Supplementary Material

Fluorescent Poly(methacryloxy Quinolin) Microparticles Allowing Simultaneous Gold Detection with Additive-Free Photocatalytic Synthesis of Raspberry-Like Gold Nanoparticles and Gold Nanoparticle Decorated Microparticles

Zeynep Dikmen, Roshan Javanifar and Vural Bütün*

Table S1. Amounts of reagents used in MP synthesis Sample

PVA SDS MAQ AIBN EGDMA CHCl3 H2O

MP1 0.20 g - 1.0 g 17 mg 0.80 mL 4.0 mL

12.0 mL

MP2 0.20 g 0.10 g 1.0 g 17 mg 0.80 mL 4.0 mL

36.0 mL

MP3 0.40 g 0.10 g 1.0 g 17 mg 0.80 mL 4.0 mL

36.0 mL

MP4 - 0.10gr 1.0 g 17 mg 0.80 mL 1.0 mL

12.0 mL

MP5 0.20 gr 0.01gr 1.0 g 17 mg 0.80 mL 4.0 mL

12.0 mL

MP6 0.40 gr 0.10 gr 1.0 g 17 mg 0.80 mL 4.0 mL

36.0 mL

N

OH

CC

CH3

O

Cl

N

CTEA

TEA ClO

O

CH2Cl2

Figure S1. Synthetic route of MAQ monomer and 1H NMR spectrum of MAQ monomer (CDCl3)

Figure S2. SEM image of PVA stabilized microparticles with smooth surfaces

Figure S3. DLS measurement of PVA stabilized microparticles (a), PVA/SDS stabilized microparticles (b).

Hydrodynamic radius (Rh) and relative variance (μ2/Γ2) datas obtained

from DLS studies. Use of PVA resulted in polydisperse and larger particles

with 400 nm-10 µm sizes. Polydisperse particle synthesis is a well known

method in usage of PVA for suspension polymerization so PVA and SDS

stalibilizers were used in coalescence. These stabilizers form associations

that lead to an electroesteric stabilization mechanism [3].Most of the

particles were about 900 nm while 400 nm- 4 µm sized particles were also

observed.

Metal content of the samples were determined with ICP-MS analysis. The samples prepared from non-radiative synthesized samples for ICP-MS analysis. Gold amount (12.3 wt%) was much higher than other metal amounts given in Table S2. The reason may be reduction of gold on the surface of MPs. Pt and Pb amounts are also higher than cadmium and silver. This situation can be attributed to affinity of functional groups belonging methacryloxy quinolin to some of these metals.

Figure S4. TEM images of AuNPs decorated MPs synthesized with nonradiative method

Table S2. ICP-MS results of diluted hybride MPs

Analyte Concentration ± SDa (µg.L-1) (n=3) Mean (µg.L-

1)%w

Ag57.94 ±

0.75 60.87 ± 3.68 52.75 ± 4.43 57.18 ± 2.961.7 %

Au341.67 ±

14.27 348.83 ± 7.11 377.32 ± 21.38 355.94 ±14.2612.3 %

Pb99.31 ±

5.68 107.08 ± 2.09 108.58 ± 3.60 104.90 ± 3.795.1 %

Cd 14.79 ± 0.75

15.29 ± 0.25 16.54 ± 1.00 15.54 ± 0.67 0.7 %

Pt101.18 ±

5.07 89.35 ± 6.77 97.82 ± 1.70 96.12 ± 4.515.3 %

aSD (Standart Deviation)

Figure S5. Detachment evolution of raspberry-like AuNPs from the surface

Figure S6. Schematic illustration of photocatalytic AuNPs synthesis on surface of MPs (5 min) (a), in solution (40 min) (b).

Figure S7. Au nanocrystal formation on the surface of PMAQ MPs with UV light excitation for 3 h.

Eventhough there is not a clear explanation on Au nanocrystal formation, it is assumed that the faceted particles are generated by a transformation

mechanism and further growth of the previously formed spherical particles and that they don’t grow independently from the spherical particles by starting their own nucleation and growth process. The presence of different growth mechanisms which act in parallel during the anisotropic growth process, as proposed before, seems to also appropriate to this system [1, 2].

Figure S8. Confocal microscopy images of gold precursor treated PMAQ MPs (exc. λ= 353 nm, emission= 465 nm) excitation for 10 min (a, b, c), excitation for 40 min (d, e, f), excitation for 3h (g, h, i).

Figure S9. Solid state fluorescence spectra (a), UV-vis diffuse reflection spectra of MPs and metal treated MPs (b).

-5

10

25

40

55

70

85

100

0 200 400 600 800

Wei

ght%

Temperature (ΣC)

Figure S10. TGA curves of MPs (MP6-black line) and AuNP decorated MPs (yellow line)

Gold amount in the sample (SEM image given in Figure S10) was determined with thermal analysis, EDX mapping and ICP-MS analysis. 15.03 wt% of the samples was determined as Au with TGA analysis and 17 wt% with EDX mapping, 12 wt% Au with ICP-MS analysis was observed.

Figure S11. XRD pattern of AuNPs decorated MPs with reference peaks for Au

References[1] D. Keller, T.R. Henninen, R. Erni, Formation of gold nanoparticles in a free-standing ionic liquid triggered by heat and electron irradiation, Micron 117 (2019) 16-21.[2] Liao et al., H.G. Liao, Y. Shao, C. Wang, Y. Lin, Y.X. Jiang, S.G. Sun ‘‘TEM study of fivefold twined gold nanocrystal formation mechanism’’ Mater. Lett., 116 (2014), pp. 299-303.[3] J.C. Ramirez, J. Herrera-Ordonez, V.A. Gonzalez, Kinetics of styrene minisuspension polymerization using a mixture PVA-SDS as stabilizer, Polymer 47(10) (2006) 3336-3343.