Characterization of Porous Carbonaceous Sorbents Using High Pressure CO2 Adsorption Data

In this paper we present adsorption isotherms of carbon dioxide on five different activated carbons from CHEMVIRON CARBON Belgium (Centaur HSV, BPL 410, F30-470, WS 42, Reactivated) and on a carbon molecular sieve from BERGBAU FORSCHUNG Gmbh (CMS II). The temperature is 303 K and the pressure ranges from 100 kPa up to 4000 kPa. Such conditions correspond to relative pressures ranging from 0.01 to 0.5. We also provide, for the same six sorbents, the nitrogen isotherms at 77 K (pressure: 0.001 to 100 kPa, relative pressure: 10^-5 to 1). A theoretical treatment based on the Dubinin-Radushkevich and Stoeckli concept is presented and applied to the experimental results in order to obtain the micropore size distribution function (considered as Gaussian) of each sorbent. Using the CO₂ data, it is possible to point out important structural differences between the six carbons. The theoretical treatment provides micropore size distribution functions in agreement with what is physically expected. Using N₂ data, the structural differences are not so well marked. As a consequence, the structural parameters provided by the theoretical treatment are not reliable: except for the total micropore volume, they fluctuate strongly when changing the relative pressure domain of the used data.     

Histone Tail Sequences Balance Their Role in Genetic Regulation and the Need To Protect DNA against Destruction in Nucleosome Core Particles Containing Abasic Sites

Abasic sites (AP) are produced 10 000 times per day in a single cell. Strand cleavage at AP is accelerated ≈100-fold within a nucleosome core particle (NCP) compared to free DNA. The lysine-rich N-terminal tails of histone proteins catalyze single-strand breaks through a mechanism used by base-excision-repair enzymes, despite the general dearth of glutamic acid, aspartic acid, and histidine—the amino acids that are typically responsible for deprotonation of Schiff base intermediates. Incorporating glutamic acid, aspartic acid, or histidine proximal to lysine residues in histone N-terminal tails increases AP reactivity as much as sixfold. The rate acceleration is due to more facile DNA cleavage of Schiff-base intermediates. These observations raise the possibility that histone proteins could have evolved to minimize the presence of histidine, glutamic acid, and aspartic acid in their lysine-rich N-terminal tails to guard against enhancing the toxic effects of DNA damage.     

Mining the cinnabaramide biosynthetic pathway to generate novel proteasome inhibitors

The cinnabaramides and salinosporamides are mixed PKS/NRPS natural products isolated from a terrestrial streptomycete and a marine actinomycete, respectively. They interfere with the proteasome and thus potentially inhibit the growth of cancer cells. The compounds exhibit a γ-lactam-β-lactone bicyclic ring structure attached to a cyclohexenyl unit and a PKS side chain. As a first step towards improving anticancer activity and permitting genetic approaches to novel analogues, we have cloned and characterized the cinnabaramide biosynthetic genes from Streptomyces sp. JS360. In addition to the expected PKS and NRPS genes, the cluster encodes functionalities for the assembly of the hexyl side chain precursor. The corresponding enzymes exhibit relaxed substrate specificities towards a number of synthesized precursors, enabling production of novel chlorinated cinnabaramides. These were isolated and analyzed for activity, revealing that derivatives bearing a chlorine atom in the PKS side chain show higher inhibitory potentials towards the proteasome's proteolytic subunits (especially the trypsin and chymotrypsin units) and higher cytotoxicities towards human tumor cell lines than the parent cinnabaramide A. Although their activities towards the proteasome were weaker than that of salinosporamide A, the cinnabaramides were found to inhibit the growth of various fungi with greater potency.     

Myo-InositolTrisPyroPhosphate treatment leads to HIF-1α suppression and eradication of early hepatoma tumors in rats

Myo-inositol trispyrophosphate (ITPP), a synthetic allosteric effector of hemoglobin, increases the regulated oxygen-releasing capacity of red blood cells (RBCs), leading to suppression of hypoxia-inducible factor 1α (HIF-1α) and to down-regulation of hypoxia-inducible genes such as vascular endothelial growth factor (VEGF). As a consequence, tumor growth is markedly affected. The effect of weekly intravenous injection of ITPP on an orthotopic, syngenic rat hepatocellular carcinoma (HCC) model was compared to that for untreated animals and animals subjected to conventional Doxorubicin chemotherapy. The longitudinal examination of HCC was performed by microCT imaging, and the cellular and molecular changes were evaluated by histology and Western blotting analysis of HIF-1α, VEGF, and caspase-3 gene expression in the tumor and in the surrounding liver. Hematologic impact was evaluated by blood cell-count measurement and determination of P50 (oxygen partial pressure for a 50 % oxygen saturation of hemoglobin). The HCC evaluation by microCT revealed a high potency of ITPP for tumor growth inhibition, thus allowing long-term survival and even cure of almost all the treated animals. The P50 value of hemoglobin in RBCs underwent a shift of 30 % following ITPP injection. Under these conditions, HIF-1α activity was strongly decreased, VEGF expression was down-regulated, and apoptosis was induced in HCC and surrounding liver cells, as indicated by Caspase-3 expression. ITPP did not affect hematologic parameters during treatment. The observations of in vivo tumor eradication suggest a significant clinical potential for ITPP in cancer therapy.     

Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.     

Direct-writing of PbS nanoparticles inside transparent porous silica monoliths using pulsed femtosecond laser irradiation

Pulsed femtosecond laser irradiation at low repetition rate, without any annealing, has been used to localize the growth of PbS nanoparticles, for the first time, inside a transparent porous silica matrix prepared by a sol-gel route. Before the irradiation, the porous silica host has been soaked within a solution containing PbS precursors. The effect of the incident laser power on the particle size was studied. X-ray diffraction was used to identify the PbS crystallites inside the irradiated areas and to estimate the average particle size. The localized laser irradiation led to PbS crystallite size ranging between 4 and 8 nm, depending on the incident femtosecond laser power. The optical properties of the obtained PbS-silica nanocomposites have been investigated using absorption and photoluminescence spectroscopies. Finally, the stability of PbS nanoparticles embedded inside the host matrices has been followed as a function of time, and it has been shown that this stability depends on the nanoparticle mean size.     

Phonons and Phasons in Icosahedral Quasicrystals

The discovery of quasicrystals not only has changed our view on long-range order, but was a breakthrough for solid state physics and chemistry, since the Bloch theorem can no longer be applied. We review some of the results obtained for icosahedral quasicrystals for lattice dynamics and phonons, as well as for phason modes, which are diffusive excitations characteristic of the quasicrystalline state.     

Effective reduction of AlN defect luminescence by fluorine implantation

We report on the effective reduction of AlN host lattice defect cathodoluminescence by high dose ion implantation of light elements such as fluorine as well as chlorine and neon with peak concentrations of 1 at.%. In order to distinguish between luminescence suppression in the visible to luminescence quenching due to radiation damage, all samples were additionally implanted with europium at fluences of 1 · 10¹³ ions/cm². After annealing the samples at 1373 K under vacuum conditions cathodoluminescence spectra were recorded at room temperature (300 K) and at cryogenic temperature (12 K). These investigations reveal that different light ion species have different influences on the defect luminescence of the AlN host lattice which is likely due to selective passivation of these defects. The best ratio of defect luminescence suppression to radiation damage induced luminescence quenching is achieved in the case of fluorine co-doping.     

Impact of mass balance calculations on adsorption capacities in microporous shale gas reservoirs

Determination of the adsorbed reservoir capacity of gas shales by adsorption analyses as done routinely by mass balance maybe in significant error if the effects of pore-size dependent void volume (porosity) is not considered. It is shown here that with increasing pressure, helium, which is invariably used to measure void volume, can access pores that are not available for adsorption to gases with larger kinetic diameters as highlighted by experiments with zeolites of known pore-size distribution. Helium can diffuse and/or adsorb in restricted pores of the microporous samples, as indicated by a larger void volume with pressure. The error in adsorption calculations due to helium void volume calibrations for high pressure methane isotherms is most significant with low organic-carbon content, moisture-equilibrated shales and mudrocks in which the overall adsorptive capacity is low. In such samples negative adsorption can be calculated due to the void volume of helium used in the mass balance calculations exceeding the void volume to methane – a reflection of greater pore-space accessibility of the smaller helium molecule than methane. The amount of the error introduced by using helium void volume in mass balance calculations is pore-size and pore-size distribution dependent. Organic-rich shales and mudrocks or coals which do not show negative methane adsorption also maybe in error but the error is masked by their larger adsorbed gas capacities. Such findings underline the importance of analysis gas-type as kinetic diameter size will influence the penetrability/diffusion of the gas through the sample and hence the calculated adsorbed gas capacities.     

Polar and Neutral Lipid Composition in the Pelagic Tunicate <Emphasis Type="Italic">Pyrosoma atlanticum</Emphasis>

Structure and functioning of colonial pyrosomes are largely undescribed and their lipid characteristics have received limited attention. The aim of this paper is to fill this gap on one of the dominant species Pyrosoma atlanticum. Lipid content is tightly coupled to size and weight. Lipid composition shows a large dominance of structural polar lipids. Neutral lipids were dominated by sterols with low levels of acylglycerols and free fatty acids. Phospholipids show a dominance of PC with intermediate percentages of PE and DPG. Other constituents (PS, PI, LPC, sphingolipids) were present at lower levels. Fatty acid composition of DAG and TAG showed a dominance of saturated acids (16:0, 14:0), DHA and intermediate levels of MUFA. Phospholipids were dominated by DHA with values exceeding 30% of total FA in all categories except for PI, where lower percentages occurred. Saturated acids were second in abundance with MUFA showing intermediate concentrations. Sterols were dominated by 24-methylcholesta-5,22E-dien-3beta-ol with more than 22% of the total sterol. Cholesterol (cholest-5-en-3beta-ol) represented only 12 % of the total while 24-methylcholesta-5,24(28)E-dien-3beta-ol accounted for 11% of the total sterols. The low levels of triacylglycerols and free fatty acids, coupled with high concentrations of glycolipids and phytoplankton-derived degraded chloropigments, is evidence of a direct link with the digestive activity and substantiate the idea of a high physiological turnover as an alternative to large lipid accumulation. The fatty acid and sterol profiles are consistent with a diverse phytoplankton diet, and a strong contribution of phospholipid classes to energy needs, including locomotion.