TY - JOUR A1 - Burger, René A1 - Rumpf, Jessica A1 - Do, Xuan Tung A1 - Monakhova, Yulia A1 - Diehl, Bernd W. K. A1 - Rehahn, Matthias A1 - Schulze, Margit T1 - Is NMR combined with multivariate regression applicable for the molecular weight determination of randomly cross-linked polymers such as lignin? JF - ACS Omega N2 - 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 molecular weight (Mw and Mn) and the polydispersity of organosolv lignins (n = 53, Miscanthus x giganteus, Paulownia tomentosa, and Silphium perfoliatum). The suitability of the models was demonstrated by cross validation (CV) as well as by an independent validation set of samples from different biomass origins (beech wood and wheat straw). CV errors of ca. 7–9 and 14–16% were achieved for all parameters with the models from the 1H NMR spectra and the DOSY NMR data, respectively. The prediction errors for the validation samples were in a similar range for the partial least squares model from the 1H NMR data and for a multiple linear regression using the DOSY NMR data. The results indicate the usefulness of NMR measurements combined with multivariate regression methods as a potential alternative to more time-consuming methods such as gel permeation chromatography. Y1 - 2021 U6 - https://doi.org/10.1021/acsomega.1c03574 SN - 2470-1343 VL - 6 IS - 44 SP - 29516 EP - 29524 PB - ACS Publications CY - Washington, DC ER - TY - JOUR A1 - Monakhova, Yulia A1 - Diehl, Bernd W. K. T1 - Simplification of NMR Workflows by Standardization Using 2H Integral of Deuterated Solvent as Applied to Aloe vera Preparations JF - Applied Magnetic Resonance N2 - 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 standard (nicotinamide) from 1H-NMR spectra, quantification was performed based on the ratio of a particular 1H-NMR compound integral and 2H-NMR signal of deuterated solvent D2O. Validation characteristics (linearity, repeatability, accuracy) were evaluated and the results showed that the method has the same precision as internal standardization in case of multicomponent screening. Moreover, a dehydration process by freeze drying is not necessary for the new routine. Now, our NMR profiling of A. vera products needs only limited sample preparation and data processing. The new standardization methodology provides an appealing alternative for multicomponent NMR screening. In general, this novel approach, using standardization by 2H integral, benefits from reduced sample preparation steps and uncertainties, and is recommended in different application areas (purity determination, forensics, pharmaceutical analysis, etc.). Y1 - 2021 U6 - https://doi.org/10.1007/s00723-021-01393-4 SN - 1613-7507 VL - 52 IS - 11 SP - 1591 EP - 1600 PB - Springer CY - Cham ER - TY - JOUR A1 - Burmistrova, Natalia A. A1 - Soboleva, Polina M. A1 - Monakhova, Yulia T1 - Is infrared spectroscopy combined with multivariate analysis a promising tool for heparin authentication? JF - Journal of Pharmaceutical and Biomedical Analysis N2 - The investigation of the possibility to determine various characteristics of powder heparin (n = 115) was carried out with infrared spectroscopy. The evaluation of heparin samples included several parameters such as purity grade, distributing company, animal source as well as heparin species (i.e. Na-heparin, Ca-heparin, and heparinoids). Multivariate analysis using principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), and partial least squares – discriminant analysis (PLS-DA) were applied for the modelling of spectral data. Different pre-processing methods were applied to IR spectral data; multiplicative scatter correction (MSC) was chosen as the most relevant. Obtained results were confirmed by nuclear magnetic resonance (NMR) spectroscopy. Good predictive ability of this approach demonstrates the potential of IR spectroscopy and chemometrics for screening of heparin quality. This approach, however, is designed as a screening tool and is not considered as a replacement for either of the methods required by USP and FDA. KW - IR spectroscopy KW - Heparin KW - Authenticity KW - Principal component analysis KW - Soft independent modeling of class analogy Y1 - 2021 SN - 0731-7085 U6 - https://doi.org/10.1016/j.jpba.2020.113811 VL - 194 IS - Article number: 113811 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Pourshahidi, Ali Mohammad A1 - Achtsnicht, Stefan A1 - Nambipareechee, Mrinal Murali A1 - Offenhäusser, Andreas A1 - Krause, Hans-Joachim T1 - Multiplex detection of magnetic beads using offset field dependent frequency mixing magnetic detection JF - Sensors N2 - Magnetic immunoassays employing Frequency Mixing Magnetic Detection (FMMD) have recently become increasingly popular for quantitative detection of various analytes. Simultaneous analysis of a sample for two or more targets is desirable in order to reduce the sample amount, save consumables, and save time. We show that different types of magnetic beads can be distinguished according to their frequency mixing response to a two-frequency magnetic excitation at different static magnetic offset fields. We recorded the offset field dependent FMMD response of two different particle types at frequencies ƒ₁ + n⋅ƒ₂, n = 1, 2, 3, 4 with ƒ₁ = 30.8 kHz and ƒ₂ = 63 Hz. Their signals were clearly distinguishable by the locations of the extremes and zeros of their responses. Binary mixtures of the two particle types were prepared with different mixing ratios. The mixture samples were analyzed by determining the best linear combination of the two pure constituents that best resembled the measured signals of the mixtures. Using a quadratic programming algorithm, the mixing ratios could be determined with an accuracy of greater than 14%. If each particle type is functionalized with a different antibody, multiplex detection of two different analytes becomes feasible. KW - colorization KW - multiplex detection KW - frequency mixing magnetic detection KW - magnetic nanoparticles Y1 - 2021 U6 - https://doi.org/10.3390/s21175859 SN - 1424-8220 N1 - This article belongs to the Special Issue "Advanced Nanomaterial-Based Sensors for Biomedical Applications" VL - 21 IS - 17 PB - MDPI CY - Basel ER - TY - JOUR A1 - Staat, Manfred T1 - An extension strain type Mohr–Coulomb criterion JF - Rock mechanics and rock engineering N2 - Extension fractures are typical for the deformation under low or no confining pressure. They can be explained by a phenomenological extension strain failure criterion. In the past, a simple empirical criterion for fracture initiation in brittle rock has been developed. In this article, it is shown that the simple extension strain criterion makes unrealistic strength predictions in biaxial compression and tension. To overcome this major limitation, a new extension strain criterion is proposed by adding a weighted principal shear component to the simple criterion. The shear weight is chosen, such that the enriched extension strain criterion represents the same failure surface as the Mohr–Coulomb (MC) criterion. Thus, the MC criterion has been derived as an extension strain criterion predicting extension failure modes, which are unexpected in the classical understanding of the failure of cohesive-frictional materials. In progressive damage of rock, the most likely fracture direction is orthogonal to the maximum extension strain leading to dilatancy. The enriched extension strain criterion is proposed as a threshold surface for crack initiation CI and crack damage CD and as a failure surface at peak stress CP. Different from compressive loading, tensile loading requires only a limited number of critical cracks to cause failure. Therefore, for tensile stresses, the failure criteria must be modified somehow, possibly by a cut-off corresponding to the CI stress. Examples show that the enriched extension strain criterion predicts much lower volumes of damaged rock mass compared to the simple extension strain criterion. Y1 - 2021 U6 - https://doi.org/10.1007/s00603-021-02608-7 SN - 1434-453X N1 - Corresponding author: Manfred Staat VL - 54 IS - 12 SP - 6207 EP - 6233 PB - Springer Nature CY - Cham ER - TY - JOUR A1 - Welden, Rene A1 - Jablonski, Melanie A1 - Wege, Christina A1 - Keusgen, Michael A1 - Wagner, Patrick Hermann A1 - Wagner, Torsten A1 - Schöning, Michael Josef T1 - Light-Addressable Actuator-Sensor Platform for Monitoring and Manipulation of pH Gradients in Microfluidics: A Case Study with the Enzyme Penicillinase JF - Biosensors N2 - The feasibility of light-addressed detection and manipulation of pH gradients inside an electrochemical microfluidic cell was studied. Local pH changes, induced by a light-addressable electrode (LAE), were detected using a light-addressable potentiometric sensor (LAPS) with different measurement modes representing an actuator-sensor system. Biosensor functionality was examined depending on locally induced pH gradients with the help of the model enzyme penicillinase, which had been immobilized in the microfluidic channel. The surface morphology of the LAE and enzyme-functionalized LAPS was studied by scanning electron microscopy. Furthermore, the penicillin sensitivity of the LAPS inside the microfluidic channel was determined with regard to the analyte’s pH influence on the enzymatic reaction rate. In a final experiment, the LAE-controlled pH inhibition of the enzyme activity was monitored by the LAPS. KW - microfluidics KW - enzyme kinetics KW - actuator-sensor system KW - light-addressable electrode KW - light-addressable potentiometric sensor Y1 - 2021 U6 - https://doi.org/10.3390/bios11060171 SN - 2079-6374 N1 - This article belongs to the Special Issue "Selected Papers from the 1st International Electronic Conference on Biosensors (IECB 2020)" VL - 11 IS - 6 PB - MDPI CY - Basel ER - TY - JOUR A1 - Akimbekov, Nuraly S. A1 - Digel, Ilya A1 - Tastambek, Kuanysh T. A1 - Sherelkhan, Dinara K. A1 - Jussupova, Dariya B. A1 - Altynbay, Nazym P. T1 - Low-rank coal as a source of humic substances for soil amendment and fertility management JF - Agriculture N2 - Humic substances (HS), as important environmental components, are essential to soil health and agricultural sustainability. The usage of low-rank coal (LRC) for energy generation has declined considerably due to the growing popularity of renewable energy sources and gas. However, their potential as soil amendment aimed to maintain soil quality and productivity deserves more recognition. LRC, a highly heterogeneous material in nature, contains large quantities of HS and may effectively help to restore the physicochemical, biological, and ecological functionality of soil. Multiple emerging studies support the view that LRC and its derivatives can positively impact the soil microclimate, nutrient status, and organic matter turnover. Moreover, the phytotoxic effects of some pollutants can be reduced by subsequent LRC application. Broad geographical availability, relatively low cost, and good technical applicability of LRC offer the advantage of easy fulfilling soil amendment and conditioner requirements worldwide. This review analyzes and emphasizes the potential of LRC and its numerous forms/combinations for soil amelioration and crop production. A great benefit would be a systematic investment strategy implicating safe utilization and long-term application of LRC for sustainable agricultural production. KW - soil remediation KW - crop yield KW - soil health KW - soil amendment KW - low-rank coal Y1 - 2021 U6 - https://doi.org/10.3390/agriculture11121261 SN - 2077-0472 N1 - This article belongs to the Special Issue "From Waste to Fertilizer in Sustainable Agriculture" VL - 11 IS - 12 PB - MDPI CY - Basel ER - TY - JOUR A1 - Kleefeld, Andreas T1 - The hot spots conjecture can be false: some numerical examples JF - Advances in Computational Mathematics N2 - The hot spots conjecture is only known to be true for special geometries. This paper shows numerically that the hot spots conjecture can fail to be true for easy to construct bounded domains with one hole. The underlying eigenvalue problem for the Laplace equation with Neumann boundary condition is solved with boundary integral equations yielding a non-linear eigenvalue problem. Its discretization via the boundary element collocation method in combination with the algorithm by Beyn yields highly accurate results both for the first non-zero eigenvalue and its corresponding eigenfunction which is due to superconvergence. Additionally, it can be shown numerically that the ratio between the maximal/minimal value inside the domain and its maximal/minimal value on the boundary can be larger than 1 + 10− 3. Finally, numerical examples for easy to construct domains with up to five holes are provided which fail the hot spots conjecture as well. KW - Numerics KW - Boundary integral equations KW - Potential theory KW - Helmholtz equation KW - Interior Neumann eigenvalues Y1 - 2021 U6 - https://doi.org/10.1007/s10444-021-09911-5 SN - 1019-7168 VL - 47 PB - Springer CY - Dordrecht ER -