Genomic basis and phenotypic manifestation of (non-)parallel serpentine adaptation in Arabidopsis arenosa.

Parallel evolution is common in nature and provides one of the most compelling examples of rapid environmental adaptation. In contrast to the recent burst of studies addressing genomic basis of parallel evolution, integrative studies linking genomic and phenotypic parallelism are scarce. Edaphic islands of toxic serpentine soils provide ideal systems for studying rapid parallel adaptation in plants, imposing strong, spatially replicated selection on recently diverged populations. We leveraged threefold independent serpentine adaptation of Arabidopsis arenosa and combined reciprocal transplants, ion uptake phenotyping, and available genome-wide polymorphisms to test if parallelism is manifested to a similar extent at both genomic and phenotypic levels. We found pervasive phenotypic parallelism in functional traits yet with varying magnitude of fitness differences that was congruent with neutral genetic differentiation between populations. Limited costs of serpentine adaptation suggest absence of soil-driven trade-offs. On the other hand, the genomic parallelism at the gene level was significant, although relatively minor. Therefore, the similarly modified phenotypes, for example, of ion uptake arose possibly by selection on different loci in similar functional pathways. In summary, we bring evidence for the important role of genetic redundancy in rapid adaptation involving traits with polygenic architecture.

Carbon microparticles as a physical carrier for ETV-ICP-MS.

In this study, carbon microparticles (CMs) as a physical carrier to enhance the analyte transport efficiency for inductively coupled plasma mass spectrometry connected with electrothermal vaporization (ETV-ICP-MS) are proposed. Carbon microparticles mixed with samples or calibration standard solutions were dosed as a slurry into the graphite furnace. The optimization of working conditions was done for the standard solution 0.5 µg L-1 of Au and Tl. The pyrolysis and vaporization temperatures were 500 and 2700 °C for Au and 400 and 1900 °C for Tl. The optimized CMs concentration was 1 g L-1 for Au and 2.5 g L-1 for Tl. For the quantification, external calibration standard solutions were used. The result obtained for Au in the digested CRM GBW 07601 (the informatory value 2.1 ±â€¯2 µg kg-1) was 2.2 ±â€¯0.1 µg kg-1. The result for Tl in the digested CRM BCR 679 (the certified value 3 ±â€¯0.3 µg kg-1) was 3.2 ±â€¯0.2 µg kg-1 and in the slurry 2.7 ±â€¯0.1 µg kg-1. The result for Tl in the CRM GBW 10052 (the certified value 57 ±â€¯11 µg kg-1) was 51 ±â€¯3 µg kg-1. The instrumental limits of detection were 0.016 ng L-1 for Au and 0.026 ng L-1 for Tl. The recoveries and repeatabilities measured on calibration standards were in the range 99-100% and 0.2-2.3% for Au and 100-111% and 2.9-6.7% for Tl.

Outerly functionalized and non-functionalized boron clusters intercalated into layered hydroxides with different modes of binding: materials for superacid storage.

Two binary boron hydrides (NH4)2B10H10 and Na2B12H12 and mono- and dicarboxy p- and m-carboranes (namely, 1-(COOH)-closo-1,7-C2B10H11, 1,12-(COOH)2-closo-1,12-C2B10H10 and 1,7-(COOH)2-closo-1,7-C2B10H10) were intercalated into ZnAl-layered double hydroxides (ZnAl-LDH) and into Zn5(OH)8(NO3)2·2H2O. The formed compounds were characterized using elemental analysis, thermogravimetry analysis, X-ray powder diffraction, infrared spectroscopy and solid state NMR. All the intercalated boron compounds are present in the interlayer space of the layered hosts as anions. It is presumed that in the case of B10H102-, B12H122- and 1,12-(COO)2-closo-1,12-C2B10H102-, the guest molecules form a monolayer, whereas in the case of 1-(COO)-closo-1,7-C2B10H111- and 1,7-(COO)2-closo-1,7-C2B10H102- a bilayer arrangement is more probable. In the case of 1,7-(COO)2-closo-1,7-C2B10H102-, the guest molecules are strongly interdigitated resulting in lowering of the interlayer distance. Two different modes of binding were found. Whereas the carboxylate derivatives of p- and m-carboranes are bonded through classical hydrogen bonds, the corresponding parent borane anions interact with the host structures by mainly dihydrogen bonding. In effect, both kinds of hydrogen bonding are mainly of an electrostatic nature. The dihydrogen bond is detected, e.g. in crystal engineering, and represents a driving force for interactions of boranes with biomolecules. Since the latter dicarboxylic acids were found to be superacids, their interactions with the host structures should be stronger than in the case of the benzoic and terephthalic acid intercalates.

An elemental analysis of conventionally, organically and self-grown carrots.

Conventionally-, organically- and self-grown carrots available across the Czech market were characterised based on their elemental, nitrate and dry matter content (218 samples, 20 parameters) in order to assess the quality of the carrots and address the question whether organic also means better. The results were compared with information describing the elemental composition of carrots published previously, recommended daily intakes, and legislative limits for contaminants in food. Significant differences in the amounts of Na, K, S, Al, Mn, Ni, As and Cd were observed between conventional and organic carrots. From the perspective of inter-element interactions, and the origin of these, a principal components analysis of the datasets found no significant differences between conventionally- and organically-grown carrots. For the consumer, it is valuable to know there are no differences between conventionally- and organically-grown carrots, and no potential harm arising from heavy metal contamination. Based on our data, carrots are an excellent source of potassium.

Green synthesis of hyaluronan fibers with silver nanoparticles.

The application of green chemistry in the nano-science and technology is very important in the area of the preparation of various materials. In this work, an eco-friendly chemical method was successfully used for the preparation of hyaluronan fibers containing silver nanoparticles (AgNPs). Thus, hyaluronic acid (HA) was dissolved in an aqueous solution of sodium hydroxide to prepare a transparent solution, which was used for the preparation of fibers by a wet-spinning technique. Consequently, silver nanoparticles inside the fiber were prepared. Different parameters affecting the preparation of final product, such as concentration of silver nitrate, hyaluronan fiber concentration, time and temperature of the reaction, pH of the reaction mixture, were studied. AgNPs were confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD), two-dimensional X-ray scattering (2D SWAXS), UV/Vis spectroscopy, inductively coupled plasma optical emission spectrometry (ICP OES) and scan electron microscopy (SEM). Mechanical properties of prepared fibers were also measured.

Elemental analysis of nutritional preparations by inductively coupled plasma mass and optical emission spectrometry.

This paper reports the development and using of ICP-MS and ICP-OES methods for determination of major, minor and trace elements in multivitamin preparations and dietary supplements and, based on results, their classification using multivariate statistical methods. The method was optimised and evaluated with the use of "in-house" reference material, commercial reference materials and spiked samples. Macroelements (Na, K, Ca, Mg, P), microelements (Cu, Fe, Mn, Zn, Se, Cr), toxic elements (As, Cd, Pb, Ni, V) and a whole series of other elements (e.g. REEs, Ti, Au, Pt, Pd, etc.) were detected with excellent limits of detection as well as other procedure parameters suitable for the purpose of the elemental analysis. As for physiologically significant elements, contents were found as follows (mgkg(-1)): Ca 560-196,000, Mg 308-70,300, Na 289-74,000, K from undetectable to 28,200, Cu 28-1460, P from undetectable to 217,000, Zn 2.1-25,000, Fe 115-39,400, Mn 28-1860, Cr 0.486-26.6, Mo 0.0418-9.88, and Se 0.395-161. It was found out, if compared with recommended daily intakes, that maximally 50% Ca, 37% Mg, 3% K, 20% P, 14% Na, 100% Cu, 160% Mn, 190% Fe, 120% Zn, 24% Cr, 29% Mo and 79% Se can be obtained from one dose. Extreme samples presenting a possible health risk (Ni content nearly 200mgkg(-1)) were indicated. Most of the remaining elements (e.g. REEs) were analysed in order to get reference values for nutritional preparation.

Quantitative LIBS analysis of vanadium in samples of hexagonal mesoporous silica catalysts.

The method for the analysis of vanadium in hexagonal mesoporous silica (V-HMS) catalysts using Laser Induced Breakdown Spectrometry (LIBS) was suggested. Commercially available LIBS spectrometer was calibrated with the aid of authentic V-HMS samples previously analyzed by ICP OES after microwave digestion. Deposition of the sample on the surface of adhesive tape was adopted as a sample preparation method. Strong matrix effect connected with the catalyst preparation technique (1st vanadium added in the process of HMS synthesis, 2nd already synthesised silica matrix was impregnated by vanadium) was observed. The concentration range of V in the set of nine calibration standards was 1.3-4.5% (w/w). Limit of detection was 0.13% (w/w) and it was calculated as a triple standard deviation from five replicated determinations of vanadium in the real sample with a very low vanadium concentration. Comparable results of LIBS and ED XRF were obtained if the same set of standards was used for calibration of both methods and vanadium was measured in the same type of real samples. LIBS calibration constructed using V-HMS-impregnated samples failed for measuring of V-HMS-synthesized samples. LIBS measurements seem to be strongly influenced with different chemical forms of vanadium in impregnated and synthesised samples. The combination of LIBS and ED XRF is able to provide new information about measured samples (in our case for example about procedure of catalyst preparation).

Analytical capabilities of inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometry (ICP-oa-TOF-MS) for multi-element analysis of food and beverages.

Analytical capabilities of ICP-oa-TOF-MS for rapid, simultaneous and reliable determination of more than 50 major, trace and ultra-trace elements in different food and beverages samples (milk and dairy based products, cereals, meat, offal, sugar and sugar products, potatoes, fats, baby food samples, fruit juices, alcoholic beverages), following microwave closed vessel digestion of samples, were described. Under optimum instrumental conditions, and by using Rh as an internal standard and an external calibration method, ICP-oa-TOF-MS enables an accurate analysis, taking about one minute per a sample for all elements and isotopes of interest even for some elements such Zn, Ni, Cu, As or Co whose assay is more difficult when using conventional quadrupole instruments. In order to verify the accuracy and precision of the proposed method, 8 commercially available reference materials representing 3 major groups of food (milk and dairy based products, meat, cereals) were analysed, yielding results in agreement with certified values and the precision bellow 15%. In addition, accuracy was confirmed by spiked analytical recoveries study and accurate isotopic ratio determinations with the precision typically better than 5% with 5s data acquisition period, also for other elements of interest whose content was not certified and different sample matrices. Limits of detection (3σ) have varied from 0.04ngg(-1) for Th to 1630ngg(-1) for Ca.

Study of contamination sources in the process of cryogenic grinding.

The study of contamination effect during cryogenic grinding of pure cellulose was carried out. The optimisation of important parameters of the grinding process (pre-cooling time, grinding time, cooling time and number of cycles) was performed and the different sources of a possible contamination of samples (earlier processed sample, metal parts of grinding tool) were evaluated. The results of ICP-oa-TOF MS analysis after microwave digestion of cellulose samples were used in this study. Significant contamination of cellulose samples by Fe at the level 130 microg kg(-1) caused by wearing of steel stoppers and an impact bar was detected. Cross-contamination by Fe, Cr, Mn and Cu at the level 400, 200, 200 and 2100 microg kg(-1), respectively was caused by previous grinding of electro-waste sample. This cross-contamination was possible to be avoided by changing of a polycarbonate part of a grinding vessel.

Characterization of industrial explosives based on the determination of metal oxides in the identification particles by microwave digestion and atomic absorption spectrometry method.

Identification particles used for the purpose of the post-blast identification of explosives have a coding system based on the combination of metal oxides and their various concentrations. These materials are composed of the polymeric matrix, iron powder (ferromagnetic properties), UV light active dyestuff and various metal oxides in a various ratios. A suitable analytical method has to be used for an accurate characterization of these metal components in the particles in order to find the required information, i.e. to determine the place and the year of production and as the case may be, also the production batch of misused explosives. In this work, the method of microwave digestion and flame atomic absorption spectrometry (F-AAS) was developed for an accurate determination of Zn, Mg, Cu and Pb in a few novel types of identification particles and applied to their characterization. When using specific sample treatment (digestion with a mixture of nitric acid with hydrochloric or hydrofluoric acid), the 3 sigma limits of detection (LODs) for the determination of Zn, Mg, Cu and Pb in 5mg original samples were 1.9, 0.2, 1.3 and 2.4 mg g(-1), respectively. The signal suppression due to the presence of HNO3+HCl or HNO3+HF was observed for Zn; therefore, the calibration solutions had to be prepared exactly with the same acids as those used for the sample mineralization. The determination of Mg, Cu and Pb was free of interferences; hence a simple calibration curve method could be adopted for attaining accurate results. The accuracy was checked by comparison of the results with those obtained by means of independent inductively coupled plasma optical emission spectrometry (ICP-OES). Good precision values, as relative standard deviation, in the range of 1-5% were obtained. A total number of 71 samples was analysed and classified by multivariate methods to prove the suitability of the procedure proposed for the purpose of the identification of explosives.

The cryogenic grinding as the important homogenization step in analysis of inconsistent food samples.

Some homogenisation approaches have been investigated to make easier and overcome troublesome preparation of inconsistent food samples. Contents of Na, Ca, Mg, P, Fe, Mn and Zn in muesli, seed and instant food samples were determined by inductively coupled plasma optical emission spectrometry after their grinding with an agate mortar, a kitchen coffee grinder and a cryogenic mill. The efficiency of a grinding step was evaluated using RSDs and homogeneity factors (H-factor). For cryogenically grinded samples, RSDs were detected about 4% and H-factors on 10, what is acceptable for the analytical purpose. The results for grinding with an agate mortar as well as a coffee grinder were quite unsatisfactory (RSDs in tens percent). Differences between RSDs and H-factors for the procedures tested were detected to be statistically significant. Different element contents were observed in differently treated samples which is probably a result of an unevenly element distribution in inhomogeneous components forming sample.

Determination of metal impurities in pure hydroxides and salts by inductively coupled plasma optical emission spectrometry.

A simple analytical method sufficient for the determination of Na, K, Ca, Mg, Al, B, Ba, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb, Sr, V and Zn at mg kg(-1) levels in pure NaOH, KOH, NaCl and KCl using the optical emission spectrometry was developed. The results of direct determination with multi-elemental aqueous standards were compared with them obtained by the internal standardisation, by the standard addition methods and with the maximal allowable contents of above-mentioned elements in pure chemicals. The method was shown to be very sensitive and exhibits following limits of detection: Na 0.90, K 3.0, Ca 0.064, Mg 0.026, Al 0.43, B 0.13, Ba 0.015, Cd 0.023, Co 0.056, Cr 0.041, Cu 0.063, Fe 0.060, Li 0.017, Mn 0.035, Mo 0.19, Ni 0.055, Pb 0.39, Sr 0.030, V 0.065 and Zn 0.043 (all in mg kg(-1)). The method presents a satisfactory precision (relative standard deviation 4-11%), high analytical recoveries, linear responses of at least four orders of magnitude, accuracy and low contamination susceptibility.