New chromophores from click chemistry for two-photon absorption and tuneable photoluminescence

New multipolar derivatives built from triazole moieties that combine full transparency and strong TPA in the visible region as well as fully tuneable fluorescence have been designed; such chromophores open a new route for optical limiting.     

Side chain liquid crystalline polymers: Electric field effects and nonlinear properties

Side chain liquid crystalline polymers offer unique advantages as a new class of organic materials with potential for nonlinear optical response. Synthesis of a number of cyanobiphenyl-based side chain polymers was carried out employing the concept of having the cyanobiphenyl species serve concomitantly as both the linear optical chromophore and the mesogenic moiety in the polymer. The thermal behavior of these polymers was studied by DSC, optical microscopy and X-ray diffraction. Thin polymeric films were spin coated and electric field poling measurements were carried out as a function of temperature. The second harmonic (SH) coefficients d₃₃ and d₃₁ were measured by Maker fringe analysis and compared with the values predicted by molecular statistical models. The results showed that one can gain in net polar ordering by starting with a liquid crystalline system. The enhancement in d₃₃ when < P<₂ > = 0,6 was found to be a factor of 2,3-3,3 over the isotropic case ( P<₂ > = 0). The relaxation process was investigated. Both the presence of liquid crystal character in the material and the temperature at which the films were stored below Tg appeared important in determining the thermal stability of the SH coefficients.     

Magnetic properties of strongly frustrated and correlated systems

While consequences of frustration of magnetic interactions are much studied in localized spin systems, much less studies have been performed on frustrated metallic systems. However, several effects of strong geometrical frustration in metallic correlated system have also been experimentally observed in rare-earth or transition metal compounds: coexistence of magnetic and non-magnetic sites in ordered magnetic structure, heavy fermion behaviour and anomalous Hall effect due to spin chirality are consequences of frustration. An overview of the experimental observations and of the proposed models is given. Other interesting effects due to magnetic frustration in metallic systems, which have been predicted theoretically, are also reviewed.     

Application of programmable temperature vaporisation injection with resistive heating-gas chromatography flame photometric detection for the determination of organophosphorus pesticides

The combination of a programmable temperature vaporisation (PTV) injector with resistive heating GC (RH-GC), a form of fast GC, has been applied to the analysis of organophosphorus (OP) pesticides. The PTV injector was optimised in the 'at-once' solvent vent mode for the injection of ethyl acetate (10-40 microL) or ACN (10 microL). The short RH-GC column (5 m x 0.25 mm ID) with fast temperature ramps (up to 153 degrees C/ min) allowed the separation of a total of 20 OP pesticides in less than 6 min. Average recoveries between 67 and 119% were obtained for pesticides spiked at 0.01 mg/kg into apple and pear matrix. Extraction of orange juice with ACN provided higher recoveries (92-104%) for methamidophos, acephate and omethoate compared to ethyl acetate (62-73%). Results for analysis of OP pesticides in samples containing incurred residues were in good agreement with those obtained using GC-MS. The overall method was rapid, allowing 20 samples to be analysed in 4 h.     

Analysis of co-aggregation of cancer based on registry data

OBJECTIVE: An exploratory analysis of co-aggregation of cancers using registry-based data. METHODS: We utilized sibships from over 18,000 families who had been recruited to the NCI-sponsored multi-institutional Cancer Genetics Network. The analysis assesses co-aggregation at the individual and family level and adjusts for ascertainment. RESULTS: We found statistically significant familial co-aggregation of lung cancer with pancreatic (adjusted p < 0.001), prostate (adjusted p < 0.003), and colorectal cancers (adjusted p = 0.004). In addition, we found significant familial co-aggregation of pancreatic and colorectal cancers (adjusted p = 0.018), and co-aggregation of hematopoietic and (non-ovarian) gynecologic cancers (adjusted p = 0.01). CONCLUSION: This analysis identified familial aggregation of cancers for which a genetic component has yet to be established.     

Flax fibers: assessing the non-cellulosic polysaccharides and an approach to supramolecular design of the cell wall

Due to their particular tensile properties and composition, flax cellulosic fibres are widely used in various applications and are important in the stem architecture, as a source of mechanical support. Here, we have examined how various chemical extractions of cell-wall polysaccharides might improve our understanding of the structure and composition of these fibres. A set of chemical extractions, which had previously been independently studied on fibres of different origins and by different laboratories, was run on the same batch of technical fibres, variety Eden, and the released non-cellulosic polysaccharides were analyzed in terms of sugar composition and size exclusion chromatography. No single-step protocol was able to extract all the non-cellulosic polysaccharides estimated to be in the range of 130–140 mg per g of dry fibres. The major polymers consisted of rhamnogalacturonan and glucomannan, while the minor ones were xyloglucan and xylan. Several types of stepwise extractions helped to elucidate the subfractions of each polymer that are differently retained within cell wall. From our data, we have pointed out a new model which might help to approach the supramolecular design of the flax cellulosic fibres and, afterwards, the relationships between their chemical composition and their mechanical properties.     

Synthesis and photochemical reactivity of caged glutamates with a π-extended coumarin chromophore as a photolabile protecting group

‘Caging’ and ‘uncaging’ bioactive substrates are key techniques in studying a wide variety of biological processes. In the present study, two-types of novel caged glutamates with a two-photon absorption (TPA) core, that is, π-extended coumarin, were synthesized and their photochemical release of glutamate was analyzed. The high yields of glutamate (>92%) were observed in the photolysis of compounds 1 and 10, respectively.     

UV-induced growth of cyanopolyyne chains in cryogenic solids

UV laser excitation of cryogenic solids doped with cyanoethyne, HC(3)N, led to an in situ creation of longer carbon-nitrogen chains, namely HC(5)N, C(4)N(2), and C(6)N(2), heralded by their strong visible luminescence. HC(5)N and C(4)N(2) molecules can form, most probably, within HC(3)N aggregates linked by hydrogen bonds, while the reaction occurring between two isolated, photochemically created C(3)N radicals yields C(6)N(2). This latter species, dicyanobutadiyne, is easily detected in Ar, Kr, N(2), as well as in parahydrogen solids. The C(6)N(2) phosphorescence is identified here for the first time. The reported carbon chain coupling reactions in rigid environments are of interest for astrochemistry of interstellar ices.