pH effect on the photochemistry of 4-methylcoumarin phosphate esters: caged-phosphate case study

There are numerous reports of coumarin ester derivatives, in particular phosphate esters, as photocleavable cages in biological systems. Despite the comprehensive analysis of the photocleavage mechanism, studies of 4-methylcoumarin caged phosphates and/or nucleotides were always performed at constant pH. In this work, we present the study of the pH effect on the photochemistry of (7-diethylaminocoumarin-4-yl)methyl phosphate (DEACM-P). Fluorescence and photocleavage quantum yields, as well as the fluorescence decay times were measured as a function of the pH. It was found that the pH produces significant changes in the overall photochemical quantum yield of DEACM-P, and the observed changes are complementary to those obtained from the fluorescence quantum yield. Deprotonation of DEACM-HPO(4)(-) to yield DEACM-PO(4)(2-), produces a decrease in the photochemical quantum yield (from 0.0045 to 0.0003) and an increase in the fluorescence quantum yield (from 0.072 to 0.092). Moreover, from the analysis of the decay times, we have also found that hydroxyl ion is not only relevant, but it is mechanistically involved in the photoreaction of DEACM-HPO(4)(-).     

Application of a quick,easy, cheap,effective, rugged and safe-based method for the simultaneous extraction of chlorophenols,alkylphenols, nitrophenols and cresols in agricultural soils,analyzed by using gas chromatography–triple quadrupole-mass spectrometry/mass spectrometry

Due to the different physico-chemical properties of phenols, the development of a methodology for the simultaneous extraction and determination of phenolic compounds belonging to several families, such as chlorophenols (CPs), alkylphenols (APs), nitrophenols (NTPs) and cresols is difficult. This study shows the development and validation of a method for the analysis of 13 phenolic compounds (including CPs, APs, NTPs and cresols) in agricultural soils. For this purpose, a quick, easy, cheap, effective, rugged and safe (QuEChERS)-based procedure was developed, validated and applied to the analysis of real samples. A derivatization step prior to the final determination by gas chromatography (GC) coupled to a triple quadrupole analyzer operating in tandem mass spectrometry (QqQ-MS/MS) was performed by using acetic acid anhydride (AAA) and pyridine (Py). The optimized procedure was validated, obtaining average extraction recoveries in the range 69–103% (10 μg kg⁻¹), 65–98% (50 μg kg⁻¹), 76–112% (100 μg kg⁻¹) and 76–112% (300 μg kg⁻¹), with precision values (expressed as relative standard deviation, RSD) ≤ 22% (except for 4-chlorophenol) involving intra-day and inter-day studies. Furthermore, 15 real soil samples were analyzed by the proposed method in order to assess its applicability. Some phenolic compounds (e.g. 2,4,6-trichlorophenol or 4-tert-octylphenol) were found in the samples at trace levels (<10 μg kg⁻¹).     

Spatial distribution of AT- and GC-rich DNA within interphase cell nuclei of Triatoma infestans Klug

Heterochromatin bodies in single- and multichromocentered interphase cell nuclei of Triatoma infestans, a vector of Chagas disease, have been suggested to contain AT-rich DNA, based on their positive response to Q-banding and Hoechst 33248 treatment. No information exists on whether GC-rich DNA is also present in these nuclei and whether it plays a role on chromatin condensation. Considering that methodologies more precise than those previously used to determine DNA base composition in situ are currently available, and that the spatial distribution of chromatin areas differing in composition in interphase cell nuclei of different species is a matter of interest, the localization of AT- and GC-rich DNA in T. infestans nuclei is revisited here. The methodologies used included DAPI/AMD and CMA(3)/Distamycin differential staining, Feulgen-DNA image analysis following Msp I and Hpa II enzymatic digestion, 5-methylcytidine immunodetection, AgNOR response, confocal microscopy, and the 5-aza-2'-deoxycytidine (5-AZA) demethylation assay. The results identified the presence of AT-rich/GC-poor DNA in chromocenters and evenly distributed AT and GC sequences in euchromatin. A GC-rich DNA zone encircling the chromocenters was also found but it could not be associated with NOR regions. To corroborate the DNA AT-richness in T. infestans nuclei, bioinformatic analyses were also performed. Methylated cytosine was evident at some points of the chromocenters' edge in single- and multichromocentered nuclei and at the euchromatin of multichromocentered nuclei and could be transiently affected by the 5-AZA treatment. The present results suggest that in the particular case of chromocenters of the hemipteran T. infestans, cytosine methylation is not a relevant factor involved in chromatin condensation.     

Chromatin supraorganization, mitotic abnormalities and proliferation in cells with increased or down-regulated lox expression: Indirect evidence of a LOX-histone H1 interaction in vivo

Lysyl oxidases (LOXs) are enzymes that permit the covalent crosslinking of the component chains of collagen and elastin. These enzymes are present inside the nuclei of certain mammalian cells. Previous studies have proposed LOX binding to histone H1 in vitro, and histone H1 is known to control global chromatin compaction and mitotic chromosome architecture. Therefore, in the present study, we analyzed chromatin supraorganizational changes, mitotic abnormalities, mitotic indices and cell death ratios in COS-7 and NRK-49F cells with high and low lox expression levels, respectively. The objective was to support biochemical data of LOX-H1 interaction, by providing evidence of chromatin remodeling in vivo, under different lox expressions. Chromatin decondensation assessed by image analysis was observed in COS-7 cells with increased lox expression. This decondensation is suggested to be promoted by LOX actions on histone H1, which loosens the DNA-H1 complex. In NRK-49F cells transfected with antisense lox or subjected to treatment with beta-aminopropionitrile (BAPN), chromatin condensation and nuclear phenotypic variability were found, which may be due to reduced LOX-H1 interaction. When lox expression was increased in COS-7 cells, the frequency of irregular chromosome plates was not affected, but cell proliferation decreased and "cell death preceded by multinucleation" increased. In NRK-49F cells there was accelerated proliferation induced by transfection with the antisense lox, and confirmed when cells were treated with BAPN. Apoptosis increased in NRK-49F cells only with BAPN treatment whereas cell death preceded by multinucleation increased only after antisense lox transfection. The data presented herein regarding chromatin remodeling indirectly support the hypothesis that LOX binds to histone H1 in vivo. Cell proliferation in COS-7 and NRK-49F cells and cell death at least in COS-7 cells agree with predicted effects of LOX interference in these processes.     

Electron capture and loss in the scattering of H+ from HOPG graphite

In this paper we report measurements of the positive (H⁺) and negative (H^?) ion fractions after H⁺ scattering from a highly oriented pyrolytic graphite (HOPG) surface. The experimental results show that for a fixed (large) exit angle the negative fraction is almost independent of the primary ion energy, while the positive fraction increases steadily. For a fixed incident energy, the H⁺ and H^? fractions show a complementary behavior with exit angle. A dynamical quantum mechanical calculation, based on the localized and extended features of the atom–surface interaction, allows us to understand many of the features of the experimental results.     

High energy excitations in ion-induced electron emission from AlF3

Measurements of electron emission spectra from surfaces of aluminum fluoride impacted by keV noble gas ions show a high-energy structure, peaking around 7 eV that increases in intensity with ion energy. The shape of this structure, identified by Factor Analysis, is independent of the nature and the energy of the impinging ions. We discuss one electron, two electron and plasmon excitation mechanisms and conclude that the high-energy structure results from the autoionization of F^? 2p⁴nl n′l′ excited by electron promotion in close atomic collisions.     

Compensation of phase-to-amplitude modulation conversion in a complete frequency conversion system with an all-fiber system

We report on an experimental demonstration of linear precompensation of nonlinear phase and amplitude transfer functions. We show the effective compensation with a linear all-fiber system of phase-to-amplitude modulation conversion due to a complete frequency conversion system including plane gratings and a nonlinear crystal.     

Experimental demonstration of linear precompensation of a nonlinear transfer function due to second-harmonic generation

We report on what we believe is the first experimental demonstration of the linear precompensation of a nonlinear transfer function due to frequency conversion. As a proof of principle, we show the effective precompensation with an interferometric filter of FM-to-AM conversion due to second-harmonic generation in a potassium titanyl phosphate crystal.     

Low-Energy Kaon�CNucleon/Nuclei Interaction Studies at DA��NE (SIDDHARTA and AMADEUS Experiments)

The DA??NE electron?Cpositron collider at the Laboratori Nazionali di Frascati of INFN has made available a unique quality low-energy negative kaons ??beam??. The SIDDHARTA experiment used this beam to perform unprecedented precision measurements on kaonic atoms, while the AMADEUS experiment plans to perform in the coming years precision measurements on kaon?Cnuclei interactions at low-energies, in particular to study the kaonic nuclei. The two experiments are briefly presented in this paper.     

Seasonality and idiosyncratic risk in mutual fund performance

This paper examines the relationship between seasonality, idiosyncratic risk and mutual fund returns using multifactor models. We use a large sample containing the return histories of 728 UK mutual funds over a 23-year period to measure fund performance. We present evidence that idiosyncratic risk cannot be eliminated, we also find evidence of seasonality in all fund categories. Specifically, we find a close relation between the seasonality and the end of the tax-year. We document that the idiosyncratic risk puzzle cannot explain seasonality in fund performance in the UK. Although, we do find that idiosyncratic risk can account for the seasonality in the month of April. Thus, the results show a link between the tax-loss selling hypothesis in April and idiosyncratic risk in that month. Finally, we report evidence that idiosyncratic risk is negatively related to expected returns for most fund classes.