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Crystallographic features and cleavage nanomorphology of chlinochlore: Specific applications

Published online by Cambridge University Press:  01 January 2024

Giovanni Valdrè ,
Daniele Malferrari  and
Maria Franca Brigatti
Giovanni Valdrè
Affiliation:
Dipartimento di Scienze della Terra e Geologico-Ambientali, Università di Bologna, Piazza Di Porta S. Donato 1, I-40127 Bologna, Italy
Daniele Malferrari
Affiliation:
Dipartimento di Scienze della Terra, Università di Modena e Reggio Emilia, Largo S. Eufemia 19, I-41100 Modena, Italy
Maria Franca Brigatti*
Affiliation:
Dipartimento di Scienze della Terra, Università di Modena e Reggio Emilia, Largo S. Eufemia 19, I-41100 Modena, Italy
*
* E-mail address of corresponding author: brigatti@unimore.it
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Abstract

Natural and synthetic micas have been used widely as substrates to study biological systems; but, as in the case of negatively charged DNA, anionic charge repulsion may render micas a less than ideal templating surface for many biological systems. The purpose of this study was to investigate the potential for the chlorite clinoclore, which contains a positively charged interlayer octahedral sheet, to serve as a substrate for DNA adsorption. The relationships between clinochlore cleavage characteristics, in terms of nano-morphology, and surface potential are investigated, as are its average crystal chemistry and topology. That the structural features of clinochlore can be used successfully to condense, order, and self assemble complex biomolecules, such as DNA is also proven.

A natural IIb-4 clinochlore [C1¯\$\end{document} symmetry, unit-cell parameters a = 0.53301(4); b = 0.92511(6); c = 1.4348(1) (nm); α = 90.420(3); β = 97.509(3); γ = 89.996(4) (°)] with chemical composition (Mg1.701Fe0.2452+Ti0.004Al0.998Cr0.0523+)Mg3(Si2.939Al1.015Fe0.0463+)O10(OH7.913F0.087)\$\end{document} was selected. The octahedral sites of the silicate layer (<M(1)−O> = 0.2080 nm and <M(2)−O> = 0.2081 nm) are equal and occupied by Mg, whereas the octahedral sites in the interlayer M(3) and M(4) (<M(3)−O> = 0.2088 nm and <M(4) − O> = 0.1939 nm) show different sizes and are mostly completely occupied by divalent (Mg2+ and Fe2+) and trivalent (Al3+) cations, respectively.

The clinochlore cleaved surface is present in two forms: (1) the stripe type (0.40 nm in height, up to several micrometers long and ranging from some nanometers to a few microns in lateral size); and (2) the triangular type (0.40 nm in height). Both features may result either from interlayer sheets whose cleavage weak directions are related to the different M(3) and M(4) site occupancy, or from weak interlayer bonding along specific directions to the 2:1 layer underneath. The cleaved surface, particularly at the cleaved edges, presents high DNA affinity, which is directly related to an average positive surface and ledge potential.

Keywords

AFMClinochloreCrystal StructureSurface ApplicationsXAS
Type
Article
Information
Clays and Clay Minerals , Volume 57 , Issue 2 , April 2009 , pp. 183 - 193
Copyright
Copyright © The Clay Minerals Society 2009

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References

Antognozzi, M. Szczelkun, M. Round, A.N. and Miles, M.J., 2002 Comparison between shear force and tapping mode AFM — high resolution imaging of DNA Single Molecules 3 105–110 10.1002/1438-5171(200206)3:2/3<105::AID-SIMO105>3.0.CO;2-#.3.0.CO;2-#>CrossRefGoogle Scholar
Antognozzi, M. Wotherspoon, A. Hayes, J.M. Miles, M.J. Szczelkun, M.J. and Valdrè, G., 2006 A chlorite mineral surface actively drives the deposition of DNA molecules in stretched conformations Nanotechnology 17 3897–3902 10.1088/0957-4484/17/15/047.CrossRefGoogle Scholar
Bailey, S.W. and Bailey, S.W., 1988 Chlorites: structures and crystal chemistry Hydrous Phyllosilicates (exclusive of micas) Chantilly, Virginia Mineralogical Society of America 347–403 10.1515/9781501508998-015.CrossRefGoogle Scholar
Bayliss, P., 1975 Nomenclature of the trioctahedral chlorites The Canadian Mineralogist 13 178–180.Google Scholar
Bruker, , 2003 APEX2 Madison, Wisconsin, USA Bruker AXS Inc..Google Scholar
Bruker, , 2003 SAINT-IRIX Madison, Wisconsin, USA Bruker AXS Inc..Google Scholar
Bustamante, C. Vesenka, J. Tang, C.L. Rees, W. Guthold, M. and Keller, R., 1992 Circular DNA molecules imaged in air by scanning force microscopy Biochemistry 31 22–26 10.1021/bi00116a005.CrossRefGoogle ScholarPubMed
Chang, D.-K. and Cheng, S.-F., 1996 On the importance of van der Waals interaction in the groove binding of DNA with ligands: restrained molecular dynamics study International Journal of Biological Macromolecules 19 279–285 10.1016/S0141-8130(96)01138-5.CrossRefGoogle Scholar
Downs, R.T. and Hazen, R.M., 2004 Chiral indices of crystalline surfaces as a measure of enantioselective potential Journal of Molecular Catalysis A: Chemical 216 273–285 10.1016/j.molcata.2004.03.026.CrossRefGoogle Scholar
Giuli, G. Paris, E. Wu, Z.Y. Brigatti, M.F. Cibin, G. Mottana, A. and Marcelli, A., 2001 Experimental and theoretical XANES and EXAFS study of tetra-ferriphlogopite European Journal of Mineralogy 13 1099–1108 10.1127/0935-1221/2001/0013-1099.CrossRefGoogle Scholar
Ha, B.Y. and Liu, A.J., 1997 Counterion-mediated attraction between two like-charged rods Physical Review Letters 79 1289–1292 10.1103/PhysRevLett.79.1289.CrossRefGoogle Scholar
Joshi, M.S. and Paul, B.K., 1977 Surface structures of trigonal bipyramidal faces of natural quartz crystals American Mineralogist 62 122–126.Google Scholar
Joshi, M.S. Kotru, P.N. and Ittiakhen, M.A., 1970 Studying dislocations in quartz by the hydrothermal-etching method Soviet Physics Crystallography 15 83–89.Google Scholar
Joswig, W. and Fuess, H., 1990 Refinement of a one-layer triclinic chlorite Clays and Clay Minerals 38 216–218 10.1346/CCMN.1990.0380215.CrossRefGoogle Scholar
Klinov, D. Dwir, B. Kapon, E. Borovok, N. Molotsky, T. and Kotlyar, A., 2006 Comparative study of atomic force imaging of DNA on graphite and mica surfaces American Institute of Physics Conference Proceedings 859 99–106 10.1063/1.2360592.Google Scholar
Krause, M.O. and Oliver, J.H., 1979 Natural widths of atomic K and L Levels, Kα X-ray lines and several KLL Auger lines Journal of Physical and Chemical Reference Data 8 329–338 10.1063/1.555595.CrossRefGoogle Scholar
Lougear, A. Grodzicki, M. Bertoldi, C. Trautwein, A.X. Steiner, K. and Amthauer, G., 2000 Mössbauer and molecular orbital study of chlorites Physics and Chemistry of Minerals 27 258–269 10.1007/s002690050255.CrossRefGoogle Scholar
Meyrowitz, R., 1970 New semi-microprocedure for determination of ferrous iron in refractory silicate minerals using a sodium metafluoroborate decomposition Analytical Chemistry 42 1110–1113 10.1021/ac60291a021.CrossRefGoogle Scholar
Parsons, R., 1990 Electrical double layer: Recent experimental and theoretical developments Chemical Reviews 90 813–826 10.1021/cr00103a008.CrossRefGoogle Scholar
Sheldrick, G.M., 2005 SADABS Germany Version 2.10. University of Göttingen.Google Scholar
Sheldrick, G.M., 1997 SHELX-97, program for crystal structure determination Germany University of Göttingen.Google Scholar
Sugimura, H. Ishida, Y. Hayashi, K. Takai, O. and Nakagiri, N., 2002 Potential shielding by the surface water layer in Kelvin probe force microscopy Applied Physics Letters 80 1459–1461 10.1063/1.1455145.CrossRefGoogle Scholar
Sushko, M.L. Shluger, A.L. and Rivetti, C., 2006 Simple model for DNA adsorption onto a mica surface in 1:1 and 2:1 electrolyte solution Langmuir 22 7678–7688 10.1021/la060356+.CrossRefGoogle Scholar
Theng, H.H. Dove, P.M. Orme, C.A. and DeYoreo, J.J., 1998 The thermodynamics of calcite growth: A baseline for understanding biomineral formation Science 282 724–727 10.1126/science.282.5389.724.CrossRefGoogle Scholar
Tombolini, F. Brigatti, M.F. Marcelli, A. Cibin, G. Mottana, A. and Giuli, G., 2002 Crystal chemical study by XANES of trioctahedral micas: the most characteristic layer silicates International Journal of Modern Physics B: Condensed Matter Physics, Statistical Physics, Applied Physics 16 1673–1679 10.1142/S0217979202011081.CrossRefGoogle Scholar
Valdrè, G., 2005 AFM observation of agglomerates, ordered structures and filaments after deposition of DNA nucleotides onto layer silicate mineral structures Scanning 27 100–102.Google Scholar
Valdrè, G., 2007 Natural nanoscale surface potential of clinochlore and its ability to align nucleotides and drive DNA conformational change European Journal of Mineralogy 19 309–319 10.1127/0935-1221/2007/0019-1732.CrossRefGoogle Scholar
Valdrè, G. Antognozzi, M. Wotherspoon, A. and Miles, M.J., 2004 Influence of properties of layered silicate minerals on adsorbed DNA surface affinity, self-assembly and nanopatterning Philosophical Magazine Letters 84 539–545 10.1080/09500830512331325082.CrossRefGoogle Scholar
Vesenka, J. Guthold, M. Tang, C.L. Keller, D. Delaine, E. and Bustamante, C., 1992 A substrate preparation for reliable imaging of DNA molecules with the scanning force microscope Ultramicro s copy 42–44 1243–1249 10.1016/0304-3991(92)90430-R.CrossRefGoogle Scholar
Waychunas, G.A., 1987 Synchrotron radiation XANES spectroscopy of titanium in minerals: Effects of titanium bonding distances, titanium valence, and site geometry on absorption edge structure American Mineralogist 72 89–101.Google Scholar
Wilson, A.J.C. and Prince, E., 1999 International Tables for X-ray Crystallography, Volume C: Mathematical, physical and chemical tables 2nd Dordrecht, The Netherlands Kluwer Academic.Google Scholar
Wu, Z. Mottana, A. Marcelli, A. Natoli, C.R. and Paris, E., 1996 Theoretical analysis of X-ray absorption near-edge structure in forsterite, Mg2SiO4-Pbnm, and fayalite, Fe2SiO4-Pbnm, at room temperature and extreme conditions Physics and Chemistry of Minerals 23 193–204 10.1007/BF00220730.CrossRefGoogle Scholar
Wu, Z. Natoli, C.R. Marcelli, A. Paris, E. Seifert, F. Zhang, J. and Liu, T., 2001 Symmetry role on the pre-edge X-ray absorption fine structure at the metal K edge Journal of Synchrotron Radiation 8 215–217 10.1107/S0909049500016502.CrossRefGoogle Scholar