Self-assembly of organic multilayers with polar order using zirconium phosphate bonding between layers

Putvinski, T. M.; Schilling, M. L.; Katz, Howard E.; Chidsey, Christopher E. D.; Mujsce, A. M.; Emerson, A. B.

doi:10.1021/la00100a007

Cited by 142 publications

(141 citation statements)

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“…Lead poisoning from extensive lead production and use during Roman times has been suggested as one of the causes of the fall of Rome (5, 9, 10). Smelter emissions from these sources have also been documented as resulting in significant local or even regional lead pollution in Europe, as evidenced, for instance, by studies of peat deposits in Britain (11,12) and lake sediments in southern Sweden (13). We show here that smelter emissions also resulted in significant contamination of the middle troposphere of the remote Arctic.…”

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confidence: 55%

Vertical Aluminophosphate Molecular Sieve Crystals Grown at Inorganic-Organic Interfaces

Feng

Bein

1994

Science

147

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Tubular aluminophosphate molecular sieve crystals were grown at an organic interface with their channels (7 angstroms in cross section) vertical to the substrate. To induce surface nucleation and oriented growth of AIPO4-5 crystals, organophosphonate layers cross-linked with Zr(lV) were assembled on a gold substrate and the modified substrate was immersed in a hydrothermal bath containing reagents for the synthesis of the molecular sieve. Reflection-absorption infrared studies demonstrated the stability of the phosphonate layers under these conditions. Drastic changes in the morphology of the surface-grown crystals from spherical agglomerates to vertical needles to thin tilted needles could be achieved by adjusting the water content of the synthesis bath. Nitrogen sorption in these structures on a piezoelectric device confirmed the presence of zeolitic microporosity. The films obtained in all of our experiments exhibited x-ray diffraction (XRD) patterns corresponding to that of the AFI structure, that is, AIPO4-5. Grazing-angle incidence (1.5°) XRD patterns of the surface-grown AlPO4-5 crystals (Fig. 3) monolayer to its poor thermal stability at acidic pH. The RAIR spectrum shows that MUP monolayers are not stable at 180°C for longer than 2 hours. When the added zirconyl layer was presented to the A1PO4-5 synthesis bath, no crystal growth was observed either, suggesting a lack of electrostatic interactions. The templating agent DABCO also plays an important role. When it was substituted with tripropylamine, no A1PO4-5 growth occurred even though the bulk synthesis proceeded without difficulty. This effect could be related to the dipositive charge on protonated DABCO and associated surface interactions.We were also interested in the nature of the strong interactions between the aluminophosphate nuclei and the phosphonate surface. We performed quenching reactions under bulk synthesis conditions to explore the association between the phophonate surface and zeolite crystal faces. Ethylphosphonic acid (H2PO3CH2CH3) (25 mmol) was added to the bulk AlPO4-5 crystallization mixture after 40 min, and the resulting suspension was placed back into the oven at 180'C for another 8 hours. The SEM and XRD data show that addition of the "quenching agent" blocks further crystal growth. The size and morphology of quenched crystals are similar to those from a regular synthesis stopped after 40 min. These results suggest that the phosphonic acid groups have a strong affinity to the growing faces of the AlPO4-5 crystals. The 10011 faces appear to interact most effectively with the phosphonate surface, thus favoring the vertical orientation of the c axes.We found that the morphology and size of surface-grown A1PO4-5 crystals can be controlled by varying the temperature and the water content of the synthesis bath. We obtained semispherical aggregates at 1500C and lower water content (d = 60). Dilution of the system produces larger hexagonal prismatic

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confidence: 55%

Vertical Aluminophosphate Molecular Sieve Crystals Grown at Inorganic-Organic Interfaces

Feng

Bein

1994

Science

147

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“…(11-Hydroxyundecyl)phosphonic acid was synthesized according to the literature. 22 The synthetic route published in [23] was modified to synthesize (12-carboxydodecyl) phosphonic. Briefly, starting with 12-bromododecanoic acid the carboxylic acid group was protected through the formation of an ethyl ether by refluxing in ethanol with the addition of concentrated sulfuric acid.…”

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confidence: 99%

Phosphonic Acid Monolayers for Binding of Bioactive Molecules to Titanium Surfaces

et al. 2006

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Two different phosphonic acid monolayer films for immobilization of bioactive molecules like the protein BMP-2 on titanium surfaces have been prepared. Monolayers of (11-hydroxyundecyl) phosphonic acid and (12-carboxydodecyl)phosphonic acid molecules were produced by a simple dipping process (the T-BAG method). The terminal functional groups on these monolayers were activated (carbonyl diimidazole for hydroxyl groups and N-hydroxysuccinimide for carboxyl groups) to bind amine containing molecules. The reactivity of the surfaces was investigated using trifluoroethylamine hydrochloride and BMP-2. Each step of the surface modification procedure was characterized by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS).

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“…ventional ionic zirconium bisphosphonate (ZP) interlayer linking chemistry, [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] where the phosphonates are sequestered by metal ion complex formation, we use the side groups of these polymer multilayers in their deprotected form 35,36 as active sites for metal ion uptake (Figure 3). 29 Covalent interlayer attachment is accomplished using adipoyl chloride.…”

Section: Figure 9 Synthetic Route To the Growth Of Covalent Polyureamentioning

confidence: 99%

“…[22][23][24][25][26][27][28] It is often difficult to quantitate the strength of the ZP bond because the equilibrium for bond formation lies far to the right, but indirect estimates indicate that it is ca. 60 kcal/mol or more under favorable conditions.…”

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confidence: 99%

“…The growth of layered assemblies using ionic interlayer linking chemistry is well established. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] While broadly useful, there are some instances where this chemistry is not ideal. To overcome this limitation, we have demonstrated covalent linking chemistry that achieves controlled layer growth using an efficient polymerization reaction (Fig.…”

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confidence: 99%

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Understanding Molecular Interactions within Chemically Selective Layered Polymer Assemblies

Blanchard¹

2009

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Self-assembly of organic multilayers with polar order using zirconium phosphate bonding between layers

Cited by 142 publications

References 0 publications

Vertical Aluminophosphate Molecular Sieve Crystals Grown at Inorganic-Organic Interfaces

Vertical Aluminophosphate Molecular Sieve Crystals Grown at Inorganic-Organic Interfaces

Phosphonic Acid Monolayers for Binding of Bioactive Molecules to Titanium Surfaces

Understanding Molecular Interactions within Chemically Selective Layered Polymer Assemblies

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