{"id":5771,"date":"2012-07-18T22:27:17","date_gmt":"2012-07-18T22:27:17","guid":{"rendered":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/?p=5771"},"modified":"2012-07-18T22:27:17","modified_gmt":"2012-07-18T22:27:17","slug":"heterogeneous-crystallization-on-engineered-surfaces","status":"publish","type":"post","link":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/heterogeneous-crystallization-on-engineered-surfaces\/","title":{"rendered":"Heterogeneous Crystallization on Engineered Surfaces"},"content":{"rendered":"

Surfaces play a vital role in heterogeneous crystallization; surface properties such as chemistry, roughness and shape impact nucleation significantly [1<\/a>] <\/sup> [2<\/a>] <\/sup> [3<\/a>] <\/sup> [4<\/a>] <\/sup> [5<\/a>] <\/sup> [6<\/a>] <\/sup> [7<\/a>] <\/sup>. Kim et al<\/em>. applied bi-functional self-assembled-monolayers (SAM) surfaces to crystallize the metastable form \u03b2-glycine as small as several hundred nanometers [8<\/a>] <\/sup> [9<\/a>] <\/sup>. Diao et al. showed that choosing different polymeric surfaces of diverse chemical functionalities and different shapes [10<\/a>] <\/sup> [11<\/a>] <\/sup> [12<\/a>] <\/sup> can strongly influence the nucleation of aspirin. Our group is exploring effects of SAMs and nanopores of varied geometries on polymorphic outcome in crystallization of nano-sized crystals. These studies would lead to better understanding of the fundamental mechanism governing heterogeneous nucleation.<\/p>\n

We designed and fabricated gold islands on silicon substrate using electron beam lithography, photolithography, and electron beam evaporation. The gold islands were coated with hydrophilic thiol SAMs while hydrophobic silane SAMs were cast on the remaining silicon surfaces. The bi-functional SAMs substrate allows formation of droplets and crystallization in droplets on hydrophilic islands. We have produced the second stable \u03b1-form glycine crystals of lateral dimension 286\u00b169 nm, 391\u00b182 nm, 652\u00b1145 nm, and 862\u00b1179 nm. The corresponding heights are 38\u00b118 nm, 73\u00b128 nm, 107\u00b134 nm, and 152\u00b149 nm. We have also proven that polymorphs of micro-sized crystals can be controlled by using different SAMs. Using interference lithography, we designed and fabricated nanopoles of different angles 30\u00b0-150\u00b0. The nanopoles imprint the surfaces of biocompatible polymer, which are then used as heteronucleants during crystallization of active pharmaceutical ingredients. Initial results indicate that in the presence of square nanopores, nucleation occurred twice as fast as in their absence and twenty times faster than in the absence of polymer.\u00a0 Analysis through powder X-ray diffraction and Raman spectroscopy of crystals grown on the films confirmed the presence of the metastable form of mefenamic acid (form II). We are investigating the effect of these geometric sites in promoting nucleation by constructing micro-sized pores on silicon wafers via photolithography. We use the patterned surfaces to monitor crystallization events in situ<\/em> to define the role of the angle during heterogeneous crystallization.<\/p>\n

\"Figure<\/a>

Figure 1. Glycine nano-crystals form on 1-\u00b5m gold islands: Left image is under optical microscope. Right image is under AFM.<\/p><\/div>\n

  1. P. G. Debenedetti,\u00a0Metastable Liquids: Concepts and Principles.<\/cite>\u00a0Princeton Univ. Press, Princeton,\u00a01996. [↩<\/a>] <\/li>
  2. J. W. Mullin, Crystallization<\/cite>\u00a04th\u00a0edn. Butterworth-Heinemann,\u00a02001. [↩<\/a>] <\/li>
  3. D. Turnbull,\u00a0\u201cKinetics of heterogeneous nucleation,\u201d\u00a0J. Chem. Phys.,<\/em>\u00a0vol. 18,\u00a0pp. 198\u2013203, 1950. [↩<\/a>] <\/li>
  4. E. Curcio, V.\u00a0Curcio, G. Di Profio,\u00a0E. Fontananova, and E.\u00a0Drioli, \u201cEnergetics of protein nucleation on rough polymeric surfaces,\u201d\u00a0J. Phys. Chem. B,<\/em>\u00a0vol. 114,\u00a0pp. 13650\u201313655, 2010. [↩<\/a>] <\/li>
  5. A. L. Briseno, S. C. B. Mannsfeld, M. M. Ling, S. Liu, R. J. Tseng, C. Reese, M. E. Roberts, Y. Yang, F. Wudl and Z. Bao,\u00a0\u201cPatterning organic single-crystal transistor arrays,\u201d Nature,<\/em>\u00a0vol. 444,\u00a0pp. 913\u2013917, 2006. [↩<\/a>] <\/li>
  6. M. D. Ward,\u00a0\u201cBulk crystals to surfaces: Combining X-ray diffraction and atomic force microscopy to probe the structure and formation of crystal interfaces,\u201d\u00a0Chem. Rev.,<\/em>\u00a0vol. 101,\u00a0pp. 1697\u20131725, 2001. [↩<\/a>] <\/li>
  7. A. Cacciuto, S.\u00a0Auer, and\u00a0D. Frenkel,\u00a0\u201cOnset of heterogeneous crystal nucleation in colloidal suspensions,\u201d Nature,<\/em>\u00a0vol. 428,\u00a0pp. 404\u2013406, 2004. [↩<\/a>] <\/li>
  8. Kim, A. Centrone, T. A. Hatton, and A. S. Myerson, \u201cPolymorphism control of nanosized glycine crystals on engineered surfaces,\u201d\u00a0Cryst. Eng. Comm., <\/em>vol. <\/em>13, pp. 1127-1131, 2011. [↩<\/a>] <\/li>
  9. K. Kim, I. S. Lee, A. Centrone, T. A. Hatton, and A. S. Myerson, \u201cFormation of nanosized organic molecular crystals on engineered surfaces,\u201d Journal of the American Chemical Society,<\/em>\u00a0vol. 131, pp. 18212-18213, 2009. [↩<\/a>] <\/li>
  10. Y. Diao, A. S. Myerson, T. A. Hatton, and B. L. Trout, \u201cSurface design for controlled crystallization: The role of surface chemistry and nanoscale pores in heterogeneous nucleation,\u201d\u00a0Langmuir,<\/em>\u00a0vol. 27, pp. 5324-5334, 2011. [↩<\/a>] <\/li>
  11. Y. Diao, M. E. Hegelson, Z. A. Siam, P. S. Doyle, A. S. Myerson, T. A. Hatton, and B. L. Trout, \u201cNucleation under soft confinement: Role of polymer-solute interactions,\u201d\u00a0Crystal Growth and Design,<\/em>\u00a0vol. 12, pp. 508-517, 2012. [↩<\/a>] <\/li>
  12. Y. Diao, T. Harada, A. S. Myerson, T. A. Hatton, and B. L. Trout, \u201cThe role of pore shape on surface-induced crystallization,\u201d\u00a0Nature Materials,<\/em>\u00a0vol. 10, pp. 867-871, 2011. [↩<\/a>] <\/li><\/ol>","protected":false},"excerpt":{"rendered":"

    Surfaces play a vital role in heterogeneous crystallization; surface properties such as chemistry, roughness and shape impact nucleation significantly [1]…<\/p>\n","protected":false},"author":1,"featured_media":5772,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":[],"categories":[6083],"tags":[6229,11586],"_links":{"self":[{"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/posts\/5771"}],"collection":[{"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/comments?post=5771"}],"version-history":[{"count":3,"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/posts\/5771\/revisions"}],"predecessor-version":[{"id":6378,"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/posts\/5771\/revisions\/6378"}],"wp:featuredmedia":[{"embeddable":true,"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/media\/5772"}],"wp:attachment":[{"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/media?parent=5771"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/categories?post=5771"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/mtlsites.mit.edu\/annual_reports\/2012\/wp-json\/wp\/v2\/tags?post=5771"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}