Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Effect of cell structure on oil absorption of highly oil absorptive polyurethane foam for on-site use

This article reports the effect of cell structure on oil absorption of highly oil-absorptive polyurethane foam (ON-PUR), which is suitable for on-site foaming. We have developed ON-PUR as an oil absorbing polyurethane foam using a very reactive recipe. ON-PUR was synthesized by mixing polyol, water, additives, and polymeric diphenylmethane diisocyanate (P-MDI) using a high-pressure foaming machine. Density, airflow, oil absorption of this foam, and cell structure by microscopy were measured. From these results, it was found that the airflow of this foam increased by crushing, and the oil absorption of this foam increased sharply in a narrow airflow range (from 0.1 to 0.8 scfm). This increase is estimated to be due to the decrease of closed cell structures by crushing treatment. Furthermore, we constituted on-site foaming system in bench scale, which was expected to be applicable to on-site preparation of ON-PUR. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 179–186, 1997     

Syndiotactic‐specific radical polymerization of N‐isopropylacrylamide in toluene at low temperatures in the presence of silyl alcohols

The radical polymerization of N‐isopropylacrylamide was carried out in toluene at low temperatures in the presence of silyl alcohols, such as triethylsilanol. Poly(N‐isopropylacrylamide) with a racemo dyad content of 75% was obtained at ? 80 °C with a 4:1 triethylsilanol to monomer ratio loading. NMR analysis suggests that the mechanism for syndiotactic induction, in the presence of silyl alcohols, may be similar to that observed with alkyl alcohols. In this case, a 1:2 complex formation, via hydrogen bonding interactions, leads to the induction of syndiotactic specificity. Copyright © 2012 Society of Chemical Industry     

Isotope scrambling in the formation of cyanopolyynes by laser ablation of carbon particles in liquid acetonitrile

Cyanopolyynes, H(CC)_nCN (n = 3–6), were formed by laser ablation of carbon particles in liquid acetonitrile. The molecules were separated according to the size n and characterized by UV absorption spectroscopy, mass spectroscopy in combination with gas-chromatographic separation, and nuclear magnetic resonance (NMR) spectroscopy. For the study of nascent carbon cluster distribution during the growth of the long carbon chain molecules, isotopomer distribution was analyzed by NMR spectroscopy for the product molecules. Two cyanopolyynes of HC₇N and HC₉N were isolated from solutions after laser ablation of isotope-enriched carbon powder (99% ¹³C) in liquid acetonitrile, CH₃CN, of natural isotopic abundance (1.1% ¹³C). With the observed chemical shift, δ, and spin–spin coupling constants, J_CH and J_CC, spectral simulation was made to determine relative abundance of possible isotopomeric forms for HC₉N. We found that the isotope of ¹²C, mostly from solvent molecules, contributes substantially for the part of carbon in the cyano group, –CN, in HC₉N. The isotopomer distribution observed for the sequence of H–CC–CC– was fairly explainable by a binomial, random distribution of the two carbon isotopes of ¹²C and ¹³C, reducing the concentration of ¹³C to 76–55%.     

Characterisation of the Dynamic Interactions between Complex N-Glycans and Human CD22

CD22 (Siglec-2) is a B-cell surface inhibitory protein capable of selectively recognising sialylated glycans, thus dampening autoimmune responses against self-antigens. Here we have characterised the dynamic recognition of complex-type N-glycans by human CD22 by means of orthogonal approaches including NMR spectroscopy, computational methods and biophysical assays. We provide new molecular insights into the binding mode of sialoglycans in complex with h-CD22, highlighting the role of the sialic acid galactose moieties in the recognition process, elucidating the conformational behaviour of complex-type N-glycans bound to Siglec-2 and dissecting the formation of CD22 homo-oligomers on the B-cell surface. Our results could enable the development of additional therapeutics capable of modulating the activity of h-CD22 in autoimmune diseases and malignancies derived from B-cells.     

Silver(I)-Ion-Mediated Cytosine-Containing Base Pairs: Metal Ion Specificity for Duplex Stabilization and Susceptibility toward DNA Polymerases

Spectroscopic characterization of Ag^I-ion-mediated C-Ag^I-A and C-Ag^I-T base pairs found in primer extension reactions catalyzed by DNA polymerases was conducted. UV melting experiments revealed that C-A and C-T mismatched base pairs in oligodeoxynucleotide duplexes are specifically stabilized by Ag^I ions in 1:1 stoichiometry in the same manner as a C-C mismatched base pair. Although the stability of the mismatched base pairs in the absence of Ag^I ions is in the order C-A≈C-T>C-C, the stabilizing effect of Ag^I ions follows the order C-C>C-A≈C-T. However, the comparative susceptibility of dNTPs to Ag^I-mediated enzymatic incorporation into the site opposite templating C is dATP>dTTP≫dCTP, as reported. The net charge, as well as the size and/or shape complementarity of the metal-mediated base pairs, or the stabilities of mismatched base pairs in the absence of metal ions, would be more important than the stability of the metallo-base pairs in the replicating reaction catalyzed by DNA polymerases.     

Size-dependent separation of graphene oxide by deformation of packed-gel in a chromatographic column

ABSTRACT

A deformable gel-packed chromatographic column was used to separate as-synthesized graphite oxide with different sizes. The synthesized gel (56 µm) was deformed by pressure of the fluid flow and the gaps in the gels showed a range of sizes. A suspension of graphene oxide (0.1 g/L, 10 mL) was injected, and graphene oxide in the elution had a size at 0.56 μm and 0.14 μm, whereas in half upper and bottom domain of the gel layer graphene oxide had a size at 33 µm and 2.9 µm, respectively, demonstrating that graphene oxide suspension was separated by size through gel layer.     

Supercritical fluid extraction of bacterial and archaeal lipid biomarkers from anaerobically digested sludge

Supercritical fluid extraction (SFE) was used in the analysis of bacterial respiratory quinone (RQ), bacterial phospholipid fatty acid (PLFA), and archaeal phospholipid ether lipid (PLEL) from anaerobically digested sludge. Bacterial RQ were determined using ultra performance liquid chromatography (UPLC). Determination of bacterial PLFA and archaeal PLEL was simultaneously performed using gas chromatography-mass spectrometry (GC-MS). The effects of pressure, temperature, and modifier concentration on the total amounts of RQ, PLFA, and PLEL were investigated by 23 experiments with five settings chosen for each variable. The optimal extraction conditions that were obtained through a multiple-response optimization included a pressure of 23.6 MPa, temperature of 77.6 °C, and 10.6% (v/v) of methanol as the modifier. Thirty nine components of microbial lipid biomarkers were identified in the anaerobically digested sludge. Overall, the SFE method proved to be more effective, rapid, and quantitative for simultaneously extracting bacterial and archaeal lipid biomarkers, compared to conventional organic solvent extraction. This work shows the potential application of SFE as a routine method for the comprehensive analysis of microbial community structures in environmental assessments using the lipid biomarkers profile.     

A Comprehensive Study of the Interaction between Peptidoglycan Fragments and the Extracellular Domain of Mycobacterium tuberculosis Ser/Thr Kinase PknB

The Mycobacterium tuberculosis Ser/Thr kinase PknB is implicated in the regulation of bacterial cell growth and cell division. The intracellular kinase function of PknB is thought to be triggered by peptidoglycan (PGN) fragments that are recognized by the extracytoplasmic domain of PknB. The PGN in the cell wall of M. tuberculosis has several unusual modifications, including the presence of N-glycolyl groups (in addition to N-acetyl groups) in the muramic acid residues and amidation of d -Glu in the peptide chains. Using synthetic PGN fragments incorporating these diverse PGN structures, we analyzed their binding characters through biolayer interferometry (BLI), NMR spectroscopy, and native mass spectrometry (nMS) techniques. The results of BLI showed that muropeptides containing 1,6-anhydro-MurNAc and longer glycan chains exhibited higher binding potency and that the fourth amino acid of the peptide stem, d -Ala, was crucial for protein recognition. Saturation transfer difference (STD) NMR spectroscopy indicated the major involvement of the stem peptide region in the PASTA-PGN fragment binding. nMS suggested that the binding stoichiometry was 1:1. The data provide the first molecular basis for the specific interaction of PGN with PknB and firmly establish PGNs as the effective ligands of PknB.     

Enhancing low-temperature energy harvesting by lead-free ferroelectric Ba(Zr0.1Ti0.9)O3

The energy-harvesting ability of the lead-free ferroelectric Ba(Zr,Ti)O₃ was investigated and greatly enhanced using the Kim novel electrothermodynamic cycle for low-temperature application. Ba(Zr,Ti)O₃ was synthesized with a Zr:Ti ratio of 10:90 (BZT10) by hot-press sintering, which exhibited a mix relaxor-ferroelectric behavior. For power generation using the Kim cycle with low and high temperatures of T_L = 25°C, T_H = 120°C, the most optimized temperature pattern occurred for a heating time of 12.5 s and a cooling time of 22.5 s. Under these conditions, the electric field increased during the novel isodisplacement process, and the displacement variation in the isoelectric step reached the highest value and maximized the BZT10 cycle loop area. Applying these conditions while lowering T_L to 20°C, an energy density N_D = 504 mJ/cm³ was achieved. This value is the highest obtained energy density in a practical test for lead-free ferroelectric bulk material in the BaTiO₃ family.