Citrafungins A and B, two new fungal metabolite inhibitors of GGTase I with antifungal activity

[structure: see text] Screening of natural products extracts led to the discovery of citrafungins A and B, two new fungal metabolites of the alkylcitrate family that are inhibitors of GGTase I of various pathogenic fungal species with IC(50) values of 2.5-15 microM. These compounds exhibited antifungal activities with MIC values of 0.40-55 microM. The isolation, structure elucidation, relative and absolute stereochemistry, and biological activities of citrafungins are described.     

Actinide uptake onto zeolite-L and SAPO-34

The characteristics of ion exchange of uranyl and americium, which are -emitting radioactive nuclides, were examined by batch and column methods. SAPO-34 showed good selectivity for uranyl ion at pH 2–3.5, and distribution coefficients of Am³⁺ and UO ₂ ²⁺ increased with equilibrium pH. -irradiation (2 MGy) did not show any significant effect on the uptake of both of actinide ions onto L and SAPO-34. Higher does of -irradiation (up to 10 MGy) created a change of equilibrium pH, and hence uptake, due to radiolysis of water and heat localization generated by -radiation and annealing processes.     

Measurement of nitrogen dioxide in cigarette smoke using quantum cascade tunable infrared laser differential absorption spectroscopy (TILDAS)

Although nitrogen dioxide (NO(2)) has been previously reported to be present in cigarette smoke, the concentration estimates were derived from kinetic calculations or from measurements of aged smoke, where NO(2) was formed some time after the puff was taken. The objective of this work was to use tunable infrared laser differential absorption spectroscopy (TILDAS) equipped with a quantum cascade (QC) laser to determine if NO(2) could be detected and quantified in a fresh puff of cigarette smoke. A temporal resolution of approximately 0.16s allowed measurements to be taken directly as the NO(2) was formed during the puff. Sidestream cigarette smoke was sampled to determine if NO(2) could be detected using TILDAS. Experiments were conducted using 2R4F Kentucky Reference cigarettes with and without a Cambridge filter pad. NO(2) was detected only in the lighting puff of whole mainstream smoke (without a Cambridge filter pad), with no NO(2) detected in the subsequent puffs. The measurement precision was approximately 1.0 ppbVHz(-1/2), which allows a detection limit of approximately 0.2 ng in a 35 ml puff volume. More NO(2) was generated in the lighting puff using a match or blue flame lighter (29+/-21 ng) than when using an electric lighter (9+/-3 ng). In the presence of a Cambridge filter pad, NO(2) was observed in the gas phase mainstream smoke for every puff (total of 200+/-30 ng/cigarette) and is most likely due to smoke chemistry taking place on the Cambridge filter pad during the smoke collection process. Nitrogen dioxide was observed continuously in the sidestream smoke starting with the lighting puff.     

Recoding the Genetic Code with Selenocysteine

Selenocysteine (Sec) is naturally incorporated into proteins by recoding the stop codon UGA. Sec is not hardwired to UGA, as the Sec insertion machinery was found to be able to site‐specifically incorporate Sec directed by 58 of the 64 codons. For 15 sense codons, complete conversion of the codon meaning from canonical amino acid (AA) to Sec was observed along with a tenfold increase in selenoprotein yield compared to Sec insertion at the three stop codons. This high‐fidelity sense‐codon recoding mechanism was demonstrated for Escherichia coli formate dehydrogenase and recombinant human thioredoxin reductase and confirmed by independent biochemical and biophysical methods. Although Sec insertion at UGA is known to compete against protein termination, it is surprising that the Sec machinery has the ability to outcompete abundant aminoacyl‐tRNAs in decoding sense codons. The findings have implications for the process of translation and the information storage capacity of the biological cell.     

Visual Displays that Directly Interface and Provide Read‐Outs of Molecular States via Molecular Graphics Processing Units

The monitoring of molecular systems usually requires sophisticated technologies to interpret nanoscale events into electronic‐decipherable signals. We demonstrate a new method for obtaining read‐outs of molecular states that uses graphics processing units made from molecular circuits. Because they are made from molecules, the units are able to directly interact with molecular systems. We developed deoxyribozyme‐based graphics processing units able to monitor nucleic acids and output alphanumerical read‐outs via a fluorescent display. Using this design we created a molecular 7‐segment display, a molecular calculator able to add and multiply small numbers, and a molecular automaton able to diagnose Ebola and Marburg virus sequences. These molecular graphics processing units provide insight for the construction of autonomous biosensing devices, and are essential components for the development of molecular computing platforms devoid of electronics.     

A Fast Deposition‐Crystallization Procedure for Highly Efficient Lead Iodide Perovskite Thin‐Film Solar Cells

Thin‐film photovoltaics based on alkylammonium lead iodide perovskite light absorbers have recently emerged as a promising low‐cost solar energy harvesting technology. To date, the perovskite layer in these efficient solar cells has generally been fabricated by either vapor deposition or a two‐step sequential deposition process. We report that flat, uniform thin films of this material can be deposited by a one‐step, solvent‐induced, fast crystallization method involving spin‐coating of a DMF solution of CH₃NH₃PbI₃ followed immediately by exposure to chlorobenzene to induce crystallization. Analysis of the devices and films revealed that the perovskite films consist of large crystalline grains with sizes up to microns. Planar heterojunction solar cells constructed with these solution‐processed thin films yielded an average power conversion efficiency of 13.9±0.7 % and a steady state efficiency of 13 % under standard AM 1.5 conditions.     

Divergent synthesis of 2-C-branched pyranosides and oxepines from 1,2-gem-dibromocyclopropyl carbohydrates

The ring opening of 1,2-(gem-dibromo)cyclopropyl carbohydrates by two different modes leads to either 2-C-(bromomethylene)pyranosides (using base) or 2-bromooxepines (using silver salts), as shown previously by us for a d-glucal-derived cyclopropane. The base-promoted ring opening is extended to encompass additional alcohol, thiol and amine nucleophiles, and diastereoisomeric cyclopropane precursors. Cross-coupling of the 2-C-(bromomethylene)pyranosides leads to extended 2-C-branched pyranosides. Silver-promoted ring expansion of the cyclopropyl carbohydrates in the presence of various alcohols is described. Cross-coupling of the resulting benzyl 2-bromooxepines affords 2-C-substituted oxepines.     

Infrared spectroscopy of the mineralogy of coprolites from Brean Down: evidence of past human activities and animal husbandry

The mineralogy of 11 concretions from the Bronze Age settlement horizons at Brean Down near Weston-super-Mare, Somerset, UK, has been examined by infrared spectroscopy. The concretions are found to contain calcite and apatite and, in some cases, quartz. Four further concretions from the later Iron Age Meare Village, soil samples from Brean Down and mineralised samples of known faecal origin from a cesspit within the Tudor Merchant's house in Tenby have been similarly examined. It is found that all samples contain calcite, but only the concretions and the Tenby cesspit samples contain apatite. None of the soil samples contain apatite, although these are relatively high in quartz. This suggests that the concretions are coprolites and that the apatite has a biological origin in small bone fragments. The infrared study is backed up by scanning electron microscopy which confirms the presence of phosphorus in the coprolite samples and shows a morphology suggestive of the presence of bone fragments; it is likely, therefore, that the coprolites result from a carnivore--most probably from dogs. The findings show the usefulness of infrared spectroscopy for the rapid identification of mineralised coprolitic material from archaeological sites.     

Spatially resolved gas phase composition measurements in supersonic flows using tunable diode laser absorption spectroscopy

We used a tunable diode laser absorption spectrometer to follow the condensation of D(2)O in a supersonic Laval nozzle. We measured both the concentration of the condensible vapor and the spectroscopic temperature as a function of position and compared the results to those inferred from static pressure measurements. Upstream and in the early stages of condensation, the quantitative agreement between the different experimental techniques is good. Far downstream, the spectroscopic results predict a lower gas phase concentration, a higher condensate mass fraction, and a higher temperature than the pressure measurements. The difference between the two measurement techniques is consistent with a slight compression of the boundary layers along the nozzle walls during condensation.     

Synthesis and ion transport activity of oligoesters containing an environment-sensitive fluorophore

A series of oligoesters based on a rigid triphenyl-diyne core is described. The molecules were readily synthesized from key intermediates, and retained good solubility properties. One of the compounds displayed modest ion transport activity in vesicles, was capable of forming highly conducting single channels in planar bilayers and exhibited an irregular non-linear current-voltage response. All the reported molecules had minimal aqueous fluorescence while being highly fluorescent in less-polar media including lipid vesicles; their partitioning into the membrane could be monitored by a significant blue-shift and increase in fluorescence intensity, as well as a decreased extent of quenching in vesicles over that in water. The combined data indicated that the compounds are highly aggregated in aqueous solution, which limits their membrane partitioning and ion transport activity, in agreement with mechanisms proposed for other 'simple' oligoester channels.