Photobleaching of xanthene dyes in a poly(vinyl alcohol) matrix

Photobleaching of three different xanthene dyes namely, Erythrosin B (ERB), Eosin Y (EOY) and Rose Bengal (ROB) in Poly(Vinyl Alcohol) (PVA) matrix has been studied. Quantum yield values of photobleaching using an argon-ion laser (514.5 nm) were determined in presence of an electron donor (TriEthAnolamine, TEA) and/or Cr(VI). Evaluated quantum yield values suggest that erythrosin B undergoes faster photobleaching than eosin Y or rose bengal in presence of TEA. Presence of Cr(VI) in addition to TEA drastically decreases the quantum yield. Possible reaction pathways of photobleaching are discussed.     

Nitrogen 1s near-edge X-ray absorption fine structure spectroscopy of amino acids: Resolving zwitterionic effects

Considerable variation is observed in the near-edge X-ray absorption fine structure (NEXAFS) spectra of amino acids. To unambiguously characterize the chemical origin of this variation, we have acquired the nitrogen 1s NEXAFS spectra of several amino acids and other model compounds and complemented these experimental measurements with ab initio calculations of isolated molecules and molecular clusters. The systematic differences observed between the zwitterionic and un-ionized forms of amino acids arise directly from the structural difference (-NH2 vs -NH3+), which leads to a change in the degree of Rydberg-valence mixing. Further change arises from quenching of this Rydberg character in the spectra of condensed amino acids. Ab initio calculations are used to explore the degree of Rydberg-valence mixing in the solid state.     

Use of streptomycin for precipitation and detection of proteinase K resistant prion protein (PrPsc) in biological samples

The ability of streptomycin to form multimolecular aggregates with pathogenic prion proteins and their recovery by precipitation via a low-speed centrifugation step has been demonstrated; these novel properties of streptomycin make it a useful substance that increases the sensitivity of laboratory diagnostic techniques for prion infections in man and animals.     

Isoquinuclidine Mimics of β‐D‐Glucopyranosides: Differences and Similarities in the Mechanism of Action of some β‐D‐Glucosidases and a β‐D‐Mannosidase

The D ‐gluco‐isoquinuclidines 3 and 4 were prepared and tested as inhibitors of the β‐glucosidases from Caldocellum saccharolyticum and from sweet almonds; the results are compared to the inhibition of snail β‐mannosidase by the D ‐manno‐isoquinuclidines 1 and 2 . Exploratory experiments in the racemic series showed that treatment of the ester epoxide 6 with benzyl alcoholates leads only to epimerisation, transesterification, and formation of the cyclopropane 9 . Ring opening of the reduced epoxide 13 by NaN₃ proceeded regioselectively to provide 14 . Treatment of the C(6)? O‐triflate 16 with AcOCs induced a rearrangement; the reaction with NaN₃ gave the C(5)‐azido derivative 14 . The acetoxy triflate 18 , however, reacted with AcOCs to provide the desired gluco‐isoquinuclidine 19 . Similarly, the enantiomerically pure acetoxy triflate 22 provided the D ‐gluco‐isoquinuclidine 24 , which was reduced and deprotected to provide 3 and 4 . The deoxy analogues 30 and 31 were obtained by reductive deiodination of the iodide 27 , derived from 22 . The D ‐gluco‐isoquinuclidines 3, 4, 30 , and 31 are much weaker inhibitors of β‐glucosidases than the D ‐manno‐analogues 1 and 2 of snail β‐mannosidase. The N‐benzyl derivative 3 is a weaker inhibitor than the N‐unsubstituted analogue in the gluco‐series, while it is a much stronger inhibitor in the manno‐series. A consideration of the pK_HA values of the isoquinuclidines 1 – 4 and the pH value of the enzyme assays suggests that the D ‐gluco‐isoquinuclidines are poor mimics of the shape of a reactive, enzyme‐bound gluco‐conformer, while the D ‐manno‐analogues are reasonably good mimics of a reactive, enzyme‐bound manno‐conformer. The inhibition results may also suggest that the glycosidase induced lengthening of the scissile bond and rehybridisation of the anomeric centre are more strongly correlated with the change of the ground‐state conformation during hydrolysis of β‐D ‐glucopyranosides than of β‐D ‐mannopyranosides.     

Cyclizations and fragmentations in the alkylation of 6-chloro-5-hydroxy-4-aminopyrimidines with aminoalkyl chlorides

Substituted aminopyrimidines are an important class of compounds, in part because they frequently show biological activity. Facile synthesis of polysubstituted aminopyrimidines is highly desirable for the synthesis of screening libraries. We describe a route to 4,6-diamino-5-alkoxypyrimidines via a S_NAr-alkylation-S_NAr sequence from readily available 4,6-dichloro-5-methoxypyrimidine, which allows the synthesis of such compounds with regiochemical control. The extension of this approach to alkylating agents bearing amino substituents led to unexpected and, in some cases, unprecedented products resulting from intramolecular S_NAr cyclization and subsequent fragmentation.     

Feature-Based Molecular Networks Identification of Bioactive Metabolites from Three Plants of the Polynesian Cosmetopoeia Targeting the Dermal Papilla Cells of the Hair Cycle

The term cosmetopoeia refers to the use of plants in folks’ cosmetics. The aerial parts of Bidens pilosa L., the leaves of Calophyllum inophyllum L. and the fruits of Fagraea berteroana A.Gray ex Benth are traditionally used in French Polynesia for hair and skin care. During the hair cycle, dermal papilla cells and their interaction with epithelial cells are essential to promote hair follicle elongation. The aim of our investigations was the identification of metabolites from these three plants and chemical families responsible for their hair growth activity. A bioactivity-based molecular network was produced by mapping the correlation between features obtained from LC-MS/MS data and dermal papilla cell proliferation, using the Pearson correlation coefficient. The analyses pointed out glycosylated flavonols and phenolic acids from B. pilosa and C. inophyllum, along with C-flavonoids, iridoids and secoiridoids from F. berteroana, as potential bioactive molecules involved in the proliferation of hair follicle dermal papilla cells. Our results highlight the metabolites of the plant species potentially involved in the induction of hair follicle growth and support the traditional uses of these plants in hair care.     

Electrochemical Determination of Uric Acid,Dopamine and Tryptophan at Zinc Hexacyanoferrate Clay Modified Electrode

A Cameroonian smectite clay has been transformed into Zn²⁺ homoionic form and then used to prepare film modified glassy carbon electrodes and carbon paste electrodes. These electrodes containing Zn²⁺ were exploited to prepare a mixed valence zinc hexacyanoferrate (ZnHCF). Cyclic voltammetry has been employed to monitor the in situ growth of ZnHCF on clay modified electrodes. Although interesting electrocatalytic properties toward UA were observed with these modified electrodes, the modified carbon paste electrodes were the most suitable for dopamine, uric acid and tryptophan detection and exhibited for these analytes extended linear range, high sensitivities, selectivity and low limit.     

Multiwavelength anomalous diffraction and diffraction anomalous fine structure to study composition and strain of semiconductor nanostructures

The aim of this paper is to illustrate the use of Multi-Wavelength Anomalous Diffraction (MAD) and Diffraction Anomalous Fine Structure (DAFS) spectroscopy for the study of structural properties of semiconductor nanostructures. We give a brief introduction on the basic principles of these techniques providing a detailed bibliography. Then we focus on the data reduction and analysis and we give specific examples of their application on three different kinds of semiconductor nanostructures: Ge/Si nanoislands, AlN capped GaN/AlN Quantum Dots and AlGaN/AlN Nanowires. We show that the combination of MAD and DAFS is a very powerful tool to solve the structural problem of these materials of high technological impact. In particular, the effects of composition and strain on diffraction are disentangled and composition can be determined in a reliable way, even at the interface between nanostructure and substrate. We show the great possibilities of this method and give the reader the basic tools to undertake its use.     

Some characteristics of the concert harp's acoustic radiation

The way a musical instrument radiates plays an important part in determining the instrument's sound quality. For the concert harp, the soundboard has to radiate the string's vibration over a range of 7 octaves. Despite the effort of instrument makers, this radiation is not uniform throughout this range. In a recent paper, Waltham and Kotlicki [J. Acoust. Soc. Am. 124, 1774-1780 (2008)] proposed an interesting approach for the study of the string-to-string variance based on the relationship between the string attachment position and the operating deflection shapes of the soundboard. Although the soundboard vibrational characteristics determine a large part of the instrument's radiation, it is also important to study directly its radiation to conclude on the origins of the string-to-string variation in the sound production. This is done by computing the equivalent acoustical sources on the soundboard from the far field sound radiation measured around the harp, using the acoustic imaging technique inverse frequency response function. Results show that the radiated sound depends on the correlation between these sources, and the played string's frequency and location. These equivalent sources thus determine the magnitude and directivity of each string's partial in the far field, which have consequences on the spectral balance of the perceived sound for each string.