1 6 hexanediol diacrylate

1,6-Hexanediol diacrylate (HDDA), phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure 819), 1-phenylazo-2-naphthol (Sudan I), and 3-(trimethoxysilyl) propyl methacrylate (TMSPM) were purchased from Sigma Aldrich. NaOH, methanol, and isopropanol were obtained from Merck.

A fluid with a small yield stress property is prepared from a monomer HDDA (1, 6 Hexanediol diacrylate, by Sigma Aldrich) added with alumina (Almatis, CT3000, Mean particle size 0.5 microns, refractive index 1.7), 4wt.% Benzoin ethyl ether (BEE, as photo-initiator) and 2.5 wt.% Phosphate ester (PE, as surfactant). Alumina powder is incrementally added while the ceria stabilized zirconia balls were used to homogenize the fluid on a pot mill. The prepared fluid is a photo-resist ceramic suspension with viscosity, surface tension, and yield stress values dependent on the volume fraction of alumina added. Modular compact rheometer (Anton paar Physica MCR301) and Wilhelmy plate method was used to measure the fluid viscosity-profile and surface tension, respectively.

All solvents were of analytic or HPLC grade and purchased from Sigma Aldrich or Fisher Scientific unless otherwise stated. All deuterated solvents were purchased from Sigma Aldrich. 1,6-Hexanediol diacrylate, 4-amino-1-butanol and γ-poly(l-glutamic acid) were purchased from Sigma-Aldrich. α-Poly(l-glutamic acid) 3.5 kDa and 18.5 kDa were purchased from Iris BioTech GmbH.

For membrane preparation, n-butyl acrylate (nBA) from Merck, 2-hydroxyethyl methacrylate (HEMA), 1,6-hexanediol diacrylate (HDDA), 2-dimethoxy-2-phenyl acetophenone (DMPP), sodium tetrakis [3,5-bis(trifluoromethyl) phenyl] borate (NaTFPB), potassium tetrakis-(4-chlorophenyl)borate (KTClPB) and potassium ionophore I from Sigma Aldrich (St. Louis, MO, USA) were used. The solvents and the metal salts included potassium chloride, copper (II) chloride dihydrate, calcium chloride and sodium chloride from Sigma Aldrich, cadmium chloride and aluminium chloride from Acros, mercury chloride from Fisher, zinc chloride and nickel chloride hexahydrate from Merck, iron(III) chloride from R&M Chemicals, tetrahydrofuran from SYSTERM and magnesium nitrate from Bendosan. Lithium acetate dihydrate from Acros, tris(hydroxymethyl)aminomethane hydrochloride, Tris-HCl, and silver chloride from Sigma Aldrich and bacto agar from Difco used for conventional reference electrode preparation. The chemicals used were the aluminium ionophore 1,1′-[(methylazanediyl)bis(ethane-2,1-diyl)]bis[3-(naphthalen-1-yl)thiourea], ACH synthesized and purified according to Kook et al. [34 (link)] and Abosadiya et al. [35 ]. All analytical grade chemicals were used as obtained. Deionized water (specific resistance, 18.0MΩ cm) was utilized throughout this work.

Triton X-100, tetraethyl orthosilicate (TEOS), 3-aminopropyltriethoxysilane (APTS), 1,6 hexanediol diacrylate, piperazine, sodium alginate, chlorhexidine diacetate, sodium acetate trihydrate, phosphate buffer solution (PBS) tablets, glutaraldehyde, Alizarin Red S, Calcein-AM, propidium iodide and “In Vitro Toxicology Assay Kit- LDH based” were purchased from Sigma-Aldrich, UK.
Cyclohexane, n-hexanol, ammonium hydroxide (35%), dichloromethane (DCM), diethyl ether, dimethyl-sulfoxide (DMSO), ethanol, methanol, glacial acetic acid and HPLC-grade acetonitrile were purchased from Fishers scientific, UK. Trihydrochloride Hoechst 33342 (Thermo Fisher Scientific, Eugene, OR, USA).
Cemex^® (Tecres^® SpA, Verona, Italy) bone cement was stored and used as from manufacturer’s guidelines.
Colorimetric ALP assay kit, picro-sirius red stain solution (ab150681), rabbit polyclonal antibodies against collagen I (ab21286), rabbit polyclonal antibodies against osteopontin (ab8448), rabbit polyclonal antibodies against osteocalcin (ab198228) and Alexa Fluor 488-labelled goat anti-rabbit IgG (ab150077) were purchased from Abcam, Cambridge, UK.
All reagents were stored according to manufacturer’s guidelines and used as received.

1,6-Hexanediol diacrylate
(HMDA) (80%), polyvinyl alcohol (25 kDa), and 2,2 dimethoxy-2-phenylacetophenone
(photoinitiator) and poly(hydroxyethyl) methacrylate were purchased
from Sigma-Aldrich. Ethyl acetate (EA), isopropyl alcohol (IPA), and
dichloromethane (DCM) were obtained from Fisher Scientific. All chemicals
were used as received without further purification. The synthetic
procedures and full characterization data for monomers A–G
have been reported previously by the authors.^{38 (link),39}