**2. Experimental**

#### *2.1. Fabrication of ZnTPP/D-g-PNIPAM and ZnTPP/D-g-PNIPAM/AuNPs Hybrid Nanosystems*

The procedures of synthesis and structural peculiarities of D-g-PNIPAM copolymers were reported previously. [14,30,31]. Initially, the copolymer with star-like structure containing dextran core with molecular weight *Mw* = 70 × 10<sup>4</sup> g/mol and 15 PNIPAM grafts was synthesized. The molecular parameters of D-g-PNIPAM are as follows: the molecular weight parameters *Mv* = 1.03 × 10<sup>6</sup> g/mol and *Mn* = 0.67 × 10<sup>6</sup> g/mol; *Mv*/*Mn* = 1.52. The reduction of Au ions took place in a mixture of aqueous solutions of the D-g-PNIPAM polymer as a matrix and HAuCl4 as a source of gold. The detailed description of synthesis and characterization of D-g-PNIPAM/Au NPs hybrid macromolecules in aqueous solution has been reported [30,31].

The ZnTPP powder was dissolved in ethanol at 40 ◦C. The obtained stock ZnTPP ethanol solution had concentration of 0.1 g/L. The aqueous stock solutions of D-g-PNIPAM (cD-g-PNIPAM = 1 g/L) and D-g-PNIPAM/AuNPs (cD-g-PNIPAM = 0.8696 g/L and cAu = 0.8529 g/L) were diluted by water at 20 ◦C to obtain solutions with different concentrations. Finally, 0.03 mL of ZnTPP ethanol solution was mixed with 2.97 mL of diluted aqueous solutions of D-g-PNIPAM or D-g-PNIPAM/AuNPs. As a result, we obtained the aqueous solutions of ZnTPP/D-g-PNIPAM or ZnTPP/D-g-PNIPAM/AuNPs nanocomposite contained 0.001 g/L of ZnTPP and various concentrations of D-g-PNIPAM and/or Au.

#### *2.2. Morphology and Size Characterization by TEM and DLS*

The transmitted electron microscopy (TEM) measurements were performed by CM12 (FEI) microscope, and images were acquired using a Megaview SIS camera. Due to the much lower contrast of D-g-PNIPAM macromolecules compared to Au NPs, polymer macromolecules and ZnTPP molecules and aggregates are not visible on the TEM images. Therefore, the size of the studied nanosystems in solution were determined by the dynamic light scattering (DLS) method. The hydrodynamic particle size distribution (PSD) of the nanosystems in water was measured by DLS method on a Zetasizer Nano-ZS90 (Malvern Panalytical) which was equipped with a 5 mW He-Ne laser operating at 633 nm. The scattered light was detected at the angle of 173◦. PSD were obtained from autocorrelation functions calculated by nonnegative truncated singular value decomposition method [54]. The DLS measurements were made in a temperature range including the LCST point. The PSD were measured at various time points (1 min—7 days) after mixing of ZnTPP ethanol solution with water, D-g-PNIPAM and D-g- PNIPAM/AuNPs aqueous solutions.

#### *2.3. Absorption and Fluorescence Spectroscopy*

The absorption spectra were measured with a Cary 60 UV-VIS spectrophotometer (Agilent). The fluorescence (FL) spectra were measured with a Shimadzu RF-6000 spectrofluorophotometer (Shimadzu) with an excitation wavelength at 421 nm. The solution samples were placed in 1 cm × 1 cm × 4 cm quartz cell. The spectra were measured in a temperature range including the LCST point. The absorption and FL measurements were carried out 1 day after mixing of ZnTPP ethanol solution with water, D-g-PNIPAM and D-g-PNIPAM/AuNPs aqueous solutions. The FL anisotropy were measured as *r* = *IVV*−*G IVH IVV*+2*G IVH* , where *Iij* is the FL intensity, *ij* indices denote an orientation of polarizers before and after the sample respectively ( *V*– vertical, *H*– horizontal), *G* = *IHV*/*IHH* is the grating factor.
