Electronic structure and magnetic properties of pyroxenes (Li,Na)TM(Si,Ge)2O6: novel low-dimensional magnets with 90 bonds

The results of the LSDA+U calculations for pyroxenes with diverse magnetic properties (Li,Na)TM(Si,Ge)$_2$O$_6$, where TM is the transition metal ion (Ti,V,Cr,Mn,Fe), are presented. We show that the anisotropic orbital ordering results in the spin-gap formation in NaTiSi$_2$O$_6$. The detailed analysis of different contributions to the intrachain exchange interactions for pyroxenes is performed both analytically using perturbation theory and basing on the results of the band structure calculations. The antiferromagnetic $t_{2g}-t_{2g}$ exchange is found to decrease gradually in going from Ti to Fe. It turns out to be nearly compensated by ferromagnetic interaction between half-filled $t_{2g}$ and empty $e_g$ orbitals in Cr-based pyroxenes. The fine-tuning of the interaction parameters by the crystal structure results in the ferromagnetism for NaCrGe$_2$O$_6$. Further increase of the total number of electrons and occupation of $e_g$ sub-shell makes the $t_{2g}-e_g$ contribution and total exchange interaction antiferromagnetic for Mn- and Fe-based pyroxenes. Strong oxygen polarization was found in Fe-based pyroxenes. It is shown that this effect leads to a considerable reduction of antiferromagnetic intrachain exchange. The obtained results may serve as a basis for the analysis of diverse magnetic properties of pyroxenes, including those with recently discovered multiferroic behavior.Comment: 11 pages, 10 figure

Agardite-(Y), Cu2+6Y(AsO4)3(OH)6·3H2O

Agardite-(Y), with a refined formula of Cu2+5.70(Y0.69Ca0.31)[(As0.83P0.17)O4]3(OH)6·3H2O [ideally Cu2+6Y(AsO4)3(OH)6·3H2O, hexacopper(II) yttrium tris(arsenate) hexahydroxide trihydrate], belongs to the mixite mineral group which is characterized by the general formula Cu2+6A(TO4)3(OH)6·3H2O, where nine-coordinated cations in the A-site include rare earth elements along with Al, Ca, Pb, or Bi, and the T-site contains P or As. This study presents the first structure determination of agardite-(Y). It is based on the single-crystal X-ray diffraction of a natural sample from Jote West mine, Pampa Larga Mining District, Copiapo, Chile. The general structural feature of agardite-(Y) is characterized by infinite chains of edge-sharing CuO5 square pyramids (site symmetry 1) extending down the c axis, connected in the ab plane by edge-sharing YO9 polyhedra (site symmetry -6..) and corner-sharing AsO4 tetrahedra (site symmetry m..). Hydroxyl groups occupy each corner of the CuO5-square pyramids not shared by a neighboring As or Y atom. Each YO9 polyhedron is surrounded by three tubular channels. The walls of the channels, parallel to the c axis, are six-membered hexagonal rings comprised of CuO5 and AsO4 polyhedra in a 2:1 ratio, and contain free molecules of lattice water

New data on hemihedrite from Arizona

Hemihedrite from the Florence Lead-Silver mine in Pinal County, Arizona, USA was first described and assigned the ideal chemical formula Pb10Zn(CrO4)(6)(SiO4)(2)F-2, based upon a variety of chemical and crystal-structure analyses. The primary methods used to determine the fluorine content for hemihedrite were colorimetry, which resulted in values of F that were too high and inconsistent with the structural data, and infrared (IR) spectroscopic analysis that failed to detect OH or H2O. Our reinvestigation using electron microprobe analysis of the type material, and additional samples from the type locality, the Rat Tail claim, Arizona, and Nevada, reveals the absence of fluorine, while the presence of OH is confirmed by Raman spectroscopy. These findings suggest that the colorimetric determination of fluorine in the original description of hemihedrite probably misidentified F due to the interferences from PO4 and SO4, both found in our chemical analyses. As a consequence of these results, the study presented here proposes a redefinition of the chemical composition of hemihedrite to the ideal chemical formula Pb10Zn(CrO4)(6)(SiO4)(2)(OH)(2). Hemihedrite is isotypic with iranite with substitution of Zn for Cu, and raygrantite with substitution of Cr for S. Structural data from a sample from the Rat Tail claim, Arizona, indicate that hemihedrite is triclinic in space group P (1) over bar, a = 9.4891(7), b = 11.4242(8), c = 10.8155(7) angstrom, alpha = 120.368(2)degrees, ss = 92.017(3)degrees, gamma = 55.857(2)degrees, V = 784.88(9) angstrom(3), Z = 1, consistent with previous investigations. The structure was refined from single-crystal X-ray diffraction data to R-1 = 0.022 for 5705 unique observed reflections, and the ideal chemical formula Pb10Zn(CrO4)(6)(SiO4)(2)(OH)(2) was assumed during the refinement. Electron microprobe analyses of this sample yielded the empirical chemical formula Pb-10.05(Zn0.91Mg0.02)(Sigma) (= 0.93) (Cr5.98S0.01P0.01)(Sigma = 6.00) Si1.97O34 H-2.16 based on 34 O atoms and six (Cr + S + P) per unit cell.NASA, Mars Science Laboratory Investigations [NNX11AP82A]12 month embargo; published online: 01 August 2017.This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Optical coherence tomography to monitor vigabatrin toxicity in children

Copyright © 2016 by the American Association for Pediatric Ophthalmology and Strabismus. Purpose The antiepileptic drug vigabatrin is known to cause permanent loss of vision. Both visual field testing and electroretinogram are used to detect retinal damage. Adult data on optical coherence tomography (OCT) shows that retinal nerve fiber layer (RNFL) thinning may be an early indicator of vigabatrin-induced retinal toxicity. The purpose of this study was to investigate whether OCT can detect early vigabatrin-induced retinal toxicity in children. Methods Pediatric patients (≤18 years of age) requiring vigabatrin for seizure control who were followed at our institution were invited to participate. Patients were examined according to manufacturer guidelines, with most examinations taking place under general anesthesia. RNFL thickness was measured by OCT (Stratus Model 3000, Zeiss) and compared to total cumulative dose of vigabatrin. In most cases, indirect ophthalmoscopy, fundus photography, and electroretinography were also performed. Results OCT and complete dosing data was available for 19 patients. Patients with tuberous sclerosis (TS, n = 12) received higher cumulative doses (mean, 1463 g) than non-TS patients (mean, 351 g, P = 0.044). RNFL thinning was detected in the nasal (P \u3c 0.01), superior (P \u3c 0.01), and inferior (P \u3c 0.05) quadrants in patients with TS, particularly once cumulative dose exceeded 1500 g. Conclusions In our study population of patients with TS, higher cumulative doses of vigabatrin were associated with RNFL thinning in the nasal, superior, and inferior quadrants. These findings were pronounced once cumulative dose exceeded 1500 g. This pattern of RNFL thinning is similar to what has been shown in adult patients taking vigabatrin

Optical coherence tomography to monitor vigabatrin toxicity in children

Copyright © 2016 by the American Association for Pediatric Ophthalmology and Strabismus. Purpose The antiepileptic drug vigabatrin is known to cause permanent loss of vision. Both visual field testing and electroretinogram are used to detect retinal damage. Adult data on optical coherence tomography (OCT) shows that retinal nerve fiber layer (RNFL) thinning may be an early indicator of vigabatrin-induced retinal toxicity. The purpose of this study was to investigate whether OCT can detect early vigabatrin-induced retinal toxicity in children. Methods Pediatric patients (≤18 years of age) requiring vigabatrin for seizure control who were followed at our institution were invited to participate. Patients were examined according to manufacturer guidelines, with most examinations taking place under general anesthesia. RNFL thickness was measured by OCT (Stratus Model 3000, Zeiss) and compared to total cumulative dose of vigabatrin. In most cases, indirect ophthalmoscopy, fundus photography, and electroretinography were also performed. Results OCT and complete dosing data was available for 19 patients. Patients with tuberous sclerosis (TS, n = 12) received higher cumulative doses (mean, 1463 g) than non-TS patients (mean, 351 g, P = 0.044). RNFL thinning was detected in the nasal (P \u3c 0.01), superior (P \u3c 0.01), and inferior (P \u3c 0.05) quadrants in patients with TS, particularly once cumulative dose exceeded 1500 g. Conclusions In our study population of patients with TS, higher cumulative doses of vigabatrin were associated with RNFL thinning in the nasal, superior, and inferior quadrants. These findings were pronounced once cumulative dose exceeded 1500 g. This pattern of RNFL thinning is similar to what has been shown in adult patients taking vigabatrin

Schwannoma in the lower lip mucosa: Unexpected diagnosis

Schwannoma is a benign tumor arising from nerve-sheath Schwann cells. When it affects the mouth, the lips are rarely involved. A MEDLINE search in the English literature from 1969 to 2009 revealed only 17 documented cases of schwannomas of the lip. This report describes the unusual case of a 52-year-old man who developed a schwannoma of the lower lip. Histopathologic examination and immunohistochemical staining studies were performed. Although rare, schwannoma should be considered in the differential diagnosis of any nodule or mass in the oral mucosa. (Quintessence Int 2010; 41: 769-771