Synthesis and isolation of <Emphasis Type="Italic">trans</Emphasis>-7, <Emphasis Type="Italic">cis</Emphasis>-9 octadecadienoic acid and other CLA isomers by base conjugation of partially hydrogenated γ-linolenic acid

CLA is of considerable interest because of reported potentially beneficial effects in animal studies. CLA, while not yet unambiguously defined, is a mixture of octadecadienoic acids with conjugated double bonds. The major isomer in natural products is generally considered to be cis-9,trans-11-octadecadienoic acid (c9, t11), which represents >75% of the total CLA in most cases. Other isomers are drawing increased attention. The t7,c9 isomer, which is often the second-most prevalent CLA in natural products, has been reported to represent as much as 40% of total CLA in milk from cows fed a high-fat diet. The need for a reference material became apparent in a recent study directed specifically at measuring t7,c9-CLA in milk, plasma, and rumen. A suitable standard mixture was produced by stirring 0.5 g of γ-linolenic acid (all cis-6,9, 12-C_18∶3) with 100 mL of 10% hydrazine hydrate in methanol for 2.5 h at 45°C. The solution was diluted with H₂O and acidified with HCl. The resulting partially hydrogenated FA were extracted with ether/petroleum ether, dried with Na₂SO₄, and conjugated by adding of 6.6% KOH in ethlylene glycol and heating for 1.5 h at 150–160°C. Approximately 20 mg each of cis-6, trans-8; trans-7, cis-9; cis-9, trans-11; and rans-10, cis-12 were obtained along with other FA. Methyl esters (FAME) of these four cis/trans isomers were resolved by Ag⁺HPLC (UV 233) and partially resolved by GC/(MS or FID) (CP-Sil 88). Treatment of these FAME with I₂ yielded all possible cis/trans (geometric) isomers for the four positions 6,8; 7,9; 9,11; and 10,12.     

Reserves Accumulated in Non-Photosynthetic Organs during the Previous Growing Season Drive Plant Defenses and Growth in Aspen in the Subsequent Growing Season

Plants store non-structural carbohydrates (NSC), nitrogen (N), as well as other macro and micronutrients, in their stems and roots; the role of these stored reserves in plant growth and defense under herbivory pressure is poorly understood, particularly in trees. Trembling aspen (Populus tremuloides) seedlings with different NSC and N reserves accumulated during the previous growing season were generated in the greenhouse. Based on NSC and N contents, seedlings were assigned to one of three reserve statuses: Low N–Low NSC, High N–Medium NSC, or High N–High NSC. In the subsequent growing season, half of the seedlings in each reserve status was subjected to defoliation by forest tent caterpillar (Malacosoma disstria) while the other half was left untreated. Following defoliation, the effect of reserves was measured on foliar chemistry (N, NSC) and caterpillar performance (larval development). Due to their importance in herbivore feeding, we also quantified concentrations of phenolic glycoside compounds in foliage. Seedlings in Low N-Low NSC reserve status contained higher amounts of induced phenolic glycosides, grew little, and supported fewer caterpillars. In contrast, aspen seedlings in High N-Medium or High NSC reserve statuses contained lower amounts of induced phenolic glycosides, grew faster, and some of the caterpillars which fed on these seedlings developed up to their fourth instar. Furthermore, multiple regression analysis indicated that foliar phenolic glycoside concentration was related to reserve chemistry (NSC, N). Overall, these results demonstrate that reserves accumulated during the previous growing season can influence tree defense and growth in the subsequent growing season. Additionally, our study concluded that the NSC/N ratio of reserves in the previous growing season represents a better measure of resources available for use in defense and growth than the foliar NSC/N ratios.     

Rawseeds ground truth collection systems for indoor self-localization and mapping

A trustable and accurate ground truth is a key requirement for benchmarking self-localization and mapping algorithms; on the other hand, collection of ground truth is a complex and daunting task, and its validation is a challenging issue. In this paper we propose two techniques for indoor ground truth collection, developed in the framework of the European project Rawseeds, which are mutually independent and also independent on the sensors onboard the robot. These techniques are based, respectively, on a network of fixed cameras, and on a network of fixed laser scanners. We show how these systems are implemented and deployed, and, most importantly, we evaluate their performance; moreover, we investigate the possible fusion of their outputs.     

Agent-based architecture for designing hybrid control systems

When designing very complex control strategy using hybrid technology, one usually faces the challenge of balancing effective realization of multi-control modeling with design simplicity. To better manage this difficulty we have used the agent paradigm as a simple and powerful bridge between asynchronous/distributed computation and Matlab environment. The proposed architecture has been used to design a complex hybrid control environment using multi-objective, fuzzy c-means, and genetic algorithms optimization to design hybrid control strategies suitable for the energy flows management on board of hybrid electric vehicles.     

Intra-Period (Within-Day) Dynamic Models for Continuous Services

To simulate important aspect of some transportation systems (e.g. demand peaks, temporary capacity variations, temporary over-saturation of supply elements, and formation and dispersion of queues) a new class of models, referred to in the literature as Dynamic Traffic Assignment (DTA) models, have been recently developed. Although Dynamic Traffic Assignment to networks is a relatively new research subject, a great number of models have been proposed in the last two decades. These can be divided in two main classes according to the typology of service they aim at simulating. These are continuous services, considering transportation services available at any time and accessible from several points, such as the services offered by individual road modes (car, bicycle etc.), and scheduled services simulating services available only at certain times and that can be accessed only at certain locations (terminals, stations, airports etc.). In this paper the focus is on continuous services. Models proposed in the literature are reviewed and classified according to basic assumptions on the flow structure, i.e. whether a continuous or a discrete approach is followed, and on the representation of time (discrete vs. continuous). A general modeling framework consisting of supply, demand, and demand-supply interaction models, and including most of the existing specifications is presented both for the discrete time-discrete flow and continuous time continuous flow cases.     

Identification and characterization of conjugated fatty acid methyl esters of mixed double bond geometry by acetonitrile chemical ionization tandem mass spectrometry

Fatty acids with conjugated double bonds have attracted great interest because of their reported potent bioactivities. However, there are currently no rapid methods for their structural characterization. We report here a convenient mass spectrometry-based strategy to establish double bond geometry by analysis of collisional dissociation products of cis/trans and trans/cis conjugated linoleic acids (CLAs), as methyl esters, and to distinguish CLAs from homoallylic (methylene-interrupted) fatty acids in a single-stage mass spectrum. A series of CLA standards with double bond positions 6,8; 7,9; 8,10; 9,11; 10,12; 11,13; 12,14; and 13,15, with all four possible geometries (cis/trans; trans/cis; cis/cis; trans/trans) were analyzed. The m/z 54 (1-methyleneimino)-1-ethenylium ion, generated by self-reaction of acetonitrile under chemical ionization conditions, reacts with unsaturated fatty acids to yield an [M + 54]+ ion, which decomposes in the single-stage mass spectrum by loss of neutral methanol to form [M + 54 - 32]+. The ratio of [M + 54]+/[M + 54 - 32]+ in the single-stage mass spectra of CLA isomers is 1 order of magnitude less than for homoallylic diene FAME. Collisional dissociation of the [M + 54]+ ion yields two diagnostic ions that contain the alpha- and omega-carbon atoms and is characteristic of double bond position in the analyte. The fragment vinylic to the trans double bond is significantly more abundant than that for the cis double bond, revealing double bond geometry. The ratio of alpha to we diagnostic ion abundances is >4.8 for cis/trans isomers, <0.5 for trans/cis isomers, and 0.7-3.2 for cis/cis and trans/trans isomers. This method provides a rapid alternative to conventional conjugated fatty acid analysis and, together with complementary elution time information provided by gas chromatography, enables rapid, positive identification of double bond position and geometry in most CLA FAME.     

Prospects for the use of high-Tc superconductors in fusion magnets and options for their test in SULTAN

In the last few years, the critical current densities of long commercially available REBa₂Cu₃O_7?x (RE-123, where RE represents Y or a rare earth element) coated conductors have reached values of 250 A/cm-width at 77 K and zero applied field. Even higher values of 600 A/cm-w (77 K, B = 0) have been demonstrated in shorter lengths. The attractive features of the use of these high-T_c superconductors (HTS) are operation temperatures above 20 K and/or magnetic fields higher than those envisaged for the ITER TF coils. Possible operation conditions for HTS fusion magnets have been studied taking into consideration the possible further improvements of RE-123 coated conductors. Investigations of stability and quench behavior indicate that stability is not a problem, whereas quench detection and protection need attention. Because of the high currents necessary for fusion magnets, many tapes need to be assembled into a transposed conductor. The qualification of HTS conductors for fusion magnets would require their test at magnetic fields of 11 T and currents well above 10 kA. The possibilities to test straight HTS conductor samples in SULTAN have been considered. For a test at 4.5 K, only the development of a low resistance joint between the HTS conductor under test and the NbTi transformer of SULTAN would be necessary. Tests up to 20 K would require that the HTS sample is connected with the NbTi transformer by a conduction-cooled HTS bus bar of large thermal resistance similar to the HTS module of a current lead. HTS conductor tests at temperatures around 50 K would be possible with modified cryogenics.     

Liquid-crystallization induced reactions. Microstructure and morphology of copolyesters synthesized by transesterification of PET with some LCP monomers

The transesterification of poly(ethylene terephthalate) (PET) with a mixture of sebacic acid (S), 4,4′-diacetoxybiphenyl (B) and 4-acetoxybenzoic acid (H), carried out under conditions expectedly favoring the formation of a p(ET-SBH) random copolyester, produces biphasic materials with an isotropic matrix and a highly fibrous, liquid-crystalline dispersed phase. Spectroscopic, calorimetric, microscopic and diffractometric characterization of the fractions separated by solvent extraction has shown that the two phases consist of practically random copolyesters having different average composition. Interestingly, the degree of aromaticity of the matrix is even lower than that of PET, whereas that of the minor phase is appreciably higher than that calculated for the SBH copolyester that would be produced from the monomer mixture in the absence of PET. This unexpected result is interpreted on the basis of an enthalpy-driven progressive diffusion of aromatic-rich material toward the mesophase which segregates at an early stage of the polycondensation within the isotropic mixture of low molar mass oligomers initially produced by the PET acidolysis. Thus, an increasing differentiation, rather than an equilibration, of the composition of the two phases takes place. It is noteworthy that, despite the strong compositional difference, the two phases of these products show fairly good compatibility and interfacial adhesion.     

H HRMAS-NMR metabolomic to assess quality and traceability of mozzarella cheese from Campania buffalo milk

The production of Mozzarella di Bufala Campana (MBC) is relevant for the agro-food economy of the Campania Region of Italy and the mark of Protected Designation of Origin (PDO) has been assigned to MBC in relation to its geographical origin. Advanced analytical methods must be then employed to assess authenticity, traceability, and quality of MBC. ¹H HRMAS-NMR (High Resolution Magic Angle Spinning Nuclear Magnetic Resonance) spectroscopy was applied here to directly identify specific metabolites in MBC intact samples without time-consuming sample pre-treatments. Overcrowded conventional ¹H HRMAS-NMR spectra were selectively simplified with two NMR pulse sequences: eCPMG and eDiff, by modulating spin-spin relaxation times and diffusion of MBC molecular components, respectively. Signal elaboration of edited spectra was combined with multivariate analyses to enable significant metabolic differentiation between MBC samples from two different production sites in Campania. Principal Components Analysis (PCA) for eCPMG spectra explained 97.54% of total variance between the two MBC groups for four metabolites (β-galactose, β-lactose, acetic acid, and glycerol). Less efficient was groups distinction by PCA for eDiff spectra, although differences in polyunsaturated acids, such as linoleic and linolenic acids, were highlighted. Similarly, Discriminant Analysis (DA) provided MBC group classification with 100% success in validation tests for eCPMG spectra, while DA prediction ability was reduced to 94.12% for eDiff spectra. Hierarchical Cluster Analysis (HCA) gave a totally correct classification between the two MBC groups only for eCPMG spectra. eCPMG spectra were also used to identify metabolites during MBC aging. As compared to fresh samples, 2 days old MBC samples showed increasing signals for isobutylic alcohol, lactic acid, and acetic acid. This work shows that ¹H HRMAS-NMR spectroscopy can rapidly characterise the metabolic profile of intact MBC samples and statistically distinguish the geographical origin of buffalo milk mozzarella and its freshness.     

Automatic laser-based identification for UF6 cylinders

We present a laser item identification system (L2IS), installed in a real facility on trial, that is capable of automatically monitoring all transfers of uranium hexafluoride (UF₆) cylinders between different process areas. Each cylinder has a unique ‘fingerprint’ represented by the 3D micro-structure of its surface which remains intact even under extreme environmental conditions. L2IS automatically identifies each cylinder through exploring the 3D frontal surface acquired by the laser scanner. The system is composed of a portable unit (operated in attended mode) and a fixed installed unit (operated without inspector presence). The efficiency and accuracy of our identification system were evaluated on a large dataset acquired during several years including a full year of field testing.