Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding

NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.

catena-Poly[[[diaquacobalt(II)]-mu-(3,5-dinitro-2-oxidobenzoato)-kappa3O1,O2:O1'-[tetraaquacobalt(II)]-mu-(3,5-dinitro-2-oxidobenzoato)-kappa3-O1:O1',O2] dihydrate]

In the structure of polymeric title compound, {[Co2(C7H2N2O7)2(H2O)6] . 2H2O}n from the reaction of 3,5-dinitrosalicylic acid with cobalt(II) acetate, both slightly distorted octahedral Co(II) centres have crystallographic inversion symmetry. The coordination sphere about one Co centre comprises four O donors from two bidentate chelate O(phenolate), O(carboxyl) and bridging dianionic ligands and two water molecules [Co-O range, 2.0249(11)-2.1386(14)A] while that about the second Co centre has four water molecules and two bridging carboxyl O donor atoms [Co-O range, 2.0690(14)-2.1364(11)A]. The coordinated water molecules as well as the water molecules of solvation give water-water and water-carboxyl hydrogen-bonding interactions in the three-dimensional framework structure.

Single crystal Raman spectroscopy of brandholzite Mg[Sb(OH)6]2•6H2O and bottinoite Ni[Sb(OH)6]2•6H2O and the polycrystalline Raman spectrum of mopungite Na[Sb(OH)6]

The single crystal Raman spectra of minerals brandholzite and bottinoite, formula M[Sb(OH)6]2•6H2O, where M is Mg+2 and Ni+2 respectively, and the non-aligned Raman spectrum of mopungite, formula Na[Sb(OH)6], are presented for the first time. The mixed metal minerals comprise of alternating layers of [Sb(OH)6]-1 octahedra and mixed [M(H2O)6]+2 / [Sb(OH)6]-1 octahedra. Mopungite comprises hydrogen bonded layers of [Sb(OH)6]-1 octahedra linked within the layer by Na+ ions. The spectra of the three minerals were dominated by the Sb-O symmetric stretch of the [Sb(OH)6]-1 octahedron, which occurs at approximately 620 cm-1. The Raman spectrum of mopungite showed many similarities to spectra of the di-octahedral minerals informing the view that the Sb octahedra gave rise to most of the Raman bands observed, particularly below 1200 cm-1. Assignments have been proposed based on the spectral comparison between the minerals, prior literature and density field theory calculations of the vibrational spectra of the free [Sb(OH)6]-1 and [M(H2O)6]+2 octahedra by a model chemistry of B3LYP/6-31G(d) and lanl2dz for the Sb atom. The single crystal data spectra showed good mode separation, allowing the majority of the bands to be assigned a symmetry species of A or E.

Hexaaquamagnesium bis(3-carboxy-4-hydroxybenzenesulfonate) dihydrate

In the structure of the title compound, [Mg(H2O)6]2+ 2(C7H5O6S-). 2(H2O), the octahedral complex cations lie on crystallographic inversion centres and are hydrogen-bonded through the coordinated waters to the substituted benzenesulfonate monoanions and the water molecules of solvation, and together with a carboxylic acid O-H...O(sulfonate) association, give a three-dimensional structure.

Mechanism of interaction of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR

The development of new materials for water purification is of universal importance. Among these types of materials are layered double hydroxides (LDHs). Non-ionic materials pose a significant problem as pollutants. The interaction of methyl orange (MO) and acidic scarlet GR (GR) adsorption on hydrocalumite (Ca/Al-LDH-Cl) were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), scanning electron microscope (SEM) and near-infrared spectroscopy (NIR). The XRD results revealed that the basal spacing of Ca/Al-LDH-MO was expanded to 2.45 nm, and the MO molecules were intercalated with a inter-penetrating bilayer model in the gallery of LDH, with 49o tilting angle. Yet Ca/Al-LDH-GR was kept the same d-value as Ca/Al-LDH-Cl. The NIR spectrum for Ca/Al-LDH-MO showed a prominent band around 5994 cm-1, assigned to the combination result of the N-H stretching vibrations, which was considered as a mark to assess MO- ion intercalation into Ca/Al-LDH-Cl interlayers. From SEM images, the particle morphology of Ca/Al-LDH-MO mainly changed to irregular platelets, with a “honey-comb” like structure. Yet the Ca/Al-LDH-GR maintained regular hexagons platelets, which was similar to that of Ca/Al-LDH-Cl. All results indicated that MO- ion was intercalated into Ca/Al-LDH-Cl interlayers, and acidic scarlet GR was only adsorped upon Ca/Al-LDH-Cl surfaces.

Poly[tetra-mu-aqua-diaquatetrakis[mu-(E)-2-nitrocinnamato]tetrarubidium]

In the structure of the title compound [Rb4(C9H6NO4)4(H~2~O)6]n, the asymmetric unit comprises four rubidium complex cations, two of which have an RbO7 coordination polyhedron with a monocapped distorted octahedral stereochemistry and two of which have a distorted RbO6 octahedral coordination. The bonding about both the seven-coordinate centres is similar, comprising one monodentate water molecule together with three bridging water molecules and three carboxylate O-atom donors, two of which are bridging. The environments about the six-coordinate cations are also similar, comprising a monodentate nitro O-atom donor, a bridging water molecule and four bridging carboxylate O-atom donors [overall Rb-O range, 2.849(2)-3.190(2)A]. The coordination leads to a two-dimensional polymeric structure extending parallel to (001), which is stabilized by interlayer water O-H...O hydrogen-bonding associations to water, carboxyl and nitro O-atom acceptors, together with weak inter-ring pi--pi interactions [minimum ring centroid separation = 3.5319(19)A].

A phenomenological model for the structure-composition relationship of the high Tc cuprates based on simple chemical principles

A simple phenomenological model for the relationship between structure and composition of the high Tc cuprates is presented. The model is based on two simple crystal chemistry principles: unit cell doping and charge balance within unit cells. These principles are inspired by key experimental observations of how the materials accommodate large deviations from stoichiometry. Consistent explanations for significant HTSC properties can be explained without any additional assumptions while retaining valuable insight for geometric interpretation. Combining these two chemical principles with a review of Crystal Field Theory (CFT) or Ligand Field Theory (LFT), it becomes clear that the two oxidation states in the conduction planes (typically d8 and d9) belong to the most strongly divergent d-levels as a function of deformation from regular octahedral coordination. This observation offers a link to a range of coupling effects relating vibrations and spin waves through application of Hund’s rules. An indication of this model’s capacity to predict physical properties for HTSC is provided and will be elaborated in subsequent publications. Simple criteria for the relationship between structure and composition in HTSC systems may guide chemical syntheses within new material systems.

Self-calibration of wireless cameras with restricted degrees of freedom

This paper presents an approach for the automatic calibration of low-cost cameras which are assumed to be restricted in their freedom of movement to either pan or tilt movements. Camera parameters, including focal length, principal point, lens distortion parameter and the angle and axis of rotation, can be recovered from a minimum set of two images of the camera, provided that the axis of rotation between the two images goes through the camera’s optical center and is parallel to either the vertical (panning) or horizontal (tilting) axis of the image. Previous methods for auto-calibration of cameras based on pure rotations fail to work in these two degenerate cases. In addition, our approach includes a modified RANdom SAmple Consensus (RANSAC) algorithm, as well as improved integration of the radial distortion coefficient in the computation of inter-image homographies. We show that these modifications are able to increase the overall efficiency, reliability and accuracy of the homography computation and calibration procedure using both synthetic and real image sequences

Poly[[diaquabis[mu-2-(4-fluorophenoxy)acetato-k2O1:O1']magnesium] 0.4-hydrate]

In the structure of the title compound, [Mg(H2O)2(C8H6FO3)2]n(0.4H2O)n, slightly distorted octahedral MgO6 complex units have crystallographic inversion symmetry, the coordination polyhedron comprising two trans-related water molecules and four carboxyl O-atom donors, two of which are bridging. Within the two-dimensional complex polymer which is parallel to (100), the coordinating water molecules form intermolecular O---H...O hydrogen-bonds with carboxylate and phenoxy O-atom acceptors, as well as with the partial-occupancy solvent water molecules.

Axial length changes with shifts of gaze direction in myopes and emmetropes

Purpose. The purpose of the study was to investigate the changes in axial length occurring with shifts in gaze direction. Methods. Axial length measurements were obtained from the left eye of 30 young adults (10 emmetropes, 10 low myopes, and 10 moderate myopes) through a rotating prism with 15° deviation, along the foveal axis, using a noncontact optical biometer in each of the nine different cardinal directions of gaze over 5 minutes. The subject's fellow eye fixated on an external distance (6 m) target to control accommodation, also with 15° deviation. Axial length measurements were also performed in 15° and 25° downward gaze with the biometer inclined on a tilting table, allowing gaze shifts to be achieved with either full head turn but no eye turn, or full eye turn with no head turn. Results. There was a significant influence of gaze angle and time on axial length (both P < 0.001), with the greatest axial elongation (+18 ± 8 μm) occurring with inferonasal gaze (P < 0.001) and a slight decrease in axial length in superior gaze (−12 ± 17 μm) compared with primary gaze (P < 0.001). In downward gaze, a significant axial elongation occurred when eye turn was used (P < 0.001), but not when head turn was used to shift gaze (P > 0.05). Conclusions. The angle of gaze has a small but significant short-term effect on axial length, with greatest elongation occurring in inferonasal gaze. The elongation of the eye appears to be due to the influence of the extraocular muscles, in particular the oblique muscles.

Electron paramagnetic resonance, optical absorption and Raman spectral studies on a pyrite/chalcopyrite mineral

Pyrite and chalcopyrite mineral samples from Mangampet barite mine, Kadapa, Andhra Pradesh, India are used in the present study. XRD data indicate that the pyrite mineral has a face centered cubic lattice structure with lattice constant 5.4179 Å. Also it possesses an average particle size of 91.9 nm. An EPR study on the powdered samples confirms the presence of iron in pyrite and iron and Mn(II) in chalcopyrite. The optical absorption spectrum of chalcopyrite indicates presence of copper which is in a distorted octahedral environment. NIR results confirm the presence of water fundamentals and Raman spectrum reveals the presence of water and sulfate ions.

Modified kaolins

A process for the preparation of a modified kaolin from a kaolin group mineral which includes expansion and contraction of layers of the kaolin group mineral. The layers comprising one Si-tetrahedral sheet and one Al-octahedral sheet. The expansion and contraction may be initiated by initial intercalation of a reagent which can penetrate kaolin layers to reach an interlayer region there between to form an intercalate. Subsequently, the intercalation may be followed by de-intercalation which involves the removal of the reagent. By the above process, there is provided crystalline modified kaolins having the following properties: (i) an increased interlayer space compared to corresponding kaolin group minerals; (ii) an increased susceptibility to intercalation by cations, anions or salts compared to corresponding kaolin group minerals; and (iii) an increased exfoliated morphology compared to corresponding kaolin group minerals.

The difference of thermal stability between Fe-substituted palygorskite and Al-rich palygorskite

Sedimentary palygorskite (SP) and hydrothermal palygorskite (HP) were characterized by XRF, TG/DSC, andXRD. The total iron and dissociative iron in palygorskite were detected using spectrophotometry. The results showed that about 3.57 wt% of Fe2O3 was detected in SP in contrast with 0.4 wt% in HP. SP was a Fe-substituted palygorskite, and HP was an Al-rich palygorskite. The occurrence of Fe substitution in SP resulted in two mass loss steps of coordinated water and resulted in a larger d spacing. The SP showed greater thermal stability than the HP. It was proposed the change of (200) diffraction peak and (240) diffraction peak reflect changes of tetrahedral and octahedral structures in palygorskite.

Tetraaquabis(3,5-dinitrobenzoato-kO')magnesium tetrahydrate

In the structure of the title compound, [Mg(C7H3N2O6)2(H2O)4] . 4H2O), the slightly distorted octahedral MgO6 coordination polyhedron comprises two trans-related carboxyl O-atom donors from mononodentate 3,5-dinitrobenzoate ligands, and four water molecules. The coordinated water molecules and the four water molecules of solvation give both intra- and inter-unit O-H...O hydrogen-bonding interactions with carboxyl, water and nitro O-atom acceptors, giving a three-dimensional structure.

Microwave synthesis and spectroscopic characterization of manganese oxalate nanocrystals

The microwave synthesis of MnC2O4·2H2O nanoparticles was performed through the thermal double decomposition of oxalic acid dihydrate (C2H2O4·2H2O) and Mn(OAc)2·4H2O solutions using a CATA-2R microwave reactor. Structural characterization was performed using X-ray diffraction (XRD), particle size and shape were analyzed using transmission electron microscopy (TEM). The chemical in the structures was investigated using electron paramagnetic resonance (EPR) as well as optical absorption spectra and near-infrared (NIR) spectroscopies. The nanocrystals produced with this method were pure and had a distorted rhombic octahedral structure.