A Synthetic Analog of the Biomineralization Process: Controlled Crystallization of an Inorganic Phase by a Polymer Matrix

Lin, J. G.; Cates, Elizabeth; Bianconi, Patricia A.

doi:10.1021/ja00090a021

Cited by 79 publications

(48 citation statements)

References 8 publications

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“…The similar concept of controlled crystallization of small molecules in host polymer matrices has been exploited in previous studies. Lin et al found strong binding of cadmium sulfide through ether oxygen atoms of polyethylene oxide (PEO) induce nucleation and resulted crystals of uniform size and morphology [46]. The sulfonic acid induced triazole crystal morphology played significant role in the regulation of proton transport in SPEI/Taz polyelectrolytes.…”

Section: Afm Image Analysismentioning

confidence: 99%

Influence of crystal morphology of 1H-1,2,4-triazole on anhydrous state proton conductivity of sulfonated bisphenol A polyetherimide based polyelectrolytes

Guhathakurta

Min

2009

Polymer

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Section: Afm Image Analysismentioning

confidence: 99%

Influence of crystal morphology of 1H-1,2,4-triazole on anhydrous state proton conductivity of sulfonated bisphenol A polyetherimide based polyelectrolytes

Guhathakurta

Min

2009

Polymer

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“…To put the above energy ranges in perspective, the rocksalt polymorph, that has been experimentally prepared and found to be metastable at atmospheric pressure for three TBSs (ZnO [33], CdS [34] and GaN [35]), is calculated for all TBSs to lie significantly higher in energy than all 26 polymorphs considered (e.g., þ29 kJ=mol AB for ZnO, þ25 kJ=mol AB for CdS, and þ94 kJ=mol AB for GaN).…”

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confidence: 99%

Apparent Scarcity of Low-Density Polymorphs of Inorganic Solids

2010

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For most inorganic solids, very few dense polymorphs and no low-density polymorphs are observed. Taking a wide range of tetrahedrally-coordinated binary solids (e.g., ZnO, GaN) as a prototypical system, we show that the apparent scarcity of low-density polymorphs is not due to significant structural or energetic limitations. Using databases of periodic networks as sources of novel crystal structures, followed by ab initio energy minimization, we predict a dense spectrum of low-density low-energy polymorphs. The diverse range of materials considered indicates that this is likely to be a general phenomenon. DOI: 10.1103/PhysRevLett.104.175503 PACS numbers: 61.50.Ah, 61.66.Fn, 71.15.Nc, 82.75.Fq The structure and properties of inorganic solids are intimately linked to such an extent that even different structures of the same composition (so-called polymorphs) often have widely differing properties and applications. For boron nitride (BN), for example, the soft hexagonal layered polymorph (h-BN) is used as a lubricant, while the cubic polymorph (wurtzite structure) is extremely hard and is employed as an industrial abrasive. Germanium also exhibits more than one polymorph (or more strictly ''allotrope'' for elemental systems) having very different optical properties; with the diamond structured -germanium having an indirect band gap, and the recently synthesized lowdensity clathrate-II structure [1] a direct gap. Evidently, having access to more than one polymorph can significantly extend the range of properties and applications of a particular compound. For the vast majority of inorganic solids, however, typically only three or fewer distinct polymorphs have been prepared experimentally and a similarly small number of hypothetical polymorphs have been proposed. Moreover, where more than one polymorph is known, these extra phases very rarely have a significantly lower density than the most stable polymorph.In stark contrast to this situation, silica (SiO 2 ) has been prepared as more than 40 polymorphs [2], the majority of which are considerably less dense than -quartz; the most stable polymorph under ambient conditions. The rich polymorphism of silica, especially in its low-density forms, allows for fine-tuning of applications (e.g., gas separation membranes) by choosing the best suited polymorph. In addition, 100 000þ hypothetical silica polymorphs have been predicted theoretically as fourfold-connected networks (4CNs) [3][4][5][6][7], a large fraction of which, after accurate theoretical evaluation as silica materials, were found to have comparable energetics to experimentally prepared polymorphs [8,9]. Similarly rich polymorphism has only been further observed for a select group of other inorganic solids, for example, aluminophosphates (AlPO 4 ). A tantalizing hint that there may as yet exist a greater pool of experimentally accessible polymorphs for many other inorganic solids is given by the recent low temperature deposition synthesis of the tetrahedral wurtzite polymorph of LiBr [10] (after previous theor...

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“…A variety of amphiphilic molecules have been shown to direct the crystallization of ionic crystals such as calcite [6,7] and other minerals. [8] Recently, this approach has been extended to the development of methods for controlling the orientation and size of semiconducting particles, a field in which a variety of other methods of controlling nucleation, [9,10] growth, [11,12] and organization [13±17] are being explored. The motivation for these studies is the technological need for tunable bandgap energy and optical properties.…”

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Uniaxial Alignment of Cadmium Sulfide on Polymerized Films: Electron Microscopy and Diffraction Study

Berman

Charych²

1999

Adv. Mater.

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Gaining control over crystal growth continues to be the focus of many modern research efforts, motivated by the possibility of producing particles of well-defined orientation, size, morphology, and structure. One strategy of controlling crystal growth borrows from biological systems, which routinely demonstrate precise control over crystal growth, by utilizing organic macromolecular ªtemplatesº or crystal ªmodifiersºÐa process broadly known as biomineralization.[1] One prominent attribute of biologically controlled crystal nucleation is crystallite co-alignment and the formation of ordered arrays. This is achieved, primarily, by the long-range order of the underlying organic matrix that templates the inorganic deposits.[2] Other characteristics of biomineralized materials include enhanced mechanical strength (due to their composite nature), uniform crystallite size and morphology, and correlation between the morphology of the inorganic constructs and their crystallography.[1±4]Using biological materials as models, simpler organic template structures, such as vesicles, reverse micelles, and surfactant thin films (e.g., Langmuir monolayers or self-assembled monolayers) are also shown to direct the orientation of a variety of crystals grown at their interfaces. [5] Structural relationships between the crystal and the artificial organic ªmatrixº can sometimes be derived or postulated. A variety of amphiphilic molecules have been shown to direct the crystallization of ionic crystals such as calcite [6,7] and other minerals. [8] Recently, this approach has been extended to the development of methods for controlling the orientation and size of semiconducting particles, a field in which a variety of other methods of controlling nucleation, [9,10] growth, [11,12] and organization [13±17] are being explored. The motivation for these studies is the technological need for tunable bandgap energy and optical properties. [18] Particle size and surface doping with organic compounds of the particles influence these properties. [19±22] Surfactant thin films (particularly fatty acids) have been shown to direct the growth of size-quantized semiconductor nanoparticles and nanoparticulate films of CdS or CdSe. [9,23] Independent of these studies, the detailed structural features and the capability of Langmuir monolayers to induce three-dimensional crystal growth at the air±solu-tion interface has been investigated. [24] Precise structural parameters of long-chain acids on subphases containing cadmium ions were measured with grazing-incidence X-ray diffraction (GIXRD), leading to the conclusion that Cd 2+ ions assume a supercell organization that is not directly juxtaposed over the carboxylate lattice.[25] Therefore, attempts to imply lattice match between an assumed structure of the fatty acid monolayer and the templated crystalline cadmium sulfide should be made with caution. It is suggested, therefore, that transfer of structural information between a cadmium salt monolayer and the templated clusters may not be based on simple ...

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A Synthetic Analog of the Biomineralization Process: Controlled Crystallization of an Inorganic Phase by a Polymer Matrix

Cited by 79 publications

References 8 publications

Influence of crystal morphology of 1H-1,2,4-triazole on anhydrous state proton conductivity of sulfonated bisphenol A polyetherimide based polyelectrolytes

Influence of crystal morphology of 1H-1,2,4-triazole on anhydrous state proton conductivity of sulfonated bisphenol A polyetherimide based polyelectrolytes

Apparent Scarcity of Low-Density Polymorphs of Inorganic Solids

Uniaxial Alignment of Cadmium Sulfide on Polymerized Films: Electron Microscopy and Diffraction Study

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