Synthesis · Ultrasmall Au(0) Inserted Hollow PCN-222 MOF for the High-Sensitive Detection of Estradiol

8 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: Main

Route 1: Hydrothermal

rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222

Metal precursors200 uL H2AuCl4 aqueous solution (20 mg mL-1)

Linker precursorspreformed HPCN-222

Solvents4 mL DMF; ethanol purification

Atmospherenot specified

Temperature80

Time4

Oxidant / reductantH2AuCl4 used as Au precursor

Work-upSonicated 10 min at room temperature; centrifuged at 10000 rpm for 5 min; purified with ethanol several times (5 x 5 mL).

ActivationGeneral MOF activation: methanol 24 h, acetone 24 h, centrifugation, vacuum drying at 120 C for 24 h.

Scalability contextPostsynthetic metalation of 20 mg preformed MOF in 12 mL Teflon-lined autoclave.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	synthesized HPCN-222	20 mg	rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222
Metal Source	H2AuCl4 aqueous solution	200 uL · 20 mg mL-1	rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222
Solvent	DMF	4 mL	rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222

Partial recipeSource: Both

Route 2: Other

rendered page 2 / article p.4567 · Synthesis of Gold Nanoparticles · Figure S1

Metal precursors2 mL of 1% (w/v) HAuCl4 solution

Solventsaqueous solution

Additives5 mL of 2% (w/v) trisodium citrate

Atmospherenot specified

Oxidant / reductanttrisodium citrate reductant/stabiliser

Work-upReaction continued until colour turned dark red; cooled to room temperature; stored at 4 C.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HAuCl4 solution	2 mL · 1% (w/v)	rendered page 2 / article p.4567 · Synthesis of Gold Nanoparticles · Figure S1
Reductant	trisodium citrate	5 mL · 2% (w/v)	rendered page 2 / article p.4567 · Synthesis of Gold Nanoparticles · Figure S1

Complete recipeSource: Main

Route 3: Hydrothermal

rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222

Metal precursors200 uL H2AuCl4 aqueous solution (20 mg mL-1)

Linker precursorspreformed SPCN-222

Solvents4 mL DMF; ethanol purification

Atmospherenot specified

Temperature80

Time4

Oxidant / reductantH2AuCl4 used as Au precursor

Work-upSonicated 10 min at room temperature; centrifuged at 10000 rpm for 5 min; purified with ethanol several times (5 x 5 mL).

ActivationGeneral MOF activation: methanol 24 h, acetone 24 h, centrifugation, vacuum drying at 120 C for 24 h.

Scalability contextPostsynthetic metalation of 20 mg preformed MOF in 12 mL Teflon-lined autoclave.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	synthesized SPCN-222	20 mg	rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222
Metal Source	H2AuCl4 aqueous solution	200 uL · 20 mg mL-1	rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222
Solvent	DMF	4 mL	rendered page 2 / article p.4567 · Gold Functionalization onto HPCN-222/SPCN-222

Complete recipeSource: Main

Route 4: Drop Cast

rendered page 2 / article p.4567 · Preparation of Electrodes

Solventswater dispersion; distilled water and ethanol cleaning solvents

Atmospheredesiccator drying atmosphere not specified

Work-upGCE polished with 0.3 and 0.05 um Al2O3 slurries, sonicated in distilled water and ethanol for 2 min; 5 uL AuHPCN-222 dispersion drop-cast and dried in a desiccator.

Scalability contextManual drop-cast laboratory electrode fabrication.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	AuHPCN-222 water dispersion	5 uL · 1 mg mL-1	rendered page 2 / article p.4567 · Preparation of Electrodes
Other	glassy carbon electrode	3 mm diameter	rendered page 2 / article p.4567 · Preparation of Electrodes
Other	Al2O3 slurry	0.3 and 0.05 um	rendered page 2 / article p.4567 · Preparation of Electrodes

Complete recipeSource: Both

Route 5: Hydrothermal

rendered page 2 / article p.4567 · Synthesis of Hollow PCN-222; Activation of Synthesized MOFs

Metal precursors10 mg zirconium tetrachloride (ZrCl4)

Linker precursors10 mg meso-tetra(carboxyphenyl)porphyrin (TCPP)

Solvents2 mL dimethylformamide (DMF) containing 200 uL H2O; ethanol wash; methanol and acetone activation solvents

Additives250 mg benzoic acid

Atmospherenot specified

Temperature120

Time8

Work-upCollected and washed several times (7 x 10 mL) with absolute ethanol by centrifugation at 10000 rpm.

ActivationDispersed in methanol for 24 h, then acetone for 24 h; centrifuged; dried under vacuum at 120 C for 24 h.

Scalability contextSmall-batch 12 mL Teflon-lined autoclave synthesis.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconium tetrachloride (ZrCl4)	10 mg	rendered page 2 / article p.4567 · Synthesis of Hollow PCN-222; Activation of Synthesized MOFs
Linker	meso-tetra(carboxyphenyl)porphyrin (TCPP)	10 mg	rendered page 2 / article p.4567 · Synthesis of Hollow PCN-222; Activation of Synthesized MOFs
Additive	benzoic acid	250 mg	rendered page 2 / article p.4567 · Synthesis of Hollow PCN-222; Activation of Synthesized MOFs
Solvent	dimethylformamide (DMF)	2 mL	rendered page 2 / article p.4567 · Synthesis of Hollow PCN-222; Activation of Synthesized MOFs
Solvent	H2O	200 uL	rendered page 2 / article p.4567 · Synthesis of Hollow PCN-222; Activation of Synthesized MOFs

Complete recipeSource: Both

Route 6: Solvothermal

rendered page 2 / article p.4567 · Synthesis of Solid PCN-222

Metal precursors35 mg ZrCl4

Linker precursors25 mg TCPP

Solvents4 mL DEF; DMF wash; acetone soak

Additives1350 mg benzoic acid

Atmospherenot specified

Temperature120

Time48

Work-upIsolated by centrifugation; washed with DMF; dipped in acetone for 24 h by three repeated cycles; dried under vacuum at 120 C for 24 h.

ActivationGeneral MOF activation: methanol 24 h, acetone 24 h, centrifugation, vacuum drying at 120 C for 24 h.

Scalability contextSmall-batch 20 mL Pyrex vial synthesis.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	35 mg	rendered page 2 / article p.4567 · Synthesis of Solid PCN-222
Linker	TCPP	25 mg	rendered page 2 / article p.4567 · Synthesis of Solid PCN-222
Additive	benzoic acid	1350 mg	rendered page 2 / article p.4567 · Synthesis of Solid PCN-222
Solvent	DEF	4 mL	rendered page 2 / article p.4567 · Synthesis of Solid PCN-222

Complete recipeSource: SI

Route 7: Other

rendered page S-4 · Synthesis of [5,10,15,20-Tetrakis(4-methoxycarbonylphenyl)porphyrin] (TCPP)

Linker precursors0.45 g TPPCOOMe

Solvents15 mL THF, 15 mL methanol, 30 mL H2O

Additives1.578 g/15 mL KOH water solution; about 23 mL 1 mol L-1 HCl

Atmospherenot specified

Temperature65 then 70

Time12 h reflux at 65 C; 1 h heating at 70 C; 12 h vacuum drying at 60 C

Work-upTHF and methanol evaporated at 70 C; water phase acidified with HCl; crystals collected by suction filtration, washed with water and vacuum dried at 60 C for 12 h.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TPPCOOMe	0.45 g	rendered page S-4 · Synthesis of [5,10,15,20-Tetrakis(4-methoxycarbonylphenyl)porphyrin] (TCPP)
Base	KOH water solution	1.578 g/15 mL	rendered page S-4 · Synthesis of [5,10,15,20-Tetrakis(4-methoxycarbonylphenyl)porphyrin] (TCPP)
Solvent	THF	15 mL	rendered page S-4 · Synthesis of [5,10,15,20-Tetrakis(4-methoxycarbonylphenyl)porphyrin] (TCPP)
Solvent	methanol	15 mL	rendered page S-4 · Synthesis of [5,10,15,20-Tetrakis(4-methoxycarbonylphenyl)porphyrin] (TCPP)
Acid	HCl	about 23 mL · 1 mol L-1	rendered page S-4 · Synthesis of [5,10,15,20-Tetrakis(4-methoxycarbonylphenyl)porphyrin] (TCPP)

Complete recipeSource: SI

Route 8: Other

rendered page S-3 · Ligand Synthesis

Linker precursorsmethyl 4-formylbenzoate and pyrrole

Solventspropionic acid; methanol, ethyl acetate and tetrahydrofuran washes

Atmospheredarkness; otherwise not specified

Temperature120

Time12

Work-upCooled to room temperature; dark purple crystals collected by suction filtration; washed by methanol, ethyl acetate and THF alternately four times; dried at 70 C for 6 h.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	methyl 4-formylbenzoate	6.9 g	rendered page S-3 · Ligand Synthesis
Linker	pyrrole	3.0 mL	rendered page S-3 · Ligand Synthesis
Solvent	propionic acid	100 mL	rendered page S-3 · Ligand Synthesis