Allan variance for optimal signal averaging—monitoring by diode-laser and CO2 laser photo-acoustic spectroscopy

The concept of the Allan variance has been utilized to test the detection abilities of two powerful experimental methods for trace gas monitoring: IR diode-laser and CO₂ laser photo-acoustic spectroscopy. The detection of stable molecules (OCS, allene, CH₃OH), and unstable species (ozone, short-lived free radical CN and molecular ion ArD⁺) have been compared. An approach for studies of the influence of the reactivity on the optimal averaging time for the minimum detectable concentration is demonstrated.     

TAaCGH Suite for Detecting Cancer—Specific Copy Number Changes Using Topological Signatures

Copy number changes play an important role in the development of cancer and are commonly associated with changes in gene expression. Persistence curves, such as Betti curves, have been used to detect copy number changes; however, it is known these curves are unstable with respect to small perturbations in the data. We address the stability of lifespan and Betti curves by providing bounds on the distance between persistence curves of Vietoris–Rips filtrations built on data and slightly perturbed data in terms of the bottleneck distance. Next, we perform simulations to compare the predictive ability of Betti curves, lifespan curves (conditionally stable) and stable persistent landscapes to detect copy number aberrations. We use these methods to identify significant chromosome regions associated with the four major molecular subtypes of breast cancer: Luminal A, Luminal B, Basal and HER2 positive. Identified segments are then used as predictor variables to build machine learning models which classify patients as one of the four subtypes. We find that no single persistence curve outperforms the others and instead suggest a complementary approach using a suite of persistence curves. In this study, we identified new cytobands associated with three of the subtypes: 1q21.1-q25.2, 2p23.2-p16.3, 23q26.2-q28 with the Basal subtype, 8p22-p11.1 with Luminal B and 2q12.1-q21.1 and 5p14.3-p12 with Luminal A. These segments are validated by the TCGA BRCA cohort dataset except for those found for Luminal A.     

Total metal concentrations in serum of dialysis patients and fractionation of Cu, Rb, Al, Fe and Zn in spent continuous ambulatory peritoneal dialysis fluids

Total metal concentrations were determined in the serum of 12 continuous ambulatory peritoneal dialysis (CAPD) patients and in fresh and spent CAPD fluids by electrothermal and flame atomic absorption spectrometry (ETAAS, FAAS). Concentrations of Cu in serum of CAPD patients ranged from 720 to 1780 ng cm⁻³, Rb from 128 to 346 ng cm⁻³, Al from 10 to 72 ng cm⁻³, Fe from 800 to 2300 ng cm⁻³ and Zn from 659 to 1310 ng cm⁻³. The accuracy of the analytical procedure was checked by the analysis of the reference material Seronom™, Trace Elements in Serum. Good agreement between the certified and determined values was obtained for Al, Cu, Fe and Zn. The data on the total metal concentrations in CAPD fluids indicated that during CAPD fluid exchange the losses of Cu from 5.0 to 35 ng cm⁻³, of Rb from 50 to 110 ng cm⁻³ and of Al from 3.0 to 14.0 ng cm⁻³ occurred through the peritoneal membrane. Although fresh CAPD fluids contained traces of Fe (3.0-5.0 ng cm⁻³), the transfer of this element took place through the peritoneal membrane into spent CAPD fluid (13.0-38.0 ng cm⁻³). Zn concentrations were in general lower in spent (20.0-80 ng cm⁻³) than in fresh CAPD fluids (∼100 ng cm⁻³). To follow the mechanisms of the transfer of trace elements through the peritoneal membrane of CAPD patients, fractionation of metals was carried out in spent CAPD fluids by size exclusion chromatography with UV and AAS detection, applying Superdex HR 10/30 column. The chromatographic run was followed at 278 nm and separated metal species also determined ‘off line’ in 1 cm³ fractions by ETAAS or FAAS. From the UV chromatograms and AAS analysis of trace elements in the separated fractions it was demonstrated that Cu, Al, Fe and Zn were bound to proteins and only partially to low molecular weight (LMW) species, while Rb was associated exclusively with LMW species. For characterisation of the high molecular weight (HMW) binding proteins, fractions containing trace elements were subjected to SDS-PAGE electrophoresis. Al and Fe were presumably bound to transferrin, but due to its low concentration in spent CAPD fluids, it was not possible to confirm its presence in the separated fractions. About 10% of Al and 15% of Fe corresponded to LMW species. A fraction of HMW proteins of Cu in spent CAPD fluids was most probably bound to albumin and Zn to albumin and globulins. About 50% of Cu and Zn existed in LMW proteins, while Zn was also found partially in ionic form.     

Determination of Cr(VI) in welding fumes by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption spectrometric detection

The applicability of an anion-exchange fast protein liquid chromatographic-electrothermal atomic absorption spectrometric procedure (FPLC-ETAAS) was investigated for the determination of Cr(VI) in welding fumes after alkaline extraction of aerosols loaded on filters. Gas tungsten arc welding (GTAW) of stainless steel was applied. Samples of welding fumes were collected during regular welding on polycarbonate membrane filters of 8 microm and 0.4 microm pore size (inhalable and respirable aerosols). Alkaline extraction (2% NaOH-3% Na2CO3) of filters in a heated ultrasonic bath was applied to leach Cr from the airborne particulate matter. 0.5 cm3 of sample extract was then injected onto an anion-exchange FPLC column. Tris-HCl buffer (0.005 mol dm(-3), pH 8.0) and the same buffer with NaCl (0.5 mol dm(-3)) were employed in gradient elution (15 min, flow rate 1 cm3 min(-1)). The separated Cr species were determined "off line" by ETAAS in 0.5 cm3 fractions. Cr(VI) was reproducibly and quantitatively eluted from 12.0 to 13.0 min with a maximum peak at 12.5 min. Good repeatability of measurement (+/-3.0%) of alkaline extracts was obtained for Cr(VI). The LOD (3s) was found to be 0.035 microg m(-3) Cr(VI), when 2 m3 of aerosols were collected on the filter. Validation of the procedure was performed by spiking alkaline extracts and by the analysis of standard reference material CRM 545, Cr(VI) in welding dust loaded on a filter. The technique was successfully applied for the determination of Cr(VI) in welding fumes.     

Deviation of the Kempster?Lipson Law from Linearity

It is shown that the larger organic molecules composed of C, H, N, and O at most crystallizing in the voluminous unit cells tend to be more loosely packed than those that crystallize in the unit cells with small volumes. This is demonstrated by the deviation from the linear relationship (Kempster? Lipson law) between the unit‐cell volumes and the sum of the non‐H‐atoms in the unit cell. This deviation can be distinguished from the effect of the varying number of H‐atoms in the described compounds: the ratio of the non‐H‐atom to the H‐atoms converges to a constant value close to 1 towards the large unit‐cell volumes. The proportion of the disordered structures increases towards the large unit‐cell volumes and thus correlates with the less dense packing of the large molecules. The deviation of the Kempster? Lipson law from linearity can be interpreted as the manifestation of decreasing ability of a crystallization of large molecules.     

Diagrammatic categorification of the Chebyshev polynomials of the second kind

We develop a diagrammatic categorification of the polynomial ring Z[x], based on a geometrically defined graded algebra. This construction generalizes to categorification of some special functions, such as Chebyshev polynomials. Diagrammatic algebras featured in these categorifications lead to the first topological interpretations of the Bernstein-Gelfand-Gelfand reciprocity property.     

Tris­(methyl­ammonium) hydrogen­phosphate di­hydrogenphosphate

The title compound, 3CH₆N⁺·HPO₄²⁻·H₂PO₄⁻, aggregates with the moieties interconnected by O—H⋯O and N—H⋯O hydrogen bonds, with O⋯O and N⋯O distances in the ranges 2.5366 (16)–2.5785 (14) and 2.7437 (16)–2.9967 (18) Å, respectively. Three C—H⋯O hydrogen bonds are also present, with C⋯O distances in the range 3.2310 (18)–3.3345 (17) Å. All H atoms are ordered. Structures with ordered hydrogenphosphate and di­hydrogen­phosphate components are rare.     

Technetium removal from the aqueous solution using zeolites A and Y containing transition metal ions Co2+ and Zn2+

Journal of Radioanalytical and Nuclear Chemistry - The adsorption properties of two zeolite types, faujasite (NaY, ZnY, CoY) and LTA-4A zeolite (NaA, ZnA, CoA), towards technetium were studied in...     

Ni speciation in tea infusions by monolithic chromatography—ICP-MS and Q-TOF-MS

For humans, Ni is not considered to be an essential trace element. Its compounds, at levels present in foodstuffs and drinks, are generally considered to be safe for consumption, but for individuals who already suffer from contact allergy to Ni and may be subject to develop systemic reactions from its dietary ingestion, dietary exposure to Ni must be kept under control. Being the second most popular beverage, tea is a potential source of dietary Ni. Present knowledge on its speciation in tea infusions is poor. Therefore, complete speciation analysis, consisting of separation by liquid chromatography using a weak CIM DEAE-1 monolithic column, “on-line” detection by inductively coupled plasma mass spectrometry (ICP-MS) and “off-line” identification of ligands by hybrid quadrupole time-of-flight mass spectrometry (Q-TOF MS), was implemented for the first time to study Ni speciation in tea infusions. Total concentrations of Ni in dry leaves of white, green, oolong and black tea (Camellia sinensis) and flowers of herbal chamomile (Matricaria chamomilla) and hibiscus (Hibiscus sabdariffa) tea were determined after microwave digestion by ICP-MS. They lay between 1.21 and 14.4 mg?kg^?1. Good agreement between the determined and the certified values of the Ni content in the standard reference material SRM 1573a tomato leaves confirmed the accuracy of the total Ni determination. During the infusion process, up to 85 % of Ni was extracted from tea leaves or flowers. Separation of Ni species was completed in 10 min by applying aqueous linear gradient elution with 0.6 mol?L^?1 NH₄NO₃. Ni was found to be present in the chromatographic fraction in which quinic acid was identified by Q-TOF in all the tea infusions analysed, which had pH values between 5.6 and 6.0. The only exception was the infusion of hibiscus tea with a pH of 2.7, where results of speciation analysis showed that Ni is present in its divalent ionic form.