Pulsed Nuclear Magnetic Resonance Research Articles

Re-examination of the intumescence mechanism of fire retarded PP with APP/pentaerythritol/zeolite-4A using advanced spectroscopic techniques

The mixture of ammonium polyphosphate (APP) and pentaerythritol (PER) is a very efficient flame retardant (FR) intumescent system suitable for polyolefins such as polypropylene (PP). The mechanisms of intumescence of this FR system in this polymer was investigated using different spectroscopic techniques including continuous wave (CW) electron paramagnetic resonance (EPR) spectroscopy and solid state nuclear magnetic resonance (NMR) technique. In this work, the intumescence mechanism of PP/APP/PER formulations with and without 4A is revisited. The intumescent system was in-depth investigated using NMR, CW EPR and pulsed EPR. The CW EPR technique confirmed that free radicals are mainly generated during the intumescence of the system between 250 and 350 °C. Thanks to the pulsed EPR and solid state NMR, it was evidenced that a key structural shift from a predominantly carbonaceous residue to a predominantly phosphorated residue. Besides, it was also evidenced that zeolite 4A totally collapses during extrusion of PP/APP/PER formulations reacting with APP to generate aluminophosphates. Then, silicophosphates are generated between 350 and 400 °C. Both alumino- and silicophosphates contribute to protect aromatic structures in the residue at high temperatures.

Physicochemical and digestive properties of curcumin stabilized by quaternized chitosan/sodium alginate nanoemulsion coatings

Curcumin (Cur) is a bioactive substance, but its instability limits its use in the food system. Thus, a new polysaccharide-based coating is developed by combining quaternized chitosan (QCS) with sodium alginate (SA) in this study to improve the bioaccessibility and stability of Cur. The microstructure of the emulsion was characterized by fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and low-field pulsed nuclear magnetic resonance imaging (LF-NMR). The thermal, ionic strength, and pH stability of emulsions were measured. Results indicate that QCS/SA (1:1)-Cur is more stable than other three nanoemulsion systems and the encapsulation rate of which reaches 90.62 %. It also shows higher stability in gastric fluid, excellent bioaccessibility and FFAs in intestinal fluid, as well as significant antibacterial property, antioxidant activity and water dispersibility. This study introduces a new method for obtaining stable, functional Cur-coated systems for food applications.

Experimental investigations of the shear strength and deformation behavior of a frozen unsaturated silt

There are limited studies in literature with respect to the deformation and shear strength behavior of frozen unsaturated soils that consider sensitive changes in temperatures below 0 °C. For this reason, the focus of the present study is directed towards investigating the shear strength and deformation behavior of a frozen unsaturated silt. As a part of the study, one-dimensional freezing tests were performed on compacted silt samples with various initial water contents and dry densities. The pulsed nuclear magnetic resonance (P-NMR) method was used to obtain distribution of unfrozen water content of silt samples; this information was used to explain the deformation behavior during freezing. The volume change behavior in unsaturated soils due to freezing can be associated to three primary factors: expansion caused by the ice-water phase transition and shrinkage induced by ice-cementation and dehydration. A critical water saturation was also observed at which the frost heave is minimum, or no volume change occurs. In addition, conventional direct shear tests were performed on compacted unsaturated silt samples both in frozen and unfrozen conditions to determine and quantify the shear strength contribution arising from the different cohesion components. The investigations in this study provide valuable information that can be used in rational explanation of the strength and deformation behavior of unsaturated frozen soils.

The influence of planting density on the oil and fatty acids content of soybean in hydroponic and soil conditions of the Ararat Valley

Background: Plant seed oils are major renewable resources from nature that can be used in multiple applications. Oils and fats are a vital component of human diets. About 1/3 of the daily energy requirements of a healthy diet come from fats. Each branch of the food industry has its own demands for the fatty acid composition of seed oils. High amounts of polyunsaturated fatty acids are a requirement of healthy diets. However, food manufacturers need highly saturated fatty acids because they need oil that is resistant to high temperatures and oxidation. Soybean oil is second only behind palm oil as the most commercially abundant plant oil globally. Soybean has been recognized for its agricultural importance and their various positive effects on human health. Objective: to identify the quantitative changes of soybean fatty acids depending on the planting density and growing conditions in the Ararat Valley of Armenia. Methods: Soybean was grown in hydroponic and soil conditions of the Ararat Valley. The seeds were sown in the middle of April. Experiments were carried out in hydroponic equipment and soil with different planting densities (30, 50, 70 and 90 plants/m2). The oil content was measured by using the pulsed nuclear magnetic resonance method. The composition of fatty acids in seed oil was analyzed by chromatographic method on "Chromatec Crystal 5000" GC. Results: Oil content ranged from 19.6% to 24.4% in all variants. The maximum content was registered in soil with 30 plant/m2 planting density. Linoleic acid content ranged from 46.35 to 51.28% of the total fatty acid content, regardless of planting density and growing media. The content of linolenic acid ranged from 4.13 to 5.11% in all variants. The maximum content of ω-3 and the minimal content of ω-9 was recorded in hydroponics at 30 plants/m2 planting density. The highest percentage of stearic acid was observed in the soil variant with a planting density of 30 plants/m2. Interestingly, the variants did not differ in the total content of the 5 main fatty acids (98.84-98.95%). Growing medium had no significant effect on the total saturated fatty acids content; in all variants it ranged from 14.29% to 14.83%. Total unsaturated fatty acids content ranged from 85.2% to 85.7%. The hydroponic variant with a planting density of 30 plants/m2 had the lowest ratio of ω-6 and ω-3 fatty acids (10:1). Conclusion: Planting density and growing media had a significant influence on the content of monounsaturated and polyunsaturated fatty acids. Under hydroponic conditions the lowest content of monounsaturated and the highest content of polyunsaturated fatty acids were observed at the lowest planting density (30 plants/m2), which can be used as a functional food for daily consumption. Keywords: Glycine max (L.) Merr., soilless culture, ω-3, ω-6, ω-9, saturated acids.

On the use of dioxane as reference for determination of the hydrodynamic radius by NMR spectroscopy

Measuring the compaction of a protein or complex is key to our understanding of the interactions within and between biomolecules. Experimentally, protein compaction is often probed either by estimating the radius of gyration (Rg) obtained from small-angle x-ray scattering (SAXS) experiments or the hydrodynamic radius (Rh) obtained, for example, by pulsed field gradient NMR (PFG NMR) spectroscopy. PFG NMR experiments generally report on the translational diffusion coefficient, which in turn can be used to estimate Rh using an internal standard to account for sample viscosity and uncertainty about the gradient strength. 1,4-Dioxane is one such commonly used internal standard, and the reference value of Rh is therefore important. We have revisited the basis for the commonly used reference value for the Rh of dioxane (2.12 Å) that is used to convert measured diffusion coefficients into a hydrodynamic radius. We followed the same approach that was used to establish the current reference value by measuring SAXS and PFG NMR data for a set of seven different proteins and using these as standards. Our analysis shows that the current Rh reference value for dioxane Rh is underestimated, and we instead suggest a new value of 2.27 ± 0.04 Å. Using this updated reference value results in a ∼7% increase in Rh values for proteins whose hydrodynamic radii have been measured by PFG NMR. These results are particularly important when the absolute value of Rh is of interest such as when determining or validating ensemble descriptions of intrinsically disordered proteins.

Towards shorter composite 180° refocusing pulses for NMR

Novel composite 180° pulses are designed for use in nuclear magnetic resonance (NMR) and verified experimentally using solution-state 1H NMR spectroscopy. Rather than being constructed from 180° pulses (as in much recent work), the new composite pulses are constructed from 90° pulses, with the aim of finding sequences that are shorter overall than existing equivalents. The primary (but not exclusive) focus is on composite pulses that are dual compensated – simultaneously broadband with respect to both inhomogeneity of the radiofrequency field and resonance offset – and have antisymmetric phase schemes, such that they can be used to form spin echoes without the introduction of a phase error. In particular, a new antisymmetric dual-compensated refocusing pulse is presented that is constructed from ten 90° pulses, equivalent to just five 180° pulses.

Diffusion and structure of propylene carbonate-metal salt electrolyte solutions for post-lithium-ion batteries: From experiment to simulation.

The diffusion of cations in organic solvent solutions is important for the performance of metal-ion batteries. In this article, pulsed field gradient nuclear magnetic resonance experiments and fully atomistic molecular dynamic simulations were employed to study the temperature-dependent diffusive behavior of various liquid electrolytes representing 1M propylene carbonate solutions of metal salts with bis(trifluoromethylsulfonyl)imide (TFSI-) or hexafluorophosphate (PF6-) anions commonly used in lithium-ion batteries and beyond. The experimental studies revealed the temperature dependence of the diffusion coefficients for the propylene carbonate (PC) solvent and for the anions following an Arrhenius type of behavior. It was observed that the PC molecules are the faster species. For the monovalent cations (Li+, Na+, K+), the PC solvent diffusion was enhanced as the cation size increased, while for the divalent cations (Mg2+, Ca2+, Sr2+, Ba2+), the opposite trend was observed, i.e., the diffusion coefficients decreased as the cation size increased. The anion diffusion in LiTFSI and NaTFSI solutions was found to be similar, while in electrolytes with divalent cations, a decrease in anion diffusion with increasing cation size was observed. It was shown that non-polarizable charge-scaled force fields could correspond perfectly to the experimental values of the anion and PC solvent diffusion coefficients in salt solutions of both monovalent (Li+, Na+, K+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations at a range of operational temperatures. Finally, after calculating the radial distribution functions between cations, anions, and solvent molecules, the increase in the PC diffusion coefficient established with the increase in cation size for monovalent cations was clearly explained by the large hydration shell of small Li+ cations, due to their strong interaction with the PC solvent. In solutions with larger monovalent cations, such as Na+, and with a smaller solvation shell of PC, the PC diffusion is faster due to more liberated solvent molecules. In the salt solutions with divalent cations, both the anion and the PC diffusion coefficients decreased as the cation size increased due to an enhanced cation-anion coordination, which was accompanied by an increase in the amount of PC in the cation solvation shell due to the presence of anions.

Study of magnetic phase transitions by helium-3 in DyF3 nanoparticles

The spin kinetics of liquid 3He in contact with a mixture of LaF3 (99.7 %) and DyF3 (0.3 %) powders at temperatures of 1.5–3 K was studied by pulsed nuclear magnetic resonance. DyF3 particles have ellipsoidal shape and average size 225 × 153 nm with the magnetic phase transition at temperature Tc = 2.45 K. The temperature dependence of the longitudinal and transverse magnetization relaxation rates of 3He nuclei with a mixture of LaF3 and DyF3 powders has a broad maximum near Tc, which is related to the magnetic phase transition. It is shown that the adsorbed layer of 3He is extremely sensitive to magnetic phase transitions. Preplating the particles surface with adsorbed nitrogen layers allowed to vary the distance from 3He nuclei to the surface of particles in a controlled way. Calculations of the nuclear magnetic relaxation rates with a change in the distance of helium-3 from the particle surface have been carried out, which is in good agreement with experimental data. It was shown that helium-3 is extremely sensitive to surface magnetism and can be used to study surface effects and surface magnetism.

Diffusion mechanism explorations on the sustainable warm mix asphalt and synchronous rejuvenated SBS-modified asphalt binder using the free volume theory

The blending degree, dominated by the diffusion process between virgin and rejuvenated asphalt, profoundly affects the performance of recycled mixtures. However, research on the blending degree in Warm Mix Asphalt (WMA) containing Styrene-Butadiene-Styrene-modified asphalt (SBSMA) mixtures remains relatively underexplored despite its significant impact on pavement performance. To this concern, a predictive model for characterizing the diffusion behavior of the WMA modified SBSMA and synchronous rejuvenated SBSMA was developed based on the free volume theory, which was validated by the pulsed field gradient nuclear magnetic resonance test. Based on the predicted diffusion coefficients, the influences of WMA additives, rejuvenator types, and temperatures on diffusion behavior were systematically investigated. Results indicated that the diffusion coefficients were affected by the interaction of WMA additives, rejuvenator types, and temperatures. The presence of the WMA additive and the increase in diffusion temperature were able to improve the blending degree by increasing the diffusion coefficient. Rebalancing the unstable colloidal structure of SBSMA can enhance the diffusion coefficient of the WMA modified SBSMA twice than that of untreated one. After further reconstruction of small SBS fragments into the triblock copolymers, the blending between the WMA modified SBSMA and synchronous rejuvenated SBSMA was completed in the form of mutual diffusion, showing the highest diffusion coefficients (10−7).

Water adsorbed in a commercial carbon: Role of nanostructure and surface chemistry

This article investigates the spatial disposition and mobility of water molecules adsorbed at room temperature in a commercial activated amorphous carbon. Previous wide-angle X-ray scattering measurements are re-examined, together with new observations, in particular by high-resolution transmission electron microscopy, high field solid-state nuclear magnetic resonance, and pulsed field gradient nuclear magnetic resonance. The dry samples are composed largely of deformed turbostratic oxidized graphitic sheets, yielding an array of slit-pores with an average spacing of more than 0.4 nm. All the adsorbed water remains close to the aromatic substrate, and the landscape of adsorption sites is extremely heterogeneous. The water molecules are mobile. Water is initially adsorbed in small confined sites. With increasing relative humidity these develop into clusters that are spatially correlated, which spread and merge, on both sides of the graphitic sheets.

1H pulsed NMR measurement of reactivity of silane coupling agents for conservation of cultural heritage sites

AbstractThe network structure and reactivity of suitable restoration agent consisting of silane coupling agents (SCAs) of the brittle walls of a cultural heritage site located underground in a desert area in Egypt were investigated using 1H pulsed nuclear magnetic resonance (pulse NMR). It should possess both high coagulation strength and ductility to ensure that it can withstand an earthquake; it should also contain ethoxy rather than methoxy groups, which generate toxic methanol. The solidification rate for the SCA or oligomer with ethoxy groups was lower than those with methoxy groups; however, the final polycondensates showed the same relaxation time (hardness). The difference spectrum was developed newly to analyze the network structure combined higher strength and ductility. The distribution of crosslinking degree of such polycondensates was narrow, and the amount of lower crosslinking degree was small. On the other hand, the distribution was wide in the polycondensates with ductility but lower strength. From the compression tests of model sand solidified with the restoration agent for both methoxy and ethoxy types showed the superior properties combined higher strength and ductility. The pulse NMR experiment was useful for estimating the solidification rate and the network structure.

Gas self-diffusion in different local environments of mixed-matrix membranes as a function of UiO-66-NH2 metal–organic framework loading

This work focuses on quantification of microscopic self-diffusion of gas molecules in mixed-matrix membranes (MMMs) formed by dispersing UiO-66-NH2 metal–organic framework (MOF) crystals in 6FDA-Durene polyimide. Self-diffusion measurements were performed by 13C pulsed field gradient nuclear magnetic resonance (PFG NMR) for pure CO2 and CH4 with the spatial resolution in the range of 0.5–24 μm and for different MOF loadings between 12.5 and 50 weight percent. Diffusion measurements performed for each gas in the MMM with the lowest MOF loading of 12.5 weight percent yielded a single diffusivity for all measured diffusion times corresponding to a diffusion under the condition of a fast exchange between the UiO-66-NH2 crystals and the surrounding polymer phase. However, as the UiO-66-NH2 loading was increased, two molecular ensembles were observed for both CO2 and CH4: 1) an ensemble corresponding to diffusion inside UiO-66-NH2 crystals and through the MOF–polymer interfaces, and 2) an ensemble corresponding to diffusion mainly in the polymer phase of the MMMs. This behavior can be explained by the formation of MOF clusters at higher MOF loadings. Quantification of the intra-cluster diffusivity, average cluster size, and the dependence of these properties on the MOF loading are presented and discussed. The reported measurements can serve as a framework to quantify discrete microscopic diffusion characteristics and sizes of interconnected MOF clusters in MMMs as MOF loading increases to reach the desired outcome of gas percolation over a spanning MOF cluster, viz a cluster of interconnected MOF crystals spanning an entire MMM.

Insight into the molecular basis of the soluble storage-state to fibrous-state structural transformation of spider pyriform silk

Pyriform (or piriform) silk is a fibrous spider silk used in a composite material to attach web silks to substrates and disparate silk types together. Argiope argentata pyriform silk is formed from a protein with a central repetitive region consisting of a 234-amino acid unit (the "Py unit") repeated 21 times. We have previously shown that the Py unit behaves modularly, with a structured core of 6 α-helices that retains its structuring upon truncation of N- and C-terminal intrinsically disordered segments. Here, we apply solution-state nuclear magnetic resonance (NMR) spectroscopy to investigate the structured core of the Py unit. Based on 15N spin relaxation measurements and reduced spectral density mapping at two field strengths, the α-helical core of the Py unit exhibits minimal backbone motion beyond the tumbling of the globular domain except for one interhelical linker that exhibits a notably higher degree of dynamics. Evaluation of rotational diffusion based on 15N spin relaxation and translational diffusion by pulsed field gradient diffusion NMR demonstrates that the core of the Py unit behaves as a compact structure, with hydrodynamic behaviour consistent with a well-packed protein. Pyriform silk protein undergoes a structural transformation upon conversion from the soluble-state to the fibrous-state, with a loss of αhelical content and gain of β-sheet content. The more dynamic segment we observe midway through the structured core of the Py core, especially in the context of the intrinsically disordered segments that flank the core, would provide an initiation point for decompaction, structural transformation, and/or intermolecular interactions.

Probing Self-Diffusion of Guest Molecules in a Covalent Organic Framework: Simulation and Experiment.

Covalent organic frameworks (COFs) are a class of porous materials whose sorption properties have so far been studied primarily by physisorption. Quantifying the self-diffusion of guest molecules inside their nanometer-sized pores allows for a better understanding of confinement effects or transport limitations and is thus essential for various applications ranging from molecular separation to catalysis. Using a combination of pulsed field gradient nuclear magnetic resonance measurements and molecular dynamics simulations, we have studied the self-diffusion of acetonitrile and chloroform in the 1D pore channels of two imine-linked COFs (PI-3-COF) with different levels of crystallinity and porosity. The higher crystallinity and porosity sample exhibited anisotropic diffusion for MeCN parallel to the pore direction, with a diffusion coefficient of Dpar = 6.1(3) × 10-10 m2 s-1 at 300 K, indicating 1D transport and a 7.4-fold reduction in self-diffusion compared to the bulk liquid. This finding aligns with molecular dynamics simulations predicting 5.4-fold reduction, assuming an offset-stacked COF layer arrangement. In the low-porosity sample, more frequent diffusion barriers result in isotropic, yet significantly reduced diffusivities (DB = 1.4(1) × 10-11 m2 s-1). Diffusion coefficients for chloroform at 300 K in the pores of the high- (Dpar = 1.1(2) × 10-10 m2 s-1) and low-porosity (DB = 4.5(1) × 10-12 m2 s-1) samples reproduce these trends. Our multimodal study thus highlights the significant influence of real structure effects such as stacking faults and grain boundaries on the long-range diffusivity of molecular guest species while suggesting efficient intracrystalline transport at short diffusion times.

The impact of magnesium content on lithium-magnesium alloy electrode performance with argyrodite solid electrolyte

Solid-state lithium-based batteries offer higher energy density than their Li-ion counterparts. Yet they are limited in terms of negative electrode discharge performance and require high stack pressure during operation. To circumvent these issues, we propose the use of lithium-rich magnesium alloys as suitable negative electrodes in combination with Li6PS5Cl solid-state electrolyte. We synthesise and characterise lithium-rich magnesium alloys, quantifying the changes in mechanical properties, transport, and surface chemistry that impact electrochemical performance. Increases in hardness, stiffness, adhesion, and resistance to creep are quantified by nanoindentation as a function of magnesium content. A decrease in diffusivity is quantified with 6Li pulsed field gradient nuclear magnetic resonance, and only a small increase in interfacial impedance due to the presence of magnesium is identified by electrochemical impedance spectroscopy which is correlated with x-ray photoelectron spectroscopy. The addition of magnesium aids contact retention on discharge, but this must be balanced against a decrease in lithium diffusivity. We demonstrate via electrochemical testing of symmetric cells at 2.5 MPa and 30∘C that 1% magnesium content in the alloy increases the stripping capacity compared to both pure lithium and higher magnesium content alloys by balancing these effects.

A study of helium-3 nuclear magnetic relaxation mechanism in contact with 20 nm DyF3 nanoparticles

The spin kinetics of adsorbed and liquid 3He in contact with a mixture of LaF3 (99.67 %) and DyF3 (0.33 %) 20 nm powders at temperatures of 1.5–4.2 K in magnetic fields up to 505mT was studied by pulsed nuclear magnetic resonance (NMR). Two-component of nuclear magnetic relaxation was observed in the experiment and theoretical relaxation model was proposed. The possible explanation of this phenomena can be carried out by a model that consider the exchange of magnetization of helium-3 nuclei located in the adsorbed layer and in the bulk of the liquid. The proposed relaxation model can be applied to other systems with the strong influence of adsorbed layer.

Exploring Crystal-Phase Molecular Dynamics of the Low-Viscous Mesogen 6CHBT: A Combined FFC and High-Field NMR Relaxometry Investigation.

The molecular dynamics study of thermotropic mesogens exhibiting the crystal phases is valuable in unraveling the complex global (collective) and local (noncollective) motions executed by liquid crystal molecules, which would further advance the existing knowledge on orientationally disordered crystalline (ODIC) phases. Toward the fulfillment of such a task, a combined nuclear magnetic resonance (NMR) relaxometry approach employing the fast field cycling (FFC) NMR (10 kHz-30 MHz) and high-field pulsed NMR (400 MHz) techniques is utilized to sample the broad frequency range offered by molecular motions in the crystal phase of 4-(trans-4'-n-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT). The validity of the observed relaxation data is tested and interpreted by the Bloembergen-Purcell-Pound (BPP) model involving the superposition of four mutually independent Lorentzian spectral densities, reflecting molecular dynamical processes on different time scales. The salient feature of the detailed analysis reveals that the lengthening of temporal dynamics in the crystal phase due to molecular rotations by jumps, which are of intermolecular origin, is evident and further supports the presence of collective-like local dynamics. The analysis does permit decoupling of the molecular reorientations about their short axes (∼100 ns) as well as long axes (∼50 ns) and methyl group rotations (∼0.5 ns) on distinct time scales. The activation energies for reorientations about the short axes and methyl group rotations are found to be 27.3 ± 2.7 and 15.8 ± 1.1 kJ/mol, respectively. The fast methyl rotations in the crystal phase of 6CHBT obtained from FFC NMR are further well complemented by high-field NMR, where 1H NMR line shapes are relatively narrow when compared to those of the nematic phase.

Analysis of complex mixtures with benchtop nuclear magnetic resonance: Solvent suppression with T2 and diffusion filters.

Benchtop nuclear magnetic resonance (NMR) spectrometers are being employed in a wide variety of applications from undergraduate teaching and research in academia to quality control and process monitoring in industrial settings. Incorporating benchtop NMR in some of these applications presents opportunities for new practical uses of the technology and challenges that truly test the capabilities of compact NMR spectrometers. For instance, the use of protonated solvents in manufacturing or process monitoring requires separating and quantitating the analyte signals of interest from the strong (overwhelming) response from the solvents. Furthermore, due to the lower field strength available with permanent magnet spectrometers, the NMR spectra of complex mixtures can be more difficult to analyze due to partial or complete signal overlap. To address some of these challenges and to extend the range of applications of benchtop NMR, we investigate NMR techniques that enable quantitative analysis of different components in mixtures. These pulse sequences can be used to suppress one or multiple solvent peaks, to filter out signals by spin-spin relaxation time (T2), or to separate signal components by a molecule's diffusion coefficient (NMR diffusometry). In this paper, we discuss quantitative analysis of excipients in buffers for therapeutic proteins to highlight the usefulness of these NMR pulse sequences in the analysis of complex samples with benchtop NMR spectrometers.

Understanding the rheological properties from linear to nonlinear regimes and spatiotemporal structure of mixed kappa and reduced molecular weight lambda carrageenan gels

Blends of different carrageenan types have proven to be useful in tuning carrageenan gels' rheological properties. However, understanding the influence of a reduced molecular weight on the gelation of mixed carrageenan gels is still limited. Here, the gelation of mixed kappa-(KC) and reduced molecular weight lambda-(LC) carrageenan systems at different mixing ratios was evaluated using rheology from linear to nonlinear regimes via large amplitude oscillatory shear (LAOS), small-angle X-ray scattering (SAXS), pulsed nuclear magnetic resonance (NMR) and particle tracking. A single-step increase in moduli was seen for mixed kappa-lambda carrageenan (KCLC) gels with decreasing temperature while LC demonstrated nongelling behavior. The LAOS response of KCLC mixed gels showed the characteristic signature of strain-stiffening corresponding to the difference in the size and dynamics of the aggregates. The cross-sectional size revealed by SAXS and dynamics of the aggregates revealed by pulsed-NMR demonstrate that KCLC gels has higher segmental mobility and formed small aggregates that reduce with decreasing the KC fraction whereas pure KC gels formed large and rigid aggregates. Thus, the spatiotemporal features of the aggregates are considered to be the origin of the strain-stiffening in mixed gels under large deformation. Moreover, the microscopic properties of the KCLC gels evaluated using particle tracking revealed a homogenous network suggesting the formation of a swollen KC network in the LC solution. Hence, our findings provide insights into the rheological behavior and network structure design of KC and reduced molecular weight LC mixed gels.

Characterization of Cocoa Butter Replacer Developed from Agricultural Waste of Mango Kernel and Rice Bran

The unique physicochemical properties of cocoa butter (CB) provide the desired physical properties in chocolate. Due to its high demand, increasing price, and limited supply, people are looking for cocoa butter alternatives (CBAs). In this study, CBA was prepared using enzymatic acidolysis on mango kernel fat stearin with rice bran oil blend. Reaction parameters (time (4-8 h), temperature (50-70°C), and enzyme load (6-10%, w/w)) were optimized using response surface methodology to produce similar triacylglycerol (TAG) composition as CB, and the properties of different proportions of CBAs with CB were assessed. Triacylglycerol content, melting behavior, solid fat content, crystal morphology, and polymorphism were investigated by high-performance liquid chromatography, differential scanning calorimetry, pulse nuclear magnetic resonance, polarized light microscopy, and X-ray diffraction, respectively. The optimum reaction condition to produce comparable percentages of monounsaturated TAGs in the final product was 8 h time, 8% enzyme load, and 50°C. After blending of CBA with CB in different proportions, no significant differences in terms of polymorphism, melting profile, and solid fat content were observed up to 20% CBA replacement. However, the TAG profile was similar up to 10% replacement of CB with CBA. In summary, the enzymatically produced CBA can potentially be used as a cocoa butter replacer up to 20% in the confectionery industry.