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

Two-dimensional string notation for representing video sequences

Most current work on video indexing concentrates on queries which operate over high level semantic information which must be entirely composed and entered manually. We propose an indexing system which is based on spatial information about key objects in a scene. These key objects may be detected automatically, with manual supervision, and tracked through a sequence using one of a number of recently developed techniques. This representation is highly compact and allows rapid resolution of queries specified by iconic example. A number of systems have been produced which use 2D string notations to index digital image libraries. Just as 2D strings provide a compact and tractable indexing notation for digital pictures, a sequence of 2D strings might provide an index for a video or image sequence. To improve further upon this we reduce the representation to the 2D string pair representing the initial frame, and a sequence of edits to these strings. This takes advantage of the continuity between frames to further reduce the size of the notation. By representing video sequences using string edits, a notation has been developed which is compact, and allows querying on the spatial relationships of objects to be performed without rebuilding the majority of the scene. Calculating ranks of objects directly from the edit sequence allows matching with minimal calculation, thus greatly reducing search time. This paper presents the edit sequence notation and algorithms for evaluating queries over image sequences. A number of optimizations which represent a considerably saving in search time is demonstrated in the paper.

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.

Random Subspace Two-Dimensional PCA for face recognition

The two-dimensional Principal Component Analysis (2DPCA) is a robust method in face recognition. Much recent research shows that the 2DPCA is more reliable than the well-known PCA method in recognising human face. However, in many cases, this method tends to be overfitted to sample data. In this paper, we proposed a novel method named random subspace two-dimensional PCA (RS-2DPCA), which combines the 2DPCA method with the random subspace (RS) technique. The RS-2DPCA inherits the advantages of both the 2DPCA and RS technique, thus it can avoid the overfitting problem and achieve high recognition accuracy. Experimental results in three benchmark face data sets -the ORL database, the Yale face database and the extended Yale face database B - confirm our hypothesis that the RS-2DPCA is superior to the 2DPCA itself.

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.

Effect of Zn concentration and grain size on prismatic slip in Mg-Zn binary alloys

Mg-Zn binary alloys with concentrations between 0 and 2.8wt% Zn have been prepared and processed via hot rolling and annealing to produce specimens with a strong basal texture and a range of grain sizes. These have been deformed in tension, a condition in which the deformation is dominated by prismatic slip. This data has been used to assess the Hall-Petch parameter as a function of Zn concentration for deformation dominated by prismatic slip. Pure magnesium showed non-linear Hall-Petch behaviour at large grain sizes, and this is compared to the values for prismatic slip measured on single crystals. The differences between critical resolved shear stress measurements made through single crystal, polycrystal and mathematical modelling techniques are also discussed.

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