Hydrogen Storage and Selective,Reversible O2 Adsorption in a Metal–Organic Framework with Open Chromium(II) Sites

A chromium(II)‐based metal–organic framework Cr₃[(Cr₄Cl)₃(BTT)₈]₂ (Cr‐BTT; BTT^3?=1,3,5‐benzenetristetrazolate), featuring coordinatively unsaturated, redox‐active Cr²⁺ cation sites, was synthesized and investigated for potential applications in H₂ storage and O₂ production. Low‐pressure H₂ adsorption and neutron powder diffraction experiments reveal moderately strong Cr–H₂ interactions, in line with results from previously reported M‐BTT frameworks. Notably, gas adsorption measurements also reveal excellent O₂/N₂ selectivity with substantial O₂ reversibility at room temperature, based on selective electron transfer to form Cr^III superoxide moieties. Infrared spectroscopy and powder neutron diffraction experiments were used to confirm this mechanism of selective O₂ binding.     

Development of a murre (<Emphasis Type="Italic">Uria</Emphasis> spp.) egg control material

The Seabird Tissue Archival and Monitoring Project (STAMP) is a collaborative Alaska-wide effort by the US Fish and Wildlife Service’s Alaska Maritime National Wildlife Refuge (USFWS/AMNWR), the US Geological Survey’s Biological Resources Division (USGS/BRD), the Bureau of Indian Affairs Alaska Region Subsistence Branch (BIA/ARSB), and the National Institute of Standards and Technology (NIST) to monitor long-term (decadal) trends in environmental contaminants using seabird eggs. To support this effort, a matrix- (seabird egg) and concentration-specific control material was needed to ensure quality during analytical work. Although a herring gull egg quality assurance (HGQA) material is available from Environment Canada (EC), contaminant concentrations in this material tended to be higher than those observed in Alaskan murre (Uria spp.) eggs. Therefore, to prepare a more appropriate control material, a total of 12 common murre (U. aalge) and thick-billed murre (U. lomvia) eggs from four Bering Sea and Gulf of Alaska nesting locations were cryohomogenized to create 190 aliquots each containing approximately 6 g. This new control material was analyzed by different methods at NIST and EC facilities for the determination of concentrations and value assignment of 63 polychlorinated biphenyl (PCB) congeners, 20 organochlorine pesticides, and 11 polybrominated diphenyl ether (PBDE) congeners. The total PCB concentration is approximately 58 ng g⁻¹ wet mass. Results obtained for analytes not listed on the certificates of analysis of the previously used control materials, HGQA and NIST’s Standard Reference Material (SRM) 1946 Lake Superior Fish Tissue, are also presented.      

Reactions of some quinazoline compounds with ethoxymethylenemalonic acid derivatives

The reactions of ethyl (1,4-dihydro-4-oxoquinazolin-2-yl)acetate 4 and 2-aminoquinazolin-4(1H)-one 5 with diethyl ethoxymethylenemalonate (EMME), (ethoxymethylene)malononitrile (EMMN) and ethyl (ethoxymethylene)cyanoacetate (EMCA) are reported, and rather different results are obtained to those previously found with quinoline analogs. Reaction of 4 with EMME gives a pyrido[1,2-a]quinazoline, while with EMMN and EMCA ethyl 2-(pyridin-2-yl)aminobenzoates are formed, presumably by ring-opening of intermediate pyrido[2,1-b]quinazolines. Reaction of 5 with EMME likewise results in ultimate cyclization onto N-1 of the quinazoline, while the EMMN and EMCA reactions give isolable pyrimido[2,1-b]quinazolines. These are readily cleaved under mild conditions.     

Zwitterionic pyrrolidine‐2,2‐diylbis(phosphonic acid) at 100, 150 and 293 K

The title compound, C₄H₁₁NO₆P₂, reveals a two‐dimensional network of P—O—H?O=P and N—H?O=P hydrogen‐bond interactions, forming molecular slabs parallel with the (010) plane. One O—H?O interaction is distinct within these sets: whilst forming the shortest intermolecular hydrogen bond, it possesses a short P—O(H) bond of 1.5291 (10) Å. Weak C—H?O contacts link individual stacks to produce a three‐dimensional array. The compound is zwitterionic: one H atom from a P—O—H group has transferred to the pyrrolidine ring N atom.     

Neuropeptide delivery to the brain: a von Willebrand factor signal peptide to direct neuropeptide secretion

Background  

Multiple neuropeptides, sometimes with opposing functions, can be produced from one precursor gene. To study the roles of the different neuropeptides encoded by one large precursor we developed a method to overexpress minigenes and establish local secretion.     

Comparison of the biological properties of several marine sponge-derived sesquiterpenoid quinones

Eight naturally occurring marine-sponge derived sesquiterpenoid quinones were evaluated as potential inhibitors of pyruvate phosphate dikinase (PPDK), a C4 plant regulatory enzyme. Of these, the hydroxyquinones ilimaquinone, ethylsmenoquinone and smenoquinone inhibited PPDK activity with IC50's (reported with 95% confidence intervals) of 285.4 (256.4-317.7), 316.2 (279.2-358.1) and 556.0 (505.9-611.0) microM, respectively, as well as being phytotoxic to the C4 plant Digitaria ciliaris. The potential anti-inflammatory activity of these compounds, using bee venom phospholipase A2 (PLA2), was also evaluated. Ethylsmenoquinone, smenospongiarine, smenospongidine and ilimaquinone inhibited PLA2 activity (% inhibition of 73.2 +/- 4.8 at 269 microM, 61.5 +/- 6.1 at 242 microM, 41.0 +/- 0.6 at 224 microM and 36.4 +/- 8.2 at 279 microM, respectively). SAR analyses indicate that a hydroxyquinone functionality and a short, hydroxide/alkoxide side-chain atC-20 is preferred for inhibition of PPDK activity, and that a larger amine side-chain at C-20 is tolerated for PLA2 inhibitory activity.     

Harvesting fibrils from bacterial cellulose pellicles and subsequent formation of biodegradable poly-3-hydroxybutyrate nanocomposites

Bacterial cellulose has the potential to be used as a biodegradable, reinforcing component in composites due to its high strength and crystallinity. However it is often problematic to use in this context as it is difficult to separate its extensively bonded fibril network. This means it can be difficult for it to be incorporated as a fine dispersion into a composite and for the true benefits of the nanofibres to be realised in terms of physical property improvement in a conventional polymer format such as injection moulding. The method of sonication (using a range of experimental conditions) was utilised to harvest fibrils from the interwoven mesh of the cellulose pellicle, and then disperse them in different solvents to allow blending and subsequent casting. The novel step identified in this process was the sonication harvesting of the nanofibres undertaken on the highly hydrated as-received pellicle fresh from the reaction media (not the dried pellicle which could not be easily separated in the selected solvent). This unique step of harvesting directly from the fresh pellicle together with conventional sonication for dispersion in chloroform produced a bacterial cellulose/poly-3-hydroxybutyrate nanocomposite which showed excellent nanofibre dispersion and significant improvement in mechanical properties.     

UVB‐Induced Inflammatory Cytokine Release,DNA Damage and Apoptosis of Human Oral Compared with Skin Tissue Equivalents

People can get oral cancers from UV (290–400 nm) exposures. Besides high outdoor UV exposures, high indoor UV exposures to oral tissues can occur when consumers use UV‐emitting tanning devices to either tan or whiten their teeth. We compared the carcinogenic risks of skin to oral tissue cells after UVB (290–320 nm) exposures using commercially available 3D‐engineered models for human skin (EpiDerm?), gingival (EpiGing?) and oral (EpiOral?) tissues. To compare the relative carcinogenic risks, we investigated the release of cytokines, initial DNA damage in the form of cyclobutane pyrimidine dimers (CPDs), repair of CPDs and apoptotic cell numbers. We measured cytokine release using cytometric beads with flow cytometry and previously developed a fluorescent immunohistochemical assay to quantify simultaneously CPD repair rates and apoptotic cell numbers. We found that interleukin‐8 (IL‐8) release and the initial CPDs are significantly higher, whereas the CPD repair rates and apoptotic cell numbers are significantly lower for oral compared with skin tissue cells. Thus, the increased release of the inflammatory cytokine IL‐8 along with inefficient CPD repair and decreased death rates for oral compared with skin tissue cells suggests that mutations are accumulating in the surviving population of oral cells increasing people's risks for getting oral cancers.     

cis-Bis[N1,N2-bis(trimethylsilyl)benz­amidinato-κ2N1,N2]chloro(4-tolyl­imido-κN)vanadium(V)

The title complex, [V(C₇H₇N)(C₁₃H₂₃N₂Si₂)₂Cl], consists of a V metal centre coordinated to five N atoms and a Cl⁻ ion in a pseudo-octahedral arrangement. The N atoms of the benzamidinate ligands form two four-membered chelate rings to V, with bite angles of 63.59 (8) and 64.36 (8)°, whilst the fifth N atom is from a p-tolyl­imido ligand [V—N—C 172.2 (2)°] located cis with respect to the Cl⁻ ion [Cl—V—N_imido 96.96 (8)°].     

Fluorogenic Probe Using a Mislow–Evans Rearrangement for Real‐Time Imaging of Hydrogen Peroxide

Hydrogen peroxide (H₂O₂) mediates the biology of wound healing, apoptosis, inflammation, etc. H₂O₂ has been fluorometrically imaged with protein‐ or small‐molecule‐based probes. However, only protein‐based probes have afforded temporal insights within seconds. Small‐molecule‐based electrophilic probes for H₂O₂ require many minutes for a sufficient response in biological systems. Here, we report a fluorogenic probe that selectively undergoes a [2,3]‐sigmatropic rearrangement (seleno‐Mislow‐Evans rearrangement) with H₂O₂, followed by acetal hydrolysis, to produce a green fluorescent molecule in seconds. Unlike other electrophilic probes, the current probe acts as a nucleophile. The fast kinetics enabled real‐time imaging of H₂O₂ produced in endothelial cells in 8 seconds (much earlier than previously shown) and H₂O₂ in a zebrafish wound healing model. This work may provide a platform for endogenous H₂O₂ detection in real time with chemical probes.