18
line between the reaction chamber and the vacuum pump. Each
filter can collect up to 500 mg of CNHs produced before filtering
efficiency is deteriorated.
1. Tetrahydrofuran (THF): THF (100 mL) is placed in a roundbottom flask, followed by the addition of metal sodium flakes
(3–4 flakes of 2 × 2 cm
2
) soaked in oil. Caution: Handle metal
sodium lumps and flakes with special care. Do not wash the
covering oil and contact of metal sodium with atmosphere
moisture must be avoided. Then add 2–3 flakes of benzophenone (1 × 1 cm
2
), acting as indicator. Equip the flask with a
condenser and a collection flask. Boil the mixture gently under
nitrogen atmosphere until the solution turns deep blue in color.
Always check that there is sufficient amount of metal sodium in
the solution. If the mixture has a greenish color, then add 1–2
more flakes of benzophenone. Then collect the dry THF solvent and transfer to the reaction flask under nitrogen.
2. Dichloromethane (DCM): DCM is placed in a round-bottom
flask, followed by the addition of 10–20% powder w/w of
anhydrous calcium chloride. Let the mixture stand overnight.
Equip the system with a condenser and a collection flask. Boil
the mixture gently, under nitrogen atmosphere, for 2 h. Then
collect dry DCM and transfer it to the reaction flask under
nitrogen.
1. Add pristine CNHs (5 mg) and 1,2-dichlorobenzene, oDCB,
(10 mL), in a round-bottom flask under nitrogen atmosphere
and bath-sonicate for 10 min (see Note 1).
2. Dissolve the tert-butoxy carbamate (BOC)-protected aniline
derivative (2.6 mmol) in acetonitrile (5 mL) (see Note 2).
3. Add the solution of the BOC-protected aniline derivative in
the reaction mixture.
4. Add isoamyl nitrite (4.0 mmol) and stir the reaction mixture
at 60 °C for 18 h (see Note 3).
5. After cooling down to room temperature, dilute the reaction
mixture with N,N-dimethylformamide, DMF (30 mL).
6. Filter the reaction mixture over a polytetrafluoroethylene
(PTFE) membrane filter with pore size of 0.2 μm (see Note 4).
7. Wash the solid residue obtained on top of the PTFE filter with
DMF and dichloromethane (50 mL) (see Note 5).
8. Recover the BOC-modified CNHs as powder and store it at
room temperature in the dark.
9. Disperse the BOC-modified CNHs (5 mg) in dry dichloromethane (10 mL).
3.2 Procedures
for Drying Solvents
3.3 Covalent
Incorporation
of Amine Moieties
on CNHs
Anastasios Stergiou and Nikos Tagmatarchis
line between the reaction chamber and the vacuum pump. Each
filter can collect up to 500 mg of CNHs produced before filtering
efficiency is deteriorated.
1. Tetrahydrofuran (THF): THF (100 mL) is placed in a roundbottom flask, followed by the addition of metal sodium flakes
(3–4 flakes of 2 × 2 cm
2
) soaked in oil. Caution: Handle metal
sodium lumps and flakes with special care. Do not wash the
covering oil and contact of metal sodium with atmosphere
moisture must be avoided. Then add 2–3 flakes of benzophenone (1 × 1 cm
2
), acting as indicator. Equip the flask with a
condenser and a collection flask. Boil the mixture gently under
nitrogen atmosphere until the solution turns deep blue in color.
Always check that there is sufficient amount of metal sodium in
the solution. If the mixture has a greenish color, then add 1–2
more flakes of benzophenone. Then collect the dry THF solvent and transfer to the reaction flask under nitrogen.
2. Dichloromethane (DCM): DCM is placed in a round-bottom
flask, followed by the addition of 10–20% powder w/w of
anhydrous calcium chloride. Let the mixture stand overnight.
Equip the system with a condenser and a collection flask. Boil
the mixture gently, under nitrogen atmosphere, for 2 h. Then
collect dry DCM and transfer it to the reaction flask under
nitrogen.
1. Add pristine CNHs (5 mg) and 1,2-dichlorobenzene, oDCB,
(10 mL), in a round-bottom flask under nitrogen atmosphere
and bath-sonicate for 10 min (see Note 1).
2. Dissolve the tert-butoxy carbamate (BOC)-protected aniline
derivative (2.6 mmol) in acetonitrile (5 mL) (see Note 2).
3. Add the solution of the BOC-protected aniline derivative in
the reaction mixture.
4. Add isoamyl nitrite (4.0 mmol) and stir the reaction mixture
at 60 °C for 18 h (see Note 3).
5. After cooling down to room temperature, dilute the reaction
mixture with N,N-dimethylformamide, DMF (30 mL).
6. Filter the reaction mixture over a polytetrafluoroethylene
(PTFE) membrane filter with pore size of 0.2 μm (see Note 4).
7. Wash the solid residue obtained on top of the PTFE filter with
DMF and dichloromethane (50 mL) (see Note 5).
8. Recover the BOC-modified CNHs as powder and store it at
room temperature in the dark.
9. Disperse the BOC-modified CNHs (5 mg) in dry dichloromethane (10 mL).
3.2 Procedures
for Drying Solvents
3.3 Covalent
Incorporation
of Amine Moieties
on CNHs
Anastasios Stergiou and Nikos Tagmatarchis