Synthesis of MIL-102, a chromium carboxylate metal-organic framework, with gas sorption analysis

A new three-dimensional chromium(III) naphthalene tetracarboxylate, CrIII3O(H2O)2F{C10H4(CO2)4}1.5.6H2O (MIL-102), has been synthesized under hydrothermal conditions from an aqueous mixture of Cr(NO3)3.9H2O, naphthalene-1,4,5,8-tetracarboxylic acid, and HF. Its structure, solved ab initio from X-ray powder diffraction data, is built up from the connection of trimers of trivalent chromium octahedra and tetracarboxylate moieties. This creates a three-dimensional structure with an array of small one-dimensional channels filled with free water molecules, which interact through hydrogen bonds with terminal water molecules and oxygen atoms from the carboxylates. Thermogravimetric analysis and X-ray thermodiffractometry indicate that MIL-102 is stable up to approximately 300 degrees C and shows zeolitic behavior. Due to topological frustration effects, MIL-102 remains paramagnetic down to 5 K. Finally, MIL-102 exhibits a hydrogen storage capacity of approximately 1.0 wt % at 77 K when loaded at 3.5 MPa (35 bar). The hydrogen uptake is discussed in relation with the structural characteristics and the molecular simulation results. The adsorption behavior of MIL-102 at 304 K resembles that of small-pore zeolites, such as silicalite. Indeed, the isotherms of CO2, CH4, and N2 show a maximum uptake at 0.5 MPa, with no further significant adsorption up to 3 MPa. Crystal data for MIL-102: hexagonal space group P(-)6 (No. 169), a = 12.632(1) A, c = 9.622(1) A.     

Coordination of XeF2 to calcium and cadmium hexafluorophosphates(V)

[M(XeF2)5](PF6)2 (M = Ca, Cd) complexes were prepared by the reaction of MF2 and XeF2 under pressure of gaseous PF5 in anhydrous HF as solvent. The coordination sphere of the Ca atom consists of nine fluorine atoms: three from two PF6(-) units (one bidentate and one monodentate) and one from each of six XeF2 molecules. The coordination sphere of the Cd atom consists of eight fluorine atoms: one from each of two PF6(-) units and one from each of six XeF2 molecules. Two of the XeF2 ligands about M in each compound are bridging ligands and are each linked to two M, generating infinite (-M-F-Xe-F-M-F-Xe-F-) chains along the b-axis in the Ca salt and along the c-axis in the Cd compound. The Cd2+ cation is smaller and more electronegative than the Ca2+ cation. These differences account for the higher F ligand coordination in the Ca2+ salt and for other structural features that distinguish them. The different stoichiometry of the PF6(-) salts when compared with their AsF6(-) analogues, which have the composition [M(XeF2)4](AsF6)2 (M = Ca, Cd), is in accord with the lower F ligand charge in the AsF6(-) when compared with that in the PF6(-) compound. Indeed, the AsF6(-) ligand charges appear to be similar to those in the XeF2-bridged species.     

Directing energy flow through quantum dots: towards nanoscale sensing

Nanoscale sensors can be created when an expected energetic pathway is created and then that pathway is either initiated or disrupted by a specific binding event. Constructing the sensor on the nanoscale could lead to greater sensitivity and lower limits of detection. To this end, quantum dots (QDs) can be considered prime candidates for the active components. Relative to organic chromophores, QDs have tunable spectral properties, show less susceptibility to photobleaching, have similar brightness, and have been shown to display electro-optical properties. In this review, we discuss recent articles that incorporate QDs into directed energy flow systems, some with the goal of building new and more powerful sensors and others that could lead to more powerful sensors. Figure     

Nanoscale characterization of single Au nanorods by confocal microscopy

We analyzed the scattering patterns of individual Au nanorods detected by means of confocal interference scattering microscopy in combination with a higher order laser mode. We placed the Au nanorods at the interface between two dielectric media and examined the influence of different interfaces on the signal amplitude, the signal-to-noise ratio as well as on the precision of topological measurements. Approaching the index matching regime allows for topological measurements with high accuracy minimizing the acquisition time. We were also able to track the position and the orientation of particles embedded in water even when they were not thoroughly sticking to the glass surface. These results underscore the potential of the presented technique for applications in life sciences.     

Poly(glyceryl glycerol): A multi‐functional hydrophilic polymer for labeling with boronic acids

The synthesis of poly(glyceryl glycerol) (PGG), a polymer featuring a polyethylene oxide backbone and 1,2‐diol groups in every repeating unit, is presented. PGG was prepared by monomer‐activated ring‐opening polymerization of (dl ?1,2‐isopropylidene glyceryl) glycidyl ether, introducing a functional azido‐ or bromo‐head group to each chain. The 1,2‐diol groups, which were released by acidic deprotection, readily reacted with boronic acid derivatives, enabling the attachment of functional moieties under mild aqueous conditions. PGG was conjugated to poly(l ‐lactide) (PLLA) via azide‐alkyne cycloaddition and the resulting copolymer assembled into nanoparticles of 70 nm diameter in aqueous solution. Labeling of the PGG–PLLA particles was achieved by simple mixing with a boronic acid‐functional fluorophore. The labeling efficiency was determined by fluorescence spectroscopy to be 85.5% for boronic acid‐functional rhodamine B compared with 0.2% for plain rhodamine B. The strong interaction of PGG with boronic acids is ascribed to its polyol structure. This study demonstrates the usefulness and versatility of PGG as a hydrophilic polymer for possible biomedical applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1822–1830     

Comparison of beaked whale detection algorithms

Due to recent advances in passive acoustic monitoring techniques, beaked whales are now more effectively detected acoustically than visually during vessel-based (e.g. line-transect) surveys. Beaked whales signals can be discriminated from those of other cetaceans by the unique characteristics of their echolocation clicks (e.g. duration >175 μs, center frequencies between 30 and 40 kHz, inter-click intervals between 0.2 and 0.4 s and frequency upsweeps). Furthermore, these same characteristics make these signals ideal candidates for testing automated detection and classification algorithms. There are several different beaked whale automated detectors currently available for use. However, no comparative analysis of detectors exists. Therefore, comparison between studies and datasets is difficult. The purpose of this study was to test, validate, and compare algorithms for detection of beaked whales in acoustic line-transect survey data. Six different detection algorithms (XBAT, Ishmael, PAMGUARD, ERMA, GMM and FMCD) were evaluated and compared. Detection trials were run on three sample days of towed-hydrophone array recordings collected by NOAA Southwest Fisheries Science Center (SWFSC) during which were confirmed visual sightings of beaked whales (Ziphius cavirostris and Mesoplodon peruvianus). Detections also were compared to human verified acoustic detections for a subset of these data. In order to measure the probabilities of false detection, each detector was also run on three sample recordings containing clicks from another species: Risso’s dolphin (Grampus griseus). Qualitative and quantitative comparisons and the detection performance of the different algorithms are discussed.     

Proteomic analysis of Pseudomonas aeruginosa grown under magnesium limitation

In this study, large-scale qualitative and quantitative proteomic technology was applied to the analysis of the opportunistic bacterial pathogen Pseudomonas aeruginosa grown under magnesium limitation, an environmental condition previously shown to induce expression of various virulence factors. For quantitative analysis, whole cell and membrane proteins were differentially labeled with isotope-coded affinity tag (ICAT) reagents and ICAT reagent-labeled peptides were separated by two-dimensional chromatography prior to analysis by electrospray ionization-tandem mass spectrometry (ESI-MS/MS) in an ion trap mass spectrometer (ITMS). To increase the number of protein identifications, gas-phase fractionation (GPF) in the m/z dimension was employed for analysis of ICAT peptides derived from whole cell extracts. The experiments confirmed expression of 1331 P. aeruginosa proteins of which 145 were differentially expressed upon limitation of magnesium. A number of conserved Gram-negative magnesium stress-response proteins involved in bacterial virulence were among the most abundant proteins induced in low magnesium. Comparative ICAT analysis of membrane versus whole cell protein indicated that growth of P. aeruginosa in low magnesium resulted in altered subcellular compartmentalization of large enzyme complexes such as ribosomes. This result was confirmed by 2-D PAGE analysis of P. aeruginosa outer membrane proteins. This study shows that large-scale quantitative proteomic technology can be successfully applied to the analysis of whole bacteria and to the discovery of functionally relevant biologic phenotypes.     

On the syntheses of 8-Heteroaryl-substituted 9-(β-D-Ribofuranosyl)-2,6-diaminopurines through Pd-catalyzed coupling in the presence of cupric oxide

Convenient methods for the preparation of 9-(β-D-ribofuranosyl) derivatives of 8-(2- and 3-thienyl)-2,6-diaminopurine and of 8-(2- and 3-furyl)-2,6-diaminopurine, which are potential antiviral agents has been worked out. The key step was a Pd(0)-catalyzed Stille coupling between 2- and 3-tributylstannylthiophene and 2- and 3-tributylstannylfuran and trimethylsilyl protected 9-(β-D-ribofuranosyl)-2,6-diamino-8-bro-mopurine. The use of N,N-dimethylformamide as solvent at 110° and dichloro(diphenylphosphine-propane)palladium(II) [PdC1₂(dppp)] with cupric oxide as co-reagent was essential in order to obtain a fast reaction and high yields.