Synthesis · Modulating the redox states in a 3D conductive MOF for sweat ascorbic acid monitoring

7 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

S3 · Synthesis of FeTHQ

Metal precursorsFeSO4.7H2O (96.9 mg, 0.348 mmol) in 10 mL water

Linker precursorsTHQ (30 mg, 0.174 mmol)

SolventsDMF (5 mL), H2O (5 mL) for THQ; 10 mL aqueous metal solution

Atmospheresealed vial; atmosphere not specified

Temperature80

Time12

Work-upcentrifugation; wash with H2O (20 mL x2) and acetone (20 mL x2)

Activationvacuum oven at 60 C for 1 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeSO4.7H2O	96.9 mg, 0.348 mmol	S3 · Synthesis of FeTHQ
Linker	THQ	30 mg, 0.174 mmol	S3 · Synthesis of FeTHQ
Solvent	DMF	5 mL	S3 · Synthesis of FeTHQ
Solvent	H2O	5 mL + 10 mL + wash	S3 · Synthesis of FeTHQ
Solvent	acetone	20 mL x 2 wash	S3 · Synthesis of FeTHQ

Partial recipeSource: SI

Route 2: Cvd

S3-S4 · Bulky sample preparation

Metal precursorspreformed FeTHQ, 10-fold scaled reactants

Linker precursorspreformed FeTHQ, 10-fold scaled reactants

Atmosphereiodine vapour, sealed container inferred from optimised route

Temperature20

Time6

Oxidant / reductantI2 vapour

Work-uppartitioned into five parts

Scalability contextReactant quantities scaled up 10-fold; five partitions tested.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	FeTHQ and I2 route reagents	10-fold scale	S3-S4 · Bulky sample preparation

Partial recipeSource: SI

Route 3: Other

S5 · Synthesis of I2@FeTHQ/FP

Metal precursorsFeSO4.7H2O via FeTHQ-like in-situ growth on FP

Linker precursorsTHQ via FeTHQ-like in-situ growth on FP

Solventsdeionized water, hydrogen peroxide, ammonia water for FP hydroxylation; FeTHQ synthesis solvents for growth

Additivesfilter paper; H2O2; ammonia water

Atmospherenot specified

Temperature60 for FP hydroxylation; 80 inferred for FeTHQ growth; iodine doping temperature not separately specified

Time1 h hydroxylation; overnight drying; FeTHQ/I2 steps as above

Substrate orientationfilter paper support

Oxidant / reductantiodine vapour for final doping

Work-upwash hydroxylated FP with water, dry overnight; later screen-print with Ag/AgCl conductive ink

Activationroom-temperature overnight drying of FP; FeTHQ/I2 operations as above

Scalability contextDemonstrated 20 x 20 cm2 flexible paper sensor; cut to 1 x 2.5 cm pieces for use.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	filter paper	not specified	S5 · Synthesis of I2@FeTHQ/FP
Oxidant	hydrogen peroxide	volume ratio 5:2:1 mixture	S5 · Synthesis of I2@FeTHQ/FP
Base	ammonia water	volume ratio 5:2:1 mixture	S5 · Synthesis of I2@FeTHQ/FP
Solvent	deionized water	volume ratio 5:2:1 mixture	S5 · Synthesis of I2@FeTHQ/FP
Other	FeTHQ growth reagents	as FeTHQ synthesis	S5 · Synthesis of I2@FeTHQ/FP
Oxidant	I2 vapour	as I2@FeTHQ synthesis	S5 · Synthesis of I2@FeTHQ/FP
Additive	commercial Ag/AgCl conductive ink	screen printed on sensor slices · 72/28	S5 · Synthesis of I2@FeTHQ/FP

Complete recipeSource: SI

Route 4: Other

S4 · Physical grinding method

Metal precursorsfreshly prepared FeTHQ

Linker precursorsfreshly prepared FeTHQ

Atmosphereambient; not specified

Oxidant / reductantsolid iodine powder 0.15, 0.75, 1.5, or 2.5 mg

Work-upphysical mixing and grinding

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	freshly prepared FeTHQ	10 mg	S4 · Physical grinding method
Oxidant	solid iodine powder	0.15, 0.75, 1.5, 2.5 mg	S4 · Physical grinding method

Complete recipeSource: SI

Route 5: Drop Cast

S5 · Preparation of working electrode

Metal precursorsfinely ground I2@FeTHQ

Linker precursorsfinely ground I2@FeTHQ

Solventsethanol 600 uL; H2O 370 uL

AdditivesNafion 30 uL

Atmosphereambient drying; not otherwise specified

Temperature80

Time12 drying

Substrate orientationITO glass substrate, 1 cm x 2 cm working electrode

Work-upsonicate ink 30 min, coat/drop-cast 45 uL on ITO

Activationdry at 80 C for 12 h

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	I2@FeTHQ	5 mg	S5 · Preparation of working electrode
Solvent	ethanol	600 uL	S5 · Preparation of working electrode
Solvent	H2O	370 uL	S5 · Preparation of working electrode
Additive	Nafion	30 uL · 5 wt% in standard protocol	S5 · Preparation of working electrode

Complete recipeSource: Both

Route 6: Cvd

S3 · Synthesis of I2@FeTHQ

Metal precursorspreformed FeTHQ

Linker precursorspreformed FeTHQ

Atmosphereiodine vapour in tightly sealed brown glass bottle

Temperature20 (optimised; also 40 and 60 studied)

Time6 (optimised; 1, 3, 6, 9 and figure-labelled 12 h studied)

Oxidant / reductantI2 powder (1.5 g) as vapour-phase redox dopant/guest

Work-upsample removed after reaction time; no workup specified for optimised powder

Scalability contextOptimisation showed 20 C for 6 h was selected; bulk 10-fold preparation also tested.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	freshly prepared FeTHQ	10 mg	S3 · Synthesis of I2@FeTHQ
Oxidant	iodine (I2) powder	1.5 g	S3 · Synthesis of I2@FeTHQ

Partial recipeSource: SI

Route 7: Other

S4 · Chemical species studies

Metal precursorsFeTHQ

Linker precursorsFeTHQ

Solventsaqueous solutions for salt/H2O2 treatments

AdditivesNaCl, NaBr, KI, NaNO3, NaIO4, H2O2, Br2, O3

Atmospheresealed vapour/gas container for Br2 and O3; solution at room temperature for salts/H2O2

Temperatureroom temperature for solution treatments; iodine-like conditions for Br2/O3

Time6 for solution treatments; similar to iodine treatment for Br2/O3

Oxidant / reductantBr2, NaIO4, H2O2, O3 as oxidative reagents; NaCl, NaBr, NaNO3, KI as non-oxidative controls

Work-upwashed with deionized water and dried under vacuum at 60 C

Activationvacuum drying at 60 C

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	FeTHQ	10 mg	S4 · Chemical species studies
Oxidant	NaIO4, NaCl, NaBr, KI, NaNO3	5 mL solution · 10 wt%	S4 · Chemical species studies
Oxidant	H2O2	5 mL solution inferred · 0.1%	S4 · Chemical species studies
Oxidant	Br2 vapor or O3 gas	not specified	S4 · Chemical species studies