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Additional Supporting Information

Smart photoluminiscent nanohybrids based on CdSe quantum dots capped with multidentate thiolated pH- and thermo-responsive polymers for nanosensing

Marta Liras*, Elena Peinado, Pedro Cañamero, Isabel Quijada-Garrido, Olga García*.

Materials.

The monomers 2-(2-methoxyethoxy)ethyl methacrylate (MEO

2

MA, Aldrich 95%), 1-ethoxy-2-

(2-methoxy-ethoxy)-ethyl methacrylate (MEO

3

MA, Aldrich 95%) and oligo(ethylene glycol) methacrylate with side chains of 8/9 ethylene oxide units (MEO

8

MA, Aldrich 95%) were purified by passing through a neutral column to remove the antioxidant inhibitor. Unless otherwise noted, reagents were commercially available and used without further purification.

1,1,4,7,10,10-Hexamethyltriethylenetetramine (HMTETA, 99%, Aldrich), ethyl 2bromoisobutyrate (EBr i B, 99%, Aldrich), CuCl (99.999%, Aldrich), and the solvent benzonitrile

(99.6%, Panreac) were used as received. For the CdSe nanocrystals, trioctylphosphine oxide

(TOPO, 99%, Aldrich), selenium powder (Aldrich), trioctylphosphine (TOP, 97%, Aldrich), cadmium oxide brown (CdO, 99%, Fluka), 1-tetradecylphosphonic acid (TDPA, 98%, Alfa Aesar) and sodium methoxide (95%, Aldrich) were used as received. Solvents were dried by standard methods or by elution through a Pure Solv Innovative Technology column drying system.

Dialysis was carried out using a regenerate cellulose membrane tubing of MWCO 50kDa from

RC Spectra/Por®7-Spectrum Labs.

1

FIGURE S1 1 H-NMR spectra in CDCl

3

at 25 o C of a sample of P(MEO

8

MA-co-AcSEMA)-7 copolymer (black line), non-hydrolized QD@P(MEO

8

MA-co-AcSEMA)-7 hybrid (red line) and hydrolized P(MEO

8

MA-co-SEMA)-7 hybrid.

FIGURE S2 FTIR-ATR spectra of multidentate dyalized hybrids of QD@P(MEO

3

MA‐co‐AcSEMA)-

7.5 non-hydrolized sample (black line) and QD@P(MEO

2

MA-co-SEMA)-7,5 hydrolyzed one (red line).

2

FIGURE S3 SEC traces of all P(MEO n

MA-co-AcSEMA)-x synthetized copolymers determiner by

GPC in a mobile phase: dimethylformamide (DMF) with LiBr (0.1 wt %) at 0.3 mL min -1 and

70 o C with a differential refractometer detector. Poly(methyl methacrylate) (PMMA) standards were employed for the calibration.

FIGURE S4 TEM images of a) CdSe@P(MEO

2

MA-co-SEMA)-5 and b) CdSe@P(MEO

2

MA-co-

SEMA)-10 above LCST.

3

FIGURE S5 a) Fluorescence emission evolution with pH and temperature for

CdSe@P(MEO

2

MA-co-SEMA)-10 starting from QD of 4.06 nm of diameter. Data obtained in

front face mode.

4

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