dose.

A New Concept for Interpretation of the Viscoelastic Behavior of Aqueous Sodium Carboxymethyl Cellulose Systems.

Viscoelastic behaviors of aqueous systems of commercially available sodium carboxymethyl cellulose (NaCMC) samples with the degrees of substitution (DS) of approximately 0.68 and 1.3, and the weight-average molar masses (Mw) higher than 200 kg mol-1 dissolved in pure water and aqueous sodium chloride solutions were investigated over a wide concentration (c) range of NaCMC samples. The dependencies of the specific viscosity (ηsp), the average relaxation time (τw), and the reciprocal of the steady-state compliance (Je-1) on c were discussed. The relationships ηsp ∝ c3, τw ∝ c2, and Je-1 ∝ c, characteristic of the rod particle suspensions, were clearly observed in a range lower than the c where the critical gel behavior was observed. Thus, a new concept based on the rheology of rod particle suspensions was employed to interpret the viscoelastic behaviors obtained in the c range. In this context, NaCMC polymer molecules are assumed to behave as extended rod particles with length (L) and diameter (d), including effective electrostatic repulsive distances, due to the dissociation of Na+ in aqueous systems. Thus, the number density of polymer molecules is given to be ν = c/Mw, and viscoelastic parameters such as ηsp, τw, and Je-1 are calculated using the theoretical model for rod particle suspensions proposed by Doi and Edwards. This concept reasonably described not only the viscoelastic data obtained in this study but also those from other groups using NaCMC samples with different DS and Mw values.

RELAXATION BEHAVIOR OF 3D PRINTED NBR-BASED RUBBER O-RINGS AS INNER PART OF ROD SEALS

ABSTRACT The viscoelastic properties of rubber polymer-based compounds are crucial for further applications but challenging in the manufacturing process using additive manufacturing techniques. The fact that the first layer is attached to the printing bed restricts free relaxation after extrusion, that the part shows a strong contraction along the printing direction after release and especially after vulcanization. In this study, the molar mass distribution and acrylonitrile (ACN) content of an NBR-based compound for the fabrication of O-rings for rod seal applications was varied to demonstrate the different degree of contraction resulting from 3D printing. An ACN content of 34% and an average molar mass Mw of 2.47·105 g·mol−1 with a dispersity index D of 2.6 was found to be a suitable compromise between the degree of contraction and compression set as a criterion for the application as O-ring as inner part of rod seals.

Protein from tiger nut meal extracted by deep eutectic solvent and alkali-soluble acid precipitation: A comparative study on structure, function, and nutrition

Protein from tiger nut meal (TNP) performance high nutritional value. This study optimized the extraction parameters for TNP (DES-TNP) using deep eutectic solvent, with HBD: HBA = 5:1, Liquid: Solid = 11:1, and the moisture content was 15 %. A comprehensive comparison was conducted with the protein extracted using alkali-soluble acid precipitation (ASAE-TNP). DES-TNP demonstrated significantly higher purity (76.21 ± 2.59 %) than ASAE-TNP (67.48 ± 1.11 %). Density functional theory confirmed the successful synthesis of DES and its strong interaction with TNP. Moreover, DES-TNP and ASAE-TNP were different in structure (microscopic, secondary, and tertiary) and molecular weight distribution. The discrepancy contributed to the different functional properties, DES-TNP exhibiting better solubility, emulsification and foaming properties at pH13 compared to ASAE-TNP. For nutritional properties, DES-TNP and ASAE-TNP exhibited similar amino acid composition and digestibility, but the total amino acid content of DES-TNP was higher. This study presented a novel method for the extraction and comprehensive utilization of TNP.

Peculiar Behavior of Methyl Methacrylate Emulsion Polymerization-Induced Self-Assembly Mediated by RAFT Using Poly(Methacrylic Acid) Macromolecular Chain Transfer Agent.

Reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of methyl methacrylate (MMA) is successfully performed in water in the presence of a poly(methacrylic acid) (PMAA) macromolecular chain transfer agent (macroCTA) leading to the formation of self-stabilized PMAA-b-PMMA amphiphilic block copolymer particles. At pH3.7, the reactions are well-controlled with narrow molar mass distributions. Increasing the initial pH, particularly above 5.6, results in a partial loss of reactivity of the PMAA macroCTA. The effect of the degree of polymerization (DPn) of the PMMA block, the solids content, the nature of the hydrophobic segment, and the pH on the morphology of the obtained diblock copolymer particles is then investigated. Worm-like micelles are formed for a DPn of PMMA of 20 (PMMA20), while "onion-like" particles and spherical vesicles are obtained for PMMA30 and PMMA50, respectively. In contrast, spherical particles are obtained for the DPns higher than 150. This unusual evolution of particle morphologies upon increasing the DPn of the PMMA block seems to be related to hydrogen bonds between hydrophilic MAA and hydrophobic MMA units.