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.

Ridge regression for two dimensional locality preserving projection

Two Dimensional Locality Preserving Projection (2D-LPP) is a recent extension of LPP, a popular face recognition algorithm. It has been shown that 2D-LPP performs better than PCA, 2D-PCA and LPP. However, the computational cost of 2D-LPP is high. This paper proposes a novel algorithm called Ridge Regression for Two Dimensional Locality Preserving Projection (RR- 2DLPP), which is an extension of 2D-LPP with the use of ridge regression. RR-2DLPP is comparable to 2DLPP in performance whilst having a lower computational cost. The experimental results on three benchmark face data sets - the ORL, Yale and FERET databases - demonstrate the effectiveness and efficiency of RR-2DLPP compared with other face recognition algorithms such as PCA, LPP, SR, 2D-PCA and 2D-LPP.

Interobserver reliability of radial head fracture classification : two-dimensional compared with three-dimensional CT

Background: The Broberg and Morrey modification of the Mason classification of radial head fractures has substantial interobserver variation. This study used a large web-based collaborative of experienced orthopaedic surgeons to test the hypothesis that three-dimensional reconstructions of computed tomography (CT) scans improve the interobserver reliability of the classification of radial head fractures according to the Broberg and Morrey modification of the Mason classification.

Methods: Eighty-five orthopaedic surgeons evaluated twelve radial head fractures. They were randomly assigned to review either radiographs and two-dimensional CT scans or radiographs and three-dimensional CT images to determine the fracture classification, fracture characteristics, and treatment recommendations. The kappa multirater measure (κ) was calculated to estimate agreement between observers.

Results: Three-dimensional CT had moderate agreement and two-dimensional CT had fair agreement among observers for the Broberg and Morrey modification of the Mason classification, a difference that was significant. Observers assessed seven fracture characteristics, including fracture line, comminution, articular surface involvement, articular step or gap of ≥2 mm, central impaction, recognition of more than three fracture fragments, and fracture fragments too small to repair. There was a significant difference in kappa values between three-dimensional CT and two-dimensional CT for fracture fragments too small to repair, recognition of three fracture fragments, and central impaction. The difference between the other four fracture characteristics was not significant. Among treatment recommendations, there was fair agreement for both three-dimensional CT and two-dimensional CT.

Conclusions: Although three-dimensional CT led to some small but significant decreases in interobserver variation, there is still considerable disagreement regarding classification and characterization of radial head fractures. Three-dimensional CT may be insufficient to optimize interobserver agreement.

Interobserver reliability of coronoid fracture classification : two-dimensional versus three-dimensional computed tomography

Purpose : This study tests the hypothesis that 3-dimensional computed tomography (CT) reconstructions improve interobserver agreement on classification and treatment of coronoid fractures compared with 2-dimensional CT.

Methods : A total of 29 orthopedic surgeons evaluated 10 coronoid fractures on 2 occasions (first with radiographs and 2-dimensional CT and then with radiographs and 3-dimensional CT), separated by a minimum of 2 weeks. Surgeons classified fractures according to the classifications of Regan and Morrey and of O'Driscoll et al., identified specific characteristics, recommended the most appropriate treatment approach, and made treatment recommendations. The kappa multirater measure (κ) was calculated to estimate agreement between observers.

Results : Regardless of the imaging modality used, there was fair to moderate agreement for most of the observations. Three-dimensional CT improved interobserver agreement in Regan and Morrey's classsication (κ3-dimensional = 0.51 vs κ2-dimensional = 0.40; p < .001) and O'Driscoll et al.'s classifications (κ3-dimensional = 0.48 vs κ2-dimensional = 0.42; p = .009). There were trends toward better reliability for 3-dimensional reconstruction in recognition of coronoid tip fractures (κ3-dimensional = 0.19, κ2-dimensional = 0.03; p = .268), comminution (κ3-dimensional = 0.41 vs κ2-dimensional = 0.29; p = .133), and impacted fragments (κ3-dimensional = 0.39 vs κ2-dimensional = 0.27; p = .094), and in surgeons' opinions on the need for something other than screws or plate for surgical fixation (κ3-dimensional = 0.31 vs κ2-dimensional = 0.15; p = .138). Interobserver agreement on treatment approach was better with 2-dimensional CT (κ3-dimensional = 0.27, κ2-dimensional = 0.32; p = .015).

Conclusions : Three-dimensional CT reconstructions improve interobserver agreement with respect to fracture classification compared with 2-dimensional CT.

Peak picking and the assessment of separation performance in two-dimensional high performance liquid chromatography

An algorithm was developed for 2DHPLC that automated the process of peak recognition, measuring their retention times, and then subsequently plotting the information in a two-dimensional retention plane. Following the recognition of peaks, the software then performed a series of statistical assessments of the separation performance, measuring for example, correlation between dimensions, peak capacity and the percentage of usage of the separation space. Peak recognition was achieved by interpreting the first and second derivatives of each respective one-dimensional chromatogram to determine the 1D retention times of each solute and then compiling these retention times for each respective fraction ‘cut’. Due to the nature of comprehensive 2DHPLC adjacent cut fractions may contain peaks common to more than one cut fraction. The algorithm determined which components were common in adjacent cuts and subsequently calculated the peak maximum profile by interpolating the space between adjacent peaks. This algorithm was applied to the analysis of a two-dimensional separation of an apple flesh extract separated in a first dimension comprising a cyano stationary phase and an aqueous/THF mobile phase as the first dimension and a second dimension comprising C18-Hydro with an aqueous/MeOH mobile phase. A total of 187 peaks were detected.

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.

Fracture modelling of DP780 sheets using a hybrid experimental-numerical method and two-dimensional digital image correlation

This paper is concerned with the construction of fracture envelopes of DP780 sheets using two methods: a hybrid experimental-numerical method; two-dimensional digital image correlation (2D-DIC). For the hybrid method, four types of ductile fracture tests were carried out covering a wide range of stress states on specimens: with a central hole; two symmetric circular notches; flat grooved; and diagonally double-notched. Based on the fracture strain and loading paths identified with finite element simulation, a fracture envelope was obtained by employing the three-parameter modified Mohr-Coulomb fracture model. In addition, the fracture surface strain was directly measured using 2D-DIC. Loading histories of each test were extracted from a surface element of a three dimensional finite element model. The comparison of fracture envelopes constructed by the two methods reveals that there is little difference. Thus, it can be concluded that 2D-DIC is applicable to fracture modelling of DP780 sheets despite the assumption of the plane stress condition even after necking

General synthesis of two-dimensional patterned conducting polymer-nanobowl sheet via chemical polymerization

A general method for the generation of two-dimensional (2D) ordered, large-area, and liftable conducting polymer-nanobowl sheet has been demonstrated via chemical polymerization for the first time. The sheet is made using the monolayer self-assembled from polystyrene (PS) spheres at the aqueous/air interface as template, followed by depositing conducting polymer on the part of PS monolayer submerging in the aqueous phase via chemical polymerization, and core extraction. During the process of polymerization, no substrate is required, which caused the as-prepared patterned conducting polymer sheet can be easily lifted-off and deposited, in full size, on any flat substrate. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectrum were used to characterize the products