Effect of axial ligands on the spectroelectrochemical properties of zinc phthalocyanine films. In situ Raman and electroreflection spectra

Electroreflection and Raman spectra (in situ and ex situ) of zinc phthalocyanine (ZnPc) films (80 nm thick) have been studied. Raman spectra were resonantly and preresonantly enhanced. Both electroreflection and Raman experiments reveal the homogeneous inclusion of electrolyte anions upon oxidation of the film. The anions coordinate preferentially axial positions of the ZnPc molecule. This process is accompanied by an out-of-plane deformation of the phthalocyanine macrocycle, which results in the change of both electroreflection and Raman spectra. The ZnPc molecule remains deformed when the film is saturated with anions. The detailed analysis of new bands and altered intensities in the Raman spectrum indicates that the molecular symmetry point group changes from the D4h point group to C2v. The influence of ZnPc oxidation on the Raman excitation mechanism has been also studied. Effects of axial ligands on the molecular geometry have been studied by quantum chemical calculations for the ZnPc+, ZnPc+Cl¿ and ZnPc+(Cl¿)2 species using the unrestricted Hartree¿Fock variant of the MNDO method. Calculation results show that the ZnPc molecule undergoes an out-of-plane deformation when one axial position is coordinated by the anion

Raman spectra of zinc phthalocyanine monolayers adsorbed on glassy carbon and gold electrodes by application of a confocal Raman microspectrometer

Raman spectra of zinc phthalocyanine monolayers, adsorbed on gold and on glassy carbon surfaces (electrodes), are presented. These spectra have been recorded with the electrodes inside and outside an electrochemical cell filled with an aqueous electrolyte. A confocal Raman microspectrometer was used. It was demonstrated that, because this spectrometer uses low laser intensifies, no damage of the monolayer occurred. The results show that the interaction of the phthalocyanine molecule with gold differs from that with glassy carbon. Because the laser excitation wavelength (660 nm) coincides with a UV-visible absorption band (Q band), a strong resonance- enhanced Raman spectrum was obtained. No signs of surface enhancement (surface-enhanced Raman scattering) effects were detected

Whole exome sequencing coupled with unbiased functional analysis reveals new Hirschsprung disease genes

Background: Hirschsprung disease (HSCR), which is congenital obstruction of the bowel, results from a failure of enteric nervous system (ENS) progenitors to migrate, proliferate, differentiate, or survive within the distal intestine. Previous studies that have searched for genes underlying HSCR have focused on ENS-related pathways and genes not fitting the current knowledge have thus often been ignored. We identify and validate novel HSCR genes using whole exome sequencing (WES), burden tests, in silico prediction, unbiased in vivo analyses of the mutated genes in zebrafish, and expression analyses in zebrafish, mouse, and human. Results: We performed de novo mutation (DNM) screening on 24 HSCR trios. We identify 28 DNMs in 21 different genes. Eight of the DNMs we identified occur in RET, the main HSCR gene, and the remaining 20 DNMs reside in genes not reported in the ENS. Knockdown of all 12 genes with missense or loss-of-function DNMs showed that the orthologs of four genes (DENND3, NCLN, NUP98, and TBATA) are indispensable for ENS development in zebrafish, and these results were confirmed by CRISPR knockout. These genes are also expressed in human and mouse gut and/or ENS progenitors. Importantly, the encoded proteins are linked to neuronal processes shared by the central nervous system and the ENS. Conclusions: Our data open new fields of investigation into HSCR pathology and provide novel insights into the development of the ENS. Moreover, the study demonstrates that functional analyses of genes carrying DNMs are warranted to delineate the full genetic architecture of rare complex diseases

Effect of compost-, sand-, or gypsum-amended waste foundry sands on turfgrass yield and nutrient content

To prevent the 7 to 11 million metric tons of waste foundry sand (WFS) produced annually in the USA from entering landfi lls, current research is focused on the reuse of WFSs as soil amendments. Th e eff ects of diff erent WFS-containing amendments on turfgrass growth and nutrient content were tested by planting perennial ryegrass (Lolium perenne L.) and tall fescue (Schedonorus phoenix (Scop.) Holub) in diff erent blends containing WFS. Blends of WFS were created with compost or acid-washed sand (AWS) at varying percent by volume with WFS or by amendment with gypsum (9.6 g gypsum kg–1 WFS). Measurements of soil strength, shoot and root dry weight, plant surface coverage, and micronutrients (Al, Fe, Mn, Cu, Zn, B, Na) and macronutrients (N, P, K, S, Ca, Mg) were performed for each blend and compared with pure WFS and with a commercial potting media control. Results showed that strength was not a factor for any of the parameters studied, but the K/Na base saturation ratio of WFS:compost mixes was highly correlated with total shoot dry weight for perennial ryegrass (r = 0.995) and tall fescue (r = 0.94). Th is was further substantiated because total shoot dry weight was also correlated with shoot K/Na concentration of perennial ryegrass (r = 0.99) and tall fescue (r = 0.95). A compost blend containing 40% WFS was determined to be the optimal amendment for the reuse of WFS because it incorporated the greatest possible amount of WFS without major reduction in turfgrass growth

Redefining Strategies to Introduce Tolerance-Inducing Cellular Therapy in Human beings to Combat Autoimmunity and Transplantation Reactions

Contains fulltext : 136669.pdf (publisher's version ) (Open Access

Pollen morphology within the Monodora clade, a diverse group of five African Annonaceae genera

Pollen morphology has played a major role in elucidating infrafamiliar-level systematics and evolution within Annonaceae, especially within the African genera. The Monodora clade is composed of five genera, Asteranthe, Hexalobus, Isolona, Monodora and Uvariastrum, which are restricted to Africa and contain together c. 50 species. A molecular phylogeny of the family showed that the monophyly of the Monodora clade is strongly supported and that it is part of a larger clade of 11 African genera. In order to support classification a detailed survey was made of the pollen morphological variation within the Monodora clade, using scanning and transmission electron microsopy. For the two most species-rich genera, Isolona and Monodora, a molecular species-level phylogeny was used to assess the taxonomic usefulness of the pollen characters. The survey showed a wide range of pollen morphological diversity. The most conspicuous variation concerned the occurrence of monads without a thicker outer foliation in the basal exine layer in Isolona in contrast to tetrads with a thicker outer foliation in Asteranthe, Hexalobus, Monodora and Uvariastrum. At the infrageneric level, Hexalobus, Isolona and Monodora showed the largest diversity, with various pollen types based on tectum morphology. Hexalobus is exceptional with three types within only five species. The pollen types defined in this study are hardly useful in characterizing major groups identified within both Isolona and Monodora, but they do illustrate relationships within smaller groups