Infrared Spectroscopy: A Novel Tool for the Physicochemical Characterization of Particulate,Monolithic and Coated Stationary Phases

The design of novel stationary phases is a permanent demanding challenge in chromatographic and electrophoretic separation science to enable analysis with enhanced selectivity, specificity and speed. Therefore, the characterization of chemical and physical properties is next to calculation of chromatographic parameters essential. Conventionally, column performance is checked by a test run which only enables to prove efficiency column by column. Chemical parameters including surface coverage is normally analyzed by burning combustion or frontal analysis, physical parameters including particle size, pore size, pore volume and surface area by SEM, mercury intrusion porosimetry and Brunauer Emmett Teller. All these methods are extremely time consuming, invasive and require, beside special equipment, some specially trained lab staff. In order to enable a fast high-throughput control of chemical and physical parameters we introduced near-infrared spectroscopy (NIRS, 4,000–10,000 cm^?1) as a non-invasive, easy-to-handle technology enabling simultaneous analysis within only a few seconds at higher precision than the conventional applied methods. The method is applicable to porous/non-porous silica gel, carbon-based nano-materials (e.g. fullerenes), polymer beads, monoliths for solid-phase extraction, liquid chromatography, micro-liquid chromatography, material-enhanced laser desorption ionization and coated capillaries for capillary electrophoresis and capillary electrochromatography. Different carriers themselves and their kind of chemical derivatization (reversed-phase, normal-phase, ion-exchanger, immobilized affinity chromatography, affinity, endcapping) can be determined by applying principal component analysis of spectra recorded. Partial least square regression enables the determination of physical parameters particle size, pore size, pore volume, porosity, total porosity and surface area with one single measurement in an established quantitative model. For a detailed investigation NIRS imaging, which benefits from the combination of a NIR spectrometer with a microscope, allows to analyze materials of interest with resolution down to 4 μm. For the optimized design of polymeric phases real-time in situ monitoring to control polymerization progress can be highly helpful. In this article, the advantages of this novel infrared-based method for the fast high-throughput quality control are introduced.     

Cohesive zone laws for fatigue crack growth: Numerical field projection of the micromechanical damage process in an elasto-plastic medium

Cohesive zone failure models are widely used to simulate fatigue crack propagation under cyclic loading, but the model parameters are phenomenological and are not closely tied to the underlying micromechanics of the problem. In this paper, we will inversely extract the cohesive zone laws for fatigue crack growth in an elasto-plastic ductile solid using a field projection method (FPM), which projects the equivalent tractions and separations at the cohesive crack-tip from field information outside the process zone. In our small-scale yielding model, a single row of discrete voids is deployed directly ahead of a crack in an elasto-plastic medium subjected to cyclic mode I K-field loading. Damage accumulation under cyclic loading is captured by the growth of voids within the micro-voiding zone ahead of the crack, while the evolution of the cohesive zone law representing the micro-voiding zone is inversely extracted via the FPM. We show that the field-projected cohesive zone law captures the essential micromechanisms of fatigue crack growth in the ductile medium: from loading and unloading hysteresis caused by void growth and plastic hardening, to the softening damage locus associated with crack propagation via a void by void growth mechanism. The results demonstrate the effectiveness of the FPM in obtaining a micromechanics-based cohesive zone law in-place of phenomenological models, which opens the way for a unified treatment of fatigue crack problems.     

Direct Strain Oscillation: a new oscillatory method enabling measurements at very small shear stresses and strains

As shown previously, a rotational rheometer equipped with an electronically commutated motor (EC-motor) allows one to conduct stress and strain experiments with the same rheometer in rotational mode. A new method has now been developed to improve further strain controlled oscillatory measurements by adjusting the strain directly within a single oscillation cycle. Generally, a strain controlled oscillatory test in a stress controlled rheometer consists of the following steps: applying one full oscillation cycle with an arbitrary stress amplitude, measuring the strain amplitude, adjusting the stress in the next oscillation cycle, and repeating this routine until the desired strain amplitude is reached. The newly developed direct strain oscillation mode employs a different approach. It does not require a full oscillation cycle but uses a real-time position control and adjusts to the desired strain directly on the sine wave. Therefore, the actual movement of the measuring system follows directly the required change in strain during each individual oscillation cycle. This new oscillatory mode has several major advantages: (1) the possibility of conducting real strain controlled tests in oscillation, (2) the exact strain setting right from the first oscillation cycle, i.e., no or only very slight overshoot in strain, (3) faster data acquisition even within an oscillation cycle, (4) it allows the measurement at extremely low angular resolution and low torques. Due to the absence of strain overshoots and the ability of testing at small deflection angles and low torques this new method is especially helpful for measurements on samples with low viscosities and weak structures such as gels, emulsions, suspensions, colloids, and foams.     

Insect Protein Content Analysis in Handcrafted Fitness Bars by NIR Spectroscopy. Gaussian Process Regression and Data Fusion for Performance Enhancement of Miniaturized Cost-Effective Consumer-Grade Sensors

Future food supply will become increasingly dependent on edible material extracted from insects. The growing popularity of artisanal food products enhanced by insect proteins creates particular needs for establishing effective methods for quality control. This study focuses on developing rapid and efficient on-site quantitative analysis of protein content in handcrafted insect bars by miniaturized near-infrared (NIR) spectrometers. Benchtop (Büchi NIRFlex N-500) and three miniaturized (MicroNIR 1700 ES, Tellspec Enterprise Sensor and SCiO Sensor) in hyphenation to partial least squares regression (PLSR) and Gaussian process regression (GPR) calibration methods and data fusion concept were evaluated via test-set validation in performance of protein content analysis. These NIR spectrometers markedly differ by technical principles, operational characteristics and cost-effectiveness. In the non-destructive analysis of intact bars, the root mean square error of cross prediction (RMSEP) values were 0.611% (benchtop) and 0.545–0.659% (miniaturized) with PLSR, and 0.506% (benchtop) and 0.482–0.580% (miniaturized) with GPR calibration, while the analyzed total protein content was 19.3–23.0%. For milled samples, with PLSR the RMSEP values improved to 0.210% for benchtop spectrometer but remained in the inferior range of 0.525–0.571% for the miniaturized ones. GPR calibration improved the predictive performance of the miniaturized spectrometers, with RMSEP values of 0.230% (MicroNIR 1700 ES), 0.326% (Tellspec) and 0.338% (SCiO). Furthermore, Tellspec and SCiO sensors are consumer-oriented devices, and their combined use for enhanced performance remains a viable economical choice. With GPR calibration and test-set validation performed for fused (Tellspec + SCiO) data, the RMSEP values were improved to 0.517% (in the analysis of intact samples) and 0.295% (for milled samples).     

Following Polymer Brush Growth Using the Quartz Crystal Microbalance Technique

Summary: The growth of surface‐initiated poly([2‐(methacryloyloxy)ethyl]trimethylammonium chloride) (pMETAC) brushes by ATRP was monitored by the quartz crystal microbalance technique with dissipation (QCM‐D). The change in mass of the quartz crystals starting from the adsorption of a thiol initiator monolayer through to the growth of the polymer brushes was determined. The use of QCM‐D allowed determination of the kinetics of polymerization from the surface. The technique can be applied to other polymers synthesised from surfaces and allows the study of varying conditions on the polymerization kinetics.

Changes in frequency of a quartz crystal during polymerization.