Kinetics of thiophene hydrodesulfurization over a supported Mo–Co–Ni catalyst

In this study, the kinetics of thiophene (TH) hydrodesulfurization (HDS) over the Mo–Co–Ni-supported catalyst was investigated. Trimetallic catalyst was synthesized by pore volume impregnation and the metal loadings were 11.5 wt % Mo, 2 wt % Co, and 2 wt % Ni. A large surface area of 243 m²/g and a relatively large pore volume of 0.34 cm³/g for the fresh Mo–Co–Ni-supported catalyst indicate a good accessibility to the catalytic centers for the HDS reaction. The acid strength distribution of the fresh and spent catalysts, as well as for the support, was determined by thermal desorption of diethylamine (DEA) with increase in temperature from 20 to 600 °C. The weak acid centers are obtained within a temperature range between 160 and 300 °C, followed by medium acid sites up to 440 °C. The strong acid centers are revealed above 440 °C. We found a higher content of weak acid centers for fresh and spent catalysts as well as alumina as compared to medium and strong acid sites. The catalyst stability in terms of conversion as a function of time on stream in a fixed bed flow reactor was examined and almost no loss in the catalyst activity was observed. Consequently, this fact demonstrated superior activity of the Mo–Co–Ni-based catalyst for TH HDS. The activity tests by varying the temperature from 200 to 275 °C and pressure from 30 to 60 bar with various space velocities of 1–4 h^?1 were investigated. A Langmuir–Hinshelwood model was used to analyze the kinetic data and to derive activation energy and adsorption parameters for TH HDS. The effect of temperature, pressure, and liquid hourly space velocity on the TH HDS activity was studied.     

Stereochemical basis for the anti-chlamydial activity of the phosphonate protease inhibitor JO146

JO146, a mixture of two diastereomers of a peptidic phosphonate inhibitor for Chlamydial HtrA (CtHtrA), has reported activity against Chlamydia species in both human and koala. In this study we isolated the individual diastereomers JO146-D1 and JO146-D2 (in ≥90% purity) and assessed their individual inhibitory activity against the serine protease human neutrophil elastase (HNE) which is structurally and functionally related to CtHtrA, as well as in Chlamydia trachomatis cell culture. JO146-D2 [S,S,R-Boc-Val-Pro-Val^P(OPh)₂], the isomer with the physiologically relevant valine at P1, had an approximate 2.5 – fold increase in in vitro HNE inhibition potency over JO146-D1 [S,S,S-Boc-Val-Pro-Val^P(OPh)₂] and greater than 100 – fold increase in cellular anti-chlamydial activity compared to JO146-D1 which possesses the unnatural valine at P1. JO146 and the individual diastereomers had excellent selectivity for the serine protease HNE over the potential off-target serine proteases trypsin and chymotrypsin. Docking studies supported the biological data with a geometrically unfavoured interaction observed between the P1 valine residue of JO146-D1 and the enzyme S1 sub-pocket.     

Synthesis of one‐, two‐ and three‐ring macrocyclic,bifunctional compounds for use in radiolabelling monoclonal antibodies

The synthesis of new linked bis‐ and tris‐ring tetraazamacrocyclic (bifunctional) reagents for use in an alternative strategy for radiolabelling antibodies is described. For comparison with the above systems, a new single ring bifunctional system incorporating a dioxocyclam ring is also reported.     

Inter-comparison and validation of computational fluid dynamics codes in two-stage meandering channel flows

This paper presents a study in the inter-comparison and validation of three-dimensional computational fluid dynamics codes which are currently used in river engineering. Finite volume codes PHOENICS, FLUENT and SSIIM; and finite element code TELEMAC3D are considered in this study. The work has been carried out by competent hydraulic modellers who are users of the codes and not involved in their development. This paper is therefore written from the perspective of independent practitioners of the techniques. In all codes, the flow calculations are performed by solving the three-dimensional continuity and Reynolds-averaged Navier–Stokes equations with the k–ε turbulence model. The application of each code was carried out independently and this led to slightly different, but nonetheless valid, models. This is particularly seen in the different boundary conditions which have been applied and which arise in part from differences in the modelling approaches and methodology adopted by the different research groups and in part from the different assumptions and formulations implemented in the different codes. Similar finite volume meshes are used in the simulations with PHOENICS, FLUENT and SSIIM while in TELEMAC3D, a triangular finite element mesh is used. The ASME Journal of Fluids Engineering editorial policy is taken as a minimum framework for the control of numerical accuracy. In all cases, grid convergence is demonstrated and conventional criteria, such as Y⁺, are satisfied. A rigorous inter-comparison of the codes is performed using large-scale experimental data from the UK Flood Channel Facility for a two-stage meandering channel. This example data set shows complex hydraulic behaviour without the additional complications found in natural rivers. Standardised methods are used to compare each model with the available experimental data. Results are shown for the streamwise and transverse velocities, secondary flow, turbulent kinetic energy, bed shear stress and free surface elevation. They demonstrate that the models produce similar results overall, although there are some differences in the predicted flow field and greater differences in turbulent kinetic energy and bed shear stress. This study is seen as an essential first step in the inter-comparison of some of the computational fluid dynamics codes used in the field of river engineering.     

Charge transport and discharge mechanism in (PVC+KClO3) polymer electrolyte films

This paper presents results of the studies on ionic conductivity and transference number measurements on potassium chlorate (KClO₃) complexed polyvinyl chloride (PVC) films prepared by solution-cast technique. Temperature dependence of ionic conductivity and transference number data indicated the dominance of ion-type charge transport in these specimens. The magnitude of conductivity increased with increase in the concentration of the salt and temperature. Using this (PVC+KClO₃) electrolyte, solid-state electrochemical cells were fabricated and their discharge profiles were studied under a constant load of 100 kΩ. Several cell profiles associated with these cells were evaluated and are reported.     

Dependence relation in pregeometries

The aim of this paper is to set a foundation to separate geometric model theory from model theory. Our goal is to explore the possibility to extend results from geometric model theory to non first order logic (e.g. ). We introduce a dependence relation between subsets of a pregeometry and show that it satisfies all the formal properties that forking satisfies in simple first order theories. This happens when one is trying to lift forking to nonelementary classes, in contexts where there exist pregeometries but not necessarily a well-behaved dependence relation (see for example [HySh]). We use these to reproduce S. Buechler's characterization of local modularity in general. These results are used by Lessmann to prove an abstract group configuration theorem in [Le2]. Received February 2, 1999; accepted in final form April 30, 2000.     

Optimizing buffer size for the retrial queue: two state space collapse results in heavy traffic

We study a single server queueing model with admission control and retrials. In the heavy traffic limit, the main queue and retrial queue lengths jointly converge to a degenerate two-dimensional diffusion process. When this model is considered with holding and rejection costs, formal limits lead to a free boundary curve that determines a threshold on the main queue length as a function of the retrial queue length, above which arrivals must be rejected. However, it is known to be a notoriously difficult problem to characterize this curve. We aim instead at optimizing the threshold on the main queue length independently of the retrial queue length. Our main result shows that in the small and large retrial rate limits, this problem is governed by the Harrison–Taksar free boundary problem, which is a Bellman equation in which the free boundary consists of a single point. We derive the asymptotically optimal buffer size in these two extreme cases, as the scaling parameter and the retrial rate approach their limits.     

Anionic polymerization and oligomerization of 4-vinyl pyridine by alkali metal methoxides

The anionic polymerization and oligomerization of 4-vinyl pyridine by methanolic alkali metal methoxides in DMSO was studied. The molecular weights increased with increasing monomer concentration and decreased with increasing methanol concentration. This fact was utilized in the preparation of oligomers. Evidence is given that initiation is an acid-base reaction. Methanol leads not only to transfer but participates in solvation of the methoxide and growing carbanions affecting the rate of reaction. The rate of reaction decreases with increasing methanol concentration.     

NMR Relaxivities of Paramagnetic Lanthanide-Containing Polyoxometalates

The current trend for ultra-high-field magnetic resonance imaging (MRI) technologies opens up new routes in clinical diagnostic imaging as well as in material imaging applications. MRI selectivity is further improved by using contrast agents (CAs), which enhance the image contrast and improve specificity by the paramagnetic relaxation enhancement (PRE) mechanism. Generally, the efficacy of a CA at a given magnetic field is measured by its longitudinal and transverse relaxivities r₁ and r₂, i.e., the longitudinal and transverse relaxation rates T₁⁻¹ and T₂⁻¹ normalized to CA concentration. However, even though basic NMR sensitivity and resolution become better in stronger fields, r₁ of classic CA generally decreases, which often causes a reduction of the image contrast. In this regard, there is a growing interest in the development of new contrast agents that would be suitable to work at higher magnetic fields. One of the strategies to increase imaging contrast at high magnetic field is to inspect other paramagnetic ions than the commonly used Gd(III)-based CAs. For lanthanides, the magnetic moment can be higher than that of the isotropic Gd(III) ion. In addition, the symmetry of electronic ground state influences the PRE properties of a compound apart from diverse correlation times. In this work, PRE of water ¹H has been investigated over a wide range of magnetic fields for aqueous solutions of the lanthanide containing polyoxometalates [Dy^III(H₂O)₄GeW₁₁O₃₉]^5– (Dy-W₁₁), [Er^III(H₂O)₃GeW₁₁O₃₉]^5– (Er-W₁₁) and [{Er^III(H₂O)(CH₃COO)(P₂W₁₇O₆₁)}₂]¹⁶⁻ (Er₂-W₃₄) over a wide range of frequencies from 20 MHz to 1.4 GHz. Their relaxivities r₁ and r₂ increase with increasing applied fields. These results indicate that the three chosen POM systems are potential candidates for contrast agents, especially at high magnetic fields.     

Solution structure of papain as studied by molecular mechanics and molecular dynamics techniques

In this paper, we report the molecular mechanics and molecular dynamics studies of the hydration of papain using the AMBER and CHARMm programs. We studied papain in an environment with minimal hydration involving only the X-ray waters and also in the hydrated environment by adding an extra 9 Å layer of water around the residues. The effect of nonbond cutoff was studied by performing minimizations with 8 Å and 15 Å nonbond cutoffs using the program AMBER. Two different solvent models—a constant dielectric and a distance-dependent dielectric—were considered. The AMBER-minimized structure and the average structure obtained from the CHARMm simulations for papain solvated with X-ray waters are presented and compared with the X-ray crystal structure results. Results of a similar comparison of the hydrated structures were also presented. The calculated root mean square deviation between the minimized structure and the X-ray structure is smaller for the hydrated system than for the system hydrated with only the X-ray waters. Results of the molecular mechanics and molecular dynamics simulations were presented for the various regions of papain. The hydration of the active site of papain and the effect of hydration on the torsional motion of the active site residues are presented. © 1996 by John Wiley & Sons, Inc.