Excited state dynamics of Zn–salophen complexes

Zn-salophen complexes are a promising class of fluorescent chemosensors for nucleotides and nucleic acids. We have investigated, by means of steady state UV-Vis, ultrafast transient absorption, fluorescence emission and time dependent density functional theory (TD-DFT) the behavior of the excited states of a salicylidene tetradentate Schiff base (Sal), its Zn(II) coordination compound (Zn-Sal) and the effect of the interaction between Zn-Sal and adenosine diphosphate (ADP). TD-DFT shows that the deactivation of the excited state of Sal occurs through torsional motion, due to its rotatable bonds and twistable angles. Complexation with Zn(II) causes rigidity so that the geometry changes in the excited states with respect to the ground state structure are minimal. By addition of ADP to a freshly prepared Zn-Sal ethanol solution, a longer relaxation constant, in comparison to Zn-Sal, was measured, indicative of the interaction between Zn-Sal and ADP. After a few days, the Zn-Sal-ADP solution displayed the same static and dynamic behavior of a solution containing only the Sal ligand, demonstrating that the coordination of the ADP anion to Zn(II)leads to the demetallation of the Sal ligand. Fluorescence measurements also revealed an enhanced fluorescence at 375 nm following the addition of ADP to the solution, caused by the presence of 2,3-diamino naphthalene that is formed by demetallation and partial decomposition of the Sal ligand. The efficient fluorescence of this species at 375 nm could be selectively detected and used as a probe for the detection of ADP in solution.[GRAPHICS]

Specific Heat Discontinuity, deltaC, at Tc in BaFe2(As0.7P0.3)2 - Consistent with Unconventional Superconductivity

We report the specific heat discontinuity, deltaC/Tc, at Tc = 28.2 K of a collage of single crystals of BaFe2(As0.7P0.3)2 and compare the measured value of 38.5 mJ/molK**2 with other iron pnictide and iron chalcogenide (FePn/Ch) superconductors. This value agrees well with the trend established by Bud'ko, Ni and Canfield who found that deltaC/Tc ~ a*Tc**2 for 14 examples of doped Ba1-xKxFe2As2 and BaFe2-xTMxAs2, where the transition metal TM=Co and Ni. We extend their analysis to include all the FePn/Ch superconductors for which deltaC/Tc is currently known and find deltaC/Tc ~ a*Tc**1.9 and a=0.083 mJ/molK**4. A comparison with the elemental superconductors with Tc>1 K and with A-15 superconductors shows that, contrary to the FePn/Ch superconductors, electron-phonon-coupled conventional superconductors exhibit a significantly different dependence of deltaC on Tc, namely deltaC/Tc ~ Tc**0.9. However deltaC/gamma*Tc appears to be comparable in all three classes (FePn/Ch, elemental and A-15) of superconductors with, e. g., deltaC/gamma*Tc=2.4 for BaFe2(As0.7P0.3)2. A discussion of the possible implications of these phenomenological comparisons for the unconventional superconductivity believed to exist in the FePn/Ch is given.Comment: some disagreement in reference and footnote numbering with the published versio

Pressure-dependence of electron-phonon coupling and the superconducting phase in hcp Fe - a linear response study

A recent experiment by Shimizu et al. has provided evidence of a superconducting phase in hcp Fe under pressure. To study the pressure-dependence of this superconducting phase we have calculated the phonon frequencies and the electron-phonon coupling in hcp Fe as a function of the lattice parameter, using the linear response (LR) scheme and the full potential linear muffin-tin orbital (FP-LMTO) method. Calculated phonon spectra and the Eliashberg functions $\alpha^2 F$ indicate that conventional s-wave electron-phonon coupling can definitely account for the appearance of the superconducting phase in hcp Fe. However, the observed change in the transition temperature with increasing pressure is far too rapid compared with the calculated results. For comparison with the linear response results, we have computed the electron-phonon coupling also by using the rigid muffin-tin (RMT) approximation. From both the LR and the RMT results it appears that electron-phonon interaction alone cannot explain the small range of volume over which superconductivity is observed. It is shown that ferromagnetic/antiferromagnetic spin fluctuations as well as scattering from magnetic impurities (spin-ordered clusters) can account for the observed values of the transition temperatures but cannot substantially improve the agreeemnt between the calculated and observed presure/volume range of the superconducting phase. A simplified treatment of p-wave pairing leads to extremely small ($\leq 10^{-2}$ K) transition temperatures. Thus our calculations seem to rule out both $s$- and $p$- wave superconductivity in hcp Fe.Comment: 12 pages, submitted to PR

The Welfare Cost of Argentine Risk

In this paper we do a couple of things: discussing a way to measure the welfare cost of country risk, and measuring it for Argentina in the period 1875-2006. There are two conclusions: a) the welfare cost of Argentine risk has been huge: for example, in the period 1976-2006 it was around 20% of GDP, several times larger than the welfare cost of any conventional distortion; b) this cost would be wholly paid by labor. These fascinating results deserve further investigation

Mergers and Acquisitions in Latin America: Industrial Productivity and Corporate Governance

This paper examines the impact of industrial productivity on transnationals M&As from OECD countries towards Latin American countries in the period 1996 to 2010. It also analyzes the relationship between external mechanism of corporate governance and transnational M&As. For this purpose we use a gravitational model at the industry level. We find that industry productivity and higher standards of corporate governance in the country of origin promote transnational M&As activity. However, it is also found that higher levels of capital and technological productivity decreases transnational M&As activity

Ultra-Low DNA Input into Whole Genome Methylation Assays and Detection of Oncogenic Methylation and Copy Number Variants in Circulating Tumour DNA

Background: Abnormal CpG methylation in cancer is ubiquitous and generally detected in tumour specimens using a variety of techniques at a resolution encompassing single CpG loci to genome wide coverage. Analysis of samples with very low DNA inputs, such as formalin fixed (FFPE) biopsy specimens from clinical trials or circulating tumour DNA is challenging at the genome-wide level because of lack of available input. We present the results of low input experiments into the Illumina Infinium HD methylation assay on FFPE specimens and ctDNA samples. Methods: For all experiments, the Infinium HD assay for methylation was used. In total, forty-eight FFPE specimens were used at varying concentrations (lowest input 50 ng); eighteen blood derived specimens (lowest input 10 ng) and six matched ctDNA input (lowest input 10 ng)/fresh tumour specimens (lowest input 250 ng) were processed. Downstream analysis was performed in R/Bioconductor for quality control metrics and differential methylation analysis as well as copy number calls. Results: Correlation coefficients for CpG methylation were high at the probe level averaged R2 = 0.99 for blood derived samples and R2 > 0.96 for the FFPE samples. When matched ctDNA/fresh tumour samples were compared, R2 > 0.91 between the two. Results of differential methylation analysis did not vary significantly by DNA input in either the blood or FFPE groups. There were differences seen in the ctDNA group as compared to their paired tumour sample, possibly because of enrichment for tumour material without contaminating normal. Copy number variants observed in the tumour were generally also seen in the paired ctDNA sample with good concordance via DQ plot. Conclusions: The Illumina Infinium HD methylation assay can robustly detect methylation across a range of sample types, including ctDNA, down to an input of 10 ng. It can also reliably detect oncogenic methylation changes and copy number variants in ctDNA. These findings demonstrate that these samples can now be accessed by methylation array technology, allowing analysis of these important sample types

Genetic dissection reveals diabetes loci proximal to the gimap5 lymphopenia gene

rats are protected from type 1 diabetes (T1D) by 34 Mb of F344 DNA introgressed proximal to the gimap5 lymphopenia gene. To dissect the genetic factor(s) that confer protection from T1D in the DRF. f/f rat line, DRF. f/f rats were crossed to inbred BBDR or DR. lyp/lyp rats to generate congenic sublines that were genotyped and monitored for T1D, and positional candidate genes were sequenced. All (100%) DR. f/f congenic sublines further refined the RNO4 region 1 interval to ϳ670 kb and region 2 to the 340 kb proximal to gimap5. All congenic DRF. f/f sublines were prone to low-grade pancreatic mononuclear cell infiltration around ducts and vessels, but Ͻ20% of islets in nondiabetic rats showed islet infiltration. Coding sequence analysis revealed TCR V␤ 8E, 12, and 13 as candidate genes in region 1 and znf467 and atp6v0e2 as candidate genes in region 2. Our results show that spontaneous T1D is controlled by at least two genetic loci 7 Mb apart on rat chromosome 4. type 1 diabetes; BB rat; T cell receptor; autoimmune CHARACTERISTICS OF TYPE 1 DIABETES (T1D) in both human and the BioBreeding spontaneously diabetes-prone (BBDP) rat include polyuria, hyperglycemia, ketoacidosis, insulitis, and insulin dependency for life. As in human T1D, islets are infiltrated by mononuclear cells at the time of onset with rapid hyperglycemia due to a complete loss of islet ␤-cells (32). The genetic etiology of human T1D remains complex and although the major histocompatibility complex (MHC) (HLA DQ) on chromosome 6 accounts for ϳ40% of T1D risk, the number of non-HLA genetic factors is increasing steadily (2, 7). The BB rat offers a powerful model to dissect both genetic contributions and mechanisms by which immunemediated beta cell killing induces T1D (3, 4, 15, 17-21, 27, 28, 46). As in humans, the major genetic determinant of susceptibility in the BB rat is the MHC (Iddm1) on rat chromosome (RNO) 20. The class II MHC locus RT1B/D. u/u ), an ortholog of human HLA DQ (9), is necessary but not sufficient for T1D in the BBDP rat and other RT1. u/u -related rat strains with spontaneous (24, 47) or induced T1D (8, 43). In BBDP, a null mutation in the gimap5 gene (lyp; Iddm2) on RNO4 (14, 27) causes lymphopenia and is tightly linked to spontaneous T1D development. The DR. lyp/lyp rat with 2 Mb of BBDP DNA encompassing gimap5 introgressed into the genome of related BBDR rats (BioBreeding resistant to spontaneous T1D) are also 100% lymphopenic and 100% spontaneously diabetic (11). With complete T1D penetrance and tight regulation of onset, the congenic DR. lyp/lyp rat line offers distinct advantages in identification of genes responsible for disease progression. It is possible to induce T1D in BBDR rats (32) and related RT1 u/u rats (8) by administration of polyinosinic: polycytidylic acid (poly I:C, an activator of innate immunity), the T reg depleting cytotoxic DS4.23 anti-ART2.1 (formerly RT6) monoclonal antibody or by viral infection (34). This indicates that the BBDR has an underlying genetic susceptibility to T1D. In crosses between WF and either BBDP or BBDR rats, a quantitative trait locus (QTL) important for induced T1D (Iddm14, previously designated Iddm4) was mapped to RNO4 (6, Interestingly, F344 DNA introgressed between D4Rat253 and D4Rhw6 into the congenic DR. lyp/lyp genetic background resulted in a lymphopenic but nondiabetic rat (designated DRF. f/f ) (11). Protection from T1D in the DRF. f/f congenic rat line led us to conclude that spontaneous T1D in the BB rat is controlled, in part, by a diabetogenic factor(s) independent of the gimap5 mutation (76.84 Mb) on RNO4. This congenic interval is encompassed within Iddm14, raising the possibility that the Iddm14 locus could be required for both spontaneous and induced T1D in the BB rat. The aim of this study was to cross the DRF. f/f rat to BBDR and DR. lyp/lyp rats and produce recombinant sublines that could be assessed for both lymphopenia and diabetes and to estimate the number of independent genes on RNO4 that control spontaneous T1D

Strange particle production in proton-proton collisions at s=0.9\sqrt{s}=0.9 TeV with ALICE at the LHC

The production of mesons containing strange quarks (K$^0_s$, $\phi$) and both singly and doubly strange baryons ($\Lambda$, Anti-$\Lambda$, and $\Xi$+Anti-$\Xi$) are measured at central rapidity in pp collisions at $\sqrt{s}$ = 0.9 TeV with the ALICE experiment at the LHC. The results are obtained from the analysis of about 250 k minimum bias events recorded in 2009. Measurements of yields (dN/dy) and transverse momentum spectra at central rapidities for inelastic pp collisions are presented. For mesons, we report yields () of 0.184 $\pm$ 0.002 stat. $\pm$ 0.006 syst. for K$^0_s$ and 0.021 $\pm$ 0.004 stat. $\pm$ 0.003 syst. for $\phi$. For baryons, we find = 0.048 $\pm$ 0.001 stat. $\pm$ 0.004 syst. for $\Lambda$, 0.047 $\pm$ 0.002 stat. $\pm$ 0.005 syst. for Anti-$\Lambda$ and 0.0101 $\pm$ 0.0020 stat. $\pm$ 0.0009 syst. for $\Xi$+Anti-$\Xi$. The results are also compared with predictions for identified particle spectra from QCD-inspired models and provide a baseline for comparisons with both future pp measurements at higher energies and heavy-ion collisions.Comment: 33 pages, 21 captioned figures, 10 tables, authors from page 28, published version, figures at http://aliceinfo.cern.ch/ArtSubmission/node/387