Copper 2 sulphate pentahydrate

Propargyl alcohol, dichlorosilicon (IV) phthalocyanine, copper(II) sulphate pentahydrate, sodium-L-ascorbate, NaN₃, iodine monochloride and all solvents were purchased from Sigma Aldrich (Saint Louis, MO, USA). All reactions were carried out under a dry argon atmosphere unless otherwise noted. Column chromatography for the purification of the crude compounds was performed on silica gel 60. The purity of the products was tested at each step using thin layer chromatography (silica gel F-254 coated TLC plates).

Copper (II) sulphate pentahydrate (Mw = 249.69 g/mol, ≥98%, Sigma Aldrich, St. Louis, MO, USA) and gold (III) chloride hydrate (Mw = 339.79 g/mol, p.a., ≥49%Au, Fluka Analytical, Munich, Germany) were used as precursor salts for Cu-Au NPs; dodecyl sulphate sodium salt (SDS, Mw = 288.38 g/mol, Ph Eur, Merck, Darmstadt, Germany) and ethylene glycol (EG, Mw = 62.07 g/mol, Chimreactiv SRL, Bucharest, Romania) were used as a capping agent and for scavenging of hydroxyl radicals, respectively. These substances were used in the as-received form, without further purifications.
Ultrapure water (18.6 MΩ produced by Simplicity UV Water Purification System, Milli-Q, Merck, Darmstadt, Germany) was used as a solvent.

Plaques with the thickness of 3 mm, produced from PC/ABS compound (LNP Thermocomp compound NX10302; SABIC, Riyadh, Saudi Arabia) by injection moulding, were used as a substrate for selective copper deposition. The Nd:YVO₄ picosecond laser Atlantic (Ekspla) with the pulse duration of 10 ps, pulse repetition rate up to 1 MHz and max average power up to 60 W was used for surface modification of the polymer. The laser beam had the Gaussian intensity distribution. Beam translation over a sample surface was performed by galvanometric scanner excelliSCAN (Scanlab GmbH, Puchheim, Germany). After the laser treatment, PC/ABS samples were washed with 99.8% ethanol (Sigma-Aldrich, Saint Louis, MO, USA) and rinsed with distilled water afterwards. For chemical activation, a highly diluted silver nitrate (Sigma-Aldrich, Saint Louis, MO, USA) solution (~10⁻⁵ M) was used. The activation step was followed by rinsing in distilled water for 1 min. Finally, the electroless copper deposition was performed for 40 min at 30 °C. The copper plating bath contained copper (II) sulphate pentahydrate (0.12 M), formaldehyde (0.3 M), sodium hydroxide (1.2 M), sodium carbonate (0.3 M) and sodium potassium tartrate (0.35) (all from (Sigma-Aldrich, Saint Louis, MO, USA) and had a pH of 12.7. All steps of the SSAIL method are shown in Figure 1.

Dichloromethane 99.9 % (ref.: 32,222), Toluene 99.7 % (ref.: 32,249) and 2-Propanol 99.9 % (ref.: 59,300) were purchased from Honeywell, Germany. Methanol (ref.: 412,722), HPLC-GOLD-Ultragradient grade, was brought from Carlo Erba reagents, Italy. n-Hexane 95 % (ref.: 363,242), high performance chromatography grade, and phenol crystalline (ref: 144852.1211) and n-heptane (ref.: 162062.1611) were provided by PanReacAppliChem, Spain. sulfuric acid reagent (ref: 34,632), orange reagent (ref: 131130.1612), sulfuric acid 95.0–97.0 % (ref: 30,743), bovine serum albumin (BSA) (ref: A9647), sodium hydroxide 98 % (ref: 30,620), sodium carbonate (ref: 222,321), potassium sodium tartrate tetrahydrate (ref: 217,255), copper (II) sulphate pentahydrate (ref: 209,198), Folin&Ciocalteu's phenol reagent (ref: F9252), magnesium sulphate monohydrate (ref: 434,183), anhydrous sodium sulphate (ref: 239,313) and fuming hydrochloric acid (ref: 84,418), high analytical reagent grade, were supplied by Sigma – Aldrich, USA. ASTM® D2887 Reference Gas Oil (ref: 48,873) and chloroform-d (ref: 225,789) provided also by Sigma Aldrich, USA.

All materials were used as received unless otherwise noted. Acetic acid (≥99.7%), cadmium(II) acetate dihydrate (98%), 3-chloroperoxybenzoic acid (m-CPBA, 77% max), copper(II) sulphate pentahydrate (>98%), dichloromethane (≥99.5%), ferrocene (98%), lead(II) acetate trihydrate (>99%), mercury(II) chloride (99%), zinc(II) nitrate hexahydrate (98%) were purchased from Sigma-Aldrich, MeReO₃ from Strem Chemical, toluene (99.98%) from OmniSolv EMD, HCl (1.0 N) from EMD Chemicals, cobalt(II) chloride hexahydrate (97%), nickel(II) chloride hexahydrate from Acros Organics, quartz wool (12 µm diameter), and Ar and H₂(5%)/Ar high purity gases were purchased from Matheson TRIGAS. Triphenylphosphine (Aldrich) was recrystallized from EtOH.

CuSO₄∙5H₂O and the support materials were obtained commercially from Sigma-Aldrich Germany GmbH (Steinheim, Germany) (copper(II) sulphate pentahydrate, CAS: 7758-99-8; silica gel 60, CAS: 112926-00-8; celite^®545, CAS: 68855-54-9; sepiolite powder, CAS: 63800-37-3; vermiculite, CAS: 1318-00-9; molecular sieve zeolite 13X, CAS: 63231-61-6; and charcoal, CAS: 7440-44-0) and used as supplied. Embottled anhydrous ammonia gas (CAS: 7664-41-7, 99.98% NH₃) was obtained from Messer Austria GmbH (Gumpoldskirchen, Austria).