Spectrum adapted the expectation-maximization algorithm for high-throughput peak shift analysis.

We introduce a spectrum-adapted expectation-maximization (EM) algorithm for high-throughput analysis of a large number of spectral datasets by considering the weight of the intensity corresponding to the measurement energy steps. Proposed method was applied to synthetic data in order to evaluate the performance of the analysis accuracy and calculation time. Moreover, the proposed method was performed to the spectral data collected from graphene and MoS2 field-effect transistors devices. The calculation completed in less than 13.4 s per set and successfully detected systematic peak shifts of the C 1s in graphene and S 2p in MoS2 peaks. This result suggests that the proposed method can support the investigation of peak shift with two advantages: (1) a large amount of data can be processed at high speed; and (2) stable and automatic calculation can be easily performed.

Lipid index to quantify the absorbed lipids in retrieved UHMWPE components of joint arthroplasty.

BACKGROUND: The ultra-high molecular weight polyethylene (UHMWPE) component of artificial joints is one of the most important factors affecting the clinical outcomes of joint arthroplasty. Although the possibility of in vivo UHMWPE degradation caused by absorbed lipids has been reported, a quantitative evaluation of this phenomenon has not yet been performed. OBJECTIVE: This study aimed to establish the lipid index (LI) as a quantitative indicator of the amount of absorbed lipids and the first step to quantify their effects on UHMWPE. METHODS: The LI was defined using the infrared spectrum obtained with a Fourier-transform infrared spectrophotometer and verified using the retrieved UHMWPE components. RESULTS: The LI was consistent with the amount of extract recovered in reflux extraction with hexane. In addition, the LI could replace lipid extraction for calculating the oxidation index (OI) because the value obtained by subtracting the LI from the OI showed good agreement with the OI obtained after lipid extraction. CONCLUSION: The LI represents the amount of lipids absorbed by UHMWPE and is useful for quantitatively evaluating the effects of lipids on UHMWPE. In addition, the LI enables OI measurements that are unaffected by absorbed lipids without requiring troublesome lipid-extraction procedures.

Theory of linear focusing in chromatographic columns with exponential retention. Part 2: Analysis of special cases.

The unified approach to studies of different separation techniques (GC, LC, etc.) adopted in Part 1 continued herein. As before, the column temperature in GC, the solvent composition in LC, etc., are represented by the concept of solute mobilization (y). General equations for dynamic (moving) linear y-gradients (gradients in y) in non-uniform columns developed in Part 1 are reduced herein to special cases of uniform columns. Only the uniform columns, the ideal sample introduction, the positive y-rates, the negative y-gradients, and the eluting solutes are considered. Equations for solute band compression, peak width, peak focusing, peak separation and others derived. All equations are expressed via dimensionless parameters eliminating unessential factors like the mobile phase type, column type and dimensions, etc. The conventional gradient elution LC is treated as a special case of the separations with y-gradients. Effects of the y-gradients on solute retention time, on band compression, on peak focusing and on peak separation are analyzed. The equations developed herein, while describing simple and familiar concepts (retention time, peak width, etc.), are, unfortunately, cumbersome in many cases. The good news is that the equations are exact and the conditions of existence of the equations are explicitly formulated so that there is no question where the equations can and where thy cannot be used.

Separation of Chromatographic Co-Eluted Compounds by Clustering and by Functional Data Analysis.

Peak overlapping is a common problem in chromatography, mainly in the case of complex biological mixtures, i.e., metabolites. Due to the existence of the phenomenon of co-elution of different compounds with similar chromatographic properties, peak separation becomes challenging. In this paper, two computational methods of separating peaks, applied, for the first time, to large chromatographic datasets, are described, compared, and experimentally validated. The methods lead from raw observations to data that can form inputs for statistical analysis. First, in both methods, data are normalized by the mass of sample, the baseline is removed, retention time alignment is conducted, and detection of peaks is performed. Then, in the first method, clustering is used to separate overlapping peaks, whereas in the second method, functional principal component analysis (FPCA) is applied for the same purpose. Simulated data and experimental results are used as examples to present both methods and to compare them. Real data were obtained in a study of metabolomic changes in barley (Hordeum vulgare) leaves under drought stress. The results suggest that both methods are suitable for separation of overlapping peaks, but the additional advantage of the FPCA is the possibility to assess the variability of individual compounds present within the same peaks of different chromatograms.

Three-Dimensional Calibration for Routine Analyses of Bromide and Nitrate Ions as Indicators of Groundwater Quality in Coastal Territories.

Nitrate and bromide ions are generally considered indicators of anthropogenic pollution and seawater intrusion, respectively, in the groundwater of coastal territories. The analysis of these species is generally carried out with routine chromatographic analyses which generally afford partially merged or poorly resolved peaks. In the present paper a simple method for the correct evaluation of their concentration in water is reported. This method does not imply utilization of other instruments or technologies, only the mathematical elaboration of the data obtained from routine analysis of standard solutions containing the two species. Standard binary solutions of nitrate and bromide ions at different concentrations, ranging between 0.1 and 2 mM, were analyzed by means of ion chromatography. Splitting two partially merged chromatographic peaks and considering each resulting area as originating from a single species produces "measured" concentration values which differ from the nominal ones. Such a procedure generates errors (one per species) which can be written as a function of the above mentioned "measured" concentrations and which can be graphically represented by means of a surface in a three-dimensional (3D) space. In this way, "measured" concentrations of bromide and nitrate ions can be corrected by calculating the errors generated under the experimental conditions at which the chromatographic separation is performed. Notably, this is analogous with the two-dimensional (2D) calibration normally carried out for analytical purposes. Indeed, both methods allow estimation of the unknown concentration of species in solution by correlating the instrumental response with the concentration of standard solutions.

Development of a design of experiments optimized method for quantification of polysorbate 80 based on oleic acid using UHPLC-MS.

The aim was to develop a straightforward UHPLC-MS quantification method for polysorbate 80 using oleic acid as surrogate marker, which was the commonest substance within the emulsifier. However, hydrolysis of polysorbate 80 and subsequent analysis of fatty acids revealed a co-elution of oleic acid and an isomer while all the other fatty acids were successfully separated by varying retention times and mass-to-charge ratios. For identification and separation of the isomer a derivatization method was evaluated. Oxidation to the corresponding dihydroxystearic acids with potassium permanganate resulted in peak separation of cis/trans and structural isomers of the 18:1 fatty acids. Hydrolyzed and derivatized polysorbate 80 was quantified indirectly in the range of 0.046-5.83 µg/mL (R2 > 0.997) with a limit of detection of 11.4 ng/mL. Quantification of polysorbate 80 using oleic acid as a surrogate marker showed good reproducibility and linearity. As all isomers of the 18:1 fatty acids were successfully separated, the previously co-eluting peak was identified as elaidic acid and was found as a component in the mixture of the emulsifier polysorbate 80. Additionally, cis-vaccenic acid was separated as a second co-eluting isomer. Therefore, derivatization led to successful chromatographical separation of cis/trans and structural 18:1 fatty acid isomers.

Acid hydrolysis of corn starch genotypes. I. Impact on morphological and molecular properties.

With respect of the partial molecular degradation of the starch polysaccharides, the impact of the acid-thinning process on the specific starch properties of two corn genotypes was investigated. A high amylose corn (HACS) and a waxy corn (WxCS) starch were hydrolyzed using HCl in the laboratory scale slurry process (40% w/w, 30 °C). The acid concentration (0.3, 0.6 and 0.9 M) as well as the hydrolysis time (4, 10 and 20 h) were graded systematically (experimental design) and the obtained modified starch genotypes characterized comprehensively. As revealed by scanning electron micoscopy (SEM), the supramolecular structure was preserved in general, and the carbohydrate solubilization was limited to about 2-3 %. Molecularly dispersed solutions were characterized by means of size exclusion chromatography-multi angle laser light scattering-differential refractive index detection (SEC-MALS-DRI). Both acid concentration and hydrolysis time reduced the molar mass (MM) of the starch [HACS: 4.4∙106 (native)…1.2∙106 g∙mol-1 (highest degree of degradation); WxCS: 49.7∙106 (native)…6.4∙106 g∙mol-1 (highest degree of degradation)], the amylose (AM) fraction as well as the amylopectin (AP) branch chain length systematically. Perceptible differences in dependence on starch variety were ascertained and discussed. The molecular properties of the investigated acid-thinned genotypes are selectively controllable with the hydrolysis process. The relationship between modification process, starch's molecular state, and resulting functional properties was examined in the second part of the study.

Biotic and abiotic characterization of bioanodes formed on oxidized carbon electrodes as a basis to predict their performance.

Bioelectrochemical systems (BESs) are based on the catalytic activity of biofilm on electrodes, or the so-called bioelectrodes, to produce electricity and other valuable products. In order to increase bioanode performance, diverse electrode materials and modification methods have been implemented; however, the factors directly affecting performance are yet unclear. In this work carbon cloth electrodes were modified by thermal, chemical, and electrochemical oxidation to enhance oxygenated surface groups, to modify the electrode texture, and consequently the electron transfer rate and biofilm adhesion. The oxidized electrodes were physically, chemically, and electrochemically characterized, then bioanodes were formed at +0.1 V vs. Ag/AgCl using domestic wastewater amended with acetate. The bioanode performance was evaluated according to the current and charge generated. The efficacy of the treatments were in the order Thermal>Electrochemical>Untreated>Chemical oxidation. The maximum current observed with untreated electrode was 0.152±0.026 mA (380±92 mA m(-2)), and it was increased by 78% and 28% with thermal and electrochemical oxidized electrodes, respectively. Moreover, the volatile solids correlated significantly with the maximum current obtained, and the electrode texture was revealed as a critical factor for increasing the bioanode performance.