Near-Infrared Reflectance Spectroscopy is a Rapid, Cost-Effective Predictor of Seagrass Nutrients

Near-infrared reflectance spectroscopy was used to analyze nutrient composition of tropical and subtropical seagrasses in Queensland, Australia, as part of a broader study of impacts of grazing by dugongs on seagrass. Seagrass samples of 10 species were collected, transported to the laboratory, and separated into leaf and root/rhizome fractions. They were dried, ground, and near-infrared spectra (400–2500 nm) were collected. We used partial least-squares regression to develop calibration equations relating spectral data to standard compositional analyses performed in the laboratory. These compositional analyses focused on attributes believed to be important determinants of nutritional quality of marine vertebrate herbivores (nitrogen, organic matter, neutral detergent fiber, acid detergent fiber, lignin, neutral starch, water-soluble carbohydrates, and in vitro dry matter digestibility). Calibration equations for each attribute were developed separately for (1) roots/rhizomes and (2) leaves, irrespective of plant species. An equation that combined both plant parts was equally robust. These studies demonstrated the utility of near-infrared spectroscopy in providing rapid and cost-effective analysis of marine plants, which, in turn, permits a rigorous statistical approach to be applied to studies of foraging by marine herbivores.     

Synthesis of 3-oxalinolenic acid and β-oxidation-resistant 3-oxa-oxylipins

3-Oxalinolenic acid (3-oxa-9(Z), 12(Z), 15(Z)-octadecatrienoic acid or (6(Z), 9(Z), 12(Z)-pentadecatrienyloxy)acetic acid) was synthesized from 5(Z), 8(Z), 11(Z), 14(Z), 17(Z)-eicosapentaenoic acid by a sequence involving the C15 aldehyde 3(Z), 6(Z), 9(Z), 12(Z)-pentadecatetraenal as a key intermediate. Conversion of the aldehyde by isomerization and two steps of reduction afforded 6(Z), 9(Z), 12(Z)-pentadecatrienol, which was coupled to bromoacetate to afford after purification by HPLC >99%-pure 3-oxalinolenic acid in 10–15% overall yield. 3-Oxalinolenic acid was efficiently oxygenated by soybean lipoxygenase-1 into 3-oxa-13(S)-hydroperoxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid, and this hydroperoxide could be further converted chemically into 3-oxa-13(S)-hydroxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid and 3-oxa-13-oxo-9(Z), 11(E), 15(Z)-octadecatrienoic acid. The 3-oxa-hydroperoxide also served as the substrate for the plant enzymes allene oxide synthase, divinyl ether synthase, and hydroperoxide lyase to produce 3-oxa-12-oxo-10, 15(Z)-phytodienoic acid and other 3-oxa-oxylipins that were characterized by MS, 3-Oxalinolenic acid was not oxygenated by 9-lipoxygenase from tomato but was converted at a slow rate into 3-oxa-9(S)-hydroperoxy-10(E), 12(Z), 15(Z)-octadecatrienoic acid by recombinant maize 9-lipoxygenase. Recombinant α-dioxygenase-1 from Arabidopsis thaliana catalyzed the conversion of 3-oxalinolenic acid into a 2-hydroperoxide, which underwent spontaneous degradation into a mixture of 6,9,12-pentadecatrienol and 6,9,12-pentadecatrienyl formate. A novel α-dioxygenase from the moss Physcomitrella patens was cloned and expressed and was found to display the same activity with 3-oxalinolenic acid as Arabidopsis thaliana α-dioxygenase-1. Lipoxygenase-generated 3-oxa-oxylipins are resistant toward β-oxidation and have the potential for displaying enhanced biological activity in situations where activity is limited by metabolic degradation.     

Impact of the guanidinium group on hybridization and cellular uptake of cationic oligonucleotides

The grafting of cationic groups to synthetic oligonucleotides (ONs) in order to reduce the charge repulsion between the negatively charged strands of a duplex or triplex, and consequently to increase a complex's stability, has been extensively studied. Guanidinium groups, which are highly basic and positively charged over a wide pH range, could be an efficient ON modification to enhance their affinity for nucleic acid targets and to improve cellular uptake. A straightforward post-synthesis method to convert amino functions attached to ONs (on sugar, nucleobase or backbone) into guanidinium tethers has been perfected. In comparison to amino groups, such cationic groups anchored to alpha-oligonucleotide phosphoramidate backbones play important roles in duplex stability, particularly with RNA targets. This high affinity could be explained by dual recognition resulting from Watson-Crick or Hoogsteen base pairing combined with cationic/anionic backbone recognition between strands involving H-bond formation and salt bridging. Molecular-dynamics simulations corroborate interactions between the cationic backbones of the alpha-ONs and the anionic backbones of the nucleic acid targets. Moreover, ONs with guanidinium modification increased cellular uptake relative to negatively charged ONs. The cellular localization of these new cationic phosphoramidate ONs is mainly cytoplasmic. The uptake of these ON analogues might occur through endocytosis.     

Distribution of selenium and phenolics in buckwheat plants grown from seeds soaked in Se solution and under different levels of UV-B radiation

Seeds of common buckwheat (Fagopyrum esculentum) were soaked in water, sodium selenate (5, 10 or 20 mg Se^VI/L), or sodium selenite (10 or 20 mg Se^IV/L) solutions. Plants grown from soaked seeds were exposed to reduced UV-B radiation, ambient, or enhanced UV-B. The mass fraction of selenium in leaves was much higher in plants obtained from seeds soaked with selenate (up to 185 ng/g) in comparison to selenite (up to 103 ng/g). In plants obtained from seeds soaked in water, regardless of UV-B levels, the highest concentration of selenium was found in leaves, where the values were between 45 and 66 ng Se/g. In buckwheat leaves 44.5–63.6 mg/100 g d.m. of fagopyrin was found, and in stems 14.3–26.4 mg/100 g d.m.; here no influence of seed soaking solution or UV-B exposure was found. The content of total flavonoids in leaves was 7.8–15.9% and in stems 1.4–4.1%.     

Self-Assembling Systems Based on Pillar[5]arenes and Surfactants for Encapsulation of Diagnostic Dye DAPI

In this paper, we report the development of the novel self-assembling systems based on oppositely charged Pillar[5]arenes and surfactants for encapsulation of diagnostic dye DAPI. For this purpose, the aggregation behavior of synthesized macrocycles and surfactants in the presence of Pillar[5]arenes functionalized by carboxy and ammonium terminal groups was studied. It has been demonstrated that by varying the molar ratio in Pillar[5]arene-surfactant systems, it is possible to obtain various types of supramolecular systems: host–guest complexes at equimolar ratio of Pillar[5]arene-surfactant and interpolyelectrolyte complexes (IPECs) are self-assembled materials formed in aqueous medium by two oppositely charged polyelectrolytes (macrocycle and surfactant micelles). It has been suggested that interaction of Pillar[5]arenes with surfactants is predominantly driven by cooperative electrostatic interactions. Synthesized stoichiometric and non-stoichiometric IPECs specifically interact with DAPI. UV-vis, luminescent spectroscopy and molecular docking data show the structural feature of dye-loaded IPEC and key role of the electrostatic, π–π-stacking, cation–π interactions in their formation. Such a strategy for the design of supramolecular Pillar[5]arene-surfactant systems will lead to a synergistic interaction of the two components and will allow specific interaction with the third component (drug or fluorescent tag), which will certainly be in demand in pharmaceuticals and biomedical diagnostics.     

Thermal stability of the optical properties of plasma deposited diamond-like carbon thin films

In present paper we studied the optical constants of the diamond-like carbon (DLC) films and their changes with annealing. The multisample modification of combined variable angle spectroscopic ellipsometry and near normal spectroscopic reflectometry was used. The optical constants of the DLC films were simulated by our recently published six-parameter dispersion model employing a parameterization of the density of electronic states (DOS). Based on the dispersion model parameters the density of π and σ electrons were evaluated. We showed that from our model and the independently determined hydrogen atomic fraction of the films before and after annealing the ratio between momentum matrix elements of π → π* and σ → σ* transitions and the correct sp³-to-sp² carbon bonding configuration ratio can be calculated. It is worth to notice that the first quantity is usually assumed to be equal to unity but we showed that this assumption may cause a significant error in the determination of the sp³-to-sp² ratio. Therefore, our suggested method represents a novelty in this field.     

Clinical and histological outcome after hepatitis B e antigen to antibody seroconversion in children with chronic hepatitis B

Data regarding the outcome of children with chronic hepatitis B after seroconversion are scarce. We describe the long-term evolution of these patients. One hundred and three children with antibody against hepatitis B e antigen and normal alanine aminotransferase (ALT) levels were followed for 0.6 to 12.5 years (mean, 6.3 years). Paired liver biopsies (before and after seroconversion) were available in 83 cases. Final biopsies were obtained 0.5 to 12.5 years (mean, 4.5 years) after seroconversion. ALT levels remained normal in most of the children (79%) throughout the follow-up. All children, except five who lost hepatitis B surface antigen, had serum viral DNA detected by polymerase chain reaction. When comparing baseline and final liver biopsies, a significant improvement (P <.001) was found in the histological activity index and in the necrosis, cytolysis, inflammation, and fibrosis scores. The histological diagnosis improvement in the final biopsy was significantly related (P <.001) to the time from seroconversion to the biopsy performance. All children had viral DNA on their final liver biopsy. In summary, seroconversion and ALT normalization are quite stable findings in children, and no differences in the long-term outcome between treated and untreated children were found. In light of the histological outcome, it seems unnecessary to perform a follow-up liver biopsy in these cases.     

Lack of effect of D2 dopamine receptor TaqI A polymorphism on smoking cessation.

One previous report (Cinciripini et al., [2004] Nicotine & Tobacco Research, 6, 229-239) found that the D2 dopamine receptor (DRD2) TaqI A polymorphism was associated with smoking cessation: Carriers of the A1 allele were less likely to quit than were those who were not carriers. If confirmed, this finding would allow one to use precessation genotyping to predict the likelihood of successful quitting. The present study reports on results of a similar smoking cessation study and uses the same methods and data analysis in a larger number of smokers. It fails to replicate the effect of DRD2 TaqI A polymorphism on smoking cessation.