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50 protocols using hexamethylene diisocyanate

1

Synthesis and Characterization of Polyurethane Biomaterials

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Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and polyethylene glycol (PEG 200) were purchased from Merck (Darmstadt, Germany), acetone from Chimopar SA (Bucharest, Romania) and 1,4-butanediol (BD) from Carl Roth GmbH (Karlsruhe, Germany). Different chlorides, phosphates and carbonates such as NaCl, KCl and MgCl2, Na2HPO4, K2HPO4, KH2PO4 and NaHCO3 were acquired from Chimopar SA (Bucharest, Romania) and used to prepare the simulated body fluid (SBF).
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2

Synthesis and Characterization of Polyester-Urethane Microparticles

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The raw materials used in the synthesis of the polyester-urethane microparticles (PeU_MP) are 1,4-butanediol (BD) from Carl Roth GmbH (Karlsruhe, Germany), the solvent (acetone) from Chimopar S.A. (Bucuresti, Romania), while the others: polyethylene-glycol (PEG, M ≈ 200), the surfactant (Tween®20), isophorone-diisocyanate (IPDI), and hexamethylene-diisocyanate (HMDI) were obtained from Merck (Darmstadt, Germany); polycaprolactone diol (PC), average Mn ~ 530) was achieved from Sigma-Aldrich (St. Louis, MO, USA). All reagents were used as received, without any previous purification. Different salts of Na and K (Cl-, HPO42-, H2PO4- and HCO3-) and HCl 1N were obtained from Chimopar S.A. (Bucuresti, Romania), and they were used to obtain a simulated body fluid, which was used as a proper degradation medium for the drug delivery system and its release profile. The drug release medium used was phosphate buffer pH 7.4, 280 mosm/L, 0.13 M.
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3

Synthesis of Iron-Crosslinked βCD Hydrogels

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All reagents were of analytical-grade. βCD (98%), polyethylene glycol PEG 1500 (99%), and ethylene glycol (99.8%) were products of Sigma-Aldrich (USA). Propylene oxide (99%), sodium hydroxide (99%), sulfuric acid (98%), FeCl3·4H2O (99%), sodium acetate (99%), N,N-dimethyl formamide (99%) and hexamethylene diisocyanate (HMDI, 99%) were obtained from Merck (Germany).
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4

Multi-component Thiol-Isocyanate Synthesis

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Trimethylolpropane tris(3-mercaptopropionate)
(S3, ≥95.0%), pentaerythritol tetrakis(3-mercaptopropionate)
(S4, >95.0%), hexamethylene diisocyanate (HDI, >98.0%), and
dibutyltin
dilaurate (DBTDL, synthesis grade) were obtained from Aldrich. 2,4-Toluene
diisocyanate (TDI, 80% with the remaining 20% being 2,6-toluene diisocyanate)
was sourced from Thermo Scientific. All products were used as received.
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5

Synthesis of Functionalized TiO2 Nanoparticles

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TiO2nanoparticles with a size of <50 nm and 4-tert-butylcyclohexanone (Merck, Germany) were used as purchased. Chloroacetyl chloride and thiourea (Merck, Germany) were used as received. Anhydrous aluminium chloride (Aldrich, Germany) was used as purchased, while hexamethylene diisocyanate, 4,4ʹ-diphenylmethane diisocyanate, 1,4-phenylenediisocyanate (all from Aldrich, 97%), and pyridine (Merck, Germany) were dried using sodium hydroxide pellets for three days. Methanol (absolute, 99.8%), ethanol (absolute, 99.9%), and acetone (Merck, Germany) were used as purchased. Carbon disulfide (Merck, Germany) was dried overnight by calcium chloride, and then distilled under reduced pressure.
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6

Synthesis and Characterization of PEG-based Polymer Composites

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Poly(ethylene glycol) (PEG, average Mn ≈400, 1k, 2k, and 6k g mol–1), pyridine–2,6–dicarboxylic acid, thionyl chloride, m–phenylenediamine, 4,4–methylenedianiline, hexamethylene diisocyanate (HMDI), di–tert–butyl dicarbonate, triethylamine (TEA), 4–(dimethylamino)pyridine (DMAP), poly(acrylic acid) (PAA, average Mv ≈450,000 g mol–1), N‐methyl‐2‐pyrrolidone (NMP), and dibutyltin dilaurate (DBTL) were purchased from Aldrich. Silicon nanopowder (Si, 99%, 30–50 nm) was purchased from NanoAmor. 1 m lithium hexafluorophosphate (LiPF6) in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (1:1 vol%) with 10 wt.% of fluoroethylene carbonate (FEC) was purchased from Welcos Co., Ltd (Korea). Trilayer polypropylene/polyethylene/polypropylene (PP/PE/PP, Celgard2320, thickness: 25 µm) was used as a separator for electrochemical analyses. All other chemicals and solvents were purchased from reliable commercial sources and used as received.
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7

Synthesis of Multifunctional Polymeric Materials

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Poly(ethylene glycol) methacrylate (Mn = 360, PEGMA), 4-vinylbenzyl chloride (90%), sodium azide (99.5%, NaN3), 2-cyano-2-propyl benzodithioate (97%, CPBD), 2-(dimethylamino)ethyl methacrylate (98%, DMAEMA), styrene (99%, St), propargyl ether (98%, dipropargyl ether), azobisisobutyronitrile (98%, AIBN), tin (II) ethyl hexanoate (95%), hexamethylene diisocyanate (99%, HMDI) copper (II) chloride (97%, CuCl2), N,N,N′,N′,N″-pentamethyldiethylenetriamine (99%, PMDETA) and ascorbic acid (reagent grade) were purchased from Sigma Aldrich. PEGMA, DMAEMA, and St were purified with activated alumina (basic, Brockman I); AIBN was recrystallized twice from methanol. All other reagents were used as received.
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8

Characterization of Osteogenic Potential

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All solvents were purchased from Fisher and used as received. Phosphate-buffered saline (PBS) solution, Dulbecco’s modified Eagle’s medium (DMEM), fungizone antimycotic (Fz), penicillin (Pen), streptomycin (Strep) and trypsin-EDTA were supplied by Gibco Life Technologies. Poly(ε-caprolactone) oligomers, hexamethylene diisocyanate, Span® 80, dibutyltin dilaurate, collagenase, paraformaldehyde (PFA), 2-phospho-l-ascorbic acid, β-glycerophosphate, DAPI, alizarin red, Triton X100 and cetylpyridinium chloride were purchased from Sigma-Aldrich. Fetal bovine serum (FBS) was obtained from PANBiotech GmbH.
Human dermal fibroblasts were isolated, using standard procedures, from foreskins of 4-year-old children with informed consent of the parents. Fibroblasts were used for the experiments between passages 4 and 6. hMSC were obtained by plastic adhesion from bone marrow samples collected from hematologically healthy patients undergoing routine total hip replacement surgery. All samples were obtained after informed consent from donors from the Hôpital d’Instruction des Armées Percy (Clamart, France).
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9

Hydrazide-Based Polymer Synthesis and Characterization

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Propanoic acid hydrazide (≥90%), O-ethylhydroxylamine hydrochloride (97%), adipic acid dihydrazide (≥98%,), O,O′-1,3-propanediylbishydroxylamine dihydrochloride (98%), propyl isocyanate, hexamethylenediisocyanate, hydrazine monohydrate, activated charcoal (Norit), sodium periodate (NaIO4) and ethylene glycol were purchased from Sigma-Aldrich. Propyl semicarbazide and N,N′-(hexane-1,6-diyl)bis(hydrazinecarboxamide) (HDCA) (1H NMR structures shown in Figures S1 and S2 in Supplementary Information) were synthesized according to literature [38 (link)]. Sodium alginate was purchased from FMC (Manugel GMB, Lot No. G9402001, Dialysis membrane (Spectra/Por®) with molecular weight cut off (MWCO) 3500 Dalton (Da) from VWR, Netherlands.
Dulbecco’s modified Eagle’s medium (DMEM, high glucose and supplemented with GlutaMAX™ and Sodium Pyruvate), DEME-F12 (low glucose), Dulbecco’s phosphate buffer saline (PBS), fetal bovine serum (FBS), penicillin/streptomycin (P/S), calcein AM, ethidium homodimer, Alexa Fluor® 488 Phalloidin, DAPI and PrestoBlue™ cell viability reagent were purchased from Thermo Fisher Scientific.
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10

Cyclodextrin-Based Drug Delivery System

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γ-cyclodextrin (γ-CD) prepolymer, lightly crosslinked with epichlorohydrin, and octakis (6-deoxy-6-amino) γ-cyclodextrin octahydrochloride were purchased from CycloLab (Budapest, Hungary). Ethylene glycol diglycidyl ether was purchased from Polysciences, Inc. (Warrington, PA). Dextran (15–25k molecular weight), hexamethylene diisocyanate, and cholesterol were purchased from Sigma-Aldrich (St. Louis, MO). Doxorubicin hydrochloride, agarose, bovine serum albumin and all other reagents, solvents, and chemicals were purchased from Thermo Fisher Scientific (Waltham, MA).
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