Radicals in carbonaceous residue deposited on mordenite from methanol

It is shown that control of the degree of coking can lead to the observation of hyperfine structures in the carbonaceous residues deposited from methanol over mordenite (H-MOR) at temperatures relevant to the conversion of methanol to hydrocarbons. EPR measurements of the catalyst samples at various times on stream have been recorded, with a rich hyperfine splitting pattern observed in the early stages of the reaction. Interpretation of the EPR data with the aid of density functional theoretical calculations has afforded the first definitive assignment of the radical cations formed in high temperature coke. The results detail a shortlist of six species: 2,3/2,6/2,7-dimethylnaphthalenium, 2,3,6-trimethylnaphthalenium, 2,3,6,7-tetramethylnaphthalenium, and anthracenium radical cations whose proton hyperfine splitting profiles match the experimental spectra; 2,3,6,7-tetramethylnaphthalenium showed the best agreement. The observation of these particular isomers of polymethylnaphthalene suggest the formation of more highly branched polyaromatic species is less likely within the confines of the H-MOR 12-membered ring channel. These radicals formed when the catalyst is active may constitute key intermediates in the conversion of methanol to light olefins

Infrared spectroscopic study of absorption and separation of CO using copper(I)-containing ionic liquids

Absorption of carbon monoxide by copper(I)-containing ionic liquids, [Cnmim][CuX2] (Cnmim = 1-alkyl-3-methylimidazolium, n = 2, 4, 6, X = Cl, Br, I) has been investigated using in situ high pressure infrared spectroscopy. For each liquid, observation of a ν(CO) band in the region 2075–2090 cm−1 indicates the formation of copper(I) monocarbonyl complexes, assigned as [Cu(CO)X2]−. The rate of growth and equilibrium intensity of the ν(CO) absorption is dependent on applied CO pressure. Binding of CO is reversible such that complete desorption occurs rapidly on heating above 100 °C and the liquids are robust over multiple gas absorption/desorption cycles. For the series of [C6mim][CuX2] salts the CO absorption ability follows the order Cl ≥ Br ≫ I. Selective absorption of CO from CO/H2 and CO/N2 gas mixtures is demonstrated by measuring the changes in headspace CO content upon absorption and desorption of gas. For [C6mim][CuCl2], a single absorb–vent–desorb cycle yields product gas containing ∼95% CO starting from a 1 : 1 CO/N2 mixture, increasing to ∼98% CO starting from a 4 : 1 CO/N2 mixture. This is particularly promising in view of the similar boiling points of CO and N2 that hinders their separation by cryogenic distillation

Foreningen for Frijsenborg Omegn til Understøttelse af gamle Husmænd og Indsiddere samt Husmænds og Indsidderes Enker og uforsørgede Børn.

Foreningen for Frijsenborg Omegn til Understøttelse af gamle Husmænd og Indsiddere samt Husmænds og Indsidderes Enker og uforsørgede Børn

Retrospective on high-level language computer architecture

High-level language computers (HLLC) have attracted interest in the architectural and programming community during the last 15 years; proposals have been made for machines directed towards the execution of various languages such as ALGOL, 1,2 APL, 3,4,5 BASIC, 6.

On the two first excited K=0 bands in U-238 and Pu-240

EO-enhanced spectra of conversion electrons taken after (alpha,alpha) and (alpha,2n) reactions and after projectile Coulomb excitation improve our knowledge about first and second excited bands in U-238 and Pu-240 built on O-2(+) and O-3(+) states which lie anomalously close together. The two bands are of different structure.</p

Development of a specific affinity-matured exosite inhibitor to MT1-MMP that efficiently inhibits tumor cell invasion in vitro and metastasis in vivo.

This is the final version of the article. It first appeared from Impact Journals via https://doi.org/10.18632/oncotarget.7780The membrane-associated matrix metalloproteinase-14, MT1-MMP, has been implicated in pericellular proteolysis with an important role in cellular invasion of collagenous tissues. It is substantially upregulated in various cancers and rheumatoid arthritis, and has been considered as a potential therapeutic target. Here, we report the identification of antibody fragments to MT1-MMP that potently and specifically inhibit its cell surface functions. Lead antibody clones displayed inhibitory activity towards pro-MMP-2 activation, collagen-film degradation and gelatin-film degradation, and were shown to bind to the MT1-MMP catalytic domain outside the active site cleft, inhibiting binding to triple helical collagen. Affinity maturation using CDR3 randomization created a second generation of antibody fragments with dissociation constants down to 0.11 nM, corresponding to an improved affinity of 332-fold with the ability to interfere with cell-surface MT1-MMP functions, displaying IC50 values down to 5 nM. Importantly, the new inhibitors were able to inhibit collagen invasion by tumor-cells in vitro and in vivo primary tumor growth and metastasis of MDA-MB-231 cells in a mouse orthotopic xenograft model. Herein is the first demonstration that an inhibitory antibody targeting sites outside the catalytic cleft of MT1-MMP can effectively abrogate its in vivo activity during tumorigenesis and metastasis.KAB was supported by a grant from the Danish Cancer Society (R40-A1838). HJD was supported in part by grants from the Danish Cancer Society, The Danish Research Council. HFK and GM were supported by Cancer Research UK and Hutchison Whampoa Ltd. HFK was also supported in part by grants from the University of Macau Start-Up Research Grant (SRG2014-00006-FHS) and Multi-Year Research Grant (MYRG2015-00065-FHS)

Visualization of Myelin Basic Protein (Mbp) T Cell Epitopes in Multiple Sclerosis Lesions Using a Monoclonal Antibody Specific for the Human Histocompatibility Leukocyte Antigen (Hla)-Dr2–Mbp 85–99 Complex

Susceptibility to multiple sclerosis (MS) is associated with the human histocompatibility leukocyte antigen (HLA)-DR2 haplotype, suggesting that major histocompatibility complex class II–restricted presentation of central nervous system–derived antigens is important in the disease process. Antibodies specific for defined HLA-DR2–peptide complexes may therefore be valuable tools for studying antigen presentation in MS. We have used phage display technology to select HLA-DR2–peptide-specific antibodies from HLA-DR2–transgenic mice immunized with HLA-DR2 molecules complexed with an immunodominant myelin basic protein (MBP) peptide (residues 85–99). Detailed characterization of one clone (MK16) demonstrated that both DR2 and the MBP peptide were required for recognition. Furthermore, MK16 labeled intra- and extracellular HLA-DR2–MBP peptide complexes when antigen-presenting cells (APCs) were pulsed with recombinant MBP. In addition, MK16 inhibited interleukin 2 secretion by two transfectants that expressed human MBP–specific T cell receptors. Analysis of the structural requirement for MK16 binding demonstrated that the two major HLA-DR2 anchor residues of MBP 85–99 and the COOH-terminal part of the peptide, in particular residues Val-96, Pro-98, and Arg-99, were important for binding. Based on these results, the antibody was used to determine if the HLA-DR2–MBP peptide complex is presented in MS lesions. The antibody stained APCs in MS lesions, in particular microglia/macrophages but also in some cases hypertrophic astrocytes. Staining of APCs was only observed in MS cases with the HLA-DR2 haplotype but not in cases that carried other haplotypes. These results demonstrate that HLA-DR2 molecules in MS lesions present a myelin-derived self-peptide and suggest that microglia/macrophages rather than astrocytes are the predominant APCs in these lesions