Sn-MCM-41--a heterogeneous selective catalyst for the Baeyer-Villiger oxidation with hydrogen peroxide

A new heterogeneous catalyst, Sn-MCM-41, is described for the Baeyer-Villiger reaction with hydrogen peroxide which selectively activates the carbonyl function for the nucleophilic attack by the oxidant, with high chemoselectivities when double bonds are present in the molecule.     

Understanding the structure/activity relationships of the iron regulatory peptide hepcidin

The peptide hormone hepcidin is a key homeostatic regulator of iron metabolism and involved in pathological regulation of iron in response to infection, inflammation, hypoxia, and anemia. It acts by binding to the iron exporter ferroportin, causing it to be internalized and degraded; however, little is known about the structure/activity relationships of the interaction of hepcidin with ferroportin. We show that there are key residues in the N-terminal region of hepcidin that influence its interaction with ferroportin, and we explore the structure/function relationships at these positions. A series of hepcidin mutants in which disulfide bonds were replaced with diselenide bonds showed no change in activity compared to native hepcidin. These results identify important constraints for the development of hepcidin congeners for the treatment of hereditary iron overload.     

Application of MALDI TOF/TOF mass spectrometry and collision-induced dissociation for the identification of disulfide-bonded peptides

This paper describes a method for the fast identification and composition of disulfide-bonded peptides. A unique fragmentation signature of inter-disulfide-bonded peptides is detected using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF)/TOF mass spectrometry and high-energy collision-induced dissociation (CID). This fragmentation pattern identifies peptides with an interconnected disulfide bond and provides information regarding the composition of the peptides involved in the pairing. The distinctive signature produced using CID is a triplet of ions resulting from the cleavage of the disulfide bond to produce dehydroalanine, cysteine or thiocysteine product ions. This method is not applicable to intra-peptide disulfide bonds, as the cleavage mechanism is not the same and a triplet pattern is not observed. This method has been successfully applied to identifying disulfide-bonded peptides in a number of control digestions, as well as study samples where disulfide bond networks were postulated and/or unknown.     

Investigation of pituitary adenylate cyclase activating polypeptide in human gynecological and other biological fluids by using MALDI TOF mass spectrometry

Pituitary adenylate cyclase activating polypeptide (PACAP) is a multifunctional and pleiotropic neuropeptide. PACAP has diverse effects in the endocrine system, among others, it plays important roles in oogenesis, implantation and development of the nervous system. However, it is not known whether PACAP is present in the fluids of the human reproductive organs. The aim of the present study was to determine, by means of mass spectrometry and radioimmunoassay, whether PACAP is present in human amniotic fluid, ovarian follicular fluid and cervico-vaginal fluid. Samples were obtained from healthy adult volunteers. Our MALDI TOF and MALDI TOF/TOF spectrometry results show that PACAP38 is present in all of the follicular fluid samples, and PACAP-like immunoreactivity was also measured by radioimmunoassay. However, we did not find the characteristic peak representing the unmodified 38 amino acid form of the peptide in normal cervico-vaginal smear and amniotic fluid samples. Furthermore, we analyzed other body fluids for comparison, such as human nasal fluid, saliva and aqueous humor. PACAP was not found in these latter samples. In summary, the present study provides evidence for the presence of PACAP in human follicular fluid, suggesting a role in oocyte function, but determination of the exact physiological significance awaits further investigation.     

Rainforests as concert halls for birds: are reverberations improving sound transmission of long song elements?

In forests reverberations have probably detrimental and beneficial effects on avian communication. They constrain signal discrimination by masking fast repetitive sounds and they improve signal detection by elongating sounds. This ambivalence of reflections for animal signals in forests is similar to the influence of reverberations on speech or music in indoor sound transmission. Since comparisons of sound fields of forests and concert halls have demonstrated that reflections can contribute in both environments a considerable part to the energy of a received sound, it is here assumed that reverberations enforce also birdsong in forests. Song elements have to be long enough to be superimposed by reflections and therefore longer signals should be louder than shorter ones. An analysis of the influence of signal length on pure tones and on song elements of two sympatric rainforest thrush species demonstrates that longer sounds are less attenuated. The results indicate that higher sound pressure level is caused by superimposing reflections. It is suggested that this beneficial effect of reverberations explains interspecific birdsong differences in element length. Transmission paths with stronger reverberations in relation to direct sound should favor the use of longer signals for better propagation.     

Substitution effect of Ba at the Sr sites in Sr(Fe,Re)O3

We study ?-meson production in nuclei to investigate the in-medium modification of the ?-meson spectral function at finite density. We consider ( ${\bar p},\phi$ ), (γ,p) and (π ^???, n) reactions to produce a ?-meson inside the nucleus and evaluate the effects of the medium modifications to reaction cross sections. The structures of the bound states, ?-mesic nuclei, are also studied. For strong absorptive interaction cases, we need to know the spectrum shape in a wide energy region to deduce the properties of ?.     

Production of Upsilon(1S) mesons from chi(b) decays in p&pmacr; collisions at sqrt

We have reconstructed the radiative decays chi(b)(1P)-->Upsilon(1S)gamma and chi(b)(2P)-->Upsilon(1S)gamma in p&pmacr; collisions at sqrt[s] = 1.8 TeV, and measured the fraction of Upsilon(1S) mesons that originate from these decays. For Upsilon(1S) mesons with p(Upsilon)(T)>8.0 GeV/c, the fractions that come from chi(b)(1P) and chi(b)(2P) decays are [27.1+/-6.9(stat)+/-4. 4(syst)]% and [10.5+/-4.4(stat)+/-1.4(syst)]%, respectively. We have derived the fraction of directly produced Upsilon(1S) mesons to be [50.9+/-8.2(stat)+/-9.0(syst)]%.     

Experiments with longitudinally polarized electrons in a storage ring using a siberian snake

We report on first measurements with polarized electrons stored in a medium-energy ring and with a polarized internal target. Polarized electrons were injected at 442 MeV (653 MeV), and a partial (full) Siberian snake was employed to preserve the polarization. Longitudinal polarization at the interaction point and polarization lifetime of the stored electrons were determined with laser backscattering. Spin observables were measured for electrodisintegration of polarized 3He, with simultaneous detection of scattered electrons, protons, neutrons, deuterons, and 3He nuclei, over a large phase space.     

Highly Efficient Photodegradation of Organic Pollutants Assisted by Sonoluminescence

The mechanism of the photodegradation of azo dyes via ultrasonication is studied using a combination of the high‐performance liquid chromatography and UV–vis spectroscopy with detailed analysis of the kinetics. Based on the kinetics studies of the sonodegradation, it was proposed that the degradation of azo dyes was a multistage process that involved: (1) the direct attack of azo bonds and phenyl rings of dyes by the sonochemically formed reactive oxygen species; (2) the activation of semiconductor particles by the light emitted during cavitation and the triggering of the photocatalytic pathways of dye degradation and (3) increase of the adsorption capacity of the semiconductor particles due to the sonomechanically induced interparticle collisions. The detailed kinetics study can help in following an effective process up‐scaling. It was demonstrated that extremely short pulses of light flashes in a cavitated mixture activated the surface of photocatalysts and significantly enhanced dye degradation processes.     

Total Synthesis of Human Hepcidin through Regioselective Disulfide‐Bond Formation by using the Safety‐Catch Cysteine Protecting Group 4,4′‐Dimethylsulfinylbenzhydryl

A safety‐catch cysteine protecting group, S‐4,4′‐dimethylsulfinylbenzhydryl (Msbh), was designed and developed to expand the capabilities of synthetic strategies for the regioselective formation of disulfide bonds in cysteine‐rich peptides. The directed regioselective synthesis of human hepcidin, which contains four disulfide bonds, was undertaken and led to a high‐resolution NMR structure under more physiologically relevant conditions than previously. Conversely, hepcidin synthesized with the formerly assigned vicinal disulfide‐bond connectivity displayed significant conformational heterogeneity under similar conditions. The two synthetic forms of human hepcidin induced ferroportin internalization with apparent EC₅₀ values of 2.0 (native fold, 1 ) and 4.4 nM (non‐native fold, 2 ), with 2 undergoing isomerization to 1 in the presence of ferroportin expressing cells.