NO adsorption on Cu-ZSM-5: assignment of IR band at 2133 cm−1

The adsorption of nitrogen oxides on Cu-ZSM-5 was studied by infrared spectroscopy to elucidate the species associated with the band at 2133 cm^–1. The band was found for both NO and NO₂ adsorption. Labeling experiments with¹⁵NO revealed that the associated surface species contained nitrogen and, most likely, an N-O bond. Co-adsorption experiments of NO and oxygen produced adsorbed nitronium, NO ₂ ⁺ , as the principal, associated species. Adsorption of nitrogen oxides on dispersed CuO and the HZSM-5 support demonstrated that the 2133 cm^–1 band was not necessarily associated with copper ions. A relatively strong correlation between the bands at 2133 and 3615 cm^–1 indicates that the primary adsorption sites of NO ₂ ⁺ are the strongly protic, bridging Si(OH)Al framework hydroxyls. Once these were filled, other, weaker acid sites began to adsorb NO ₂ ^O .     

The solubility of methane in aqueous solutions of monoethanolamine,diethanolamine and triethanolamine

The solubility of methane in 3 kmol/m³ solutions of monoethanolamine, diethanolamine, and triethanolamine was measured from 25° to 125°C and pressures up to about 13 MPa. Measurements were also made for the solubility of methane in water at 25° to 125°C and pressures up to 18 MPa in order to confirm the accuracy of the experimental technique. It is demonstrated that methane is more soluble (in terms of mole fraction) in the amine solution than in pure water. Furthermore, the solubility is an increasing function of the size of the alkanolamine. The solubility data were modeled using a Henry's-law approach and the results summarized in terms of salting-in coefficients.     

Chemical composition of Cold Lake bitumen

A detailed analysis has been carried out on the deasphaltened Cold Lake bitumen using two different series of chromatographic separations followed by i.r., u.v., n.m.r. and computerized GC/MS studies of the separated fractions: saturates (21.3), monoaromatics (8.3), diaromatics (3.6), polyaromatics and non-specific polar compounds (24.35), acids (15.2), bases (6.38), and neutral nitrogen compounds (1.15% of bitumen). The acyclic paraffin content of the maltene is low but decidedly higher than in the related Athabasca bitumen, indicating that the Cold Lake bitumen suffered a less complete biodegradation. Straight-chain paraffins and the isoprenoids phytane and pristane are present. The mono- and diaromatic fractions were analysed by high-voltage, low-resolution mass spectrometry. The monoaromatic fraction contains alkylbenzenes, naphthenebenzenes and dinaphthenebenzenes in a ratio of approximately 1:1:1. The ratio for naphthalenes, acenaphthenes + dibenzofurans and fluorenes in the diaromatic fraction is approximately 1:0.9:0.6. The composition of Cold Lake bitumen closely resembles that of the Athabasca bitumen except that its asphaltene content is somewhat lower and its acidic and saturate content is slightly higher.     

Using machine learning models to explore the solution space of large nonlinear systems underlying flowsheet simulations with constraints

Flowsheet simulations of chemical processes on an industrial scale require the solution of large systems of nonlinear equations,so that solvability becomes a practical issue.Additional constraints from technical,economic,environmental,and safety considerations may further limit the feasible solution space beyond the convergence requirement.A priori,the design variable domains for which a simulation converges and fulfills the imposed constraints are usually unknown and it can become very time-consuming to distinguish feasible from infeasible design variable choices by simply running the simulation for each choice.To support the exploration of the design variable space for such scenarios,an adaptive sampling technique based on machine learning models has recently been proposed.However,that approach only considers the exploration of the convergent domain and ignores additional constraints.In this paper,we present an improvement which particularly takes the fulfillment of constraints into account.We successfully apply the proposed algorithm to a toy example in up to 20 dimensions and to an industrially relevant flowsheet simulation.     

Prodynorphin and Proenkephalin in Cerebrospinal Fluid of Sporadic Creutzfeldt–Jakob Disease

Proenkephalin (PENK) and prodynorphin (PDYN) are endogenous opioid peptides mainly produced in the striatum and, to a lesser extent, in the cerebral cortex. Dysregulated metabolism and altered cerebrospinal fluid (CSF) levels of PENK and PDYN have been described in several neurodegenerative diseases. However, no study to date investigated these peptides in the CSF of sporadic Creutzfeldt–Jakob disease (sCJD). Using liquid chromatography-multiple reaction monitoring mass spectrometry, we evaluated the CSF PDYN- and PENK-derived peptide levels in 25 controls and 63 patients with sCJD belonging to the most prevalent molecular subtypes (MM(V)1, VV2 and MV2K). One of the PENK-derived peptides was significantly decreased in each sCJD subtype compared to the controls without a difference among subtypes. Conversely, PDYN-derived peptides were selectively decreased in the CSF of sCJD MV2K, a subtype with a more widespread overall pathology compared to the sCJD MM(V)1 and the VV2 subtypes, which we confirmed by semiquantitative analysis of cortical and striatal neuronal loss and astrocytosis. In sCJD CSF PENK and PDYN were associated with CSF biomarkers of neurodegeneration but not with clinical variables and showed a poor diagnostic performance. CSF PDYN and PENK-derived peptides had no significant diagnostic and prognostic values in sCJD; however, the distinct marker levels between molecular subtypes might help to better understand the basis of phenotypic heterogeneity determined by divergent neuronal targeting.     

Spacer effects on in vivo properties of DOTA-conjugated dimeric [Tyr3]octreotate peptides synthesized by a "Cu(I)-click" and "sulfo-click" ligation method

We report on the SSTR2-binding properties of a series of four dimeric [Tyr3]octreotate analogues with different spacer lengths (nine, 19, 41, and 57 atoms) between the peptides. Two analogues (9 and 57 atoms) were selected as precursors for the design, synthesis, and biological evaluation of DOTA-conjugated dimeric [Tyr3]octreotate analogues for tumor targeting. These compounds were synthesized by using a two-stage click ligation procedure: a Cu(I) -catalyzed 1,3-dipolar cycloaddition ("copper-click" reaction) and a thio acid/sulfonyl azide amidation ("sulfo-click" reaction). The IC(50) values of these DOTA-conjugated [Tyr3]octreotate analogues were comparable, and internalization studies showed that the nine-atom (111) In-DOTA-labeled [Tyr3]octreotate dimer had rapid and high receptor binding. Biodistribution studies with BALB/c nude mice bearing subcutaneous AR42J tumors showed that the (111) In-labeled [Tyr3]octreotate dimer (nine atoms) had a high tumor uptake at 1 h p.i. (38.8 ± 8.3 % ID g(-1) ), and excellent tumor retention at 4 h p.i. (40.9 ± 2.5 % ID g(-1) ). However, the introduction of the extended hydrophilic 57 atoms spacer led to rapid clearance from the circulation; this limited tumor accumulation of the radiotracer (21.4 ± 4.9 % ID g(-1) at 1 h p.i.). These findings provide important insight on dimerization and spacer effects on the in vivo properties of DOTA-conjugated [Tyr3]octreotate dimers.     

Hydrogen sensor based on a graphene – palladium nanocomposite

A composite material was prepared from graphene and palladium nanoparticles (PdNP) by layer-by-layer deposition on gold electrodes. The material was characterized by absorption spectroscopy, scanning electron microscopy, Raman spectroscopy and surface plasmon resonance. Cyclic voltammetry demonstrated the presence of electrocatalytic centers in the palladium decorated graphene. This material can serve as a sensor material for hydrogen at levels from 0.5 to 1% in synthetic air. Pure graphene is poorly sensitive to hydrogen, but incorporation of PdNPs increases its sensitivity by more than an order of magnitude. The effects of hydrogen, nitrogen dioxide and humidity were studied. Sensor regeneration is accelerated in humid air. The sensitivity of the nanocomposite depends on the number of bilayers of graphene–PdNPs.     

The molecular structure of asphaltene: an unfolding story

From detailed chemical and thermal degradation studies, a host of structural units have been identified in Alberta asphaltenes. It has been shown that the extent of aromatic condensation is low and that highly condensed pericyclic aromatic structures are present in very low concentrations. From the available data reported to date, it is concluded that petroleum asphaltenes were mainly derived through the catalytic cyclization, aromatization and condensation of n-alkanoic, probably fatty acids, precursors.     

Arduino-based slider setup for gas–liquid mass transfer investigations: Experiments and CFD simulations

The implementation of traditional sensors is a drawback when investigating mass transfer phenomena within microstructured devices, since they disturb the flow and reactor characteristics. An Arduino based slider setup is developed, which is equipped with a computer-vision system to track gas–liquid slug flow. This setup is combined with an optical analytical method allowing to compare experimental results against CFD simulations and investigate the entire lifetime of a single liquid slug with high spatial and temporal resolution. Volumetric mass transfer coefficients are measured and compared with data from literature and the mass transfer contribution of the liquid film is discussed.