A vibrational spectroscopic study of the sulphate mineral glauberite

The mineral glauberite is one of many minerals formed in evaporite deposits. The mineral glauberite has been studied using a combination of scanning electron microscopy with energy dispersive X-ray analysis and infrared and Raman spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by sulphur, calcium and sodium. Glauberite is characterized by a very intense Raman band at 1002 cm-1 with Raman bands observed at 1107, 1141, 1156 and 1169 cm-1 attributed to the sulphate ν3 antisymmetric stretching vibration. Raman bands at 619, 636, 645 and 651 cm-1 are assigned to the ν4 sulphate bending modes. Raman bands at 454, 472 and 486 cm-1 are ascribed to the ν2 sulphate bending modes. The observation of multiple bands is attributed to the loss of symmetry of the sulphate anion. Raman spectroscopy is superior to infrared spectroscopy for the determination of glauberite.

Vibrational spectroscopy of the multianion mineral gartrellite from the Anticline Deposit, Ashburton Downs, Western Australia

The multianion mineral gartrellite PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2 has been studied by a combination of Raman and infrared spectroscopy. The molecular structure of gartrellite is assessed. Gartrellite is one of the tsumcorite mineral group based upon arsenate and/or 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 two water molecules per formula unit, or monoclinic in the other cases. Characteristic Raman spectra of the mineral gartrellite 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 AsO3/4 anion.

Quality based frame selection for face clustering in news video

Clustering identities in a broadcast video is a useful task to aid in video annotation and retrieval. Quality based frame selection is a crucial task in video face clustering, to both improve the clustering performance and reduce the computational cost. We present a frame work that selects the highest quality frames available in a video to cluster the face. This frame selection technique is based on low level and high level features (face symmetry, sharpness, contrast and brightness) to select the highest quality facial images available in a face sequence for clustering. We also consider the temporal distribution of the faces to ensure that selected faces are taken at times distributed throughout the sequence. Normalized feature scores are fused and frames with high quality scores are used in a Local Gabor Binary Pattern Histogram Sequence based face clustering system. We present a news video database to evaluate the clustering system performance. Experiments on the newly created news database show that the proposed method selects the best quality face images in the video sequence, resulting in improved clustering performance.

Constrained control design for dynamic positioning of marine vehicles with control allocation

In this paper, we address the control design problem of positioning of over-actuated marine vehicles with control allocation. The proposed design is based on a combined position and velocity loops in a multi-variable anti-windup implementation together with a control allocation mapping. The vehicle modelling is considered with appropriate simplifications related to low-speed manoeuvring hydrodynamics and vehicle symmetry. The control design is considered together with a control allocation mapping. We derive analytical tuning rules based on requirements of closed-loop stability and performance. The anti- windup implementation of the controller is obtained by mapping the actuator-force constraint set into a constraint set for the generalized forces. This approach ensures that actuation capacity is not violated by constraining the generalized control forces; thus, the control allocation is simplified since it can be formulated as an unconstrained problem. The mapping can also be modified on-line based on actuator availability to provide actuator-failure accommodation. We provide a proof of the closed-loop stability and illustrate the performance using simulation scenarios for an open-frame underwater vehicle.

The molecular structure of the vanadate mineral mottramite [PbCu(VO4)(OH)] from Tsumeb, Namibia – a vibrational spectroscopic study

We have studied a mineral sample of mottramite PbCu(VO4)(OH) from Tsumeb, Namibia using a combination of scanning electron microscopy with EDX, Raman and infrared spectroscopy. Chemical analysis shows principally the elements V, Pb and Cu. Ca occurs as partial substitution of Pb as well as P and As in substitution to V. Minor amounts of Si and Cr were also observed. The Raman band of mottramite at 829 cm-1, is assigned to the ν1 symmetric (VO-4) ) stretching mode. The complexity of the spectra is attributed to the chemical composition of the Tsumeb mottramite. The ν3 antisymmetric vibrational mode of mottramite is observed as very low intensity bands at 716 and 747 cm-1. The series of Raman bands at 411, 439, 451 cm-1 and probably also the band at 500 cm-1 are assigned to the (VO-4) ν2 bending mode. The series of Raman bands at 293, 333 and 366 cm-1 are attributed to the (VO-4) ) ν4 bending modes. The ν3, ν3 and ν4 regions are complex for both minerals and this is attributed to symmetry reduction of the vanadate unit from Td to Cs.

Synthesis and spectroscopic characterization of copper zinc aluminum nanoferrite particles

Copper doped zinc aluminium ferrites are synthesized by the solid-state reaction route is cubic crystalline with unit cell parameter varying from 8.39 to 8.89 Å. TEM pictures clearly indicating that fundamental unit is composed of octahedral and tetrahedral blocks and joined strongly shown in (a). EPR spectra is compositional dependent at lower Al/Cu concentration EPR spectra is due to Fe3+ and at a higher content of Al/Cu the EPR spectra is due to Cu2+. Absence of EPR spectra at room temperature indicates that the sample is perfectly ferromagnetic. EPR results at low temperature indicate that the sample is paramagnetic, and that copper is placed in the tetragonal elongation (B) site with magnetically non-equivalent ions in the unit cell having strong exchange coupling between them. This is shown in (b). (a) TEM image of ferrite with x = 0.15. (b) EPR spectrum of ferrite with x = 0.75.

Vibrational spectroscopic study of the sulphate mineral glaucocerinite (Zn,Cu)10Al6(SO4)3(OH)32⋅18H2O – a natural layered double hydroxide

We have studied the molecular structure of the mineral glaucocerinite (Zn,Cu)5Al3(SO4)1.5(OH)16�9(H2O) using a combination of Raman and infrared spectroscopy. The mineral is one of the hydrotalcite supergroup of natural layered double hydroxides. The Raman spectrum is characterised by an intense Raman band at 982 cm�1 with a low intensity band at 1083 cm�1. These bands are attributed to the sulphate symmetric and antisymmetric stretching mode. The infrared spectrum is quite broad with a peak at 1020 cm�1. A series of Raman bands at 546, 584, 602, 625 and 651 cm�1 are assigned to the m4 (SO4)2� bending modes. The observation of multiple bands provides evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 762 cm�1 is attributed to a hydroxyl deformation mode associated with AlOH units. Vibrational spectroscopy enables aspects of the molecular structure of glaucocerinite to be determined.

The synthesis and structure of the symmetrical isomer of C5H-

The ion (C2CHC2)(-) is formed in the gas phase by the process -C=C-CH(OCOR)-C=CD --> (C2CHC2)(-) + ('RDCO2') [R = H, Me or Et]; the ground state structure is a singlet, with C-2 nu symmetry.

Vibrational spectroscopic characterization of the sulphate mineral leightonite K2Ca2Cu(SO4)4⋅2H2O – Implications for the molecular structure

The mineral leightonite, a rare sulphate mineral of formula K2Ca2Cu(SO4)4.2H2O, has been studied using a combination of electron probe and vibrational spectroscopy. The mineral is characterized by an intense Raman band at 991 cm-1 attributed to the SO2- 4 m1 symmetric stretching mode. A series of Raman bands at 1047, 1120, 1137, 1163 and 1177 cm-1 assigned to the SO2- 4 m3 antisymmetric stretching modes. The observation of multiple bands shows that the symmetry of the sulphate anion is reduced. Multiple Raman and infrared bands in the OH stretching region shows that water in the structure of leightonite is in a range of molecular environments.

Vibrational spectroscopy of the copper (II) disodium sulphate dihydrate mineral kröhnkite Na2Cu(SO4)2 · 2H2O

A natural single-crystal specimen of the kröhnkite from Chuquicamata, Chile, with the general formula Na2Cu(SO4)2 · 2H2O, was investigated by Raman and infrared spectroscopy. The mineral kröhnkite is found in many parts of the world's arid areas. Kröhnkite crystallizes in the monoclinic crystal system with point group 2/m and space group P21/c. It is an uncommon secondary mineral formed in the oxidized zone of copper deposits, typically in very arid climates. The Raman spectrum of kröhnkite dominated by a very sharp intense band at 992 cm−1 is assigned to the ν1 symmetric stretching mode and Raman bands at 1046, 1049, 1138, 1164, and 1177 cm−1 are assigned to the ν3 antisymmetric stretching vibrations. The infrared spectrum shows an intense band at 992 cm−1. The Raman bands at 569, 582, 612, 634, 642, 655, and 660 cm−1 are assigned to the ν4 bending modes. Three Raman bands observed at 429, 445, and 463 cm−1 are attributed to the ν2 bending modes. The observation that three or four bands are seen in the ν4 region of kröhnkite is attributed to the reduction of symmetry to C2v or less.

Location of hydrogen atoms in hydronium jarosite

Various models for the crystal structure of hydronium jarosite were determined from Rietveld refinements against neutron powder diffraction patterns collected at ambient temperature and also single-crystal X-ray diffraction data. The possibility of a lower symmetry space group for hydronium jarosite that has been suggested by the literature was investigated. It was found the space group is best described as R3¯m, the same for other jarosite minerals. The hydronium oxygen atom was found to occupy the 3¯m site (3a Wyckoff site). Inadequately refined hydronium bond angles and bond distances without the use of restraints are due to thermal motion and disorder of the hydronium hydrogen atoms across numerous orientations. However, the acquired data do not permit a precise determination of these orientations; the main feature up/down disorder of hydronium is clear. Thus, the highest symmetry model with the least disorder necessary to explain all data was chosen: The hydronium hydrogen atoms were modeled to occupy an m (18 h Wyckoff site) with 50 % fractional occupancy, leading to disorder across two orientations. A rigid body description of the hydronium ion rotated by 60° with H–O–H bond angles of 112° and O–H distances of 0.96 Å was optimal. This rigid body refinement suggests that hydrogen bonds between hydronium hydrogen atoms and basal sulfate oxygen atoms are not predominant. Instead, hydrogen bonds are formed between hydronium hydrogen atoms and hydroxyl oxygen atoms. The structure of hydronium alunite is expected to be similar given that alunite supergroup minerals are isostructural.

Poly[μ-aqua-bis(μ5-2,4-dichlorobenzoato)dipotassium

In the title compound, [K2(C7H3Cl2O2)2(H2O)]n, the potassium salt of 2,4-dichlorobenzoic acid, the repeating unit in the polymeric structure consists of two identical irregular KO6Cl complex units related by twofold rotational symmetry, linked by a bridging water molecule lying on the twofold axis. The coordination polyhedron about each K+ comprises a carboxyl O-atom and a Cl-atom donor from a bidentate chelate ligand interaction, four O-atom donors from a doubly bridging bidentate carboxyl (O,O')-chelate interaction and the water molecule. A two-dimensional layered coordination polymer structure lying parallel to (100) is generated through a series of conjoined cyclic bridges between K centres and is stabilized by water O-H...O(carboxyl) hydrogen-bonding interactions.

Multi-shot person re-identification via relational stein divergence

Person re-identification is particularly challenging due to significant appearance changes across separate camera views. In order to re-identify people, a representative human signature should effectively handle differences in illumination, pose and camera parameters. While general appearance-based methods are modelled in Euclidean spaces, it has been argued that some applications in image and video analysis are better modelled via non-Euclidean manifold geometry. To this end, recent approaches represent images as covariance matrices, and interpret such matrices as points on Riemannian manifolds. As direct classification on such manifolds can be difficult, in this paper we propose to represent each manifold point as a vector of similarities to class representers, via a recently introduced form of Bregman matrix divergence known as the Stein divergence. This is followed by using a discriminative mapping of similarity vectors for final classification. The use of similarity vectors is in contrast to the traditional approach of embedding manifolds into tangent spaces, which can suffer from representing the manifold structure inaccurately. Comparative evaluations on benchmark ETHZ and iLIDS datasets for the person re-identification task show that the proposed approach obtains better performance than recent techniques such as Histogram Plus Epitome, Partial Least Squares, and Symmetry-Driven Accumulation of Local Features.

Control design for positioning of underwater vehicles with control allocation

In this paper, we address the control design problem of positioning of over-actuated underwater vehicles. The proposed design is based on a control architecture with combined position and velocity loops and a control tuning method based on the decoupled models. We derive analytical tuning rules based on requirements of closed-loop stability, positioning performance, and the vehicle velocity dynamic characteristics. The vehicle modelling is considered from force to motion with appropriate simplifications related to low-speed manoeuvring hydrodynamics and vehicle symmetry. The control design is considered together with a control allocation mapping. This approach makes the control tuning independent of the characteristics of the force actuators and provides the basis for control reconfiguration in the presence of actuator failure. We propose an anti-wind-up implementation of the controller, which ensures that the constraints related to actuation capacity are not violated. This approach simplifies the control allocation problem since the actuator constraints are mapped into generalised force constraints.

Upregulated MT1-MMP/TIMP-2 axis in the TSU-Pr1-B1/B2 model of metastatic progression in transitional cell carcinoma of the bladder

Muscle invasive transitional cell carcinoma (TCC) of the bladder is associated with a high frequency of metastasis, resulting in poor prognosis for patients presenting with this disease. Models that capture and demonstrate step-wise enhancement of elements of the human metastatic cascade on a similar genetic background are useful research tools. We have utilized the transitional cell carcinoma cell line TSU-Pr1 to develop an in vivo experimental model of bladder TCC metastasis. TSU-Pr1 cells were inoculated into the left cardiac ventricle of SCID mice and the development of bone metastases was monitored using high resolution X-ray. Tumor tissue from a single bone lesion was excised and cultured in vitro to generate the TSU-Pr1-B1 subline. This cycle was repeated with the TSU-Pr1-B1 cells to generate the successive subline TSU-Pr1-B2. DNA profiling and karyotype analysis confirmed the genetic relationship of these three cell lines. In vitro, the growth rate of these cell lines was not significantly different. However, following intracardiac inoculation TSU-Pr1, TSU-Pr1-B1 and TSU-Pr1-B2 exhibited increasing metastatic potential with a concomitant decrease in time to the onset of radiologically detectable metastatic bone lesions. Significant elevations in the levels of mRNA expression of the matrix metalloproteases (MMPs) membrane type 1-MMP (MT1-MMP), MT2-MMP and MMP-9, and their inhibitor, tissue inhibitor of metalloprotease-2 (TIMP-2), across the progressively metastatic cell lines, were detected by quantitative PCR. Given the role of MT1-MMP and TIMP-2 in MMP-2 activation, and the upregulation of MMP-9, these data suggest an important role for matrix remodeling, particularly basement membrane, in this progression. The TSU-Pr1-B1/B2 model holds promise for further identification of important molecules.