Bernd Diehl

Spectral Service AG,

Chia seed oil has a high content of polyunsaturated fatty acids (PUFAs), giving it nutritionally beneficial qualities, although determining its high susceptibility to oxidative deterioration. Microencapsulation and natural antioxidants are alternatives to protect this oil during its processing and storage. This work aims to study the physicochemica...

Nuclear magnetic resonance (NMR) spectrometric methods for the quantitative analysis of pure heparin in crude heparin is proposed. For quantification, a two-step routine was developed using a USP heparin reference sample for calibration and benzoic acid as an internal standard. The method was successfully validated for its accuracy, reproducibility...

Although plenty of successful applications of benchtop nuclear magnetic resonance (NMR) spectroscopy in quantitative mixture analysis exist, the possibility of calibration transfer remains mostly unexplored, especially between high-and low-field NMR. For the first time, the calibration transfer of partial least squares (PLS) regressions (weight ave...

Although several successful applications of benchtop nuclear magnetic resonance (NMR) spectroscopy in quantitative mixture analysis exist, the possibility of calibration transfer remains mostly unexplored, especially between high-and low-field NMR. For the first time, the calibration transfer of partial least squares (PLS) regressions (weight avera...

Lignin is a promising renewable biopolymer being investigated worldwide as an environmentally benign substitute of fossil-based aromatic compounds. For its successful implementation into process streams, a quick, easy, and reliable method is needed for the molecular weight determination of lignin. An approach using 1 H spectra of benchtop as well a...

Lignin is a promising renewable biopolymer being investigated worldwide as an environmentally benign substitute of fossil-based aromatic compounds, e.g. for the use as an excipient with antioxidant and antimicrobial properties in drug delivery or even as active compound. For its successful implementation into process streams, a quick, easy, and rel...

NMR standardization approach that uses the ²H integral of deuterated solvent for quantitative multinuclear analysis of pharmaceuticals is described. As a proof of principle, the existing NMR procedure for the analysis of heparin products according to US Pharmacopeia monograph is extended to the determination of Na⁺ and Cl⁻ content in this matrix. Q...

In this study, a recently proposed NMR standardization approach by 2H integral of deuterated solvent for quantitative multicomponent analysis of complex mixtures is presented. As a proof of principle, the existing NMR routine for the analysis of Aloe vera products was modified. Instead of using absolute integrals of targeted compounds and internal...

The molecular weight properties of lignins are one of the key elements that need to be analyzed for a successful industrial application of these promising biopolymers. In this study, the use of ¹H NMR as well as diffusion-ordered spectroscopy (DOSY NMR), combined with multivariate regression methods, was investigated for the determination of the mo...

The goal of the qNMR Summit is to take stock of the status quo and the recent developments in qNMR research and applications in a timely and accurate manner. It provides a platform for both advanced and novice qNMR practitioners to receive a well-rounded update and discuss potential qNMR-related applications and collaborations. For over a decade, s...

A multilayer microencapsulation process was carried out to protect and deliver chia oil, which presents high nutritional value but also a high susceptibility to lipid oxidation. A high-pressure homogenization was performed with deoiled or hydrolyzed sunflower lecithins (pH 5) to obtain the primary emulsion. The secondary and tertiary layers were de...

Quantitative nuclear magnetic resonance (qNMR) is considered as a powerful tool for multicomponent mixture analysis as well as for the purity determination of single compounds. Special attention is currently paid to the training of operators and study directors involved in qNMR testing. To assure that only qualified personnel are used for sample pr...

As a low-input crop, Miscanthus offers numerous advantages that, in addition to agricultural applications, permits its exploitation for energy, fuel, and material production. Depending on the Miscanthus genotype, season, and harvest time as well as plant component (leaf versus stem), correlations between structure and properties of the correspondin...

As a low-input crop, Miscanthus offers numerous advantages that, in addition to agricultural applications, permits its exploitation for energy, fuel, and material production. Depending on the Miscanthus genotype, season, and harvest time as well as plant component (leaf versus stem), correlations between structure and properties of the correspondin...

As a low-input crop, Miscanthus offers numerous advantages that, in addition to agricultural applications, permits its exploitation for energy, fuel, and material production. Depending on the Miscanthus genotype, season, and harvest time as well as plant component (leaf versus stem), correlations between structure and properties of the correspondin...

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Lignin represents the largest renewable source for aromatic compounds on earth and can be extracted from different biomasses: wood, grasses or agricultural residues by various extraction processes: Catalyst-free organosolv treatment using environmentally benign aqueous ethanol as solvent is an appropriate method to produce lignins of high purity. [...

Heparin is an anticoagulant medication that is usually injected subcutaneously. The quality of a set of commercial heparin injections from different producers was examined by NMR, IR, UV-Vis spectroscopies and potentiometric multisensor system. The type of raw material regarding heparin animal origin and producer, heparin molecular weight and activ...

Quantitative nuclear magnetic resonance (qNMR) is routinely performed by the internal or external standardization. The manuscript describes a simple alternative to these common workflows by using NMR signal of another active nuclei of calibration compound. For example, for any arbitrary compound quantification by NMR can be based on the use of an i...

NMR spectroscopy has recently been utilized to determine the absolute amounts of organic molecules with metrological traceability since signal intensity is directly proportional to the number of each nucleus in a molecule. The NMR methodology that uses hydrogen nucleus (¹H) to quantify chemicals is called quantitative ¹H-NMR (¹H qNMR). The quantita...

Besides hard and soft wood, so-called low-input plants are of special interest as lignocellulose feedstock (LCF) for second generation biorefineries [1,2]. This contribution presents data obtained for lignins isolated from different low-input crops: perennial grasses of different genotype (including M. x giganteus, M. sinensis, M. robustus, M. naga...

Hydroperoxides are formed as the primary product during lipid oxidation, being analyzed as the peroxide value to detect the degradation level of oils and fats. As an alternative to the classical titration method according to Wheeler, a ¹H‐{³¹P} decoupled NMR method is developed using triphenylphosphine (TPP) as a tagging agent. TPP reacts with pero...

Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food...

This paper introduces an 1H NMR method to identify individual divalent metal cations Be2+, Mg2+, Ca2+, Sr2+, Zn2+, Cd2+, Hg2+, Sn2+, and Pb2+ in aqueous salt solutions through their unique signal shift and coupling after complexation with the salt of ethylenediamine tetraacetic acid (EDTA). Furthermore, quantitative determination applied for the di...

Herein we describe for the first time a practical analytical method for determining the enantio-purity of L-α-glycerophosphocholine (L-α-GPC) by chiral derivatization. The use of a suitable chiral boronic acid allowed the formation of a mixture of two diastereomeric boronate esters whose ratio, carefully analyzed by 1HNMR spectroscopy, reflects L-α...

Calibration transfer is commonly used for spectra obtained on different spectrometers or other conditions. This paper reports a multivariate transfer approach for 2D diffusion‐ordered spectroscopy (DOSY) measurements among high‐resolution nuclear magnetic resonance (NMR) spectrometers on the basis of partial least squares (PLS) regression. As the t...

The aim of this research was to investigate the effect of herring roe phospholipids (PLs) on the oxidative stability of cod liver oil during storage. The effect of PLs on the oxidative stability of cod liver oil was assessed in terms of peroxide value, free fatty acids, secondary oxidation products and pyrrolisation. The results show that the PV wa...

The composition and properties of heparin preparations are studied by NMR spectrometry. Approaches to the determination of the most important heparin quality indicators (biological origin and manufacturing company) based on multivariate modeling of the NMR profile of a sample are considered. Chemometric modeling of two-dimensional (2D) NMR spectra...

The quantification of a drug, its impurities, and e.g. components of a mixture has become routine in NMR laboratories and many applications have been described in the literature. However, besides simply using 1D 1H or 13C NMR, a number of more advanced methods has been developed and used in the past. Here, we want to describe the applicability of n...

Heparin is a carbohydrate polymer, which is clinically used as an anticoagulant for the treatment of thrombotic disorders. The anticoagulant process is mainly mediated by the interaction of heparin with antithrombin followed by inhibition of clotting factors IIa (FIIa) and Xa (FXa). The influence of polymer disaccharide structure, average molecular...

The present work deals with the study of the physicochemical properties of microencapsulated chia seed oil by spray‐dried method, with different oil content, using Maillard reaction products (MRPs) generated from different heat treatments (0, 60, or 100°C, 30 min) of sodium caseinate‐lactose mixture as wall material. With an absorbance at 465 nm, t...

NMR spectroscopy has become an essential diagnostic tool for pharmaceutical preparations worldwide, with many runs performed annually on a routine basis. In this study multivariate analysis was performed on a big dataset of 990 NMR heparin spectra recorded over six years (2012–2017) in our laboratory. Several steps of statistical analysis of accumu...

This study deals with the physicochemical characterization of powdered chia oil microparticles produced from mono and bi-layered emulsions using modified sunflower lecithins (Deoiled (DL); Phosphatidylcholine-enriched fraction (PC)), chitosan, and maltodextrin as wall materials. The powders were stored (20 ± 2 °C, RH 33%, 120d) and characterized by...

L-ascorbic acid 2-phosphate magnesium (APMg) salt is a vitamin C derivative frequently used in cell culture media for research purposes. It is also used as a raw material in the GMP-manufacturing of gene-, cell- and tissue advanced therapy medicinal products (ATMPs). However, quality methods are currently lacking. Therefore, a LC method was develop...

Krill oil is currently among the most highly promoted products in the dietary supplement market, which, due to its high price, can be potentially adulterated with fish species and artificial oil. For a holistic control of krill oil quality, ¹H, ¹³C, and ³¹P nuclear magnetic resonance (NMR) spectroscopies were used. The fatty acid and phospholipid c...

Fatty acid conjugates of hydroxy-metabolites of tetrahydrocannabinol (THC) or cannabinol have already been reported as metabolites in rats. In the herein presented investigation, palmitic acid esters of THC and its primary metabolite 11-hydroxy-delta9-tetrahydrocannabinol (11-OH-THC) were synthesized using esterification with palmitic acid chloride...

A high‐resolution ³¹P NMR method for determining the concentration of phospholipid (PL) species in krill oil was proficiency tested using an international interlaboratory study. Fourteen laboratories from five countries tested five different krill oil samples providing 17 datasets. Krill oil samples were prepared by the organizer using liquid–liqui...

Nuclear magnetic resonance (NMR) spectroscopy is widely applied in the field of metabolomics due to its quantitative nature and the reproducibility of data generated. However, one of the main challenges in routine NMR analysis is to obtain valuable information from large datasets of raw data in a high-throughput, automatic, and reproducible manner....

Human milk oligosaccharides (HMO) are the third most abundant solid component of human milk. It is likely that they are responsible for at least some of the benefits experienced by breast-fed infants. Until recently HMO were absent from infant formula, but 2′-fucosyllactose (2′-FL) and lacto-N-neoteraose (LNnT) have recently become available as ing...

Nuclear magnetic resonance spectrometry (NMR) finds numerous applications in pharmacy, cosmetic and food control as well as in developing tools for “big data” analysis. However, there remains a need for automated tools to assess instrument system suitability in real time for each particular routine sample. An automated procedure has been introduced...

BACKGROUND Chia oil possesses a very high content of polyunsaturated fatty acids, mainly α‐linolenic acid. This characteristic makes this oil possess beneficial properties to health but gives it a high susceptibility to the oxidation process. The microencapsulation and the addition of natural antioxidants are alternatives to protect chia oil agains...

Streptomyces cinnamonensis A495 is a variant of the monensin producer which instead of the native polyether antibiotic gives rise to antibiotic and anti‐tumor shunt‐product premonensin. Through the supplementation of the fermentation medium with suitable precursors, premonensin can be derivatized via the incorporation of new‐to‐nature extender unit...

Heparin is a linear, highly sulfated glycosaminoglycan (GAG), which consists of repeating disaccharide units of β-d-glucuronic acid or α-l-iduronic acid and α-d-glucosamine. While robust analytical approaches exist for the characterization of organic composition of heparin preparations, there is a lack of methods for the simultaneous quantification...

Nuclear magnetic resonance (NMR) spectroscopy is regarded as one of the most powerful and versatile analytical approaches to assure the quality of heparin preparations. In particular, it was recently demonstrated that by using ¹H NMR coupled with chemometrics heparin and low molecular weight heparin (LMWH) samples derived from three major animal sp...

molecularweight heparin (LMWH) also requires the determination of average molecular weight, which is closelyrelated to the pharmaceutical properties of anticoagulant drugs.To determine average molecular weight of these animal-derived polymer products, partial least squaresregression (PLS) was utilized for modelling of diffused-ordered spectroscopy...

Chia oil constitutes a vegetal source of ω-3 polyunsaturated fatty acids (PUFAs) and natural antioxidants, although it is susceptible to the oxidation process. Emulsion-based delivery systems could be adequate for its protection and incorporation into foods. In this study chia bilayer O/W emulsions were obtained applying layer-by-layer deposition t...

High resolution (600MHz) nuclear magnetic resonance (NMR) spectroscopy is used to distinguish heparin and low-molecular weight heparins (LMWHs) produced from porcine, bovine and ovine mucosal tissues as well as their blends. For multivariate analysis several statistical methods such as principal component analysis (PCA), factor discriminant analysi...

The effect of buttermilk powder addition post-curd formation or buttermilk addition to cheese milk on total and individual phospholipid content, chemical composition, enzyme activity, microbial populations and microstructure within Cheddar-style cheese was investigated. Buttermilk or buttermilk powder addition resulted in significant increases in t...

This research studies the physical properties of microcapsules formulated with different concentrations of chia oil, using Maillard Reaction Products (MRPs) with different protein:carbohydrate ratio as encapsulants. Microcapsules were obtained from freeze-drying of O/W emulsions composed by non-heated/heated aqueous phases containing NaCas (10%wt)...

A proton ((1)H) NMR spectroscopic method was established for the quality assessment of vegetable oils. To date, several research studies have been published demonstrating the high potential of the NMR technique in lipid analysis. An interlaboratory comparison was organized with the following main objectives: (1) to evaluate an alternative analysis...

In our recent paper a new technique for automated spectra integration and quality control of the acquired results in qNMR was developed and validated [Y.B. Monakhova, B.W.K. Diehl Magn.Res. Chem. 2017. doi: 10.1002/mrc.4591]. The present study is focused on the influence of acquisition and post-acquisition parameters on the developed automated rout...

Blood species identification is an important challenge in forensic science. Conventional methods used for blood species analysis are destructive and associated with time-consuming sample preparation steps. Nuclear magnetic resonance (NMR) spectroscopy is known for its nondestructive properties and fast results. This research study presents a proton...

Nuclear magnetic resonance (NMR) is a fast and accurate analytical method. Associated with chemometrics, it gradually becomes more important tool for the pharmaceutical industry. In this review studies dealing with the applications of multivariate analysis to NMR spectroscopic profiles were grouped and discussed according to the analytical problem...

Quantitative nuclear magnetic resonance (qNMR) is considered as a powerful tool for measuring the absolute amount of small molecules in complex mixtures. However, verification of the accuracy of such quantification is not a trivial task. In particular, preprocessing and integration steps are particularly challenging and potentially erroneous.A scri...

An ¹H NMR method was developed to control five phospholipid (PL) species, namely, phosphatidylcholine (PC), sphingomyelin (SPH), phosphatidylethanolamine (PE), phosphatidylserine (PS) and phosphatidylinositol (PI) in infant nutrition. The ¹H NMR method for the PC, SPH, PE and PI species was validated according to the good laboratory practice (GLP)...

A nuclear magnetic resonance (NMR) method was developed to quantify cations in mineral water. The procedure was based on integration of signals from metal-ethylenediaminetetraacetic acid (EDTA) complexes at δ 2.70 ppm for Mg²⁺ and δ 2.56 ppm for Ca²⁺. The limits of detection were below 0.5 mg/L. Lack of precision did not exceed 5%. Linearity was be...

Discrimination between street heroin consumption and poppy seed ingestion represents a major toxicological challenge in daily routine work. Several difficulties associated with conventional street heroin markers originate from their versatile occurrence in various poppy seed products and medications, respectively, as well as to small windows of det...

Recent classification of Aloe vera whole-leaf extract by the International Agency for Research and Cancer as a possible carcinogen to humans as well as the continuous adulteration of A. vera's authentic material have generated renewed interest in controlling A. vera. The existing NMR spectroscopic method for the analysis of A. vera, which is based...

A methodology utilizing 1H NMR spectroscopy has been developed to measure the concentration of hydrogen peroxide in hair sprays, nail treatments, hydrogen peroxide solutions for disinfection and chemical reagents. For sample preparation, only a dilution with DMSO-d6 to prevent coalescence of OH peaks and addition of internal standard is required. T...

The NMR spectroscopy is a technique which is accurate and precise enough to rival chromatographic and titration methods, especially in the edible oils analysis. The successful participation in inter-laboratory tests is a suitable opportunity to ensure the ability of NMR laboratories to provide accurate and precise results. In order to become accept...

The assessment of quality and authenticity of edible oils is traditionally performed based on several separate analytical methods. These methods were developed and standardized several decades ago undergoing only minor changes since then, which makes oil analysis time-consuming and sometimes even erroneous. A proton nuclear magnetic resonance (1H N...

The detailed analysis of krill oil is of importance to be able to differentiate other oils, identify adulterated products, and provide the highest quality associated with its beneficial health effects. The objective of this study was to demonstrate the usefulness of the combination of 31P, 1H and 13C nuclear magnetic resonance (NMR) spectroscopies...

In recent years the number of spectroscopic studies utilizing multivariate techniques and involving different laboratories has been dramatically increased. In this paper the protocol for calibration transfer of partial least square regression model between high-resolution nuclear magnetic resonance (NMR) spectrometers of different frequencies and e...

A rapid, accurate and specific proton nuclear magnetic resonance (1H NMR) spectroscopic method is developed to determine ethanol in blood, known as the blood alcohol concentration (BAC). The limits of detection and quantification are 0.02g/L and 0.07g/L, respectively. The 1H NMR spectra show linearity for whole blood and serum samples of a concentr...

The application of the glucansucrase GTF180 from Lactobacillus reuteri 180 in fruit juice concentrates for the synthesis of glucooligosaccharides was investigated. Reaction parameters such as temperature, pH, substrate and enzyme loading, Ca+2 addition and incubation time were investigated in high concentration sucrose solutions. The optimum condit...

Nuclear Magnetic Resonance (NMR) spectroscopy has been mainly used for the elucidation and confirmation of structures. For the last decade, cryogenic probe technology has opened a wide door for routine analysis due to an increase of the signal to noise ratio by a factor of 5. NMR methods have been introduced to quantitative analysis in any composit...

This chapter focuses on sunflower lecithin. Sunflower lecithin is not produced in considerable amounts worldwide. This fact is mainly because of the low lecithin content of crude sunflower oil as compared with 2.9% for soybean, 1.9% for rapeseed, 2.4% for cottonseed, and 2.0-2.7% for corn oil (normalized at 70% of insolubles in acetone). In Argenti...

NMR spectroscopy was used to distinguish pure sunflower lecithin from that blended with soy species, and to quantify the degree of such adulteration. Sample preparation included liquid extraction of lecithin blends and measurement of polar and non-polar fractions using 31P and 1H NMR spectrometry. Several phospholipid species, linolenic acid and st...

Background: Due to possible falsification of sugar cane products with cheaper alternative (sugar beet) on the market, a simple analytical methodology has to be developed to control the authenticity of sugar products. Results: A direct (13) C NMR method has been validated to differentiate between sucrose-based sugar products produced from sugar b...

Most commonly processes for lecithin modification are deoling, fractionation with absolute ethanol to produce phosphatidylcholine or phosphatidylinositol enriched fractions or enzymatic hydrolysis of these compounds. These modifications are important for achieving an optimal balance between hydrophilic and lipophilic compounds (HLB) and ensure a go...

(1)H NMR spectroscopy was used to distinguish pure porcine heparin and porcine heparin blended with bovine species and to quantify the degree of such adulteration. For multivariate modelling several statistical methods such as partial least squares regression (PLS), ridge regression (RR), stepwise regression with variable selection (SR), stepwise p...

Analyzing egg liqueurs for compliance with legal requirements means several different time consuming preparations and analytical processes. In this paper, we describe the approach to use quantitative 1H NMR spectroscopy as an accurate alternative technique. 1H NMR analysis comprised two different rapid sample preparations for water-soluble or nonpo...

A nuclear magnetic resonance (NMR) spectroscopic method was tested to control twelve vitamins and accompanying substances in multivitamin preparations. The limits of detection (LODs) and limits of quantification (LOQs) varied in the 9.0-77.0 mg/kg and in the 34.5-93.5 mg/kg range respectively. The coefficients of variation (CVs) ranged between 0.9%...

Canadian condiment yellow mustard seeds (also called white), oriental and brown mustard seed and flour extracts and commercially produced Indian mustard oils were examined for bioactive phenolics primarily to identify the antioxidant properties. Phenolic compounds, namely sinapic acid, sinapoyl glucose and canolol, were quantified using high-perfor...

Background Herring roe is an underutilized source of n-3 polyunsaturated fatty acids (PUFAs) for human consumption with high phospholipid (PL) content. Studies have shown that PL may improve bioavailability of n-3 PUFAs. Arctic Nutrition’s herring roe product MOPL™30 is a PL: docosahexaenoic acid (DHA)-rich fish oil mixture, with a DHA:eicosapentae...

The main objective of this study was to investigate the oxidative stability and non-enzymatic browning reactions of marine PL in the presence or in the absence of primary amine group from aminophospholipids and amino acids. Marine phospholipids liposomal dispersions were prepared from two authentic standards (phosphatidylcholine and phosphatidyleth...

Against the background of the scandal about low-grade silicone breast implants of the French manufacturer Poly Implant Prothese (PIP), several types of implants were examined using (1)H NMR spectroscopy. The intention was to classify an implant according to its silicone structure. Therefore, the certificated raw material of the American silicone pr...

Fractions enriched in specific phospholipids are desirable for different industrial purposes because of their characteristic physicochemical and functional properties. We studied the fractionation process of sunflower lecithin using different absolute-ethanol/water ratios and pHs and then evaluated the emulsifying properties of phosphatidyl-choline...