Quantitative Chemical Profiling of Commercial Glyceride Excipients via 1H NMR Spectroscopy

Saraf, Isha; Kushwah, Varun; Weber, Hedda K.; Modhave, Dattatray; Yeoh, Thean; Paudel, Amrit

doi:10.1208/s12249-020-01883-x

Cited by 11 publications

(8 citation statements)

References 20 publications

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“…As these physical properties are potentially critical to maintain a consistent product performance and stability, it may also be important to have specified values of the individual chemical isomers of MDG to ensure product quality. Our recent publication 34 demonstrated a validated qNMR method to quantify the individual chemical isomers of MDG.…”

Section: Molecularmentioning

confidence: 99%

“…To obtain accurate quantitative results in the smallest possible period of time, a very broad range of relaxation delays and recycling times were tested in the acquisition of the 1 H NMR spectra. As a result of these tests, the acquisition parameters used were: spectral width 7997.6 Hz, relaxation delay 1.0 s, the number of scans 16, acquisition time 2.049 s, and pulse width 45°(for the resonance values taken for the quantification of chemical composition, please refer to our publication 34 ). Preliminary data processing was carried out using VnmrJ 2.2D software.…”

Section: Introductionmentioning

confidence: 99%

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Interplay of Aging and Lot-to-Lot Variability on the Physical and Chemical Properties of Excipients: A Case Study of Mono- and Diglycerides

et al. 2021

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The present study investigates the chemical composition governing the physical properties of mono- and diglycerides (MDGs) at the microstructural level, as a function of aging and lot-to-lot variability. The physical structure of the MDG plays a vital role in ameliorating the emulsion stability and is widely explored in diverse research horizons related to the pharmaceutical, cosmetic, and food industries. In an effort to understand the mechanism of emulsion stabilization, physical properties were extensively evaluated in selective commercial lots to determine if there is a correlation between the chemical composition of MDG and physical properties. The solid state of the MDG samples with different aging profiles was characterized using X-ray scattering, differential scanning calorimetry, attenuated total reflection-Fourier transform infrared spectroscopy, and NMR relaxometry. Moreover, the kinetic aspect of solid-state transformation was also evaluated via treating MDG samples with a heat–cool cycle. The chemical composition of MDGs was quantified using a quantitative NMR (qNMR) method. Interestingly, the X-ray scattering results demonstrated a change in the MDG polymorphic form and an increase in the %β content as a function of aging. The increase in the %β content led to the formation of rigid crystal structures of MDG, as evident from the NMR relaxometry. Chemical quantification of isomeric composition revealed chemical composition change as a potentially critical factor responsible for the altered physical structures of MDG with respect to aging and lot-to-lot variability. The findings correlated the solid-state transformation with the change in the chemical composition of the MDG as a combined effect of aging and lot-to-lot variability. This work serves as a basis to better understand the interdependency of the physicochemical properties of MDG. Furthermore, the present work can also be used as guidance for setting up the specifications of MDG, as per the required polymorphic form for a multitude of applications.

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Section: Molecularmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Interplay of Aging and Lot-to-Lot Variability on the Physical and Chemical Properties of Excipients: A Case Study of Mono- and Diglycerides

et al. 2021

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“…The reconstituted solution was filtered by a piece of defatted cotton and at least 500 μL of the subsequent filtrate was transferred to a 5 mm NMR tube. The 1 H-NMR spectra were recorded on a 600 MHz NMR spectrometer (Bruker Ascend, Karlsruhe, Germany) with a cryoprobe by employing the following parameters: temperature at 298K, relaxation delay = 40 s, number of scans = 64, number of dummy scans = 16, acquisition time = 8.41s (128K points), and spectra width 13.0 ppm centered at 6.2 ppm ( Saraf et al, 2021 ).…”

Section: Methodsmentioning

confidence: 99%

In situ Chemical Profiling and Imaging of Cultured and Natural Cordyceps sinensis by TOF-SIMS

Liu

Jiang

et al. 2022

Front. Chem.

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Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a sensitive surface analytical technology, which can simultaneously acquire diverse chemical components and their precise locations on the surfaces of samples without any requirements for chemical damage pretreatments or additional matrices. Commonly, the quality control of TCMs (traditional Chinese medicines) is limited by the qualitative and quantitative evaluations of the specifically extractive constituents. In this study, a practical sample preparation strategy named two-layered media embedding sample preparation was developed to obtain ideal freezing sections of dried materials of Cordyceps sinensis. Meanwhile, the well-established sample preparation method was applied for in situ chemical profiling and imaging of natural (NCS) and cultured Cordyceps sinensis (CCS) by using TOF-SIMS. More than 200 components were tentatively identified and imaged in NCS and CCS at the same time. Mass spectrometry imaging revealed that most components have even distributions in caterpillars of Cordyceps sinensis, while TAGs, DAGs, MAGs, and FAs only have distributions outside caterpillars’ digestive chambers. This is the first time that components were in situ imaged for Cordyceps sinensis to exhibit the chemical distributions which have never been achieved by other analytical techniques so far. In addition, chemometrics was used to simplify and explain the massive TOF-SIMS mass data sets, which revealed the high chemical similarity between CCS and NCS. Furthermore, the relative quantification of TOF-SIMS data showed that CCS has comparable proportions of amino acids, nucleosides, monosaccharides, sphingolipids, sterols and other principles to NCS except for fatty acids, glycerides and glycerophospholipids. The higher amounts of TAGs and DAGs in CCS were confirmed by quantitative 1H-NMR, indicating reliable relative quantification of TOF-SIMS. In general, our research developed a novel approach of TOF-SIMS for in situ chemical analysis of TCMs, and its successful application in comparative study of CCS and NCS suggested that TOF-SIMS is an advanced and promising analytical technology for the research of TCMs.

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“…High-resolution 1 H NMR spectra of isolated type-1 and type-2 crystals dissolved in CDCl 3 are shown in Figure 3. We assigned relevant peaks in the acquired NMR spectra from MDG by using a previously published reference NMR spectra of 1-MG, 2-MG, 1,2-DG, 1,3-DG, and TG by Saraf et al 39 In Figure 3, overlapping peaks in the range 0.5−2.6 ppm arise from the acyl groups, residual fatty acid, and residual PO chains and, therefore cannot be used to identify different glycerides. However with age and exposure to high temperatures.…”

Section: Crystallization Of Mdg In Paraffinmentioning

confidence: 99%

Crystallization and Rheology of Mono- and Diglycerides and Their Role in Stabilization of Emulsion Droplets in Model Topical Ointments

et al. 2022

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The crystallization behavior of commercial monoand diglycerides (MDG) in paraffin oil is studied to develop an indepth understanding of the polymorphic transitions useful for the physical stability of petroleum oil-based topical emulsions. Optical microscopy and differential scanning calorimetry measurements showed the formation of plate-like and spherulite crystals at high and low temperatures, in sequence, while cooling a solution of MDG dissolved in oil. High-resolution NMR and X-ray scattering demonstrate that 1-monoglycerides (mixture of 1-glyceride monostearate and 1-glyceride monopalmitate) cocrystallize to an inverse-lamellar structure (L α polymorph) that mainly forms platelike crystals at a higher temperature. The L α polymorph is seen to exist up to room temperature during the cooling process. At lower temperatures, 1,3-diglycerides (mixture of 1,3-glyceryl distearate and 1,3-glyceryl dipalmitate) crystallize into β-polymorphs that form spherulites. The spherulites tend to assemble into elongated strands via aggregation, leading to the formation of a percolating network structure. The sizes of both types of crystals decrease with an increasing cooling rate, leading to a higher mechanical modulus due to the increased network connectivity of spherulites. In an emulsion, monoglycerides in the form of L α polymorphs having plate-like crystal morphology show a higher affinity to the polar liquid/oil interface, thereby providing better interfacial stability compared to the spherulitic β-polymorphs. However, diglycerides in the form of spherulites form bulk network structures which provide network stabilization to the suspended droplets. This work demonstrates that MDG, a commercially available ingredient that combines the differential functionality of monoglycerides and diglycerides, is an effective, bifunctional, emulsifying agent for petrolatum-based topical emulsions.

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Quantitative Chemical Profiling of Commercial Glyceride Excipients via 1H NMR Spectroscopy

Cited by 11 publications

References 20 publications

Interplay of Aging and Lot-to-Lot Variability on the Physical and Chemical Properties of Excipients: A Case Study of Mono- and Diglycerides

Interplay of Aging and Lot-to-Lot Variability on the Physical and Chemical Properties of Excipients: A Case Study of Mono- and Diglycerides

In situ Chemical Profiling and Imaging of Cultured and Natural Cordyceps sinensis by TOF-SIMS

Crystallization and Rheology of Mono- and Diglycerides and Their Role in Stabilization of Emulsion Droplets in Model Topical Ointments

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