Formation of neutral molecules of potential stellar interest by neutralisation of negative ions in a mass spectrometer. The application of experiment and molecular modelling in concert

This paper is a modified version of a lecture which describes the synthesis, structure and reactivity of some neutral molecules of stellar significance. The neutrals are formed in the collision cell of a mass spectrometer following vertical Franck-Condon one electron oxidation of anions of known bond connectivity. Neutrals are characterised by conversion to positive ions and by extensive theoretical studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory. Four systems are considered in detail, viz (i) the formation of linear C(4) and its conversion to the rhombus C(4), (ii) linear C(5) and the atom scrambling of this system when energised, (iii) the stable cumulene oxide CCCCCO, and (iv) the elusive species O(2)C-CO. This paper is not intended to be a review of interstellar chemistry: examples are selected from our own work in this area.     

Pullout Behavior of Granular Pile-Anchors in Expansive Clay Beds In Situ

Granular pile anchors (GPA) are one of the recent innovative foundation techniques devised for mitigating the problems posed by swelling clay beds. In a granular pile anchor, the footing is anchored to an anchor plate at the bottom of the granular pile. This makes the granular pile tension resistant and enables it to absorb the tensile force caused on the foundation by the swelling clay. An understanding of the amount of uplift resistance offered by the GPA is important in the design of granular pile-anchor foundations in field situations causing tensile forces on foundations, such as in expansive clay beds. This paper presents the results of a field-scale test program conducted to study the pullout response of GPAs embedded in expansive clay beds. Pullout load tests were conducted on GPAs of varying lengths and diameters. It was found from the field pullout load tests that granular pile anchors of larger surface area resulted in higher pullout capacity. Of the various single granular pile anchors with l/d values between 2.5 and 10, the GPA of length 1000?mm and diameter 200?mm (l/d = 5) showed the best pullout load response when tested alone, resulting in a failure uplift capacity of 14.71?kN. Increase in diameter and length of granular pile anchor increased the uplift capacity. When the length of the GPA was increased from 500 to 750 and 1000?mm, the percentage increase in the uplift load required for an upward movement of 25?mm was 33.3 and 55.5% respectively. The pullout load of the GPA when tested under group was 18?kN as against a 12?kN for the GPA when tested single.     

Exosomes in bodily fluids are a highly stable resource of disease biomarkers

Biomarkers are measurable indicators of a biological state. As our understanding of diseases meliorates, it is generally accepted that early diagnosis renders the best chance to cure a disease. In the context of proteomics, the discovery phase of identifying bonafide biomarkers and the ensuing validation phase involving large cohort of patient samples are impeded by the complexity of bodily fluid samples. High abundant proteins found in blood plasma make it difficult for the detection of low abundant proteins that may be potential biomarkers. Extracellular vesicles (EVs) have reignited interest in the field of biomarker discovery. EVs contain a tissue-type signature wherein a rich cargo of proteins and RNA are selectively packaged. In addition, as EVs are membranous structures, the luminal contents are protected from degradation by extracellular proteases and are highly stable in storage conditions. Interestingly, an appealing feature of EV-based biomarker analysis is the significant reduction in the sample complexity compared to whole bodily fluids. With these prescribed attributes, which are the rate-limiting factors of traditional biomarker analysis, there is immense potential for the use of EVs for biomarker detection in clinical settings. This review will discuss the current issues with biomarker analysis and the potential use of EVs as reservoirs of disease biomarkers.     

Synthesis of cobalt-doped barium cerate-zirconate and its evaluation for hydrogen production and electrochemical characterization

Cobalt-doped barium cerate-zirconate was synthesized using an oxalate co-precipitation route. The material was characterized using X-ray diffraction, transmission and scanning transmission electron microscopy coupled with X-ray energy dispersive spectroscopy. Results indicated that homogeneous cubic phase material was obtained at very high heat-treatment temperatures. Catalytic activity of the material toward CH₃OH partial-oxidation was tested at different temperatures and O₂:CH₃OH ratios. High hydrogen yields were obtained indicating that the material was a suitable catalyst for hydrogen generation. Impedance spectroscopy tests were conducted at different conditions to understand conduction processes occurring in the material. Results suggested mixed protonic–electronic conductivity in the presence of hydrogen. Thus, material is a potential candidate for the bi-functional role of electro-ceramic catalyst for simultaneous hydrogen generation and purification.     

Creating Shared Information Spaces to Support Collaborative Design Work

The provision of computer support for collaborative work is a central concern for Information Systems (IS) research and practice. In this paper we present the details of an information flow study undertaken in the household division of a large European design and manufacturing company (Delta). The goal of the study was to elicit user requirements for a computer system to facilitate the collaborative work of new product design teams. These requirements form the basis for the design and development of a Web-based LIRÉ (Living Repository) prototype system, the functionalities, features, and rationale of which are discussed. We also present the results of the evaluation of LIRÉ by the users at Delta and our observations on enhancing the sophistication and usefulness of this class of system. A production version based on the prototype but using commercially available software is currently in use by the New Product Development group at Delta.     

Controllable optimized designs of an ideal reactive distillation system using genetic algorithm

The steady state economic optimization to obtain the most economical controllable design of a double feed ideal reactive distillation (RD) column is demonstrated using real coded genetic algorithm. The novelty of the work is in the development of a simple procedure based on steady state criteria for controllability. The optimization is performed for four scenarios corresponding to a sequential increase in the number of design variables. Results show that limiting the optimization search space to only those designs that satisfy the controllability criteria leads to optimized designs that are only slightly (<2%) more expensive than the most economical design without controllability considerations. The former designs however exhibit much better controllability in terms of effectively handling a large through-put change using two-point temperature inferential control and avoiding a steady state transition under open loop operation. Results also show that the location of the fresh feeds is a dominant design variable with designs that do not constrain the feed tray location to be immediately above and below the reactive zone being substantially more economical.     

Computation of approximate optimal policies in a partially observed inventory model with rain checks

This paper proposes a new methodology to solve partially observed inventory problems. Generally, these problems have infinite-dimensional states that are conditional distributions of the inventory level. Our methodology involves linearizing the state transitions via unnormalized probabilities. It then uses an appropriate functional basis to represent the state. Considering the speed and stability of computations, we choose truncated Chebyshev polynomials as the basis. We use Fast Fourier Transforms along with an appropriate discretization of inventory levels to speed up the computations. These main ideas are blended to obtain an iterative algorithm to solve a partially observed inventory model with rain checks. In this model, the inventory manager (IM) does not know the inventory level when it is positive. Otherwise, the IM fully observes it. This model provides a context to illustrate our methodology, which applies to other such models. Although this model has been studied mathematically in the literature, the use of our algorithm provides a numerical approximation of the optimal order quantities. These are compared to the orders released under a base mean-stock policy, where the IM replaces the unobserved inventory level with its mean and applies the well-known base stock policy. We show numerically that the optimal order quantity is very close to the base mean-stock order quantity, when the variance of the inventory distribution is small. When the mean of the inventory distribution is large, the optimal order quantity is more than the base mean-stock quantity, and it is the other way around when the mean is small or negative. These insights are explained via uncertainty and information effects and their interplay. We expect this interplay to show up in other partially observed inventory models.     

A novel electrical-mobility-based instrument for total number concentration measurements of ultrafine particles

A novel electrical-mobility-based technique to measure total particle number concentration over a selected size range is presented. Charged particles are condensed out onto an electrode that is shaped such that the product of its transfer function and the particle charging efficiency is a constant, independent of particle size. The resulting total current is then proportional to the number concentration of the sampled particles over the collected size range. The theoretical approach for the calculation of the electrode shape function is described. The extension of this technique for measurement of higher moments of the particle size distributions over a desired size range is briefly discussed.This concept is used to design a new instrument, called the tailored electrode concentration sensor (TECS). For validation of the theoretical concept, the collection electrode in the TECS instrument is designed for concentration measurements over a size range of 30–90 nm. In the TECS, the collection section is located downstream of an electrostatic precipitator section, where the sampled flow is split into aerosol and sheath flows, similar to the design of the MEAS [Ranjan, M., & Dhaniyala, S., (2007), Theory and design of a new miniature electrical-mobility aerosol spectrometer, Journal of Aerosol Science, 38(9), 950–963]. This results in a compact, low pressure drop instrument. Experimental results confirm that the response of the optimally-shaped electrode in the TECS system is only proportional to total number concentration over the selected size range.