A new framework topology in the dehydrated form of zeolite levyne.

0003-004X/13/1112\u20132063$05.00/DOI: http://dx.doi.org/10.2138/am.2013.4583 2063 A new framework topology in the dehydrated form of zeolite levyne Rossella Arletti1, Giovanna Vezzalini2, Simona Quartieri3, Fernando C\ue1mara1 and Matteo Alvaro4,* 1Dipartimento di Scienze della Terra, Universit\ue0 di Torino, via Valperga Caluso n. 35, 10125 Torino, Italy 2Dipartimento di Scienze Chimiche e Geologiche, Universit\ue0 di Modena e Reggio Emilia, via Giuseppe Campi, 183, 41125 Modena, Italy 3Dipartimento di Fisica e Scienze della Terra, Universit\ue0 di Messina, Viale F. Stagno D\u2019Alcontres, 31, 98122 Messina, Italy 4Dipartimento di Scienze della Terra e dell\u2019Ambiente, Universit\ue0 degli Studi di Pavia, Italy; and International Research School of Planetary Sciences, Universit\ue0 G. d\u2019Annunzio, Chieti, Italy A bstract The thermoelastic behavior and structural evolution of a natural levyne-Ca [(Ca7.8 Na2.2K1.1)\u3a311.1 Al20.0Si34.2O108 c551.5H2O; R3m; a = 13.377(4) \uc5, c = 22.870(1) \uc5, V = 3544.1(3) \uc53] were studied by both T-resolved synchrotron X\u2011ray powder diffraction (SR-XRPD) between room temperature and 800 \ub0C, and by conventional-source high-temperature single-crystal X\u2011ray diffraction (SC-XRD). Above 230 \ub0C, water loss and reallocation of extraframework cations induce the straining and consequent breaking of T-O-T bridges in the D6R, with resulting migration of tetrahedral cations to new tetrahedral sites. The new tetrahedra share an edge with the previously occupied tetrahedra. This phenomenon gives rise to a new topology, which coexists to about 40%, with the original one. The new framework consists of a sequence of a novel zeolitic cage (described as a 20-hedron formed by fourteen 6mR and six 4mR) and two consecutive cancrinite cages along [0001]. This topology, which is reported in the database of the hypothetical zeolite structures as 166_2_293, belongs to the ABC-6 family and can be described by the following sequence of 6-rings: ABCBCACAB, to be compared with that of levyne AABCCABBC. In the new topology the extraframework cations are distributed over 3 new sites: one at the center of the 6mR a5 [0001] shared by the two cancrinite cages, one near the center of the 6mR a5 [0001] at the base of the new cage, and a last one in a 6mR window of the new cage. The 8mR bidimensional channel system originally present in levyne is therefore absent in the new topology and hence molecular diffusion is likely to be partially hindered in the dehydrated form. The phase transition is not completely reversible, at least in the short term, as only partial rehydration was demonstrated

Crystal-fluid interactions in open-framework materials at high pressure

The number of experiments on the high-pressure behavior of open-framework materials increased significantly in the last decade [1,2]. The framework topology, the chemical composition and the so-called \u201chost-guest\u201d interactions (between the framework and the extraframework components) were found to significantly influence the response of zeolites to the applied pressure. However, the HP-behavior of zeolites may also be influenced by crystal-fluid interactions when P-transmitting fluids (PTF) are used to generate hydrostatic compression, and in particular when the PTF is \u201cpore-penetrating\u201d. In such a case, the P-induced penetration of PTF molecules into the zeolite structural voids leads to a change of the physical-chemical properties of the studied material, for example inducing a stiffening of the elastic behavior or leading to the hyperconfinement of supramolecular aggregates (in the zeolite channels) with functional properties [3]. In this study, we describe the HP-behavior and the crystal-fluid interactions of two synthetic zeolites with empty channels and cages, i.e. all-silica ferrierite (Si-FER) and ALPO4-5 (AlPO4), compressed with non-penetrating (silicone oil, s.o.) and potentially pore-penetrating PTF. The compression of Si-FER in s.o. evidences the remarkable flexibility of this framework: a first displacive phase transition was observed from the Pmnn to the P121/n1 space group at ~ 0.7 GPa. A second displacive phase transition, involving a significant unit-cell volume contraction, was observed at ~ 1.24 GPa from the P121/n1 to the P21/n11 space group (through an intermediate P-1 structure, \u201ctype-II\u201d transition according to Christy [4]). The high-P P21/n11 polymorph was found to be stable at least up to 3.00(7) GPa, whereas - upon pressure release - the starting Pmnn structure was fully recovered. The three polymorphs were found to share a virtually identical bulk elastic behavior, being their average volume compressibility \u3b2V: 0.051(4), 0.056(9) and 0.055(3) GPa-1, respectively. The compression of Si-FER and ALPO-5 in potentially pore-penetrating PTF showed a lower bulk compressibility, different phase-transition paths (for Si-FER) and diverse atomic-scale deformation mechanisms with respect to the compression in silicone oil, suggesting the onset of significant crystal-fluid interactions, likely due to the P-induced penetration of PTF molecules. In addition, the HPbehavior of Si-FER is strongly influenced by the process kinetics, which was found to control the P-induced molecules intrusion phenomena and, as consequence, the P-induced phase transitions in this material. The authors acknowledge the Italian Ministry of Education, MIUR-Project: \u201cFuturo in Ricerca 2012 - ImPACTRBFR12CLQD\u201d. [1] G.D. Gatta, Y. Lee Mineral. Mag. 2014, 78, 267-291. [2] G. Vezzalini, R. Arletti, S. Quartieri Acta Cryst. 2014, B70, 444-471. [3] M. Santoro, F.A. Gorelli, R. Bini, J. Haines, A. Van der Lee Nat. Commun. 2013, 4, 1557-1563. [4] A.G. Christy Acta Cryst. 1993, B49, 987-996

Rapid recognition of drug-resistance/sensitivity in leukemic cells by Fourier transform infrared microspectroscopy and unsupervised hierarchical cluster analysis.

We tested the ability of Fourier Transform (FT) InfraRed (IR) microspectroscopy (microFTIR) in combination with unsupervised Hierarchical Cluster Analysis (HCA) in identifying drug-resistance/sensitivity in leukemic cells exposed to tyrosine kinase inhibitors (TKIs). Experiments were carried out in a well-established mouse model of human Chronic Myelogenous Leukemia (CML). Mouse-derived pro-B Ba/F3 cells transfected with and stably expressing the human p210(BCR-ABL) drug-sensitive wild-type BCR-ABL or the V299L or T315I p210(BCR-ABL) drug-resistant BCR-ABL mutants were exposed to imatinib-mesylate (IMA) or dasatinib (DAS). MicroFTIR was carried out at the Diamond IR beamline MIRIAM where the mid-IR absorbance spectra of individual Ba/F3 cells were acquired using the high brilliance IR synchrotron radiation (SR) via aperture of 15 7 15 \u3bcm(2) in sizes. A conventional IR source (globar) was used to compare average spectra over 15 cells or more. IR signatures of drug actions were identified by supervised analyses in the spectra of TKI-sensitive cells. Unsupervised HCA applied to selected intervals of wavenumber allowed us to classify the IR patterns of viable (drug-resistant) and apoptotic (drug-sensitive) cells with an accuracy of >95%. The results from microFTIR + HCA analysis were cross-validated with those obtained via immunochemical methods, i.e. immunoblotting and flow cytometry (FC) that resulted directly and significantly correlated. We conclude that this combined microFTIR + HCA method potentially represents a rapid, convenient and robust screening approach to study the impact of drugs in leukemic cells as well as in peripheral blasts from patients in clinical trials with new anti-leukemic drugs

Defective CFTR Expression and Function Are Detectable in Blood Monocytes: Development of a New Blood Test for Cystic Fibrosis

BACKGROUND: Evaluation of cystic fibrosis transmembrane conductance regulator (CFTR) functional activity to assess new therapies and define diagnosis of cystic fibrosis (CF) is cumbersome. It is known that leukocytes express detectable levels of CFTR but the molecule has not been characterized in these cells. In this study we aim at setting up and validating a blood test to evaluate CFTR expression and function in leukocytes. DESCRIPTION: Western blot, PCR, immunofluorescence and cell membrane depolarization analysis by single-cell fluorescence imaging, using the potential-sensitive DiSBAC(2)(3) probe were utilized. Expression of PKA phosphorylated, cell membrane-localized CFTR was detected in non-CF monocytes, being undetectable or present in truncated form in monocytes derived from CF patients presenting with nonsense mutations. CFTR agonist administration induced membrane depolarization in monocytes isolated from non-CF donors (31 subjects) and, to a lesser extent, obligate CFTR heterozygous carriers (HTZ: 15 subjects), but it failed in monocytes from CF patients (44 subjects). We propose an index, which values in CF patients are significantly (p<0.001) lower than in the other two groups. Nasal Potential Difference, measured in selected subjects had concordant results with monocytes assay (Kappa statistic 0.93, 95%CI: 0.80-1.00). RESULTS AND SIGNIFICANCE: CFTR is detectable and is functional in human monocytes. We also showed that CFTR-associated activity can be evaluated in 5 ml of peripheral blood and devise an index potentially applicable for diagnostic purposes and both basic and translational research: from drug development to evaluation of functional outcomes in clinical trials

Dehydration mechanism in brewsterite: single-crystal X-ray diffraction study

The crystal structure of the zeolite brewsterite (space group P2(1)/m, ideal formula (Sr,Ba)(2)Al4Si12O32. 10H(2)O) was studied at different dehydration levels. Six single crystals were kept in evacuated capillaries at different temperatures and for different treatment times, and the X-ray diffraction data were collected at room temperature. The following results were obtained. 1, The structure refinements of the partially dehydrated brewsterite indicate that, as dehydration advances, the cell volume decreases, the channels are contracted and the exchangeable cations spread over several sites, which were occupied in the original structure by water molecules. These results are in agreement with a previous in situ powder diffraction study. 2. The T-O-T bridge breaking and the consequent formation of new 4- and 5-coordinated (Si,Al) polyhedra, already observed in a previous single-crystal dehydration study, are caused by the necessity of the exchangeable cations to be coordinated by the framework oxygens when the water loss is almost complete. This phenomenon was not observed in the in situ powder diffraction experiment, probably owing to the presence of residual water. 3. The effect of the heating time was also evaluated: a longer exposure of the crystal at high temperature in vacuum favors a higher percentage of T-O-T bridge breaking, and induces the complete depopulation of the original Sr site, with a wider spreading of the extra-framework cations. (C) 2000 Elsevier Science B.V. All rights reserved

Calcio-ancylite-(Nd), a new REE-carbonate from Baveno, Italy

Calcio-ancylite-(Nd), a new basic hydrated carbonate of calcium and REE, occurs as pink pine-cone-like crystals in miarolitic cavities of Baveno granite, Italy. Electron microprobe analysis yields the formula: (Nd0.90Co0.64Sm0.33Gd0.28Y0.26Pr0.15La0.14Dy0.07 Tm0.03) Σ=2.80 Ca1.20(CO3)3.98(OH)2.84.1.01H2O (Z = 1). The mineral is monoclinic, Pm11, with a = 4.976(2), b = 8.468(2), c = 7.212(2) Å, α = 90.04(3)°; dmeas > 4.02 and dcalc = 4.08 g/cm3; hardness (Mohs) 4-4.5; biaxial (-). A re-examination of the discredited mineral "weibyeite' from Baveno shows that it is a calcio-ancylite (Ce) with variable REE content

Structural refinement of two barrerites from Alaska

The crystal structure of two samples of barrerite from Kuiu Island (South Alaska) was refined by single crystal methods and compared to that of the type locality. A chemical parameter, besides the structural investigation, is proposed to distinguish between barrerite and stilbite

Scandiobabingonite, a new mineral from Baveno pegmatite, Piedmont, Italy

Scandiobabingtonite, ideally Ca2(Fe2+,Mn)ScSi5O14(OH) is the scandium analogue of babingtonite; it was found in a pegmatitic cavity of the Baveno granite associated with orthoclase, albite, muscovite, stilbite, and fluorite. Its optics are biaxial (+) with 2V = 64(2)°, α = 1.686(2), β = 1.694(3), γ = 1.709(2). D(meas) = 3.24(5) g/cm3, D(calc) = 3.24 g/cm3, and Z = 2. Scandiobabingtonite is colorless or pale gray-green, transparent, with vitreous luster. It occurs as submillimeter sized, short, tabular crystals, slightly elongated on [001], and characterized by the association of forms {010}, {001}, {110}, {110}, and {101}. It occurs also as a thin rim encrusting small crystals of babingtonite. The strongest lines in the X-ray powder pattern are at 2.969 (S), 2.895 (S), 3.14 (mS), and 2.755 (mS) Å. The mineral is triclinic, space group P1, with a = 7.536(2), b = 11.734(2), c = 6.748(2) Å, α = 91.70(2), β = 93.86(2), γ = 104.53(2)°. Scandiobabingtonite is isostructural with babingtonite, with Sc replacing Fe3+ in sixfold coordination, but no substitution of Fe2+ by Sc takes place. Due to the lack of a suitably large crystal of the new species, such a replacement has been confirmed by refining the crystal structure of a Sc-rich babingtonite (final R = 0.047) using single-crystal X-ray diffraction (XRD) data