Matrix-assisted laser desorption/ionisation mass spectrometry for the direct analysis of enzymatically digested kappa- iota- and hybrid iota/nu-carrageenans

Enzymatically digested oligosaccharides of kappa-, iota- and hybrid iota/nu-carrageenans were analysed using matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry in the negative-ion mode. nor-Harmane was used as matrix. Depending on the stock concentration and the laser intensity applied, the oligosaccharides exhibited losses of sulphate units (neutralised by the Na+ ion, and thus non-stable), leaving the primary backbone structure in most cases with only the deprotonated sulphate groups (carrying the negative charge, stable). This meant that kappa- and iota-oligosaccharides could not be easily distinguished from one another since they share the same primary backbone structure. However, for the hybrid iota/nu-oligosaccharides the primary backbone structure could be identified since the nu-carrageenan repeating unit differs from that of the kappa/iota-carrageenan unit. For all types of oligosaccharides, the results indicated cleavage of an anhydrogalactose unit from the non-reducing end. Specifically, for the hybrid oligosaccharides of iota/nu-carrageenans, this type of fragmentation means that the nu-carrageenan unit is not positioned on the non-reducing end of the hybrid oligosaccharides. Dehydration reactions, and exchange reactions of Na+ with K+ and Ca2+, were also observed.     

Heat transfer in tube assemblies under conditions of laminar axial,transverse and inclined flow

This paper considers laminar flow heat transfer in tube assemblies. The main interest is focused on the virtually unexplored cases of heat transfer under conditions of fully-developed flow inclined to the axes of the tubes and of purely transverse developing flow. The limiting cases of purely axial or purely transverse fully-developed flow are also examined. In all cases, the thermal boundary condition on the tubes is constant heat flux. Governing differential equations are expressed in terms of curvilinear-orthogonal coordinates and solved using finite-differences. Results are compared with available theoretical and experimental data. The effect of the transverse component of the flow on the temperature distribution is found to remain very strong even in nearly-axial flows and therefore considerably higher heat transfer coefficients are exhibited by a nearly-axial flow than a purely axial one.     

Ion implantation effects on the microhardness and microstructure of GaN

We study the effect of N⁺ and O⁺ implantation on the microhardness and the microstructure of epitaxially grown GaN. The microhardness is measured using a Knoop diamond indenter while information on the effect of implantation on the surface morphology, microstructure and electronic structure is provided by atomic force microscopy, cross-section transmission electron microscopy and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It is demonstrated that implantation increases the surface microhardness. A possible mechanism for the surface hardening effect is based on the formation of N interstitials that pin the dislocations and prohibit the plastic deformation. In addition to the hardening effect, the implantation induced N interstitials introduce a characteristic resonance in the NEXAFS spectra, at 1.4 eV below the absorption edge.     

Tandem mass spectrometry for the characterisation of sulphated-phosphorylated analogues of the carbohydrate-protein linkage region of proteoglycans

Carbohydrate-protein linkage region of proteoglycans is a key oligosaccharide structure because their sulphated and/or phosphorylated analogues control the biosynthesis of glucosaminoglycans or galactosaminoglycans. Therefore, synthesised sulphated and/or phosphorylated analogues were characterised by tandem mass spectrometry in the negative-ion mode. Results demonstrated that the product ion profile was characterised by glycosidic and cross-ring cleavages depending on the position and the type of the charged group (sulphate, phosphate or carboxylate). When the above compounds were sulphated and phosphorylated, the ion found at m/z 79 was the only one that demonstrated a phosphate group on the structure. The data also suggested that when a sodium cation was present in a sulphated and phosphorylated structure, the phosphate group in most cases was neutralised by the sodium cation, and therefore cleaved off the molecule, while the sulphate group was carrying the negative charge.     

Critical features in electromagnetic anomalies detected prior to the L’Aquila earthquake

Earthquakes (EQs) are large-scale fracture phenomena in the Earth’s heterogeneous crust. Fracture-induced physical fields allow a real-time monitoring of damage evolution in materials during mechanical loading. Electromagnetic (EM) emissions in a wide frequency spectrum ranging from kHz to MHz are produced by opening cracks, this can be considered as the so-called precursors of general fracture. We emphasize that the MHz radiation appears earlier than the kHz on both laboratory and geophysical scales. An important challenge in this field of research is to distinguish characteristic epochs in the evolution of precursory EM activity and identify them with the equivalent last stages in the EQ preparation process. Recently, we proposed the following two-stage model. (i) The first epoch, which includes the initial emergent MHz EM emission, is thought to be due to the fracture of a highly heterogeneous system that surrounds a family of large high-strength asperities distributed along the activated fault sustaining the system. (ii) The second epoch, which includes the emergent strong impulsive kHz EM radiation, is due to the fracture of the asperities themselves. A catastrophic EQ of magnitude Mw=6.3 occurred on 6 April, 2009 (06/04/09) in central Italy. The majority of the damage occurred in the city of L’Aquila. Clear kHz–MHz EM anomalies had been detected prior to the L’Aquila EQ. Here, we investigate the seismogenic origin of the MHz part of the anomalies. The analysis, which is in terms of intermittent dynamics of critical fluctuations, reveals that the candidate EM precursor (i) can be described as analogous to a thermal continuous phase transition and (ii) has anti-persistent behavior. These features suggest that this candidate precursor was triggered by microfractures in the highly disordered system that surrounded the backbone of asperities of the activated fault. A criterion for underlying strong critical behavior is introduced. In this field of research, reproducibility of results is desirable; and is best done by analyzing a number of precursory MHz EM emissions. We refer to previous studies of precursory MHz EM activities associated with nine significant EQs that have occurred in Greece in recent years. We conclude that all the MHz EM precursors studied, including the present one, can be described as analogous to a continuous second-order phase transition having strong criticality and anti-persistent behavior.     

On-line liquid chromatography-electrospray ionisation mass spectrometry for kappa-carrageenan oligosaccharides with a porous graphitic carbon column

Enzymatically digested oligosaccharides of kappa-carrageenans were separated on a porous graphitic carbon (PGC) column and characterised on-line by electrospray ionisation mass spectrometry (ESI-MS). Two different developing ions were applied. Among them ammonium hydrogencarbonate showed more eluting power as it should on normal anion-exchange stationary phases. The oligosaccharides were detected by ESI-MS as fully deprotonated oligosaccharides.     

Methodology to Assess the Effects of Rice Cultivation Under Flooded Conditions on van Genuchten’s Model Parameters and Pore Size Distribution

The effects of rice (Oryza sativa L.) cultivation under flooded conditions on soil’s physical-hydraulic properties were studied in this article, using a new methodology based on a combined analysis on soil water retention curve (WRC) and pore size distribution (PSD). WRC analysis was carried out through the changes of van Genuchten’s model parameters, the characteristics of WRC at the inflection point, and the specific water capacity curve. Analysis of PSD was performed on the volume changes of porosity fractions through a detailed pore size classification, while different pore size classifications based on their hydraulic and structural characteristics were also used. The methodology was applied using a small dataset obtained from fine-textured Entisol soils which were subjected to rice cultivation under flooded conditions in Axios River plain (Northern Greece). Measurements of WRC were obtained at four depths of the soil profile from two fields, before and after the growing season of rice. The analysis indicated that the van Genuchten’s model parameters (θ _s, a, and n) and the WRC characteristics at the inflection point (pressure head h _i , pore equivalent diameter D _i , and slope S _i ) significantly changed after the growing season following similar patterns, along the soil profile in both fields. The parameters θ _s, a, D _i , and S _i were decreased, while n and h _i were increased. The h _i and a were the most sensitive parameters, while the values of (h _i and 1/a) in each layer before and after the growing season for each field were linearly correlated and shifted to higher values because of compaction, indicating that it could be applied as a tool to evaluate the degree of soil compaction to similarly textured soils. The peaks of the specific water capacity curves were compressed (lower values of slope S _i ) and shifted to lower water potentials (h _i ) that corresponded to pores of equivalent diameter D _i between 2 and 6 μm. The soils had few structural pores (>9 μm) and low air-filled porosity (>30 μm) before the growing season, which presented accessory reduction after the growing season in both fields. Total porosity was reduced at the expense of structural porosity along the soil profile, while the pore size class of 5–3 μm was identified as the threshold where the smaller pores’ volume started to increase in all layers of both fields. The results indicated that the changes in the WRC and the PSD follow specific trends, which can be used in future studies to model temporal variability of soil’s physical-hydraulic properties.     

Forest fire retardancy evaluation of carbonate minerals using DTG and LOI

Two methods were employed for measuring fire retardancy of minerals hydromagnesite, huntite and natural hydromagnesite/huntite mixtures, on forest species. The first was based on DTG under N₂ atmosphere, to isolate pyrolysis of forest species and the second on LOI for combustion measurements. The selected forest species: Pinus halepensis Mill. and Cistus incanus L., were collected from a WUI zone and were treated with 5, 10, 15 and 20 mass/mass% of minerals. Regarding DTG analysis, the minerals decrease pyrolysis rate and increase mass residue of forest species. Regarding LOI tests, minerals increase pilot ignitability of forest fuels. Hydromagnesite exhibits the best overall performance.