Synthesis · Modular conductive MOF-gated field-effect biosensor for sensitive discrimination on the small molecular scale

5 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

main p.2 · 2.4 Fabrication of disposable four-channel extended-gate

Metal precursorsSnO2/ITO-coated glass substrate (commercial/pre-existing coating; not synthesised here)

AdditivesFour-channel PDMS well

AtmosphereO2 plasma for bonding

Temperature60

Time0.083 for 60 C anneal; 90 s plasma

Substrate orientationGlass substrate with SnO2 (70 nm)/ITO (300 nm)

Oxidant / reductantO2 plasma, 70 W, 30 sccm O2 for 90 s

Work-upPDMS channels attached to ITO substrate through plasma bonding; annealed at 60 C for 5 min.

Scalability contextFour-channel disposable extended gate; each PDMS channel surface area 0.5 cm2.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	polydimethylsiloxane (PDMS)	four-channel PDMS; 0.8 cm diameter holes; surface area 0.5 cm2	main p.2 · 2.4 Fabrication of disposable four-channel extended-gate
Oxidant	O2 plasma	70 W, 30 sccm O2, 90 s	main p.2 · 2.4 Fabrication of disposable four-channel extended-gate

Partial recipeSource: Main

Route 2: Other

main p.2 · 2.5 Fabrication

Metal precursorsCo(OAc)2 replacing Cu(OAc)2

Linker precursorsHHTP ligand

SolventsEthanol, by analogy to Cu3HHTP2 route

AdditivesAPTES self-assembled monolayer, by analogy to Cu3HHTP2 route

AtmosphereNot separately reported; similar procedure to Cu3HHTP2

Temperaturesimilar procedure to Cu3HHTP2; 90 C APTES cure in parent route

Timesimilar procedure to Cu3HHTP2; exact cycle count not stated

Substrate orientationSnO2/ITO extended gate electrode

Oxidant / reductantO2 plasma by analogy to Cu3HHTP2 route

Work-upSimilar procedure to Cu3HHTP2 route.

ActivationNot separately specified; similar to Cu3HHTP2 route.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(OAc)2	not specified · not specified; replacement for Cu(OAc)2	main p.2 · 2.5 Fabrication
Linker	HHTP ligand	not specified · not specified; analogous to Cu3HHTP2 route	main p.2 · 2.5 Fabrication
Solvent	ethanol	not separately specified	main p.2 · 2.5 Fabrication

Complete recipeSource: Main

Route 3: Other

main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film

Metal precursorsCu(OAc)2, 0.1 mM in ethanol

Linker precursorsTCPP ligand, 0.01 mM in ethanol

SolventsEthanol

AdditivesAPTES self-assembled monolayer on hydroxylated EG

AtmosphereRoom atmosphere not explicitly controlled; O2 plasma pretreatment

Temperatureroom temperature for SAM/growth; 90 C APTES cure; oven drying temperature not specified

TimeAPTES 1 h; cure 0.25 h; each cycle includes 20 min Cu solution and 40 min TCPP solution; oven dry 24 h

Substrate orientationSnO2/ITO extended gate electrode

Oxidant / reductantO2 plasma hydroxylation at 70 W for 90 s

Work-upAPTES-treated surface washed with ethanol three times and sonicated with ethanol for 1 min; residual reactants washed with pure ethanol each cycle; final films washed with ethanol twice.

ActivationDried in an oven for 1 day.

Scalability context80 uL injections into each EG well; 10 growth cycles for main device films.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	3-aminopropyltriethoxysilane (APTES)	80 uL per EG well · fresh 5 vol% APTES in ethanol	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film
Metal Source	Cu(OAc)2	80 uL per injection · 0.1 mM in ethanol	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film
Linker	TCPP ligand	80 uL per injection · 0.01 mM in ethanol	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film
Solvent	ethanol	washing solvent and solution solvent	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film

Complete recipeSource: Main

Route 4: Other

main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film

Metal precursorsCu(OAc)2, 0.1 mM in ethanol

Linker precursorsHHTP ligand, 0.01 mM in ethanol

SolventsEthanol

AdditivesAPTES self-assembled monolayer on hydroxylated EG

AtmosphereRoom atmosphere not explicitly controlled; O2 plasma pretreatment

Temperatureroom temperature for SAM/growth; 90 C APTES cure; oven drying temperature not specified

TimeAPTES 1 h; cure 0.25 h; each cycle includes 20 min Cu solution and 40 min HHTP solution; oven dry 24 h

Substrate orientationSnO2/ITO extended gate electrode

Oxidant / reductantO2 plasma hydroxylation at 70 W for 90 s

Work-upAPTES-treated surface washed with ethanol three times and sonicated with ethanol for 1 min; residual reactants washed with pure ethanol each cycle; final films washed with ethanol twice.

ActivationDried in an oven for 1 day.

Scalability context80 uL injections into each EG well; 10 growth cycles for main device films.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	3-aminopropyltriethoxysilane (APTES)	80 uL per EG well · fresh 5 vol% APTES in ethanol	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film
Metal Source	Cu(OAc)2	80 uL per injection · 0.1 mM in ethanol	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film
Linker	HHTP ligand	80 uL per injection · 0.01 mM in ethanol	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film
Solvent	ethanol	washing solvent and solution solvent	main p.2 · 2.5 Fabrication of Cu3HHTP2 and Cu2TCPP thin film

Complete recipeSource: Main

Route 5: Other

main p.6 · 3.3 c-MOF thin films as active sensing layer · Fig. 4d; Figs. S14-S17

Metal precursorsCu(OAc)2, 0.1 mM in ethanol

Linker precursorsHHTP ligand, 0.01 mM in ethanol

SolventsEthanol

AdditivesAPTES self-assembled monolayer

AtmosphereRoom atmosphere not explicitly controlled; O2 plasma pretreatment

Temperatureroom temperature for growth; 90 C APTES cure

TimeGrowth cycles varied: 5, 10, 15 and 20 cycles; each cycle uses 20 min metal solution and 40 min ligand solution

Substrate orientationSnO2/ITO extended gate electrode

Oxidant / reductantO2 plasma

Work-upSame washing and drying process as the main Cu3HHTP2 film route.

ActivationOven dried for 1 day.

Scalability contextFilm thickness tuned by number of layer-by-layer growth cycles.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	80 uL per injection · 0.1 mM in ethanol	main p.6 · 3.3 c-MOF thin films as active sensing layer · Fig. 4d; Figs. S14-S17
Linker	HHTP ligand	80 uL per injection · 0.01 mM in ethanol	main p.6 · 3.3 c-MOF thin films as active sensing layer · Fig. 4d; Figs. S14-S17
Additive	APTES	80 uL per EG well · fresh 5 vol% in ethanol	main p.6 · 3.3 c-MOF thin films as active sensing layer · Fig. 4d; Figs. S14-S17
Solvent	ethanol	Not specified	main p.6 · 3.3 c-MOF thin films as active sensing layer · Fig. 4d; Figs. S14-S17