Metal-Crown Ether-Porphyrin Decorated Gold Nanoparticles as High Sensitive Raman Ion Probe
Li et al.
2. EXPERIMENT SECTION
2.3. Synthesis of 5,15-biphenyl-10-(4-nitrophenyl)-
20-(4-aminophenyl-benzo-15-crown-5)
Porphyrin
Benzaldehyde, propionic acid, TFA, hydrochloric acid,
DMSO and EtOH were purchased from Sinopharm Chemi-
cal Reagent Co., Ltd. Dichloromethane, Pd (ꢀ3-1-PhC3H4)
(ꢀ5-C5H5), Pd2dba3, XPhos, tin(II) chloride and thiol buty-
rolactone were purchased from Aladdin reagent Co., Ltd.
High-purity water from a Milli-Q Academic water purifi-
cation system (Millipore Corp., Billerica, MA, USA) was
used in all experiments. All reagents and solvents are
of analytical grade and further purification and drying
by standard method were employed. Gold nanoparticles
(GNPs) with diameter between 30∼50 nm were laboratory
To 50 mL three-neck flask was added Pd (ꢀ3-1-PhC3H4ꢃ
(ꢀ5-C5H5) or Pd2dba3 (0.5–4 mol%), XPhos (1–8 mol%, Pd
: L = 1 ꢄ 2) and degassed toluene (2 mL) followed by air
replacementwithargon.Thenthemixturewasstirredat70ꢀC
for 15 min. Then 5,15-biphenyl-10-( 4-nitrophenyl)-20-
(4-bromophenyl)porphyrin (1 mmol), 3-amine-15-crown-5
(1.1 mmol) and NaOt Bu (1.4 mmol) were added succes-
ꢀ
sively and the reaction mixture was kept at 70 ∼ 100 C.
After completion of reaction monitored by TLC, the mixture
was cooled and filtered, the precipitate was purified by col-
umn chromatography(silica gel, Hexanes/EtOAc:1/3 v/v) to
give223 mg (52%)5,15-biphenyl-10-(4-nitrophenyl)-20-(4-
1
synthesized. H-NMR spectra were recorded by a Bruker
AV-500 spectrometer (Bruker, Germany). UV-Vis spectra
were recorded on an UV-3600 spectrometer (Shimadzu,
Japan). SERS spectra were recorded on a Micro-Raman
spectrometer (Ranishaw, England) with laser wavelength at
786 nm. Morphologies of GNPs were observed via Ziess,
Ultra plus FE-SEM with voltage of 5 kV.
ꢀ
aminophenyl-benzo-15-crown-5)porphyrin. mp > 300 C.
1HNMR (500 MHz, DMSO) : ꢁ = 3ꢂ75 (t, J = 6 Hz, 8H),
3.92 (t, J = 7 Hz ,4H), 4.15 (t, J = 6 Hz ,4H), 6.89 (d, J =
7 Hz, 3H), 7.82 (d, J = 7 Hz, 8H), 8.21 (d, J = 6 Hz, 5H),
8.33 (d, J = 9 Hz, 3H), 8.35 (d, J = 9 Hz, 2H), 8.83 (s, 8H).
2.4. Synthesis of 5,15-biphenyl-10-(4-aminophenyl)-
20-(4-aminophenyl-benzo-15-crown-5)
2.1. Synthesis of 5,10,15-Triphenyl-20-
(4-bromophenyl) Porphyrin
Porphyrin
A
mixture of benzaldehyde (3.18 g, 30 mmol),
5,15-biphenyl-10-(4-nitrophenyl)-20-(4-aminophenyl-
benzo-15-crown-5)porphyrin (80 mg, 0.025 mmol) was
dissolved in concentrated hydrochloric acid (10 mL), then
4-brombenzaldehyde (1.84 g, 10 mmol) and freshly dis-
tilled pyrrole (2.68 g, 40.0 mmol) in propionic acid
(140 mL) was refluxed for 3 h. After completion of
IP: 92.85.55.79 On: Sun, 17 Jun 2018 20:50:07
tin(II) chloride (220 mg, 0.975 mmol) was carefully added
Copyright: American Scientific Publishers
the reaction monitored by TLC, the mixture was cooled
under stirring. The final mixture was heated and kept at
65 ꢀC for 1 h under argon followed by being poured
into cold water (100 mL). The aqueous solution was
neutralized by ammonium hydroxide and then extracted
with dichloromethane until colorless. The combined
organic phase was concentrated under reduced pressure
and the resulting residue was purified by alumina column
using dichloromethane for elution. The final product
was recrystallized from methanol (55.3 mg yield 54%),
Delivered by Ingenta
in an ice-water bath and the crude product was fil-
tered and washed thoroughly with methanol (100 mL)
and dichloromethane (30 mL), respectively. The resulting
purple product was dried and purified by column chro-
matography (silica gel, DCM/n-hexane: 1/5 V/V),38–40 then
recrystallization from ethanol gave pure products (0.6 g,
ꢀ
1
13%) mp > 300 C. H NMR (500 MHz, DMSO) : ꢁ =
7ꢂ82 (d, J = 7 Hz, 8H), 8.21 (d, J = 6 Hz, 6H), 8.33
(d, J = 9 Hz, 3H), 8.35 (d, J = 9 Hz, 2H), 8.83 (s, 8H).
ꢀ
1
mp > 300 C. H NMR (500 MHz, DMSO) : ꢁ = 3ꢂ75 (t,
J = 6 Hz, 8H), 3.92 (t, J = 5 Hz, 4H), 4.15 (t, J = 7 Hz,
4H), 6.89 (d, J = 7 Hz, 3H), 7.82 (d, J = 7 Hz, 8H),
8.21 (d, J = 6 Hz, 5H), 8.33 (d, J = 9 Hz, 3H), 8.35
(d, J = 9 Hz, 2H), 8.83 (s, 8H).
2.2. Synthesis of 5,15-biphenyl-10-(4-nitrophenyl)-
20-(4-bromophenyl) Porphyrin
To a solution of 5,10,15-Triphenyl-20-(4-bromophenyl)
porphyrin (160 mg, 0.261 mmol) in TFA (10 mL)
was added sodium nitrite (660 mg, 9.57 mmol).
After stirring at 25 ꢀC for 50 min, the reaction
was quenched with water (100 mL) and the mix-
ture was extracted with dichloromethane (6 × 25 mL).
The organic layers were washed with saturated aqueous
NaHCO3 and then dried by anhydrous Na2SO4. Recrys-
tallization from dichloromethane gave 120 mg (62%)
of 5,15-biphenyl-10-(4-nitrophenyl)-20-(4-bromophenyl)
2.5. Synthesis of 5,15-biphenyl-10-
(4-thiolbutanephenyl)-20-(4-amino-
phenyl-benzo-15-crown-5) Porphyrin
To a three-neck flask was added 5,15-biphenyl-10-(4-
aminophenyl)-20-(4-aminophenyl-benzo-15-crown-5) por-
phyrin (0.3 g, 0.33 mmol) and DMSO (20 mL), then thiol
butyrolactone (0.10 g, 0.33 mmol) was added followed
by air replacement with argon. The reaction mixture was
ꢀ
stirred at 110 C for 3 h and then cooled to room tem-
1
porphyrin. Mp > 300ꢀC. H NMR (500 MHz, DMSO) :
perature. After filtered, the precipitate was purified by col-
umn chromatography (Hexanes/EtOAc) to give the product
(0.21 g, 48%), mp > 300 ꢀC. 1H NMR (500 MHz, DMSO)
ꢁ = 7ꢂ82 (d, J = 7 Hz, 8H), 8.21 (d, J = 6 Hz, 5H), 8.33
(d, J = 9 Hz, 3H), 8.35 (d, J = 9 Hz, 2H), 8.83 (s, 8H).
2564
J. Nanosci. Nanotechnol. 18, 2562–2568, 2018