Selectivity in separation using π electron-rich stationary phases for the comprehensive two-dimensional analysis of cafe espresso

The multidimensional high-performance liquid chromatography separations of the complex sample matrix found in café espresso coffee were completed on the propyl phenyl and butyl phenyl columns that contain 3 and 4 carbon atoms in the spacer chain, respectively. Phenyl type stationary phases are able to undergo unique π–π interactions with aromatic compounds. Previous works have found that there are differences in retention characteristics between these chain lengths and this was explored further here. It was found that when analysing the separations by quadrants, using a geometric approach to factor analysis and by measuring the normalised mean radius, subtle differences in the separations were observed and the butyl phenyl phase was more selective for the high to medium polarity species. However, there was very little difference in separation behaviour for the hydrophobic components within the coffee sample. Overall, the analysis of the entire separation showed very little difference.

Improving peak shapes with counter gradients in two-dimensional high performance liquid chromatography

To achieve the greatest peak capacity in two-dimensional high performance liquid chromatography (2D-HPLC) a gradient should be operated in both separation dimensions. However, it is known that when an injection solvent that is stronger than the initial mobile phase composition is deleterious to peak performance, thus causing problems when cutting a portion from one gradient into another. This was overcome when coupling hydrophilic interaction with reversed phase chromatography by introducing a counter gradient that changed the solvent strength of the second dimension injection. It was found that an injection solvent composition of 20% acetonitrile in water gave acceptable results in one-dimensional simulations with an initial composition of 5% acetonitrile. When this was transferred to a 2D-HPLC separation of standards it was found that a marked improvement in peak shape was gained for the moderately retained analytes (phenol and dimethyl phthalate), some improvement for the weakly retained caffeine and very little change for the strongly retained n-propylbenzene and anthracene which already displayed good chromatographic profiles. This effect was transferred when applied to a 2D-HPLC separation of a coffee extract where the indecipherable retention profile was transformed to a successful application multidimensional chromatography with peaks occupying 71% of the separation space according to the geometric approach to factor analysis.

Determination of neurotransmitters and their metabolites using one- and two-dimensional liquid chromatography with acidic potassium permanganate chemiluminescence detection

High-performance liquid chromatography with chemiluminescence detection based on the reaction with acidic potassium permanganate and formaldehyde was explored for the determination of neurotransmitters and their metabolites. The neurotransmitters norepinephrine and dopamine were quantified in the left and right hemispheres of rat hippocampus, nucleus accumbens and prefrontal cortex, and the metabolites vanillylmandelic acid, 3,4-dihydrophenylacetic acid, 5-hydroxyindole-3-acetic acid and homovanillic acid were identified in human urine. Under optimised chemiluminescence reagent conditions, the limits of detection for these analytes ranged from 2.5 × 10−8 to 2.5 × 10−7 M. For the determination of neurotransmitter metabolites in urine, a two-dimensional high-performance liquid chromatography (2D-HPLC) separation operated in heart-cutting mode was developed to overcome the peak capacity limitations of the one-dimensional separation. This approach provided the greater separation power of 2D-HPLC with analysis times comparable to conventional one-dimensional separations.

DryLab® optimised two-dimensional high performance liquid chromatography for differentiation of ephedrine and pseudoephedrine based methamphetamine samples

In-silico optimised two-dimensional high performance liquid chromatographic (2D-HPLC) separations of a model methamphetamine seizure sample are described, where an excellent match between simulated and real separations was observed. Targeted separation of model compounds was completed with significantly reduced method development time. This separation was completed in the heart-cutting mode of 2D-HPLC where C18 columns were used in both dimensions taking advantage of the selectivity difference of methanol and acetonitrile as the mobile phases. This method development protocol is most significant when optimising the separation of chemically similar chemical compounds as it eliminates potentially hours of trial and error injections to identify the optimised experimental conditions. After only four screening injections the gradient profile for both 2D-HPLC dimensions could be optimised via simulations, ensuring the baseline resolution of diastereomers (ephedrine and pseudoephedrine) in 9.7 min. Depending on which diastereomer is present the potential synthetic pathway can be categorized.

Objective classification of fabric pilling based on the two-dimensional discrete wavelet transform

A number of methods for automated objective ratings of fabric pilling based on image analysis are described in the literature. The periodic structure of fabrics makes them suitable candidates for frequency domain analysis. We propose a new method of frequency domain analysis based on the two-dimensional discrete wavelet transform to objectively measure pilling intensity in sample images. We present a preliminary evaluation of the proposed method based on analysis of two series of standard pilling evaluation test images. The initial results suggest that the proposed method is feasible, and that the ability of the method to discriminate between levels of pilling intensity depends on the wavelet analysis scale being closely matched to the fabric interyarn pitch. We also present a heuristic method for optimal selection of an analysis wavelet and associated analysis scale.

Evaluating the robustness of objective pilling classification with the two-dimensional discrete wavelet transform

Previously, we proposed a new method of frequency domain analysis based on the two-dimensional discrete wavelet transform to objectively measure pilling intensity in sample fabric images. We have further evaluated this method, and our results indicate that it is robust to small horizontal and/or vertical translations and to significant variations in the brightness of the image under analysis, and is sensitive to rotation and to dilation of the image. These results suggest that as long as precautions are taken to ensure fabric test samples are imaged under consistent conditions of weave/knit pattern alignment (rotation) and apparent interyarn pitch (dilation), the method will yield repeatable results.

Objective assessment of pilling of nonwoven fabrics using the two dimensional discrete wavelet transform

Fabric pilling is a serious problem for the apparel industry, causing an unsightly appearance and premature wear. Woolen products are particularly prone to pilling. Recently, a process for production of woolen nonwoven apparel fabrics has been commercialized in Australia, and may lead to new markets for Australian wool. However, the success of such nonwoven fabrics will partly rely on their propensity to pill. A key element in the control of fabric pilling is the evaluation of resistance to pilling by testing. Resistance to pilling is normally tested in the laboratory by processes that simulate accelerated wear, followed by a manual assessment of the degree of pilling by an expert based on a visual comparison of the sample to a set of test images. To bring more objectivity into the pilling rating process, a number of automated systems based on image analysis have been developed. The authors previously proposed a new method of image analysis based on the two-dimensional discrete wavelet transform to objectively measure the pilling intensity for woven fabrics. This paper presents preliminary work in extending this method to nonwoven fabrics.

Compositional dynamics of a commercial wine fermentation using two-dimensional FTIR correlation analysis

We have demonstrated that compositional changes occurring during a commercial red wine fermentation can be effectively monitored using FTIR spectroscopy and modelled with the aid of two-dimensional correlation techniques. This study represents a novel application of two-dimensional spectroscopy and showed that the reaction rates for the conversion of fructose and glucose to alcohol were different, with the latter being more rapid. The use of a simple three-component model serves to aid interpretation of the data and the results obtained confirm the value of two-dimensional FTIR correlation spectroscopy as a chemometric tool which has considerable potential for process monitoring.

The assessment of тт-тт selective stationary phases for two-dimensional HPLC analysis of foods : application to the analysis of coffee

Differences between alkyl, dipole–dipole, hydrogen bonding, and π-π selective surfaces represented by non-resonance and resonance π-stationary phases have been assessed for the separation of ‘Ristretto’ café espresso by employing 2DHPLC techniques with C18 phase selectivity detection. Geometric approach to factor analysis (GAFA) was used to measure the detected peaks (N), spreading angle (β), correlation, practical peak capacity (n_p) and percentage usage of the separations space, as an assessment of selectivity differences between regional quadrants of the two-dimensional separation plane. Although all tested systems were correlated to some degree to the C18 dimension, regional measurement of separation divergence revealed that performance of specific systems was better for certain sample components. The results illustrate that because of the complexity of the ‘real’ sample obtaining a truly orthogonal two-dimensional system for complex samples of natural origin may be practically impossible.

The analysis of café espresso using two-dimensional reversed phase–reversed phase high performance liquid chromatography with UV-absorbance and chemiluminescence detection

In this study, an activity based screening technique combining two-dimensional liquid chromatography (2DHPLC) with UV-absorbance and chemiluminescence detection was applied to study “Ristretto”, "Decaffeinatto” and “Volluto” espresso coffees. This technique, which coupled the separation power of 2DHPLC with the sensitivity and selectivity of the chemiluminescence detection, offers great potential for screening complex samples for antioxidant compounds. Detailed information regarding the complexity of the sample, and the variation between these three coffees could be obtained using this multidimensional-hyphenated method of analysis.

Peak modeling approach to accurate assignment of first-dimension retention times in comprehensive two-dimensional chromatography

Modeling of first-dimension retention of peaks based on modulation phase and period allows reliable prediction of the modulated peak distributions generated in the comprehensive two-dimensional chromatography experiment. By application of the inverse process, it is also possible to use the profile of the modulated peaks (their heights or areas) to predict the shape and parameters of the original input chromatographic band (retention time, standard deviation, area) for the primary column dimension. This allows an accurate derivation of the firstdimension retention time (RSD 0.02%) which is equal to that for the non-modulated experiment, rather than relying upon the retention time of the major modulated peak generated by the modulation process (RSD 0.16%). The latter metric can produce a retention time that differs by at least the modulation period employed in the experiment, which displays a discontinuity in the retention time vs modulation phase plot at the point of the 180° out-ofphase modulation. In contrast, the new procedure proposed here gives a result that is essentially independent of modulation phase and period. This permits an accurate value to be assigned to the first-dimension retention. The proposed metric accounts for the time on the seconddimension, the phase of the distribution, and the holdup time that the sampled solute is retained in the modulating interface. The approach may also be based on the largest three modulated peaks, rather than all modulated peaks. This simplifies the task of assigning the retention time with little loss of precision in band standard deviation or retention time, provided that these peaks are not all overloaded in the first or second dimension.

Effects of variation in modulator temperature during cryogenic modulation in comprehensive two-dimensional gas chromatography

Many modulation systems in comprehensive 2D GC (GC×GC) are based on cryogenic methods. High trapping temperatures in these systems can result in ineffective trapping of the more volatile compounds, whilst temperatures that are too low can prevent efficient remobilisation of some compounds. To better understand the trapping and release of compounds over a wide range of volatilities, we have investigated a number of different constant temperature modulator settings, and have also examined a constant temperature differential between the cryo-trap and the chromatographic oven. These investigations have led us to modify the temperature regulation capabilities of the longitudinally modulated cryogenic system (LMCS). In contrast to the current system, where the user sets a constant temperature for the cooling chamber, the user now sets the temperature difference between the cryo-trap and the chromatographic oven. In this configuration, the cooling chamber temperature increases during the chromatographic run, tracking the oven temperature ramp. This produces more efficient, volatility-dependent modulation, and increases the range of volatile compounds that can be analysed under optimal trap-and-release conditions within a single analytical run. This system also reduces cryogenic fluid consumption.

Two-dimensional correlation localized surface plasmon resonance spectroscopy for analysis of the interaction between metal nanoparticles and bovine serum albumin

Time-resolved extinction spectra assisted with two-dimensional correlation spectroscopy (2DCOS) analysis and principal component analysis (PCA) were employed to investigate the interaction between bovine serum albumin (BSA) and metal nanoparticles (NPs). A series of localized surface plasmon resonance (LSPR) spectra of metal NPs were measured just after a small amount of BSA was added into metal colloids. Through 2DCOS analysis, remarkable changes in the intensities of the LSPR were observed. The interaction process was totally divided into three periods according to the PCA. Transmission electron microscopy, dynamic light scattering, and ζ-potential measurements were also employed to characterize the interaction between BSA and metal NPs. The addition of BSA brings silver NPs to aggregate through the electrostatic interaction between them, but it has less effect on gold NPs. In a gold and silver mixed system, gold NPs can affect the interaction of silver NPs and BSA, leading it to weaken. The combination of 2DCOS analysis and LSPR spectroscopy is powerful for exploring the LSPR spectra of the metal NP involved systems. This combined technique holds great potential in LSPR sensing through analysis of slight, slim spectral changes of metal colloids