Preparation of Carboxylate-terminated poly(amidoamine)-type polyhedral

oligosilsesquioxane (POSS)-core dendrimer (POSS-COOH)

All reactions are done under a nitrogen atmosphere.
Synthesis of POSS-NH3+ [2]
Schlenk flask with magnetic stirrer and nitrogen purge
800 mL MeOH placed into flask
100 mL of (3-Aminopropyl)triethoxysilane drop wise into flask
135 mL of 12 M HCl quickly into flask
Close flask once fume production has stopped (takes about ~5 minutes)
Stir mixture under nitrogen until white powder has precipitated (~ 5 10 days)
Wash powder with cold DRY MeOH
Dry under vacuum
Recrystallization using hot MeOH
t-Butyl Ester-Terminated POSS-Core Dendrimer (POSS-CO2But)[1]
Preparation of Amberlite IRA-400 ion exchange resin (30g)
4 x 150 mL rinses with H2O
3 x 150 mL rinses with 1 M NaOH
6 x 150 mL rinses with H2O
6 x 150 mL rinses with MeOH
Chill the resin in -10 C for 2 hours in MeOH before use
Load 15g of resin beads into a 3.5 cm diameter column
Use other 15g to dissolve suspension of neutralized POSS-NH3+ (1.43 g, 1.22 mmol) in
minimum amount of solvent below 0 C
Elution across column produces MeOH solution of neutralized POSS-NH3
70 mL t-butyl acrylate immediately via syringe
Heat mixture for 48 hours at 80 C
Crude POSS-CO2But (oil like substance) purified by size exclusion chromatography
Carboxylic Acid-Terminated POSS-Core Dendrimer (POSS-COOH)
20 mL of HCOOH to 0.144 g of POSS-CO2But
Heat mixture for 24 hours at 80 C
Remove HCOOH by azerotropic distillation with water under reduced pressure
POSS-COOH should be a white powder

Precipitation of Vaterite Composite Particles

Prepare stock solution of POSS-COOH (2.5 x 10-2 mmol) in DI Water
Add dilute NaOH to adjust pH to 11
Prepare 0.1 M CaCl2
Add aqueous NH3 to adjust pH to 8.5
Add 0.5 mL of CaCl2 to 4.5 mL of the stock solution
Stir gently at 30 C for 1 hour
Prepare 0.1 M (NH4)2CO3
Add aqueous NH3 to adjust pH to 10.0
Add 0.5 mL of (NH4)2CO3 solution to mixture
Stir gently at 30 C for 1 hour
Collect precipitated CaCO3 product using a 0.1 um pore sized membrane filter
Wash product with multiple portions of water
Dry at RT with reduced pressure

Fabricating Free-Standing Calcite Thin Films

Sonicate glass slide in acetone for 30 minutes
Rinse with water
Sonicate in wash solution (1% KOH + 39% Water + 60% EtOH) for 30 minutes
Rinse with water
Dry with N2 stream
Immerse glass slide in PDDA solution (5 mg/ mL) for 15 minutes
Rinse with DI Water in three different vials
Dry with gentle air stream
Immerse glass slide in ethanol dispersion of precipitated CaCO3 (4 mg/ mL pH= 11) for 15
minutes
Immerse glass slide in ethanol solution of PDDA (1 mg/ mL) for 15 minutes
Rinse glass slide with ethanol for 1 minute x 3
Dry with gentle air stream

Repeat bolded section sequentially 10 x

Coat top layer with PDDA (vaterite)10/ PDDA
Immerse glass slide in DI Water in 30 C for 5 days (calcite)1
Immerse glass slide in aqueous PDDA (3 mg / 3 mL) for 15 minutes
Rinse with DI Water in three different vials
Dry with N2 stream
Immerse glass slides in ethanol dispersion of CaCO3 for 15 minutes
Immerse glass slide in ethanol solution of PDDA for 15 minutes
Rinse glass slide with ethanol for 1 minutes x 3
Dry with gentle air stream
Repeat bolded section sequentially 10 x
Coat top layer with PDDA (calcite)1/ (vaterite)10/ PDDA
Immerse glass slide in DI water in 30 C for 5 days (calcite)2

References:
[1] Feher, FrankJ, and Kevin D Wyndham. "Amine and ester-substituted silsesquioxanes:
synthesis, characterization and use as a core for starburst dendrimers." Chemical
communications 3 (1998): 323-324.
[2] Gravel, M-C., et al. "Octa (3-chloroammoniumpropyl) octasilsesquioxane." (1999).