Sample preparation techniques coupled to advanced chromatographic methods for marine organisms investigation

Objective

of this work was to develop suitable extraction methodologies for the isolation of lipids from fish, mussels and clams from the Mediterranean sea, and their successive analysis by means of advanced chromatographic instrumentation. More specifically, three different sample preparation methodologies were adopted: Folch’s, Bligh & Dyer’s and maceration. The lipidic extracts, after application of two different methylation procedures, were subjected to monodimensional and comprehensive two-dimensional GC analyses, in order to compare the fingerprints of samples derived from different extraction and transesterification methodologies. Triacylglycerols (TAGs) were analyzed by an off-line combination of silver-ion liquid chromatography with non-aqueous reversed phase liquid chromatography. In both LC and GC analyses, mass spectrometric detectors were used, which greatly supported the identification procedure. In particular, with respect to HPLC, mass spectrometry with atmospheric pressure chemical ionization in positive mode was applied.     

<Superscript>13</Superscript>C NMR analysis of cellulose samples from different preparation methods

Alpha-cellulose is a part of the wooden material that preserves isotopic composition during tree-growth, and therefore provides important indirect data for paleoclimatological studies. For this reason, it is exceptionally important to extract the alpha-cellulose component from plants, e.g. from tree rings of wood. Since the cell wall of plant cells consists of multicomponent polysaccharides, the extraction of cellulose from wood is not an obvious task. In this paper, we describe, evaluate and compare nine methods, based on the literature and experimental observations, for obtaining cellulose from tree rings of wood. We show that the distortionless enhancement by polarization transfer (DEPT-135) variant of liquid-state ¹³C NMR spectroscopy is a powerful analytical method for monitoring the preparation process. Trifluoroacetic acid was applied as solvent for the NMR analysis. We proved that all the preparation methods give pure cellulose samples without hemicellulose and lignin content, and we propose methods resulting in non-fragmented cellulose. ¹³C and ¹⁸O isotope ratio measurements have shown that all the applied extraction methods result in similar isotope ratios, thus they are suitable for paleoclimatological studies.     

Broadband 10 Gb/s operation of graphene electro‐absorption modulator on silicon

High performance integrated optical modulators are highly desired for future optical interconnects. The ultra‐high bandwidth and broadband operation potentially offered by graphene based electro‐absorption modulators has attracted a lot of attention in the photonics community recently. In this work, we theoretically evaluate the true potential of such modulators and illustrate this with experimental results for a silicon integrated graphene optical electro‐absorption modulator capable of broadband 10 Gb/s modulation speed. The measured results agree very well with theoretical predictions. A low insertion loss of 3.8 dB at 1580 nm and a low drive voltage of 2.5 V combined with broadband and athermal operation were obtained for a 50 μm‐length hybrid graphene‐Si device. The peak modulation efficiency of the device is 1.5 dB/V. This robust device is challenging best‐in‐class Si (Ge) modulators for future chip‐level optical interconnects.     

Scalability of Coarse‐Grained Potentials Generated from Iterative Boltzmann Inversion for Polymers: Case Study on Polycarbonates

Using systematic coarse‐grained (CG) techniques such as iterative Boltzmann inversion (IBI) is an efficient means to simulate high molecular weight polymer melts within reasonable computational time. One drawback of such an approach is however the need to carry out extensive atomistic simulations in order to extrapolate the necessary distributions to derive the inter and intrabead force field parameters. Here it is shown that it is possible to use atomistic simulations of relative short oligomers to develop the CG model for high molecular weight polymers. In particular for the specific case of polycarbonates, it is found that the structural properties (end‐to‐end distance, radius of gyration and their distributions) are similar irrespective of whether the CG potentials are derived from 5‐mer or 10‐mer melt systems. Dynamical properties of the CG systems are smoother and faster than the atomistic ones. Scaling factor, derived by overlapping the CG mean square displacement curves (obtained from different CG IBI potentials) over the atomistic ones, also scales the autocorrelation functions. A prediction of the dynamical scaling factor in the case of the unavailability of atomistic simulations is also discussed. The dynamical properties of the CG melts are modeled reasonably well by all the CG potentials derived from atomistic simulations of short oligomers.

     

Amorphous and crystalline states of ultrasoft colloids: a molecular dynamics study

In this work, we study the temperature-induced development of “dynamically arrested” states in dense suspensions of “soft colloids” (multi-arm star polymers and/or block-copolymers micelles) by means of molecular dynamics (MD) simulations. Temperature increase in marginal solvents results in “soft sphere” swelling, dynamical arrest, and eventually crystallization. However, two distinct “dynamically arrested” states were found, one almost amorphous (“glassy”) and one with a considerable degree of crystallinity, yet lower than that of the fully equilibrated crystal. It is remarkable that even that latter state permitted self-diffusion in the timescale of the simulations, an effect that underlies the importance of the “ultra-soft” nature of inter-particle potential. The “number of connections” criterion for crystallinity proved to be very successful in identifying the ultimate thermodynamic trend from the very early stages of the α-relaxation. This paper was presented at the Third Annual Rheology Conference, AERC 2006, April 27–29, 2006, Crete, Greece.     

Fluorescence Dynamics of Monocyclodextrin– and Bis(thiol‐cyclodextrin)–Coumarin C153 Complexes

The solvation and confinement of coumarin C153 within supramolecular host/guest complexes based on β‐cyclodextrin (β‐CD) and 6‐deoxy‐6‐thio‐β‐cyclodextrin (β‐CD‐SH) in water are studied by fluorescence spectroscopy. For β‐CD/C153, the 1:1 complex is proposed, and for β‐CD‐SH/C153 both the 1:1 and 2:1 complexes are believed to be formed. The 2:1 β‐CD‐SH/C153 complex has an association constant of 4.2×10⁵ M ^?1 and a C153 population of 82 %, which are interestingly high values, indicating that the proposed β‐CD‐SH dimers structure are connected by covalent disulfide bonds; this is supported by mass spectrometry. Solvation related to fast hydrogen‐bond rearrangement as a part of fluorescence relaxation is determined by the ultrafast components of time‐resolved spectroscopy to be 3 and 7 ps for the 1:1 β‐CD/C153 and 2:1 β‐CD‐SH/C153 complexes, respectively.     

Universal Singular Sets in the Calculus of Variations

For regular one-dimensional variational problems, Ball and Nadirashvilli introduced the notion of the universal singular set of a Lagrangian L and established its topological negligibility. This set is defined to be the set of all points in the plane through which the graph of some absolutely continuous L-minimizer passes with infinite derivative. Motivated by Tonelli’s partial regularity results, the question of the size of the universal singular set in measure naturally arises. Here we show that universal singular sets are characterized by being essentially purely unrectifiable—that is, they intersect most Lipschitz curves in sets of zero length and any compact purely unrectifiable set is contained within the universal singular set of some smooth Lagrangian with given superlinear growth. This gives examples of universal singular sets of Hausdorff dimension two, filling the gap between previously known one-dimensional examples and Sychëv’s result that universal singular sets are Lebesgue null. We show that some smoothness of the Lagrangian is necessary for the topological size estimate, and investigate the relationship between growth of the Lagrangian and the existence of (pathological) rectifiable pieces in the universal singular set. We also show that Tonelli’s partial regularity result is stable in that the energy of a “near” minimizer u over the set where it has large derivative is controlled by how far u is from being a minimizer.     

Cycling in proofs and feasibility

There is a common perception by which small numbers are considered more concrete and large numbers more abstract. A mathematical formalization of this idea was introduced by Parikh (1971) through an inconsistent theory of feasible numbers in which addition and multiplication are as usual but for which some very large number is defined to be not feasible. Parikh shows that sufficiently short proofs in this theory can only prove true statements of arithmetic. We pursue these topics in light of logical flow graphs of proofs (Buss, 1991) and show that Parikh's lower bound for concrete consistency reflects the presence of cycles in the logical graphs of short proofs of feasibility of large numbers. We discuss two concrete constructions which show the bound to be optimal and bring out the dynamical aspect of formal proofs. For this paper the concept of feasible numbers has two roles, as an idea with its own life and as a vehicle for exploring general principles on the dynamics and geometry of proofs. Cycles can be seen as a measure of how complicated a proof can be. We prove that short proofs must have cycles.

     

Surface composition of siloxane-containing polymers

X-ray photoelectron spectroscopy was used to study relationships between the surface and bulk composition in block copolymers and blends of poly(dimethyl-siloxane), poly(bisphenol A sulfone) and poly(bisphenol A carbonate). In all cases the polymer surfaces were highly enriched in siloxane. At a fixed siloxane concentration in the bulk the highest enrichment was observed in the blends of homopolymers and the lowest in the copolymers. It was found that the addition of small quantities of a siloxane-rich copolymer to another copolymer having a lower siloxane content may reduce the surface siloxane concentration of the latter. This unusual surface behavior was explained by the formation of an over-layer in which the macromolecules of the siloxane-rich copolymer are oriented nearly parallel to the sample surface.