Building confidence in models for multiple audiences: The modelling cascade

This paper reports on a model building process developed to enable multiple audiences, particularly non-experts, to appreciate the validity of the models being built and their outcomes. The process is a four stage reversible cascade. This cascade provides a structured, auditable/transparent, formalized process from “real world” interviews generating a rich qualitative model through two intermediate steps before arriving at a quantitative simulation model. There are a number of advantages of the cascade process including; achieving comprehensiveness, developing organizational learning, testing the veracity of multiple perspectives, modeling transparency, achieving common understanding across many audiences and promoting confidence building in the models. The paper, based on extensive work with organizations, discusses both the cascade process and its inherent benefits.     

Combining Electronic and Steric Effects for Highly Stable Unsymmetric Pentacenes

This paper describes the reactivity of unsymmetrically substituted pentacenes to photochemical oxidation. Acenes in general, and pentacenes in particular, are a key family of compounds for a variety of organic electronics applications. The instability of many pentacene derivatives, particularly to oxidation, is an important restriction in their applicability. Several substitution strategies for decreasing the reactivity of pentacene exist, but these almost always involve symmetrically substituted derivatives, restricting the chemical space of structures from which to choose. In this paper, we demonstrate that combining electronic and steric effects yields highly stable unsymmetrically substituted pentacenes.     

Comparison of Flow and Transport Experiments on 3D Printed Micromodels with Direct Numerical Simulations

Understanding pore-scale flow and transport processes is important for understanding flow and transport within rocks on a larger scale. Flow experiments on small-scale micromodels can be used to experimentally investigate pore-scale flow. Current manufacturing methods of micromodels are costly and time consuming. 3D printing is an alternative method for the production of micromodels. We have been able to visualise small-scale, single-phase flow and transport processes within a 3D printed micromodel using a custom-built visualisation cell. Results have been compared with the same experiments run on a micromodel with the same geometry made from polymethyl methacrylate (PMMA, also known as Perspex). Numerical simulations of the experiments indicate that differences in experimental results between the 3D printed micromodel and the Perspex micromodel may be due to variability in print geometry and surface properties between the samples. 3D printing technology looks promising as a micromodel manufacturing method; however, further work is needed to improve the accuracy and quality of 3D printed models in terms of geometry and surface roughness.

     

Demonstration of High Speeds with Low Pressure Drops Using 1.8 μm Particles in SFC

The literature contains few, if any, references to the use of sub-2 μm particles in supercritical fluid chromatography (SFC). In this study, the use of 1.8 μm particles in SFC is demonstrated, producing high efficiency chromatograms, less than 1 min long for each of a diverse range of solute families, including steroids, sulfonamides, profens, nucleic acids and xanthenes. Most of the solutes eluted from bare silica with surprisingly good peak shapes. The 3 × 100 mm column packed with 1.8 μm spherical silica particles, produced as many as 22,400 plates (80% of theoretical). Column head pressure did not exceed 410 bar and pressure drops did not exceed 240 bar, even at flows of 3 mL min^?1, or modifier concentration as high as 65%. Such performance produced the fastest solvation based chromatography (LC–SFC) reported to date. The chromatographic hardware requirements are met by older (400 bar max.) LC equipment. The speeds observed exceed even ultra high performance liquid chromatography (UHPLC), which requires dramatically higher pressure capability. Sub 2-μm particles appear suitable for routine use, employing common 400 bar LC equipment, only slightly modified to perform SFC, although faster detectors and smaller flow cells enhance performance.     

Separation of 9 Sulfonamide Drugs in ≈4 Min by Ultra-High Performance Supercritical Fluid Chromatography (UHPSFC): with a Feasibility Study for Detection in Milk

Nine widely used veterinary sulfonamide drugs were baseline separated (R _s ≥1.5) in just over 4 min using a 3 × 100 mm, 1.8 μm RX-Sil column, with 9.2 % methanol in carbon dioxide, at 110 bar and 30 °C, with direct UV detection at 260 nm using a 3 mm, 2 μL tapered flow cell. Pressure drop was only 172 bar. Optimization was difficult due to the similarity in structures. Small changes in modifier concentration, temperature and pressure, each tended to improve the resolution of some peak pairs but degraded the resolution of others. There were four critical pairs, each responding differently to changes in conditions. Optimization was performed by plotting resolution between pairs as a function of modifier concentration first, temperature second, and outlet pressure third. Retention time was then minimized by changing flow rate. The estimated limit of quantitation (LOQ, S/N >10), for direct injections, was ≈200–400 ng/g of each, inadequate for regulatory requirements. Solid phase extraction (SPE) attempted to pre-concentrate samples spiked with sulfamethazine by ≈20:1. From water, the limit of detection (LOD) was ≈2.7 ng/mL with LOQ ≈9 ng/mL using UV at 260 nm. The LOD for milk was 6.2 ng/mL, and LOQ was 20.1 ng/mL. A better pre-concentration step or a more sensitive detector such as MS–MS is required. Even with these inadequacies, SFC was shown to be a feasible, faster, “greener” alternative to HPLC for the separation of these drugs.

     

A stochastic programming model for scheduling call centers with global Service Level Agreements

We consider the issue of call center scheduling in an environment where arrivals rates are highly variable, aggregate volumes are uncertain, and the call center is subject to a global service level constraint. This paper is motivated by work with a provider of outsourced technical support services where call volumes exhibit significant variability and uncertainty. The outsourcing contract specifies a Service Level Agreement that must be satisfied over an extended period of a week or month. We formulate the problem as a mixed-integer stochastic program. Our model has two distinctive features. Firstly, we combine the server sizing and staff scheduling steps into a single optimization program. Secondly, we explicitly recognize the uncertainty in period-by-period arrival rates. We show that the stochastic formulation, in general, calculates a higher cost optimal schedule than a model which ignores variability, but that the expected cost of this schedule is lower. We conduct extensive experimentation to compare the solutions of the stochastic program with the deterministic programs, based on mean valued arrivals. We find that, in general, the stochastic model provides a significant reduction in the expected cost of operation. The stochastic model also allows the manager to make informed risk management decisions by evaluating the probability that the Service Level Agreement will be achieved.     

Identification of amino-tadalafil and rimonabant in electronic cigarette products using high pressure liquid chromatography with diode array and tandem mass spectrometric detection

A high-pressure liquid chromatography-diode array detection and multi-mode ionization tandem mass spectrometry (HPLC-DAD–MMI-MS/MS) method was used to identify amino-tadalafil and rimonabant in electronic cigarette (e-cigarette) cartridges. Amino-tadalafil is a drug analogue of the commercially approved Cialis? (i.e. tadalafil). Rimonabant is a drug that was, at one time, approved for weight loss in Europe (although approval has been retracted), but not in the United States. In addition, poor quality control over the e-cigarette products analyzed here is shown by the presence of nicotine in products labeled as containing no nicotine or by the presence of significant amounts of rimonabant oxidative degradant in e-cigarette products containing rimonabant. Identification was accomplished by comparing the retention time of relevant peaks in the sample with those of standard compounds, in addition to comparison of the UV spectra, mass spectra and/or product ion mass spectra.     

Occurrence and sequence of Sphaeroides Heme Protein and Diheme Cytochrome C in purple photosynthetic bacteria in the family <Emphasis Type="Italic">Rhodobacteraceae</Emphasis>

Background  

Sphaeroides Heme Protein (SHP) was discovered in the purple photosynthetic bacterium, Rhodobacter sphaeroides, and is the only known c-type heme protein that binds oxygen. Although initially not believed to be widespread among the photosynthetic bacteria, the gene has now been found in more than 40 species of proteobacteria and generally appears to be regulated. Rb. sphaeroides is exceptional in not having regulatory genes associated with the operon. We have thus analyzed additional purple bacteria for the SHP gene and examined the genetic context to obtain new insights into the operon, its distribution, and possible function.     

[Bis(trispivalatodimolybdenum (II))-μ-bis(4′-carboxylato-2,2′:6′,2″-terpyridine) ruthenium (II)] (2+) Tetrafluoroborate: Photophysical Studies

The photophysical properties of the title compound have been studied by fs and ns transient absorption spectroscopy. The electronic absorption spectrum consists of three principle absorptions assigned to terpy ¹LLCT at ~300 nm, ruthenium (II) t_2g⁶ to terpy ¹MLCT at ~470 nm and Mo₂ δ to terpycarboxylate at ~670 nm. The compound shows weak room temperature emission in THF solution at ~1,100 nm when excited into each of the aforementioned bands. This emission is assigned to the T₁ state, ³MMδδ*. Transient absorption spectroscopy indicates a lifetime for T₁ of 9.6 μs. This paper is dedicated to Prof. C. N. R. Rao.