Single crystal raman spectroscopy of natural paulmooreite Pb2As2O5 and in comparison with the synthesised analogue

The single crystal Raman spectra of natural mineral paulmooreite Pb2As2O5 from the Långban locality, Filipstad district, Värmland province, Sweden are presented for the first time. It is a monoclinic mineral containing an isolated [As2O5]4-. Depolarised and single crystal spectra of the natural and synthetic sample compare favorably and are characterized by strong bands around 186 and 140 cm-1 and three medium bands at 800 – 700 cm-1. Band assignments were made based on band symmetry and spectral comparison between experimental band positions and those resulting from Hartree-Fock calculation of an isolated [As2O5]4- ion. Spectral comparison was also made with lead arsenites such as synthetic PbAs2O4 and Pb2(AsO2)3Cl and natural finnemanite in order to determine the contribution of the terminal and bridging O in paulmooreite. Bands at 760 – 733 cm-1 were assigned to terminal As-O vibrations, whereas stretches of the bridging O occur at 562 and 503 cm-1. The single crystal spectra showed good mode separation, allowing bands to be assigned a symmetry species of Ag or Bg.

Personalised search – a hybrid approach for web information retrieval and its evaluation

Nowadays, everyone can effortlessly access a range of information on the World Wide Web (WWW). As information resources on the web continue to grow tremendously, it becomes progressively more difficult to meet high expectations of users and find relevant information. Although existing search engine technologies can find valuable information, however, they suffer from the problems of information overload and information mismatch. This paper presents a hybrid Web Information Retrieval approach allowing personalised search using ontology, user profile and collaborative filtering. This approach finds the context of user query with least user’s involvement, using ontology. Simultaneously, this approach uses time-based automatic user profile updating with user’s changing behaviour. Subsequently, this approach uses recommendations from similar users using collaborative filtering technique. The proposed method is evaluated with the FIRE 2010 dataset and manually generated dataset. Empirical analysis reveals that Precision, Recall and F-Score of most of the queries for many users are improved with proposed method.

Magnetic resonance spectroscopy and neurocognitive dysfunction in obstructive sleep apnea before and after CPAP treatment

STUDY OBJECTIVES: To determine whether cerebral metabolite changes may underlie abnormalities of neurocognitive function and respiratory control in OSA. DESIGN: Observational, before and after CPAP treatment. SETTING: Two tertiary hospital research institutes. PARTICIPANTS: 30 untreated severe OSA patients, and 25 age-matched healthy controls, all males free of comorbidities, and all having had detailed structural brain analysis using voxel-based morphometry (VBM). MEASUREMENTS AND RESULTS: Single voxel bilateral hippocampal and brainstem, and multivoxel frontal metabolite concentrations were measured using magnetic resonance spectroscopy (MRS) in a high resolution (3T) scanner. Subjects also completed a battery of neurocognitive tests. Patients had repeat testing after 6 months of CPAP. There were significant differences at baseline in frontal N-acetylaspartate/choline (NAA/Cho) ratios (patients [mean (SD)] 4.56 [0.41], controls 4.92 [0.44], P = 0.001), and in hippocampal choline/creatine (Cho/Cr) ratios (0.38 [0.04] vs 0.41 [0.04], P = 0.006), (both ANCOVA, with age and premorbid IQ as covariates). No longitudinal changes were seen with treatment (n = 27, paired t tests), however the hippocampal differences were no longer significant at 6 months, and frontal NAA/Cr ratios were now also significantly different (patients 1.55 [0.13] vs control 1.65 [0.18] P = 0.01). No significant correlations were found between spectroscopy results and neurocognitive test results, but significant negative correlations were seen between arousal index and frontal NAA/Cho (r = -0.39, corrected P = 0.033) and between % total sleep time at SpO(2) < 90% and hippocampal Cho/Cr (r = -0.40, corrected P = 0.01). CONCLUSIONS: OSA patients have brain metabolite changes detected by MRS, suggestive of decreased frontal lobe neuronal viability and integrity, and decreased hippocampal membrane turnover. These regions have previously been shown to have no gross structural lesions using VBM. Little change was seen with treatment with CPAP for 6 months. No correlation of metabolite concentrations was seen with results on neurocognitive tests, but there were significant negative correlations with OSA severity as measured by severity of nocturnal hypoxemia. CITATION: O'Donoghue FJ; Wellard RM; Rochford PD; Dawson A; Barnes M; Ruehland WR; Jackson ML; Howard ME; Pierce RJ; Jackson GD. Magnetic resonance spectroscopy and neurocognitive dysfunction in obstructive sleep apnea before and after CPAP treatment.

Non-invasive, quantitative analysis of drug mixtures in containers using spatially offset Raman spectroscopy (SORS) and multivariate statistical analysis

In this paper, spatially offset Raman spectroscopy (SORS) is demonstrated for non-invasively investigating the composition of drug mixtures inside an opaque plastic container. The mixtures consisted of three components including a target drug (acetaminophen or phenylephrine hydrochloride) and two diluents (glucose and caffeine). The target drug concentrations ranged from 5% to 100%. After conducting SORS analysis to ascertain the Raman spectra of the concealed mixtures, principal component analysis (PCA) was performed on the SORS spectra to reveal trends within the data. Partial least squares (PLS) regression was used to construct models that predicted the concentration of each target drug, in the presence of the other two diluents. The PLS models were able to predict the concentration of acetaminophen in the validation samples with a root-mean-square error of prediction (RMSEP) of 3.8% and the concentration of phenylephrine hydrochloride with an RMSEP of 4.6%. This work demonstrates the potential of SORS, used in conjunction with multivariate statistical techniques, to perform non-invasive, quantitative analysis on mixtures inside opaque containers. This has applications for pharmaceutical analysis, such as monitoring the degradation of pharmaceutical products on the shelf, in forensic investigations of counterfeit drugs, and for the analysis of illicit drug mixtures which may contain multiple components.

Forensic analysis of fibres by vibrational spectroscopy

Fibres are extremely common. They can originate directly from human and animal hair, and also from textiles in the form of clothing, upholstery and carpets. Hair and textile fibres are relatively easily shed and transferred, which means that it is highly likely that fibres will be found at crime scenes. If such fibres are carefully characterised they can be of immense value in the forensic environment. Vibrational spectroscopy is one of the most important methods for the characterisation of natural and synthetic fibres. The vibrational spectrum, whether mid-IR or Raman, can be considered to be a fingerprint of the molecular structure of the fibre and as such has a very high information content.

A hybrid shifting bottleneck procedure algorithm for the parallel-machine job-shop scheduling problem

In practice, parallel-machine job-shop scheduling (PMJSS) is very useful in the development of standard modelling approaches and generic solution techniques for many real-world scheduling problems. In this paper, based on the analysis of structural properties in an extended disjunctive graph model, a hybrid shifting bottleneck procedure (HSBP) algorithm combined with Tabu Search metaheuristic algorithm is developed to deal with the PMJSS problem. The original-version SBP algorithm for the job-shop scheduling (JSS) has been significantly improved to solve the PMJSS problem with four novelties: i) a topological-sequence algorithm is proposed to decompose the PMJSS problem into a set of single-machine scheduling (SMS) and/or parallel-machine scheduling (PMS) subproblems; ii) a modified Carlier algorithm based on the proposed lemmas and the proofs is developed to solve the SMS subproblem; iii) the Jackson rule is extended to solve the PMS subproblem; iv) a Tabu Search metaheuristic algorithm is embedded under the framework of SBP to optimise the JSS and PMJSS cases. The computational experiments show that the proposed HSBP is very efficient in solving the JSS and PMJSS problems.

Vibrational spectroscopy of synthetic archerite (K,NH4)H2PO4 : and in comparison with the natural cave mineral

In order to mimic the formation of archerite in cave minerals, the mineral analogue has been synthesised. The cave mineral is formed by the reaction of the chemicals in bat guano with calcite substrates. X-ray diffraction proves that the synthesised archerite analogue was pure. The vibrational spectra of the synthesised mineral are compared with that of the natural cave mineral. Raman and infrared bands are assigned to H2PO4-, OH and NH stretching and bending vibrations. The Raman band at 917 cm-1 is assigned to the HOP stretching vibration of the H2PO4- units. Bands in the 1200 to 1800 cm-1 region are associated with NH4+ bending modes. Vibrational spectroscopy enables the molecular structure of archerite to be analysed.

Raman spectroscopy of the multianion mineral gartrellite-PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2

The multianion mineral gartrellite PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2 has been studied by a combination of Raman and infrared spectroscopy. The vibrational spectra of two gartrellite samples from Durango and Ashburton Downs were compared. Gartrellite is one of the tsumcorite mineral group based upon arsenate and sulphate anions. Crystal symmetry is either triclinic in the case of an ordered occupation of two cationic sites, triclinic due to ordering of the H bonds in the case of species with 2 water molecules per formula unit, or monoclinic in the other cases. Characteristic Raman spectra of the minerals enable the assignment of the bands to specific vibrational modes. These spectra are related to the structure of gartrellite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO4 anion.

Vibrational spectroscopy and solubility study of the mineral stringhamite CaCuSiO4•H2O

Stringhamite CaCuSiO4·H2O is a hydrated calcium copper silicate and is commonly known as a significant ‘healing’ mineral and is potentially a semi-precious jewel. Stringhamite is a neosilicate with Cu2+ in square planar coordination. Vibrational spectroscopy has been used to characterise the molecular structure of stringhamite. The intense sharp Raman band at 956 cm−1 is assigned to the ν1 (A1g) symmetric stretching vibration. Raman bands at 980, 997, 1061 cm−1 are assigned to the ν3 (A2u, B1g) antisymmetric stretching vibrations. Splitting of the ν3 vibrational mode supports the concept that the stringhamite SiO4 tetrahedron is strongly distorted. The intense bands at 505 and 519 cm−1 and at 570 cm−1 are assigned to the ν2 and ν4 vibrational modes. The question arises as to whether the mineral stringhamite can actually function as a healing mineral. An estimation of the solubility product at pH < 5 shows that the cupric ion can be released. The copper ion is a very powerful antibiological agent and thus the mineral stringhamite may well function as a healing mineral.

Deep Raman spectroscopy for the non-invasive standoff detection of concealed chemical threat agents

Deep Raman spectroscopy has been utilized for the standoff detection of concealed chemical threat agents from a distance of 15 meters under real life background illumination conditions. By using combined time and space resolved measurements, various explosive precursors hidden in opaque plastic containers were identified non-invasively. Our results confirm that combined time and space resolved Raman spectroscopy leads to higher selectivity towards the sub-layer over the surface layer as well as enhanced rejection of fluorescence from the container surface when compared to standoff spatially offset Raman spectroscopy. Raman spectra that have minimal interference from the packaging material and good signal-to-noise ratio were acquired within 5 seconds of measurement time. A new combined time and space resolved Raman spectrometer has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than picosecond-based laboratory systems.

Development of an Innovative Hybrid-Composite Floor System

This paper discusses the research carried out towards the development of a hybrid-composite floor plate systems (HCFPS) using polyurethane (PU), glass-fibre reinforced cement (GRC) and thin perforated steel laminate. HCFPS is configured in such a way where positive inherent properties of individual component materials are combined to offset any weakness and achieve the optimum performance. Finite Element modeling of HCFPS with ABAQUS 6.9-1, comparative studies of HCFPS with the steel deck composite system and experimental investigations which will be carried out are briefly described in the paper.

Raman spectroscopy of synthetic CaHPO4•2H2O– and in comparison with the cave mineral brushite

The mineral brushite has been synthesised by mixing calcium ions and hydrogen phosphate anions to mimic the reactions in a Cave. The vibrational spectra of the synthesised brushite were compared with that of the natural Cave mineral. Bands attributable to the PO43- and HPO42- anions are observed. Brushite, both synthetic and natural, is characterised by an intense sharp band at 985 cm-1 with a shoulder at 1000 cm-1. Characteristic bending modes are observed in the 300 to 600 cm-1 region. The spectra of the synthesised brushite matches very well the spectrum of brushite from the Moorba Cave, Western Australia.

Raman spectroscopy of the borate mineral ameghinite NaB3O3(OH)4

The molecular structure of the sodium borate mineral ameghinite NaB3O3(OH)4 has been determined by the use of vibrational spectroscopy. The crystal structure consists of isolated [B3O3(OH)4]- units formed by one tetrahedron and two triangles. H bonds and Na atoms link these polyanions to form a 3-dimensional framework. The Raman spectrum is dominated by an intense band at 1027 cm-1, attributed to BO stretching vibrations of both the trigonal and tetrahedral boron. A series of Raman bands at 1213, 1245 and 1281cm-1 are ascribed to BOH in-plane bending modes. The infrared spectra are characterized by strong overlap of broad multiple bands. An intense Raman band found at 620 cm-1 is attributed to the bending modes of trigonal and tetrahedral boron. Multiple Raman bands in the OH stretching region are observed at 3206, 3249 and 3385 cm-1. Raman spectroscopy coupled with infrared spectroscopy has enabled aspects about the molecular structure of the borate mineral ameghinite to be assessed.

Real-time detection of concealed chemical hazards under ambient light conditions using Raman spectroscopy

Current concerns regarding terrorism and international crime highlight the need for new techniques for detecting unknown and hazardous substances. A novel Raman spectroscopy-based technique, spatially offset Raman spectroscopy (SORS), was recently devised for non-invasively probing the contents of diffusely scattering and opaque containers. Here, we demonstrate a modified portable SORS sensor for detecting concealed substances in-field under different background lighting conditions. Samples including explosive precursors, drugs and an organophosphate insecticide (chemical warfare agent surrogate) were concealed inside diffusely scattering packaging including plastic, paper and cloth. Measurements were carried out under incandescent and fluorescent light as well as under daylight to assess the suitability of the probe for different real-life conditions. In each case, it was possible to identify the substances against their reference Raman spectra in less than one minute. The developed sensor has potential for rapid detection of concealed hazardous substances in airports, mail distribution centers and customs checkpoints.

Unit commitment in power systems with plug-in hybrid electric vehicles

With the continued development of renewable energy generation technologies and increasing pressure to combat the global effects of greenhouse warming, plug-in hybrid electric vehicles (PHEVs) have received worldwide attention, finding applications in North America and Europe. When a large number of PHEVs are introduced into a power system, there will be extensive impacts on power system planning and operation, as well as on electricity market development. It is therefore necessary to properly control PHEV charging and discharging behaviors. Given this background, a new unit commitment model and its solution method that takes into account the optimal PHEV charging and discharging controls is presented in this paper. A 10-unit and 24-hour unit commitment (UC) problem is employed to demonstrate the feasibility and efficiency of the developed method, and the impacts of the wide applications of PHEVs on the operating costs and the emission of the power system are studied. Case studies are also carried out to investigate the impacts of different PHEV penetration levels and different PHEV charging modes on the results of the UC problem. A 100-unit system is employed for further analysis on the impacts of PHEVs on the UC problem in a larger system application. Simulation results demonstrate that the employment of optimized PHEV charging and discharging modes is very helpful for smoothing the load curve profile and enhancing the ability of the power system to accommodate more PHEVs. Furthermore, an optimal Vehicle to Grid (V2G) discharging control provides economic and efficient backups and spinning reserves for the secure and economic operation of the power system