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.

Ruthenium(II) dichloro or dithiocyanato complexes with 4,4′:2′,2″:4″,4‴-quaterpyridinium ligands : towards photosensitisers with enhanced low-energy absorption properties

Fourteen new complexes of the form cis-\[RuIIX2(R2qpy2+)2]4+ (R2qpy2+ = a 4,4′:2′,2″:4″,4‴-quaterpyridinium ligand, X = Cl− or NCS−) have been prepared and isolated as their PF6− salts. Characterisation involved various techniques including 1H NMR spectroscopy and +electrospray or MALDI mass spectrometry. The UV–Vis spectra display intense intraligand π → π∗ absorptions, and also metal-to-ligand charge-transfer (MLCT) bands with two resolved maxima in the visible region. Red-shifts in the MLCT bands occur as the electron-withdrawing strength of the pyridinium groups increases, while replacing Cl− with NCS− causes blue-shifts. Cyclic voltammograms show quasi-reversible or reversible RuIII/II oxidation waves, and several ligand-based reductions that are irreversible. The variations in the redox potentials correlate with changes in the MLCT energies. A single-crystal X-ray structure has been obtained for a protonated form of a proligand salt, \[(4-(CO2H)Ph)2qpyH3+]\[HSO4]3·3H2O. Time-dependent density functional theory calculations give adequate correlations with the experimental UV–Vis spectra for the two carboxylic acid-functionalised complexes in DMSO. Despite their attractive electronic absorption spectra, these dyes are relatively inefficient photosensitisers on electrodes coated with TiO2 or ZnO. These observations are attributed primarily to weak electronic coupling with the surfaces, since the DFT-derived LUMOs include no electron density near the carboxylic acid anchors.

Deformation behaviour of nanocrystalline Mg-AI alloys during nanoindentation

The deformation behaviour of Mg-5%AI alloys and its dependence with gain size and strain rate were investigated using nanoindentation. The grain sizes were successfully reduced below 100 nm via mechanical alloying method. It was found that the strain rate sensitivity increased with decreasing grain size. The smaller activation volumes and the plastic deformation mechanisms involving grain boundary activities are considered to contribute to the increase of strain rate sensitivity in the nanocrystalline alloys.

Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O – a mineral found in lithium bearing pegmatites

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O from Boa Vista mine, Galiléia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm−1 are assigned to the symmetric stretching mode of and units. Raman bands at 548, 564, 599 and 634 cm−1 are assigned to the ν4 bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm−1 and infrared bands at 2623, 2838, 3136 and 3185 cm−1 are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed.

Load-unloading response of intact and artificially degraded articular cartilage correlated with near infrared (NIR) absorption spectra

The conventional mechanical properties of articular cartilage, such as compressive stiffness, have been demonstrated to be limited in their capacity to distinguish intact (visually normal) from degraded cartilage samples. In this paper, we explore the correlation between a new mechanical parameter, namely the reswelling of articular cartilage following unloading from a given compressive load, and the near infrared (NIR) spectrum. The capacity to distinguish mechanically intact from proteoglycan-depleted tissue relative to the "reswelling" characteristic was first established, and the result was subsequently correlated with the NIR spectral data of the respective tissue samples. To achieve this, normal intact and enzymatically degraded samples were subjected to both NIR probing and mechanical compression based on a load-unload-reswelling protocol. The parameter δ(r), characteristic of the osmotic "reswelling" of the matrix after unloading to a constant small load in the order of the osmotic pressure of cartilage, was obtained for the different sample types. Multivariate statistics was employed to determine the degree of correlation between δ(r) and the NIR absorption spectrum of relevant specimens using Partial Least Squared (PLS) regression. The results show a strong relationship (R(2)=95.89%, p<0.0001) between the spectral data and δ(r). This correlation of δ(r) with NIR spectral data suggests the potential for determining the reswelling characteristics non-destructively. It was also observed that δ(r) values bear a significant relationship with the cartilage matrix integrity, indicated by its proteoglycan content, and can therefore differentiate between normal and artificially degraded proteoglycan-depleted cartilage samples. It is therefore argued that the reswelling of cartilage, which is both biochemical (osmotic) and mechanical (hydrostatic pressure) in origin, could be a strong candidate for characterizing the tissue, especially in regions surrounding focal cartilage defects in joints.

Water absorption, permeability, and resistance to chloride-ion penetration of lightweight aggregate concrete

This paper presents an experimental study to evaluate effect of cumulative lightweight aggregate (LWA) content (including lightweight sand) in concrete [water/cement ratio (w/c) = 0.38] on its water absorption, water permeability, and resistance to chloride-ion penetration. Rapid chloride penetrability test (ASTM C 1202), rapid migration test (NT Build 492), and salt ponding test (AASHTO T 259) were conducted to evaluate the concrete resistance to chloride-ion penetration. The results were compared with those of a cement paste and a control normal weight aggregate concrete (NWAC) with the same w/c and a NWAC (w/c = 0.54) with 28-day compressive strength similar to some of the lightweight aggregate concrete (LWAC). Results indicate that although the total charge passed, migration coefficient, and diffusion coefficient of the LWAC were not significantly different from those of NWAC with the same w/c of 0.38, resistance of the LWAC to chloride penetration decreased with increase in the cumulative LWA content in the concretes. The water penetration depth under pressure and water sorptivity showed, in general, similar trends. The LWAC with only coarse LWA had similar water sorptivity, water permeability coefficient, and resistance to chloride-ion penetration compared to NWAC with similar w/c. The LWAC had lower water sorptivity, water permeability and higher resistance to chloride-ion penetration than the NWAC with similar 28-day strength but higher w/c. Both the NWAC and LWAC had lower sorptivity and higher resistance to chloride-ion penetration than the cement paste with similar w/c.

Raman spectroscopic study of the mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3, a pegmatite phosphate mineral from Santa Ana pegmatite, Argentina

The pegmatite mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3 has been studied by a combination of SEM and EMP, Raman and infrared spectroscopy. The studied sample was collected from the Santa Ana pegmatite, Argentina. The mineral occurs as a primary mineral in lithium bearing pegmatite, in association with beausite and lithiophilite. The Raman spectrum is characterized by a very sharp intense Raman band at 980 cm�1 assigned to the PO3�4 symmetric stretching mode. Multiple Raman bands are observed in the PO3�4 antisymmetric stretching region, providing evidence for the existence of more than one phosphate unit in the structure of qingheiite and evidence for the reduction in symmetry of the phosphate units. This concept is affirmed by the number of bands in the m4 and m2 bending regions. No intensity was observed in the OH stretching region in the Raman spectrum but significant intensity is found in the infrared spectrum. Infrared bands are observed at 2917, 3195, 3414 and 3498 cm�1 are assigned to water stretching vibrations. It is suggested that some water is coordinating the metal cations in the structure of qingheiite.

Vibrational spectroscopic characterization of the phosphate mineral kulanite Ba(Fe2+,Mn2+,Mg)2(Al,Fe3+)2(PO4)3(OH)3

The mineral kulanite BaFe2Al2(PO4)3(OH)3, a barium iron aluminum phosphate, has been studied by using a combination of electron microscopy and vibrational spectroscopy. Scanning electron microscopy with EDX shows the mineral is homogenous with no other phases present. The Raman spectrum is dominated by an intense band at 1022 cm−1 assigned to the PO43-ν1 symmetric stretching mode. Low intensity Raman bands at 1076, 1110, 1146, 1182 cm−1 are attributed to the PO43-ν3 antisymmetric stretching vibrations. The infrared spectrum shows a complex spectral profile with overlapping bands. Multiple phosphate bending vibrations supports the concept of a reduction in symmetry of the phosphate anion. Raman spectrum at 3211, 3513 and 3533 cm−1 are assigned to the stretching vibrations of the OH units. Vibrational spectroscopy enables aspects on the molecular structure of kulanite to be assessed.

First-principle study of adsorption of hydrogen on ti-doped Mg(0001) surface

Ab initio density functional theory (DFT) calculations are performed to study the adsorption of H2 molecules on a Ti-doped Mg(0001) surface. We find that two hydrogen molecules are able to dissociate on top of the Ti atom with very small activation barriers (0.103 and 0.145 eV for the first and second H2 molecules, respectively). Additionally, a molecular adsorption state of H2 above the Ti atom is observed for the first time and is attributed to the polarization of the H2 molecule by the Ti cation. Our results parallel recent findings for H2 adsorption on Ti-doped carbon nanotubes or fullerenes. They provide new insight into the preliminary stages of hydrogen adsorption onto Ti-incorporated Mg surfaces.

Atomic hydrogen diffusion in novel magnesium nanostructures : the impact of incorporated subsurface carbon atoms

Ab initio Density Functional Theory (DFT) calculations are performed to study the diffusion of atomic hydrogen on a Mg(0001) surface and their migration into the subsurface layers. A carbon atom located initially on a Mg(0001) surface can migrate into the sub-surface layer and occupy a fcc site, with charge transfer to the C atom from neighboring Mg atoms. The cluster of postively charged Mg atoms surrounding a sub-surface C is then shown to facilitate the dissociative chemisorption of molecular hydrogen on the Mg(0001) surface, and the surface migration and subsequent diffusion into the subsurface of atomic hydrogen. This helps rationalize the experimentally-observed improvement in absorption kinetics of H2 when graphite or single walled carbon nanotubes (SWCNT) are introduced into the Mg powder during ball milling.

Vibrational spectroscopy of the phosphate mineral lazulite – (Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm-1 assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO2/4- units. Two Raman bands at 1102 and 1137 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm-1 are attributed to the m1 PO3/4- symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm-1 are assigned to the v3PO3/4- antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm-1 are assigned to the m4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm-1 are attributed to the m2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm-1 are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood.

Protective effects of sweroside on human MG-63 cells and rat osteoblasts

Herbal Fructus Corni is a folk medicine with a long history of safe use for treating osteoporosis in postmenopausal women or elderly men in Asia. Sweroside is a bioactive herbal ingredient isolated from Fructus Corni, which has been widely used for the treatment of osteoporosis in traditional Chinese medicine (TCM). Unfortunately, the working mechanisms of this compound are difficult to determine and thus remain unclear. The aim of the study was performed to determine the potential molecular mechanism of the anti-osteoporotic effect of sweroside on the human MG-63 cells and rat osteoblasts. 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) test was used to observe the effect of sweroside on cell proliferation. The activity of alkaline phosphatase (ALP) and the amount of osteocalcin were also assayed the cell differentiation. Sweroside significantly increased the proliferation of human MG-63 cells and rat osteoblasts (P<0.01). It increased the activity of ALP, and osteocalcin was also elevated in response to sweroside (P<0.05). Of note, flowcytometer assay showed that sweroside can attenuate and inhibit apoptosis. Sweroside has a direct osteogenic effect on the proliferation and differentiation of cultured human MG-63 cells and rat osteoblasts in vitro. These data will help in understanding the molecular mechanisms of therapeutic efficacy of sweroside, and highlight insights into drug discovery. In the current study, sweroside has been suggested to be a promising osteoporosis therapeutic natural product.

The molecular structure of the borate mineral inderite Mg(H4B3O7)(OH)⋅5H2O – A vibrational spectroscopic study

We have undertaken a study of the mineral inderite Mg(H4B3O7)(OH)⋅5H2O a hydrated hydroxy borate mineral of magnesium using scanning electron microscopy, thermogravimetry and vibrational spectroscopic techniques. The structure consists of [B3O3(OH)5]2-[B3O3(OH)5]2- soroborate groups and Mg(OH)2(H2O)4 octahedra interconnected into discrete molecules by the sharing of two OH groups. Thermogravimetry shows a mass loss of 47.2% at 137.5 °C, proving the mineral is thermally unstable. Raman bands at 954, 1047 and 1116 cm−1 are assigned to the trigonal symmetric stretching mode. The two bands at 880 and 916 cm−1 are attributed to the symmetric stretching mode of the tetrahedral boron. Both the Raman and infrared spectra of inderite show complexity. Raman bands are observed at 3052, 3233, 3330, 3392 attributed to water stretching vibrations and 3459 cm−1 with sharper bands at 3459, 3530 and 3562 cm−1 assigned to OH stretching vibrations. Vibrational spectroscopy is used to assess the molecular structure of inderite.

Synthesis and spectroscopic characterization of magnesium oxalate nano-crystals

Synthesis of MgC2O4⋅2H2O nano particles was carried out by thermal double decomposition of solutions of oxalic acid dihydrate (C2H2O4⋅2H2O) and Mg(OAc)2⋅4H2O employing CATA-2R microwave reactor. Structural elucidation was carried out by employing X-ray diffraction (XRD), particle size and shape were studied by transmission electron microscopy (TEM) and nature of bonding was investigated by optical absorption and near-infrared (NIR) spectral studies. The powder resulting from this method is pure and possesses distorted rhombic octahedral structure. The synthesized nano rod is 80 nm in diameter and 549 nm in length.

Silver absorption on burns after the application of Acticoat : data from pediatric patients and a porcine burn model

Silver dressings have been widely used to successfully prevent burn wound infection and sepsis. However, a few case studies have reported the functional abnormality and failure of vital organs, possibly caused by silver deposits. The aim of this study was to investigate the serum silver level in the pediatric burn population and also in several internal organs in a porcine burn model after the application of Acticoat. A total of 125 blood samples were collected from 46 pediatric burn patients. Thirty-six patients with a mean of 13.4% TBSA burns had a mean peak serum silver level of 114 microg/L, whereas 10 patients with a mean of 1.85% TBSA burns had an undetectable level of silver (<5.4 microg/L). Overall, serum silver levels were closely related to burn sizes. However, the highest serum silver was 735 microg/L in a 15-month-old toddler with 10% TBSA burns and the second highest was 367 microg/L in a 3-year old with 28% TBSA burns. In a porcine model with 2% TBSA burns, the mean peak silver level was 38 microg/L at 2 to 3 weeks after application of Acticoat and was then significantly reduced to an almost undetectable level at 6 weeks. Of a total of four pigs, silver was detected in all four livers (1.413 microg/g) and all four hearts (0.342 microg/g), three of four kidneys (1.113 microg/g), and two of four brains (0.402 microg/g). This result demonstrated that although variable, the level of serum silver was positively associated with the size of burns, and significant amounts of silver were deposited in internal organs in pigs with only 2% TBSA burns, after application of Acticoat.