New validation of molecular mass measurements by means of 2D DOSY 1H NMR experiments: Application to surfactants

Hologne, Maggy; Gaubert, Alexandra; Sanglar, Corinne; Bordes, Claire; Casabianca, Hervé

doi:10.1016/j.crci.2014.05.008

Cited by 6 publications

(2 citation statements)

References 25 publications

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“…Internal diffusion standards were trimethylsilylpropionate (TSP), formic acid, and salicylic acid. All diffusion values were referenced to TSP [ 25 , 26 , 27 ]. ( Bottom ) DOSY-estimated MW vs. Actual MW for observed compounds.…”

Section: Figurementioning

confidence: 99%

Using Nuclear Magnetic Resonance to Troubleshoot a Stability Issue in a Real-World Formulation Chassis—Application to Consumer Oral Healthcare

Coban,

Sykes,

Kulkarni

et al. 2024

Pharmaceutics

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With direct application to current and future consumer healthcare products, this research sheds light on the importance of packaging and its potential effects on both Active Pharmaceutical Ingredient (API) delivery and stability. Industrially sourced, proprietary experimental formulations (PEFs), specifically oral cleansers, based on salicylic acid and hydrogen peroxide, discolored over time at different rates, depending on packaging type used. This discoloration stemmed from an interplay of two factors, involving both spontaneous formulation degradation and the interaction of both degradants and salicylic acid with the internal surface of the packaging. This manuscript reports on the investigation to uncover the origins of discoloration. To investigate this real-world, industrial pipeline problem, we exploited the high dimensionality and simple sample preparation uniquely afforded by NMR. Using a combination of 1D/2D NMR and diffusion-ordered NMR spectroscopy (DOSY) to leverage molecular mass estimations from, we not only quickly confirmed the identities of these degradants, but also assessed their formation as a function of temperature and pH, providing insight into the mechanisms underlying their formation. We were able to identify catechol as the main source of discoloration over a period of several weeks, being formed at the ppm level. Furthermore, we evaluated the formulation–container interaction, employing NMR, ICP-MS, and ATR-IR. Despite this comprehensive analysis, the root causes of discoloration could only tentatively be assigned to a surface Ti complex of salicylic acid and other hydroxy carboxylic acids. Through the understanding of formulation degradation pathways, we were able to support further toxicology assessment, vital to both consumer safety and the manufacturer. This work underscores the invaluable role of NMR in the analysis of intricate proprietary mixtures with a consumer-centric purpose. Our findings demonstrate that conventional analytical techniques falter in the face of such complexity, requiring extensive preparation and pre-analytical processing, highlighting the novelty and crucial relevance of NMR research to manufacturers and consumers. Such an analysis is of value in the pursuit of materials within the consumer-healthcare space, which meet the requirements for successful recycling or re-use.

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Section: Figurementioning

confidence: 99%

Using Nuclear Magnetic Resonance to Troubleshoot a Stability Issue in a Real-World Formulation Chassis—Application to Consumer Oral Healthcare

Coban,

Sykes,

Kulkarni

et al. 2024

Pharmaceutics

View full text Add to dashboard Cite

show abstract

“…However, there are very few reports on the application of NMR for studying commercial detergent formulations. In research dating 30–40 years back, a few references describe the application of 13 C NMR for identification of surfactants (Carminati et al, ; Kalinoski and Jensen, ; Kosugi et al, ), whereas more recent publications seem to focus on diffusion and behavior of surfactants and micelles (Griffith et al, ; Hologne et al, ; McLachlan et al, ; Nicolle et al, ; Soderman et al, ). In addition, Visser et al described the specific analysis of polycarboxylate polymers in detergents using liquid extraction, followed by size‐exclusion chromatography ‐ nuclear magnetic resonance (Visser et al, ), and Fournial et al have reported the NMR‐based characterization of commercial nonionic surfactants (Fournial et al, ).…”

Section: Introductionmentioning

confidence: 99%

Rapid and Simple Identification and Quantification of Components in Detergent Formulations by Nuclear Magnetic Resonance Spectroscopy

Hansen

Damhus

Brask

2019

J Surfact & Detergents

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A rapid, inexpensive, and simple high‐resolution NMR spectroscopic method is outlined for determining the content of surfactants and other low‐molecular‐weight organic compounds in detergent formulations. With simple sample preparation, quantitative results can be obtained from an internal standard and/or the method can be used as a fingerprint analysis of the surfactant composition. The NMR sample is prepared by suspending the detergent sample in deuterated acetic acid and thus dissolving surfactants and other organic compounds. Any content of carbonate will be liberated as CO2, whereas other inorganic materials are removed by centrifugation. From one‐dimensional 1H and two‐dimensional HSQC NMR spectra, the surfactant components and low‐molecular‐weight organic compounds can be identified from reference spectra. Intensities of signature signals in the one‐dimensional 1H NMR spectrum are used for quantification by comparing with an internal standard. Furthermore, it is demonstrated how 31P NMR can be used to identify and quantify phosphonate‐type chelators.

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Extraction of Reliable Molecular Information from Diffusion NMR Spectroscopy: Hydrodynamic Volume or Molecular Mass?

Zaccaria

Zuccaccia

Cipullo

et al. 2019

Chemistry A European J

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Measuringa ccurate translational self-diffusion coefficients (D t )b yN MR techniques with modern spectrometers has becomer ather routine. In contrast, the derivation of reliablem oleculari nformation therefrom still remains an ontrivial task. In this paper,t wo established approaches to estimating molecular size in termso fh ydrodynamicv olume( V H ) or molecular weight (M) are compared. Ad hoc designede xperiments allowed the criticala spects of their application to be explored by translatingr elativelyc omplex theoretical principles into practical take-homem essages. For instance, comparing the D t values of three isosteric Cp 2 MCl 2 complexes (Cp = cyclopentadienyl,M = Ti,Z r, Hf), having significantly differentm olecularm ass, provided an empiricald em-onstration that V H is the criticalm olecular property affecting D t .T his central concept served to clarify the assumptions behindt he derivation of D t = f(M) power laws from the Stokes-Einstein equation. Somep itfalls in establishing log (D t )v ersus log (M) linear correlations for as et of species have been highlighted by further investigations of selected examples. The effectiveness of the Stokes-Einstein equation itself in describing the aggregation or polymerization of differently shaped speciesh as been explored by comparing, for example, ab all-shaped silsesquioxane cage with its cigarlike dimeric form, or styrenew ith polystyrene macromolecules.[a] Dr.Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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New validation of molecular mass measurements by means of 2D DOSY 1H NMR experiments: Application to surfactants

Cited by 6 publications

References 25 publications

Using Nuclear Magnetic Resonance to Troubleshoot a Stability Issue in a Real-World Formulation Chassis—Application to Consumer Oral Healthcare

Using Nuclear Magnetic Resonance to Troubleshoot a Stability Issue in a Real-World Formulation Chassis—Application to Consumer Oral Healthcare

Rapid and Simple Identification and Quantification of Components in Detergent Formulations by Nuclear Magnetic Resonance Spectroscopy

Extraction of Reliable Molecular Information from Diffusion NMR Spectroscopy: Hydrodynamic Volume or Molecular Mass?

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