Aromatic compounds produced by endophytic fungi isolated from red alga Asparagopsis taxiformis - Falkenbergia stage

Endophytic fungi were isolated from red alga Asparagopsis taxiformis - Falkenbergia stage, collected from the Brazilian coast, and were identified as Annulohypoxylon stygium (AT-03) and A. yungensis (AT-06) based on their macro/micromorphological and molecular features. Bioassay-guided fractionation of the EtOAc extract from laboratory cultures of both strains yielded known compounds pyrogallol from A. stygium, (3R)-scytalone and (3R,4R)-4-hydroxy-scytalone from A. yungensis. Pyrogallol was active against methicillin-resistant Staphylococcus aureus (MRSA) and Escherichia coli strains. An inactive fraction from A. stygium afforded two additional compounds, (3R,4R)-3,4,5-trihydroxy-1-tetralone and tyrosol. Optically active compounds had their stereochemistry determined by circular dichroism (CD) spectroscopy.     

Kβ X-Ray Emission Spectroscopic Study of a Second-Row Transition Metal (Mo) and Its Application to Nitrogenase-Related Model Complexes

In recent years, X-ray emission spectroscopy (XES) in the Kβ (3p-1s) and valence-to-core (valence-1s) regions has been increasingly used to study metal active sites in (bio)inorganic chemistry and catalysis, providing information about the metal spin state, oxidation state and the identity of coordinated ligands. However, to date this technique has been limited almost exclusively to first-row transition metals. In this work, we present an extension of Kβ XES (in both the 4p-1s and valence-to-1s [or VtC] regions) to the second transition row by performing a detailed experimental and theoretical analysis of the molybdenum emission lines. It is demonstrated in this work that Kβ₂ lines are dominated by spin state effects, while VtC XES of a 4d transition metal provides access to metal oxidation state and ligand identity. An extension of Mo Kβ XES to nitrogenase-relevant model complexes shows that the method is sufficiently sensitive to act as a spectator probe for redox events that are localized at the Fe atoms. Mo VtC XES thus has promise for future applications to nitrogenase, as well as a range of other Mo-containing biological cofactors. Further, the clear assignment of the origins of Mo VtC XES features opens up the possibility of applying this method to a wide range of second-row transition metals, thus providing chemists with a site-specific tool for the elucidation of 4d transition metal electronic structure.     

Parallel Versus Antiparallel β-Sheet Structure in Cyclic Peptide Hybrids Containing γ- or δ-Cyclic Amino Acids

Cyclic peptides with disc-shaped structures have emerged as potent building blocks for the preparation of new biomaterials in fields ranging from biological to material science. In this work, we analyze in depth the self-assembling properties of a new type of cyclic peptides based on the alternation of α-residues and cyclic δ-amino acids (α,δ-CPs). To examine the preferred stacking properties adopted by cyclic peptides bearing this type of amino acids, we carried out a synergistic in vitro/in silico approximation by using simple dimeric models and then extended to nanotubes. Although these new cyclic peptides (α,δ-CPs) can interact either in a parallel or antiparallel fashion, our results confirm that although the parallel β-sheet is more stable, it can be switched to the antiparallel stacking by choosing residues that can establish favorable cross-strand interactions. Moreover, the subsequent comparison by using the same methodology but applied to α,γ-CPs models, up to the moment assumed as antiparallel-like d,l -α-CPs, led to unforeseen conclusions that put into question preliminary conjectures about these systems. Surprisingly, they tend to adopt a parallel β-sheet directed by the skeleton interactions. These results imply a change of paradigm with respect to cyclic peptide designs that should be considered for dimers and nanotubes.     

Pd-catalyzed borylative polycyclization of enediynes to allylboronates

Pd-catalyzed dicyclization of 6-ene-1,11-diynes with bis(pinacolato)diboron affords synthetically useful allylboronates under smooth conditions. Two new C-C and one C-B bonds are stereospecifically formed in a single operation. The stereochemical outcome depends on the starting alkene configuration. The reaction is general and has been applied to differently substituted enediynes. Isolation of intermediate 1,3-dienes suggests a regioselective beta-hydrogen elimination along the reaction pathway.     

Systematic comparison of delta34S measurements by multicollector inductively coupled plasma mass spectrometry and evaluation of full uncertainty budget using two different metrological approaches

A systematic comparison of delta34S measurements by multicollector inductively coupled plasma mass spectrometry (MCICPMS) using two different standardisation approaches and two different reference materials as working standards is reported for the first time. Full uncertainty budgets have been calculated using the Kragten approach. Internal standardisation by measuring Si ratios and external standardisation by bracketing samples with either NIST RM8553 or NIST RM8554 have been compared to correct for the effects of mass bias. The delta34S value and the associated uncertainty ( per thousand) were found to be slightly different when using different approaches. Corrected 34S:32S ratios for NIST RM8553 and NIST RM8554 differed from those previously reported by 0.1 to 0.5% when using external standardisation. 34S:32S ratios for NIST RM8553 and NIST RM8554 differed from those previously reported by 0.06 to 0.15% when using Si internal standardisation. This indicated that in order to minimise deviation from true ratio values, Si internal standardisation would be a more appropriate option when using a Neptune MCICPMS instrument. delta(34)S values were obtained for four different methionine samples and expanded uncertainties (k = 2) expressed in delta34S ( per thousand) ranged from 0.7 per thousand to 1.6 per thousand. Regardless of the approach used for the mass bias correction, three parameters provided the major contributions to the standard uncertainty of the delta34S(V-CDT) value. These were the measured 34S:32S in the sample, the measured 34S:32S for the working standard and the known delta34S(V-CDT) value of the working standard. Results using both approaches are compared and the Si internal standardisation approach is used to provide results for an inter-laboratory comparison.     

One-step growth of gold nanorods using a β-diketone reducing agent

The synthesis and characterisation of gold nanorods have been carried out by reduction of the gold salt HAuCl₄. This has been done using a single reducing agent, acetylacetone, rather than the two reducing agents, sodium borohydride and ascorbic acid, normally required by standard wet chemistry methods of gold nanorod formation. Using this novel method, the nanorods were synthesised at several different pH values which were found to greatly affect both the rate at which the nanorods form and their physical dimensions. The concentrations of acetylacetone and silver nitrate used relative to the gold salt were found to alter the aspect ratio of the nanorods formed. Rods with an average length of 42 nm and an aspect ratio of 4.6 can be easily and reproducibly formed at pH 10 using this method. Nanorods formed under optimum conditions were investigated using TEM. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Electrochemical synthesis of PEDOT derivatives bearing imidazolium‐ionic liquid moieties

Novel poly(3,4‐ethylenedioxythiophene) (PEDOT) polymers bearing imidazolium‐ionic liquid moieties were synthesized by electrochemical polymerizations. For this purpose, new functional monomers were synthesized having an 3,4‐ethylenedioxythiophene (EDOT) unit and an imidazolium‐ionic liquid with different anions such as tetrafluoroborate (BF), bis(trifluoromethane)sulfonimide ((CF₃SO₂)₂N^?), and hexafluorophosphate (PF). Next, polymer films were obtained by electrochemical synthesis in dicholoromethane solutions. Obtained polymers were characterized, revealing the characteristics of PEDOT in terms of electrochemical and spectroelectrochemical properties, FTIR, ¹H NMR, and AFM microscopy. Interestingly, the hydrophobic character of electropolymerized films could be modified depending on the anion type. The hydrophobicity followed the trend PF > (CF₃SO₂)₂N^? > BF > pure PEDOT as determined by water contact angle measurements. Furthermore, the polymers could be dissolved in a range of polar organic solvents such as dimethylformamide, propylene carbonate, and dimethyl sulfoxide making these polymers interesting candidates for wet processing methods. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3010–3021, 2009     

Optical sensing in microfluidic lab-on-a-chip by femtosecond-laser-written waveguides

We use direct femtosecond laser writing to integrate optical waveguides into a commercial fused silica capillary electrophoresis chip. High-quality waveguides crossing the microfluidic channels are fabricated and used to optically address, with high spatial selectivity, their content. Fluorescence from the optically excited volume is efficiently collected at a 90° angle by a high numerical aperture fiber, resulting in a highly compact and portable device. To test the platform we performed electrophoresis and detection of a 23-mer oligonucleotide plug. Our approach is quite powerful because it allows the integration of photonic functionalities, by simple post-processing, into commercial LOCs fabricated with standard techniques. Figure Femtosecond laser written waveguides can selectively excite fluorescence in a microfluidic channel of a commercial lab-on-a-chip. A compact scheme for on-chip detection by laser induced fluorescence is applied to capillary electrophoresis of a 23-mer Cy3-labeled oligonucleotide