Synthesis · A mixed-organic ligands Ru(bpy)32+@Zn mMOFs-NH2 nanoreactors integrated co-reaction accelerator and morphologic regulator for the electrochemiluminescence detection of ATP

6 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Electrochemical

3 · 2.2 · Scheme 1C

Metal precursors2 mM HAuCl4 for AuNP film

Linker precursorsATP aptamer; aptamer complementary DNA; Ru(bpy)3(2+)@Zn mMOFs-NH2-CP

SolventsPBS; ethanol and ultrapure water for cleaning

AdditivesTCEP

Atmospherenot reported

Temperature90 hybridisation; 4 AP immobilisation; 37 probe incubation

Time200 s electrodeposition; 10 min hybridisation; overnight AP immobilisation; 90 min ATP incubation; 90 min probe incubation

Substrate orientationglassy carbon electrode working electrode

Oxidant / reductantTCEP reduction of AP; HAuCl4 electrodeposition at -0.2 V

Work-upmodified electrodes gently rinsed with PBS after each step

Activationpolished GCE; AuNP film electrodeposition

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	HAuCl4	2 mM	3 · 2.2 · Scheme 1C
Reductant	TCEP	Not specified	3 · 2.2 · Scheme 1C
Other	AP solution	2 uM	3 · 2.2 · Scheme 1C
Other	Ru(bpy)3(2+)@Zn mMOFs-NH2-CP	1.0 uM	3 · 2.2 · Scheme 1C
Electrolyte	K2S2O8	50 mM for ECL detection	3 · 2.2 · Scheme 1C

Partial recipeSource: Main

Route 2: Other

3 · 2.2 · Scheme 1B

Linker precursorsRu(bpy)3(2+)@Zn mMOFs-NH2; carboxylated DNA capture probe

SolventsPBS

AdditivesEDC; NHS

Atmospherenot reported

Temperature4 storage

Time1 h CP activation; 1.5 h coupling

Work-upcentrifugation; washed with PBS; redissolved in PBS; stored at 4 C

ActivationEDC/NHS activation of CP for 60 min

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CP	200 uL · 1.25 uM	3 · 2.2 · Scheme 1B
Additive	EDC and NHS	200 uL · c/c = 4:1	3 · 2.2 · Scheme 1B
Other	Ru(bpy)3(2+)@Zn mMOFs-NH2	500 uL · 1 mg mL-1	3 · 2.2 · Scheme 1B
Solvent	PBS	Not specified	3 · 2.2 · Scheme 1B

Partial recipeSource: Main

Route 3: Solvothermal

3 · 2.1 · Scheme 1A

Metal precursors1 g Zn(CH3COO)2.2H2O; 20.7 mg Ru(bpy)3Cl2.6H2O

Linker precursors30 mg NH2-BDC; 270 mg BDC

SolventsDMF, total 60 mL; ethanol for washing

Additivestriethylamine, amount not reported

Atmospherenot reported

Temperature130

Time24

Work-upcentrifugal separation; washed thoroughly with DMF and ethanol

Activationnot reported for target sample

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	NH2-BDC	30 mg	3 · 2.1 · Scheme 1A
Linker	BDC	270 mg	3 · 2.1 · Scheme 1A
Solvent	DMF	20 mL + 40 mL	3 · 2.1 · Scheme 1A
Base	triethylamine	not reported	3 · 2.1 · Scheme 1A
Metal Source	Zn(CH3COO)2.2H2O	1 g	3 · 2.1 · Scheme 1A
Other	Ru(bpy)3Cl2.6H2O	20.7 mg · Ru(bpy)3(2+) to NH2-BDC molar ratio 1:6	3 · 2.1 · Scheme 1A

Partial recipeSource: SI

Route 4: Solvothermal

S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs

Metal precursors1 g Zn(CH3COO)2.2H2O; 20.7 mg Ru(bpy)3Cl2.6H2O

Linker precursors300 mg BDC

SolventsDMF, total 60 mL; ethanol for washing

Additivestriethylamine, amount not reported

Atmospherenot reported

Temperature130; drying at 50

Time24 h reaction; 12 h drying

Work-upcentrifugation; washed several times with DMF and ethanol

Activationdried under vacuum at 50 C for 12 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	BDC	300 mg	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs
Solvent	DMF	20 mL + 40 mL	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs
Base	triethylamine	not reported	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs
Metal Source	Zn(CH3COO)2.2H2O	1 g	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs
Other	Ru(bpy)3Cl2.6H2O	20.7 mg	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs

Partial recipeSource: SI

Route 5: Solvothermal

S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs-NH2

Metal precursors1 g Zn(CH3COO)2.2H2O; 20.7 mg Ru(bpy)3Cl2.6H2O

Linker precursors300 mg NH2-BDC

SolventsDMF, total 60 mL; ethanol for washing

Additivestriethylamine, amount not reported

Atmospherenot reported

Temperature130; drying at 50

Time24 h reaction; 12 h drying

Work-upcentrifugation; washed several times with DMF and ethanol

Activationdried under vacuum at 50 C for 12 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	NH2-BDC	300 mg	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs-NH2
Solvent	DMF	20 mL + 40 mL	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs-NH2
Base	triethylamine	not reported	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs-NH2
Metal Source	Zn(CH3COO)2.2H2O	1 g	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs-NH2
Other	Ru(bpy)3Cl2.6H2O	20.7 mg	S5-S6 · 3. Synthesis of Ru(bpy)3(2+)@Zn MOFs-NH2

Partial recipeSource: SI

Route 6: Other

S5 · 3. Synthesis of Zn mMOFs-NH2

Metal precursors1 g Zn(CH3COO)2.2H2O

Linker precursors30 mg NH2-BDC; 270 mg BDC

SolventsDMF, total 60 mL; ethanol for washing

Additivestriethylamine, amount not reported

Atmospherenot reported

Temperatureroom temperature; drying at 50

Time2 h reaction; 12 h drying

Work-upcentrifugation; washed several times with DMF and ethanol

Activationdried under vacuum at 50 C for 12 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	NH2-BDC	30 mg	S5 · 3. Synthesis of Zn mMOFs-NH2
Linker	BDC	270 mg	S5 · 3. Synthesis of Zn mMOFs-NH2
Solvent	DMF	20 mL + 40 mL	S5 · 3. Synthesis of Zn mMOFs-NH2
Base	triethylamine	not reported	S5 · 3. Synthesis of Zn mMOFs-NH2
Metal Source	Zn(CH3COO)2.2H2O	1 g	S5 · 3. Synthesis of Zn mMOFs-NH2