Synthesis and characterization of reusable nano-order SO<Subscript>3</Subscript>H-KIT-5 as a heterogeneous catalyst for eco-friendly synthesis of 1,4-dihydropyridines

A novel nanocatalyst silica-bonded sulfuric acid supported on KIT-5 as an organic–inorganic hybrid with high activity was prepared successfully. The KIT-5 with high surface area was reacted with chlorosulfonic acid via simple and rapid method. This efficient and reusable heterogeneous catalyst sulfuric acid nanocatalyst catalyzed one-pot synthesis of β-dicarbonyl compounds, aldehyde and ammonium acetate in the presence of 0.05 g of nanocatalyst at room temperature via solvent-free conditions to afford excellent yields of 1,4-dihydropyridines. This nanocatalyst was fully characterized by XRD, SEM–EDXS and Map analyses. The morphology of the catalyst surface by SEM images shows all porous of KIT-5 after the reaction was filled with the SO₃H groups. The average size determines around 22–24 nm. This catalyst can be reused five times without any significant loss of activity, too. The ease of separation, high activity, high surface area and reaction under open air condition are the main advantages of this catalyst.     

Iron (III)-silica interactions in aqueous solution: insights from X-ray absorption fine structure spectroscopy

The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (m_Fe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H₂O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (N_edge = 1-2; N_corner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Fe_edge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe₂Si_1-2 and Fe₃Si_2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO₆-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (R_Fe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters.     

Microplastics as contaminants in the marine environment: a review

Since the mass production of plastics began in the 1940s, microplastic contamination of the marine environment has been a growing problem. Here, a review of the literature has been conducted with the following objectives: (1) to summarise the properties, nomenclature and sources of microplastics; (2) to discuss the routes by which microplastics enter the marine environment; (3) to evaluate the methods by which microplastics are detected in the marine environment; (4) to assess spatial and temporal trends of microplastic abundance; and (5) to discuss the environmental impact of microplastics. Microplastics are both abundant and widespread within the marine environment, found in their highest concentrations along coastlines and within mid-ocean gyres. Ingestion of microplastics has been demonstrated in a range of marine organisms, a process which may facilitate the transfer of chemical additives or hydrophobic waterborne pollutants to biota. We conclude by highlighting key future research areas for scientists and policymakers.     

The formation age of ores from the Pebble Cu-Au-Mo giant deposit (Alaska,United States)

Zircons from the porphyry-like quartz-diorite boss of the Pebble Cu-Au-Mo deposit (southwest Alaska) have been examined. By their appearance and internal structure (cathode luminescence and electron probing), the zircons have been subdivided into four genetic groups: (1) xenogenic detrital (mainly rounded); (2) magmatogene (protolith crystal in the center and growth zone at the edge); (3) hydrothermally altered (with new-formed regeneration edges in growth zones); (4) metamict-altered (unconsolidated center of the crystal and sectoring in growth zones). Based on SHRIMP U-Pb dating for the principal heterogeneous elements in every group, the following stages of ore formation have been identified for the Pebble deposit: (a) crystallization of quartz diorite-porphyry bosses (95–92 Ma, the concordant age is 94.7 ± 1.5 Ma); (b) late magmatic metasomatic alterations with copper-molybdenum mineralization (92–85 Ma, the concordant age is 90.15 ± 0.78 Ma); (c) postmagmatic argillization with epithermal gold-sulfide mineralization (82–80 Ma, the concordant age is 82.9 ± 2.7 Ma).     

THE ELECTRICAL CURRENT PATTERN INDUCED BY AN OSCILLATING MAGNETIC DIPOLE IN A SEMI INFINITE CONDUCTIVE THIN PLATE*

In a paper by Koefoed and Kegge (1968), which was based on previous work of Wesley (1958), the electrical current pattern has been derived that is induced by an oscillating magnetic dipole in a semi-infinite thin plate of infinitesimal resistivity. In the present paper, the range of validity of the assumptions, on which the work of Wesley is based, is subjected to a theoretical analysis. It is found that the decisive factor for the validity of Wesley's derivation is the quotient of the square of the penetration depth of the electrical current over the product of the thickness of the plate and a distance that is indicative of the size of the current loops in the plate. Wesley's derivation is shown to be valid only when this factor is negligible. It is also shown that in this condition the imaginary component of the anomaly must be negligible. Model experiments are described in which the electrical current pattern is studied also in the range in which the derivation of Wesley is not valid. The procedure used in these model experiments was to measure the tangential component of the magnetic field strength very close to the metal plate that simulated the conductive dyke. In order to express the results of the measurements in terms of the imaginary to real ratio, these results are compared with an interpretation graph for field measurements that was published by Hedström and Parasnis (1958). It is found that the current pattern in the plate is essentially the same as that which follows from Wesley's derivation, provided that the imaginary to real ratio is less than one third. The measurements do not permit to draw conclusions regarding the current pattern in the plate in conditions that correspond to larger values of the imaginary to real ratio.     

Nature of polymerization and properties of silicate melts and glasses at high pressure

The structures of sodium silicate and aluminosilicate glasses quenched from melts at high pressure (6-10 GPa) with varying degrees of polymerization (fractions of nonbridging oxygen) were explored using solid-state NMR [¹⁷O and ²⁷Al triple-quantum magic-angle spinning (3QMAS) NMR]. The bond connectivity in melts among four and highly coordinated network polyhedra, such as ^[4]Al, ^[5,6]Al, ^[4]Si, and ^[5,6]Si, at high pressure is shown to be significantly different from that at ambient pressure. In particular, in the silicate and aluminosilicate melts, the proportion of nonbridging oxygen (NBO) generally decreases with increasing pressure, leading to the formation of new oxygen clusters that include 5- and 6-coordinated Si and Al in addition to 4-coordinated Al and Si, such as ^[4]Si-O-^[5,6]Si, ^[4]Si-O-^[5,6]Al and Na-O-^[5,6]Si. While the fractions of ^[5,6]Al increase with pressure, the magnitude of this increase diminishes with increasing degrees of ambient-pressure polymerization under isobaric conditions. Incorporating the above structural information into models of melt properties reproduces the anomalous pressure-dependence of O²⁻ diffusivity and viscosity often observed in silicate melts.     

Earthquake awareness and perception of risk among the residents of Istanbul

Awareness and perception of risk are among the most crucial steps in the process of taking precautions at individual level for various hazards. In this study, we investigated the factors affecting better knowledge and greater risk perception about earthquakes among residents of Istanbul. A field survey was carried out, and a total of 1,123 people were interviewed in two districts of Istanbul with different seismic risk levels and from three (low, moderate and high) socio-economic levels (SEL). The findings showed that although the level of knowledge regarding earthquakes and preparedness for them was promising, it could be improved. The results indicated that future preparedness programmes should target people with lower educational and socio-economic levels. The media were the leading source of information among the respondents. Location of the home was a strong influence on individuals having above average earthquake knowledge and even more on high risk perception. Socio-economic parameters (educational level, economic status, SEL of the sub-district and tenure of the home), gender and attitude score were other factors influencing greater risk perception with regard to earthquakes.     

Patterns of resource use by livestock during and after drought on the commons of Namaqualand, South Africa

The aim of this study was to determine the effect of drought on grazing patterns of livestock in a communal rangeland in Namaqualand. Water points were the foci of almost all grazing routes even after the drought, and the areas away from the water points were less heavily utilized. The mountains could be regarded as key resource areas for livestock since the grazing intensity was higher in the elevated areas of the rangeland than on the surrounding low lying areas during and immediately after drought. Spatial patterns of resource use by livestock on the commons did not differ during the drought and post-drought period. The lengths of the daily grazing routes were similar for both periods. This may be a consequence of the weakness of animals during the drought when forage was scarce which prevented them from walking further. The size of home ranges of the herds did not change during the two monitoring periods. We attribute this to social reasons because herders try to avoid the mixing of herds. In the commons of Namaqualand, herders are also spatially constrained and this restricts their options to adapt to drought, and hence many animals died.