Hydrochloric acid 37

p-type
Si wafers with 0.00055–0.001
Ω cm resistivity, (100)-oriented were purchased from Siltronix
(France). Hydrofluoric acid (HF) (48%, AR grade) was purchased from
Scharlau (Australia). Potassium ferrocyanide (K₄[Fe(CN)₆]), potassium ferricyanide (K₃[Fe(CN)₆]), undecylenic acid, N-hydroxysuccinimide (NHS), N(3-dimethylaminopropyl) N-ethylcarbodiimide
hydrochloride (EDC), phosphate-buffered saline (PBS) tablets, 2-(N-morpholino)-ethanesulfonic acid (MES), (3-aminopropyl)
triethoxysilane (APTES), (3-glycidylxypropyl) trimethoxysilane (GPTMS),
sodium chloride, tris(hydroxymethyl)aminomethane, hydrochloric acid
(37%), and fluorescein isothiocyanate (FITC) were purchased from Sigma-Aldrich
(Australia). Cyanine5 amine (Cy5-NH₂) was purchased from
Luminoprobe (USA). The acetylene gas cylinder (1 m³ industrial
grade, dissolved) was purchased from BOC (Australia). All the DNA
strands were purchased from Integrated DNA Technologies, Inc. The
sequence of the amino-modified ssDNA capture probe was 5′-/5AmMC6/GTC
CAC GCC GTA AAC GAT GTC GAC TTG G-3′. The amino-modified nonspecific
ssDNA capture probe was 5′-/5AmMC6/CAC AAA TTC GGT TCT ACA
GGG TA-3′. The sequence of the target ssDNA was 5′-CCA
AGT CGA CAT CGT TTA CGG CGT GGA C-3′.

The solvents used were commercial ethanol 95% v/v for the preparation of the extracts, methanol HPLC grade (VWR Chemicals, Radnor, PA, USA) and acetonitrile HPLC grade (Merck KGaA, Darmstadt, Germany) for the high-performance liquid chromatography (HPLC) analyses. Other reagents were phloroglucinol, L-ascorbic acid, sodium acetate, Folin-Ciocalteu reagent, vanillin, hydrochloric acid 37%, formic acid 98%, phosphoric acid 85% (Sigma Aldrich Co., St. Louis, MO, USA), sodium carbonate, acetic acid 100% (Merck KGaA, Darmstadt, Germany). The standards used for the determination of the response factors for the HPLC analysis (phloroglucinolysis method) were (+)-catechin, (−)-epicatechin, (−)-epicatechin-3-O-gallate (Sigma Aldrich Co., St. Louis, MO, USA). C-18 solid phase extraction cartridges (Sep-Pak tC18 1g, Waters, Milford, MA, USA) were used. Ultrapure water from a Milli-Q gradient A10 instrument system (Millipore Corporation, Billerica, MA, USA) was used throughout the experiment.

Lymphoprep™ gradient was purchased from Progen (Heidelberg, Germany). RPMI 1640 medium, fetal calf serum, trypsin 10x (25 mg/mL), trypsin-EDTA 10x (5 mg/mL trypsin and 2.2 mg/mL EDTA), and phosphate buffered saline (PBS, without Ca and Mg) were from PAA Laboratories Gmbh (Coelbe, Germany). L-Glutamine, penicillin, and streptomycin were from Invitrogen (Karlsruhe, Germany). Camptothecin was from Tocris (Eching, Germany); Triton-X 100, milk powder, and N,N,N′,N′-tetramethyl-1-,2-diaminomethane (Temed) were from Carl Roth (Karlsruhe, Germany); DMSO, lipopolysaccharide (LPS), phorbol, 12-myristate 13-acetate, CFSE, ammonium persulfate, bovine serum albumin, ethanol absolute, hydrochloric acid (37%), leupeptin hemisulfate, p-coumaric acid, pepstatin A, Ponceau S, trypan blue, Tween 20, and ionomycin were from Sigma-Aldrich (Taufkirchen, Germany).
Antibodies against p-38 (Thr180/Tyr182), p-ERK1/2 (Thr202/Tyr204), p-JNK, and p-c-Jun (Ser73) and the horseradish peroxidase- (HRP-) labelled secondary antibodies, anti-mouse and anti-rabbit, were from Cell Signaling Technology (Boston, USA); anti-human COX-2 was from R&D Systems (Wiesbaden, Germany); anti-human COX-1 and anti-human 5-LOX (mouse monoclonal, clone 33) were from Santa Cruz Biotechnology (Heidelberg, Germany); and mAb against β-actin was from Sigma-Aldrich (Taufkirchen, Germany).

Ciprofloxacin, Terbium(III) oxide, hydrochloric acid (37%), poly(ethylene oxide) (PEO) (average Mv 600,000), human serum (from human male AB plasma), and spermine were purchased from Sigma-Aldrich (Korea). Deionized water purified with Millipore was used throughout the whole experiment. Terbium(III) oxide (0.1 mmol) was dissolved in dilute hydrochloric acid at 90°C for 1h. The mixture was evaporated using a rotary evaporator and then dried at 50°C in a vacuum oven. Finally, the final product was dissolved in 10 ml of H₂O to make Tb³⁺ precursor solution.

Collagen has both a reducing and a stabilizing role in Au NP formation. A stock solution of gold salt was prepared by dissolving 1 g hydrogen tetrachloroaurate (III) hydrate (99.9% metal basis, Alfa Aesar, Karlsruhe, Germany) in 50 mL ultrapure water. A solution of collagen was prepared by mixing 10 mL ultrapure water with 0.02 g of collagen from bovine Achilles tendon (Sigma-Aldrich, Darmstadt, Germany) in the presence of 500 µL hydrochloric acid 37% (Sigma-Aldrich). One-point-five milliliters of collagen solution (0.02 g collagen in 10 mL water) was mixed with 0.5 mL ethanol. Subsequently, 90 mL of ultrapure water were added to the collagen-ethanol solution, which was then mixed with 1 mL of gold salt solution. The mixture was heated and stirred until boiling. When it started to boil, the solution was neutralized by quickly adding 2 mL of 1% Sodium hydroxide, and the heating was turned off. Instantly, the solution turned into a wine-red color, and its pH was 7. Sodium hydroxide (Sigma-Aldrich), ethanol and sodium chloride (Merck, Darmstadt, Germany) were of analytical grade. All solutions were prepared in ultrapure water with a resistance higher than 18 MΩ (Direct-Q 3 UV, Merck Millipore, Darmstadt, Germany). The protocol is given in full detail in the Supporting Information. The Raman spectrum of collagen-coated Au NPs is presented in Figure S1.

Tetraethylortosilicate (TEOS), triethanolamine (TEAH₃), sodium hydroxide (NaOH), N-cetyltrimethylammonium bromide (CTAB), Pluronic 123 (P123), hydrochloric acid 37% (HCl), aqueous ammonia 28% (NH₄OH), trifluoroacetic acid (TFA), (3-aminopropyl)triethoxysilane (APTES), N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (EDC), rhodamine B (RhB), oleic acid (OA) and all the chemicals for the digestive fluids (bile salts included) were provided by Sigma (Sigma-Aldrich Química S.L., Madrid, Spain). Ethanol (extra pure), dimethyl sulfoxide (DMSO), acetonitrile (ACN) and acetone were purchased from Scharlab (Scharlab S.L., Barcelona, Spain). 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) was provided by ThermoFisher (Thermo Fisher Scientific Inc., Madrid, Spain). Phosphate Buffer Solution (PBS), Dulbecco’s Modified Eagle’s Medium (DMEM), Fetal Bovine Serum (FBS), penicillin/streptomycin antibiotic (P/S), non-essential amino acids and all the needed mediums for cell culture were provided by Labclinics (Labclinics S.A., Barcelona, Spain).