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)

Single-channel qEEG characteristics distinguish delirium from no delirium, but not postoperative from non-postoperative delirium

OBJECTIVE: This exploratory study examined quantitative electroencephalography (qEEG) changes in delirium and the use of qEEG features to distinguish postoperative from non-postoperative delirium. METHODS: This project was part of the DeltaStudy, a cross-sectional,multicenterstudy in Intensive Care Units (ICUs) and non-ICU wards. Single-channel (Fp2-Pz) four-minutes resting-state EEG was analyzed in 456 patients. After calculating 98 qEEG features per epoch, random forest (RF) classification was used to analyze qEEG changes in delirium and to test whether postoperative and non-postoperative delirium could be distinguished. RESULTS: An area under the receiver operatingcharacteristic curve (AUC) of 0.76 (95% Confidence Interval (CI) 0.71-0.80) was found when classifying delirium with a sensitivity of 0.77 and a specificity of 0.63 at the optimal operating point. The classification of postoperative versus non-postoperative delirium resulted in an AUC of 0.50 (95%CI 0.38-0.61). CONCLUSIONS: RF classification was able to discriminate delirium from no delirium with reasonable accuracy, while also identifying new delirium qEEG markers like autocorrelation and theta peak frequency. RF classification could not distinguish postoperative from non-postoperative delirium. SIGNIFICANCE: Single-channel EEG differentiates between delirium and no delirium with reasonable accuracy. We found no distinct EEG profile for postoperative delirium, which may suggest that delirium is one entity, whether it develops postoperatively or not