Chloroform d cdcl3

4,4′-thiodiphenol (99%, 4TDP), furfurylamine (≥99%, fa), bisphenol A (≥99%, BA), and paraformaldehyde (95%, PFA) were purchased from Sigma-Aldrich. 3,3’-dihydroxydiphenyl disulfide (95%, 3DPDS) was purchased from abcr GmbH, and 4,4′-dihydroxydiphenyl disulfide (98%, 4DPDS) was purchased from TCI Europe. Phenolic resin (>99.5%, PR), with product name DUREZ 31459 was purchased from SBHPP (Sumitomo Bakelite Co., Ltd.). Hexamethylenetetramine (HMT) was supplied by Ineos Paraform. Toluene (≥99.5%), chloroform (CHCl₃), chloroform-d (CDCl₃) and dimethylformamide (DMF) were supplied from Sigma-Aldrich. All chemicals were used as received without any further purification.

All ¹H-NMR were recorded in chloroform-d (CDCl₃; Sigma-Aldrich, St. Louis, MO, USA) on a 400 MHz Bruker spectrometer using the solvent as the reference. Chemical shifts are given in parts per million (ppm). The ¹³C-NMR was recorded in either chloroform-d or methanol-d₄ (CD₃OD; Sigma-Aldrich, St. Louis, MO, USA), depending on the solubility of the sample.

PLGA-COOH is purchased from lactel polymers, NH₂-PEG-COOH was purchased from Lysan Bio, Inc. PEG-COOH, HO-PEG-OH were purchased from BDH chemicals. 4,4’-dithiodibutyric acid (DBA, 95% purchased from Sigma-Aldrich), Dodecanedioic acid (DDA, >98% purchased from Fluka Chemika), 1,6-hexanediol (16HD, purchased from Sigma Aldrich, Oakville, ON, Canada), 2-dihydroxyethyl disulfide (2HDS, technical grade, purchased from Sigma Aldrich), anhydrous dichloromethane (DCM, 99.8%, purchased from Anachemia, Montreal, QC, Canada), methanol (MeOH, HPLC grade, 99.9%), N-hydroxysuccinimide (NHS, 98%), N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC, commercial grade), N,N-diisopropylethylamine (DIEA, 99%), N,N-dimethylformamide (DMF, 99.9%), dimethylsulfoxide (99.5%), 4′(dimethylamino)pyrimidine, (DMAP, 99%, purchased from Sigma Aldrich), N,N’-dicyclohexycarbodiimide (DIC, 99%, purchased from Alfa Aesar, Wardhill, MA, USA), acetonitrile (can, >99.8%, purchased from Sigma Aldrich), and chloroform-D (CDCl3, purchased from Sigma Aldrich).

LA, pyridinium p-toluenesulfonate (PPTS), and chloroform-d (CDCl₃) were obtained from Sigma (St. Louis, MO, USA). Methylene blue, 2-methoxypropene (MxP), N,N’-dicyclohexylcarbodiimide (DCC), 4-(dimethylamino)pyridine (DMAP), and dimethyl sulfone were purchased from Wako Pure Chemical Co. (Osaka, Japan). All other reagents were of the highest grade available.

Acetonitrile, methanol, ethyl acetate, water, formic acid (LC-MS-grade), Davisil grade 633 amorphous precipitated silica (pore size 60 A, mesh size 200–425 μm), Sephadex LH-20, p-Anisalde hyde, vanillin, sulfuric acid, and the deuterated solvents chloroform-d (CDCl3) and dimethyl sulfoxide-d6 (DMSO-d₆) were obtained from Sigma-Aldrich (Gillingham, UK). Glass columns for column chromatography was purchased from Rotaflo, Fisher Sceintific, Loughborough, UK. TLC-grade silica gel (60H) and TLC silica gel 60 F254 precoated aluminum sheet and the HPLC-grade solvents ethyl acetate, methanol, Acetonitrile, n-hexane, and absolute ethanol were ordered from Merck, Darmstadt, Germany. Alamar blue^® BUF 012B (AbD Serotec^®, Oxford, UK), HMI-9 medium (Invitrogen, Oxford, UK), RPMI-1640 (Lonza, Verviers, Belgium), L-glutamine (Life Tech, Paisley, UK), Penicillin/Streptomycin (Life Tech, Paisley, UK), fetal bovine serum (FBS) (Sigma-Aldrich, Gillingham, UK), U937 cell cultures (obtained from ECACC, Porton Down, Salisbury, UK), 96-well plates (Corning^®, Sigma-Aldrich), and a plate reader (Perkin Elmer, Buckinghamshire, UK) were also obtained.

Thin layer chromatography (TLC) of samples was performed using pre-coated 250 µm thick silica gel 60 PF254+366 aluminum-backed plates, supplied by Sigma-Aldrich (St. Louis, MI, USA). Preparative Thin Layer Chromatography (PTLC) was done using 20 cm × 20 cm glass plates coated with 250 µm- thick silica gel 60 GF254, supplied by Analtech (Newark, DE, USA). Gravity column chromatography (CC) was carried out using silica gel 60, 70–230 mesh (Sigma–Aldrich). Gel filtration (size exclusion chromatography) was performed using Lipophilic Sephadex (Sephadex^® LH-20) with a bead size of 25–100 µm (Sigma-Aldrich).
The compounds were visualized by exposing the TLC plates to shortwave (254 nm) and longwave (375 nm) ultraviolet light coupled with staining with PMA stain (phosphomolybdic acid (12 g) in ethanol (250 mL)).
The melting points of the isolated compounds were acquired on a Reichert micro melting point apparatus. ¹H, ¹³C, ¹H-¹³C HSQC, ¹H-¹³C HMBC, ¹H-¹H COSY, and DEPT-135 NMR experiments were done on a Bruker 600 MHz Avance III Ultrashield Plus Spectrometer at 25 °C. Samples submitted for NMR analysis were dissolved in chloroform-d (CDCl₃) (Sigma Aldrich). All chemical shifts were referenced to the internal standard tetramethylsilane (TMS). Mass spectroscopy was performed by Electrospray Ionization (ESI) in a Bruker MicrOTOF-Q Spectrometer (Billerica, MA, USA).

N-Isopropylacrylamide
(NIPAm,
97%), 2-(dimethyl amino)ethyl methacrylate (DMAEMA, 98%), β-cyclodextrin
(β-CD), 2-bromoisobutyryl bromide (BiBB, 98%), 1-methyl-2-pyrrolidone
(NMP), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA, 97%),
dichloromethane (DCM), copper powder (Cu⁰, 99.7%, 45 cm² g^–1), Rose Bengal (RB, 95%), Crystal violet
(CV, ≥90.0%), diethylenetriaminepentaacetic acid gadolinium(III)
dihydrogen salt (Gd-DTPA, 97%), ethyl 2-bromoisobutyrate (EBiB, 98%),
copper(I) bromide (CuBr, ≥99.95%), copper(II) bromide (CuBr₂, ≥99.995%), potassium fluoride (KF, 99%), basic alumina,
and chloroform-d (CDCl₃) were obtained from Sigma-Aldrich.
(2-Trimethylsiloxy)ethyl methacrylate (HEMA-TMS) was purchased from
Scientific Polymer Products. Tris(2-dimethylaminoethyl) amine (Me₆TREN, ≥99%), gadolinium(III) chloride hexahydrate (GdCl₃·6H₂O, 99%), anisole (99%), and N,N-dimethylformamide (DMF, 99%) were purchased from
Alfa Aesar. HNO₃ (70%, trace metal grade), Silwet L-77,
and H₂O₂ (30%, ACS grade) were purchased from
Fisher Scientific. Dialysis bags with desired molecular weight cutoffs
were purchased from Spectrum lab (Spectra/Por 7). The DMAEMA monomer
was purified by passing it through basic alumina to remove the inhibitor.
Other chemicals were used as-received without further purification.