Terminal Acrylate Groups Research Articles

Enhancing the Activity of Surface Immobilized Antimicrobial Peptides Using Thiol-Mediated Tethering to Poly(ethylene glycol).

Considering the need for versatile surface coatings that can display multiple bioactive signals and chemistries, the use of more novel surface modification methods is starting to emerge. Thiol-mediated conjugation of biomolecules is shown to be quite advantageous for such purposes due to the reactivity and chemoselectivity of thiol functional groups. Herein, the immobilization of poly(ethylene glycol) (PEG) and antimicrobial peptides (AMPs) to silica colloidal particles based on thiol-mediated conjugation techniques, along with an assessment of the antimicrobial potential of the functionalized particles against Pseudomonas aeruginosa and Staphylococcus aureus is investigated. Immobilization of PEG to thiolated Si particles is performed by either a two-step thiol-ene "photo-click" reaction or a "one-pot" thiol-maleimide type conjugation using terminal acrylate or maleimide functional groups, respectively. It is demonstrated that both immobilization methods result in a significant reduction in the number of viable bacterial cells compared to unmodified samples after the designated incubation periods with the PEG-AMP-modified colloidal suspensions. These findings provide a promising outlook for the fabrication of multifunctional surfaces based upon the tethering of PEG and AMPs to colloidal particles through thiol-mediated biocompatible chemistry, which has potential for use as implant coatings or as antibacterial formulations that can be incorporated into wound dressings to prevent or control bacterial infections.

Synthesis and Evaluation of Cytocompatible Alkyne-Containing Poly(β-amino ester)-Based Hydrogels Functionalized via Click Reaction.

Although poly(β-amino esters) (PAEs) have been widely applied in nonviral gene transfection, drug delivery systems, and regenerative medicine, the multifunctional modification of PAEs and bio-orthogonal strategies of PAE-based hydrogel functionalization is still a challenge. Herein, a strategy of poly(β-amino ester)-based hydrogel functionalization was developed via bio-orthogonal reactions in this study. Acrylate-terminated poly(β-amino esters) containing alkyne groups were synthesized by Michael addition reaction. Alkyne groups on poly(β-amino esters) could conjugate bioactive molecules with azide of K(N3)RGD via copper-catalyzed azide-alkyne cycloaddition, and terminal acrylate groups could in situ polymerize to prepare a hydrogel. A biomimetic peptide K(N3)RGD functionalized hydrogel was prepared by polymerization of acrylate-terminated poly(β-amino esters) containing conjugated peptide and polyethylene glycol diacrylate (PEGDA). The storage modulus and mechanical properties exhibited an increased trend with the increased concentration; nevertheless, swelling ratio and surface wetting properties demonstrated a decreased tendency by increased concentrations. Cell proliferation and live/dead staining showed that Schwann cells plated on the hydrogel with an elastic modulus of 25.39 KPa are more suitable for proliferation and function exertion of Schwann cells compared with that of 42.11 and 57.86 KPa, and KRGD-conjugated hydrogel could increase the elongation of Schwann cells relative to nonconjugated hydrogels. This azide-alkyne strategy may be a promising candidate for hydrogel functionalization in tissue engineering and other biomedical applications.

Fabrication of unimolecular micelle-based nanomedicines from hyperbranched polymers containing both terminal and internal reactive groups

Unimolecular micelles are an attractive type of nanocarriers for drug delivery, but developing unimolecular micelle-based nanomedicine with high drug loading capacity and excellent unimolecular stability is challenging. Herein, we report the design and synthesis of hyperbranched polymers containing both terminal and internal reactive groups for fabricating the unimolecular micelle-based nanocarriers with high drug loading ability and superior unimolecular stability using selective modification. Specifically, we synthesized hyperbranched poly(amino ester)s containing terminal acrylate groups and internal R groups (named HBPAE-R) via the Michael addition polymerization of A2 + BʹB2-R monomers, wherein A represents acrylate, and B, Bʹ represents the hydrogen in primary amine and secondary amine group, respectively, whereas R represents hydroxy, alkene or alkyne groups that do not participate in the polymerization process but assist in additional modification. Then, poly(ethylene glycol) (PEG) chains were linked to the surface of HBPAE-OH (representative molecules) with the subsequent conjugation of doxorubicin (DOX, representative drug) to the internal hydroxy groups through an acid-labile hydrazide bond, to afford anti-cancer drug-loaded hyperbranched star copolymers PEG-HBPAE-DOX. The obtained nanomedicines exhibited good unimolecular stability, relatively high drug loading content and a controlled drug release behavior. The in vitro cytotoxicity experiments further demonstrated the anti-tumor efficacy of these unimolecular nanomedicines. Our approach is expected to further boost research on the fabrication of multifunctional unimolecular nanomedicines from hyperbranched polymers containing both terminal and internal reactive groups.

Preparation of Degradable Polymenthide and Its Elastomers from Biobased Menthide via Organocatalyzed Ring-opening Polymerization and UV Curing

Development of degradable polyester elastomers plays an important role in the applications of soft mateirals. Noncrystalline polymenthides (PMs) from menthol derived lactone monomers are excellent soft segments for preparing degradable polyester elastomers. By using cyclic trimeric phosphazene base (CTPB) as an organocatalyst, we successfully synthesized PMs with different molecular weights (8.2 kDa to 100.7 kDa) in high yields via ring-opening polymerization (ROP) of menthide. When a CTPB/urea binary catalytic system was adopted, the polymerizations proceeded in a more controlled manner. Using glycerol as initiator, star shaped PMs with well-defined structure were synthesized and subsequently end-capped by acrylate. UV irradiation of the terminal acrylate groups in the star-shaped PMs resulted in formation of chemically cross-linked polyester elastomers without heat or other stimuli. The obtained polyester elastomers exhibit matched modulus (3.8–5.5 MPa), tensile strength (0.56–0.68 MPa), and strain at break (280%–320%) with soft body tissues, displaying great potential in biomedical applications.

Photo-stable cross-linked micron bead with functionalized quantum via suspension polymerization for color conversion

Acrylate groups were introduced on quantum dots (QD) via ligand exchange followed by nucleophilic reaction. The QDs were then polymerized with other multi-functional acrylic monomers in this study. Two acrylate groups were introduced at the end of an elongated ligand and the ligands with two acrylate groups were fully coordinated on the entire surface of the QD. This ligand modification scheme made the QDs highly reactive and also compatible with common organic solvents. No decrease in the quantum yield of the QDs was observed after ligand modification and the adduction reaction. The acrylate functional groups in the QDs were verified by 1H NMR and FT-IR. The prepared QDs with a terminal acrylate group were reacted with trimethylolpropane triacrylate and 1,6-hexanediol diacrylate to form micrometer scale beads via suspension polymerization. The diameter of the spherical beads was in the range of 80–150 μm and QDs 13 nm in diameter were found to be evenly dispersed in the polymer beads. The QD-polymer beads were applied to color conversion layers (CCL) on a blue light emitting diode (LED). The QD-polymer beads showed a 50% reduction over 72 h from the initial optical efficiency, while the QD embedded in the PMMA matrix (QD-PMMA) was reduced by 50% for 14 h.

Hydrosilylation of Reactive Quantum Dots and Siloxanes for Stable Quantum Dot Films.

The reactive acrylate-terminated CdZnSeS/ZnS quantum dots (QDs) were designed and prepared by the effective synthetic route to bond with a siloxane matrix via hydrosilylation. The conventional QD with oleic acid ligands does not have any reactivity, so the QDs were functionalized to assign reactivity for the QDs by the ligand modification of two step reactions. The oleic acid of the QDs was exchanged for hydroxyl-terminated ligands as an intermediate product by one-pot reaction. The hydroxyl-terminated QDs and acrylate-containing isocyanates were combined by nucleophilic addition reaction with forming urethane bonds and terminal acrylate groups. No degradation in quantum yield was observed after ligand exchange, nor following the nucleophilic addition reaction. The modification reactions of ligands were quantitatively controlled and their molecular structures were precisely confirmed by FT-IR and 1H-NMR. The QDs with acrylate ligands were then reacted with hydride-terminated polydimethylsiloxane (H-PDMS) to form a QD-siloxane matrix by thermal curing via hydro-silylation for the first time. The covalent bonding between the QDs and the siloxane matrix led to improvements in the stability against oxygen and moisture. Stability at 85 °C and 85% relative humidity (RH) were both improved by 22% for the QD-connected siloxane QD films compared with the corresponding values for conventional QD-embedded poly(methylmethacrylate) (PMMA) films. The photo-stability of the QD film after 26 h under a blue light-emitting diode (LED) was also improved by 45% in comparison with those of conventional QD-embedded PMMA films.

Poly(urethane-acrylate) aerogels from the isocyanurate trimer of isophorone diisocyanate

Poly(urethane acrylate) aerogels were synthesized from radical polymerization of a dendritic monomer having an isocyanurate-based rigid/aliphatic core, urethane linkages and nine terminal acrylate groups. The rigidity of the core comes from the triisocyanate, an isophorone diisocyanate trimer (IPDI). The material properties of those aerogels were compared to the properties of related literature materials derived from triisocyanates with flexible/aliphatic or rigid/aromatic cores, bearing (a) three, or (b) nine terminal acrylate groups. Data support that material properties such as the primary particle size and the BET surface areas are determined mainly by the degree of crosslinking (i.e., the monomer multifunctionality), while the molecular rigidity vs flexibility of the triisocyanate core plays only a secondary role. Addition of ethylene glycol dimethacrylate (EG) in the sol as a chain extender increased the hydrophilicity of the aerogels and their ability to absorb water.

Poly(Urethane-Acrylate) Aerogels via Radical Polymerization of Dendritic Urethane-Acrylate Monomers.

The purpose of this work was to investigate the effect of multifunctionality on material properties of synthetic polymer aerogels. For this purpose, we present the synthesis and characterization of monolithic dendritic-type urethane-acrylate monomers based on an aliphatic/flexible (Desmodur N3300), or an aromatic/rigid (Desmodur RE) triisocyanate core. The terminal acrylate groups (three at the tip of each of the three branches, nine in total) were polymerized with 2,2′-azobis(isobutyronitrile) (AIBN) via free radical chemistry. The resulting wet-gels were dried with supercritical fluid (SCF) CO2. Aerogels were characterized with ATR-FTIR and solid-state 13C NMR. The porous network was probed with N2-sorption and scanning electron microscopy (SEM). The thermal stability of aerogels was studied with thermogravimetric analysis (TGA). Most aerogels were macroporous materials (porosity > 80%), with high thermal stability (up to 300 °C). Aerogels were softer at low monomer concentrations and more rigid at higher concentrations. The material properties were compared with those of analogous aerogels bearing only one acrylate moiety at the tip of each branch and the same cores, and with those of analogous aerogels bearing norbornene instead of acrylate moieties. The nine-terminal acrylate-based monomers of this study caused rapid decrease of the solubility of the growing polymer and made possible aerogels with much smaller particles and much higher surface areas. For the first time, aliphatic/flexible triisocyanate-based materials could be made with similar properties in terms of particle size and surface areas to their aromatic/rigid analogues. Finally, it was found that with monomers with a high number of crosslinkable groups, material properties are determined by multifunctionality and thus aerogels based on 9-acrylate- and 9-norbornene-terminated monomers were similar. Materials with aromatic cores are carbonizable with satisfactory yields (20–30% w/w) to mostly microporous materials (BET surface areas: 640–740 m2 g−1; micropore surface areas: 360–430 m2 g−1).

Double-Cross-Linked Hydrogel Strengthened by UV Irradiation from a Hyperbranched PEG-Based Trifunctional Polymer.

Conventional wound healing materials suffer from low efficiency, poor mechanical strength, and nontunable properties. Responsive hydrogels are appealing candidates for tissue engineering. Herein, we developed a double-cross-linked hydrogel system composed of hyperbranched PEG-based polymer, comprising pre-cross-linked acetal structure and numerous terminal acrylate groups, which can form hydrogels in situ and can be further strengthened by UV irradiation. The hyperbranched glycidyl methacrylate-co-poly(ethylene glycol) diacrylate polymers (HB-GMA-PEGs) were first synthesized via in situ deactivation enhanced atom transfer radical polymerization (DE-ATRP). A series of pre-cross-linked materials were achieved after postfunctionalization. The material can absorb a high amount of water to form hydrogels, and the gel stiffness was evaluated in detail before and after UV irradiation. The in vitro cytotoxicity experiments were conducted with the resulting materials and have demonstrated their good biocompatibility. The results indicate that this type of hydrogel with high water uptake capacity has appealing potential as a responsive biomaterial for wound closure.

Effect of fluorine groups and different terminal chains on the electro-isomerization of azobenzene liquid crystals**Project supported by the National Natural Science Foundation of China (Grant Nos. 61435008 and 61575063).

A series of azobenzene liquid crystals with one or two terminal acrylate groups were synthesized and their polymers were fabricated. The azobenzene liquid crystals and their polymers achieved the photoisomerization from the liquid crystalline trans-isomer to the isotropic cis-isomer with UV irradiation. Then, the cis to trans isomerization induced by an electric field was studied, the time required for electro-isomerization was measured, the texture change and absorption variation from cis to trans form induced by the electric field were observed clearly, and the time required for electro-isomerization was much shorter than that for thermal relaxation. The influence of the polar group (fluorine), terminal acrylate group, and flexible alkyl chain on the time of electro-isomerization was studied. The results show that the compounds with polar fluorine group require shorter time for electro-isomerization and the polymerization of terminal acrylate group delays the electro-isomerization.

Novel ABC miktoarm star terpolyphosphoesters: Facile construction and high‐flame retardant property

ABSTRACTA combination of ring‐opening metathesis polymerization (ROMP), ring‐opening polymerization (ROP), and acyclic diene metathesis (ADMET) polymerization approach was first time utilized in the preparation of novel ABC miktoarm star terpolyphosphoesters (PPEs). Acrylate‐terminated monotelechelic PPE was first prepared through ROMP of 7‐membered cyclic phosphate monomer in the presence of a terminating agent, and then terminal acrylate group was readily converted, by thiol‐Michael addition click reaction and esterification, to a heterodifunctional PPE with hydroxyl and acrylate groups, which was a key precursor for the preparation of ABC miktoarm terpolymers. ROP of the cyclic phosphoester monomer initiated by this PPE was successively carried out to generate the acrylate‐functionalized block PPE, which utilized as a selective macromolecular chain stopper in subsequent ADMET polymerization of α,ω‐diene phosphate monomer, finally producing miktoarm terpolyphosphoester. These prepared miktoarm star terpolyphosphoesters demonstrated superior thermal and flame retardant properties via TGA, limiting oxygen index, and microscale combustion calorimetry tests. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 692–701

One‐Pot Sequential Ring‐Opening Metathesis Polymerization and Acyclic Diene Metathesis Polymerization Synthesis of Unsaturated Block Polyphosphoesters

A novel divergent approach is presented for the one‐pot synthesis of unsaturated block poly­phosphoester (PPE) structures by a sequential ring‐opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polymerization. A linear functional PPE bearing one or two terminal acrylate groups is first prepared through the third generation Grubbs catalyst‐mediated ROMP of seven‐membered cyclic phosphate monomer, in the presence of a symmetrical multifunctional terminating agent or chain transfer agent. The functional PPE is then utilized as a selective macromolecular chain stopper in subsequent ADMET polymerization of phosphoester functional asymmetric α,ω‐diene monomer, yielding unsaturated block PPEs. The thermal properties of block PPEs are studied and their thermal degradation and flame‐retardant properties are evaluated. Furthermore, the prepared block PPEs can spontaneously self‐assemble in a selective solvent to form polymeric micelles, which are characterized in detail by dynamic light scattering, atom force microscopy, transmission electron microscopy, and scanning electron microscopy analyses. image

Facile synthesis of linear–hyperbranched polyphosphoesters via one‐pot tandem ROMP and ADMET polymerization and their transformation to architecturally defined nanoparticles

ABSTRACTA convenient one‐pot synthesis of linear–hyperbranched polyphosphoesters (l–HBPPEs) was accomplished by a tandem ring‐opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polymerization procedure. A linear monotelechelic poly(norbornene) with a terminal acrylate and many pendent thiol groups is first prepared through adding an internal cis‐olefin terminating agent to the reaction mixture immediately after the completion of the living ROMP, and then utilized as a macromolecular chain stopper in subsequent ADMET polymerization of a phosphoester functional AB2 monomer, yielding l–HBPPEs as the reaction time prolonged. These l–HBPPEs bearing lots of pendent thiol groups in linear poly(norbornene) and peripheral acrylate groups in HBPPE could be self‐crosslinked in ultradilute solution through thiol‐Michael addition click reaction between acrylate and thiol to give single‐molecule nanoparticles with comparatively uniform size. This facile approach can be extended toward the fabrication of novel nanomaterials with sophisticated structures and tunable multifunctionalities. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 964–972

Facile Synthesis of Thiol‐Functionalized Long‐Chain Highly Branched ROMP Polymers and Surface‐Decorated with Gold Nanoparticles

The synthesis of thiol-functionalized long-chain highly branched polymers (LCHBPs) has been accomplished in combination of ring-opening metathesis polymerization (ROMP) and thiol-Michael addition click reaction. A monotelechelic polymer with a terminal acrylate and many pendent thiol groups is first prepared through adding an internal cis-olefin terminating agent to the reaction mixture immediately after the completion of the living ROMP, and then utilized as an ABn -type macromonomer in subsequent thiol-ene reaction between acrylate and thiol, yielding LCHBPs as the reaction time prolonged. Au nanoparticles are then covalently conjugated onto the surface of thiol-functionalized LCHBP to fabricate novel hybrid nanostructures, which is shown as one interesting application of such functionalized metathesis polymers. This facile approach can be extended toward the fabrication of novel nanomaterials with sophisticated structures and tunable multifunctionalities.

Novel Polymerizable Nonionic Surfactants (Surfmers) Corporate with Alkenylsuccinic Anhydride: Synthesis, Surface, and Thermodynamic Properties

In this article, nine polymerizable surfactants (surfmers) were prepared with terminal acrylate group on the hydrophilic moiety. The prepared surfmers were classified into three groups according to hydrophobic chain lengths; the first group (group I) was single-tailed with different hydrophobic chain lengths, the second group (group II) was asymmetric double-tailed, one of them was dodecenyl and the other is octyl or tetradecyl or octadecyl from fatty alcohols, and the third group (group III) is symmetric double-tailed. The chemical structures of the prepared nonionic surfmers were confirmed by mass spectra, elemental analysis, acid value titration, and FTIR and 1H NMR spectroscopy. The surface and thermodynamic parameters of the prepared surfmers were determined at 25°C including, surface tension (γ) and effectiveness, maximum surface excess (Γmax) and minimum surface area (Amin). Also, the standard free energy of micellization and adsorption were recorded. The results show that the surface and thermodynamic parameters of the prepared surfmers were sensitive to the discrepancy of surfmer tail length and their expected shape on the interface.

Functional polyisobutylenes via a click chemistry approach

1-(ω-Azidoalkyl)pyrrolyl-terminated polyisobutylene (PIB) was successfully synthesized both by substitution of the terminal halide of 1-(ω-haloalkyl)pyrrolyl-terminated PIB with sodium azide and by in situ quenching of quasiliving PIB with a 1-(ω-azidoalkyl)pyrrole. Azide substitution of the terminal halide was carried out in 50/50 heptane/DMF at 90 °C for 24 h using excess azide. The 1-(ω-haloalkyl)pyrrolyl-PIB precursors included 1-(2-chloroethyl)pyrrolyl-PIB, 1-(2-bromoethyl)pyrrolyl-PIB, and 1-(3-bromopropyl)pyrrolyl-PIB. In situ quenching involved direct addition of 1-(2-azidoethyl)pyrrole to quasiliving PIB initiated from 5-tert-butyl-1,3-di(1-chloro-1-methylethyl)benzene (bDCC)/TiCl4 at −70 °C in hexane/CH3Cl (60/40, v/v). 1H NMR analysis of the quenched product revealed mixed isomeric end groups in which PIB was attached at either C2 or C3 of the pyrrole ring (C2/C3 = 0.40/0.60). SEC indicated the absence of coupled PIB under optimized conditions, confirming exclusive mono-substitution on each pyrrole ring. 1-(3-Azidopropyl)pyrrolyl-PIB was reacted in modular fashion with various functional alkynes, propargyl alcohol, propargyl acrylate, glycidyl propargyl ether, and 3-dimethylamino-1-propyne, via a Huisgen 1,3-dipolar cycloaddition (Click) reaction, using Cu(I)Br/N,N,N′,N″,N″-pentamethyldiethylenetriamine or bromtris(triphenylphosphine)Cu(I) as catalyst. The reactions were quantitative and produced PIBs bearing terminal hydroxyl, acrylate, glycidyl, or dimethylaminomethyl groups attached via exclusively four-substituted triazole linkages. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2533–2545, 2010

Mesomorphic phase transition behaviour of photopolymerisable liquid crystalline triphenylene ether compounds

This report discusses the preparation and the unusual mesomorphism of three homologues of photopolymerisable triphenylene ether compounds. These homologues showed ‘a cold crystallisation’ on heating differential scanning calorimetry curves, and this phenomenon is attenuated with increase methylene units, spacers between the triphenylene core and the terminal photopolymerisable acrylate group. Classical textures of hexagonal columnar (Colh) mesophase were observed by polarising optical microscopy for all three photopolymerisable mesophase compounds described here. Also described is the mesomorphism of their intermediates, hydroxylalkoxytriphenylenes. In some cases, the discotic columnar hexagonal mesophases were confirmed by wide angle X-ray scattering techniques.

Physical Hydrogels Photo-Cross-Linked from Self-Assembled Macromers for Potential Use in Tissue Engineering

To engineer artificial extracellular matrices (ECMs) enabling degradation-independent cell migration that mimicked nonproteolytic cell migration through physically stabilized ECMs in biological systems, polymers having a hydrophilic chain flanked by a terminal self-assembling leucine zipper domain and a terminal photoreactive acrylate group were molecularly engineered to form photo-cross-linkable physical hydrogels. Physical association of the leucine zippers resulted in multifunctional macromers, which were photo-cross-linkable into hydrogels. Gel formation was confirmed by rheological measurements. The physical nature of the hydrogel networks was shown by hydrogel disassembly in denaturing solutions that disrupted the secondary structure of the leucine zippers. Outgrowth of encapsulated fibroblast aggregates was observed in these physical hydrogels but not observed in a control hydrogel in which leucine zippers were covalently linked. The collective properties of these hydrogels, including the physical nature, the photo-cross-linkable characteristic, and the flexibility for systematic engineering of material properties, will provide unique opportunities for tissue engineering.

Degradation Behavior of the Hydrogel Poly(vinyl alcohol)‐graft‐Poly[(rac‐lactide)‐co‐Glycolide)] under Different Conditions

AbstractSummary: The hydrogel poly(vinyl alcohol)‐graft‐poly[(rac‐lactide)‐co‐glycolide)] [PVA‐g‐P(LGA)], containing nine ester groups in the polyester grafts (lactide:glycolide ratio 50:50) grafted onto PVA to an extent of 13%, and crosslinked via terminal acrylate groups was subjected to degradation experiments in phosphate buffer solution (pH 7.4) at room temperature and at 37 °C during 8 weeks. In the course of degradation, the properties of the hydrogel change as a result of the decrease of the polyester content. The increased temperature has a significant influence on the degradation rate but its amount varies with the methods applied. Thus, a large drop of the elastic modulus takes place in samples degraded at 37 °C with time and relative to RT. Thermal and IR analysis show changes while the initial difference between two sets of samples in contact angle is reduced with time.

Photo-Cross-Linked PLA-PEO-PLA Hydrogels from Self-Assembled Physical Networks: Mechanical Properties and Influence of Assumed Constitutive Relationships

Poly(lactide)-block-poly(ethylene oxide)-block-poly(lactide) (PLA-PEO-PLA) triblock copolymers are known to form physical hydrogels in water as a result of the polymer's amphiphilicity. Their mechanical properties, biocompatibility, and biodegradability have made them attractive for use as soft tissue scaffolds. However, the network junction points are not covalently cross-linked, and in a highly aqueous environment these hydrogels adsorb more water, transform from gel to sol, and lose the designed mechanical properties. In this article, a hydrogel was formed by the use of a novel two-step approach. In the first step, the end-functionalized PLA-PEO-PLA triblock was self-assembled into a physical hydrogel through hydrophobic micelle network junctions, and in the second step, this self-assembled physical network structure was locked into place by photo-cross-linking the terminal acrylate groups. In contrast with physical hydrogels, the photo-cross-linked gels remained intact in phosphate-buffered solution at body temperature. The swelling, degradation, and mechanical properties were characterized, and they demonstrated an extended degradation time (approximately 65 days), an exponential decrease in modulus with degradation time, and a tunable shear modulus (1.6-133 kPa). We also discuss the various constitutive relationships (Hookean, neo-Hookean, and Mooney-Rivlin) that can be used to describe the stress-strain behavior of these hydrogels. The chosen model and assumptions used for data fitting influenced the obtained modulus values by as much as a factor of 3.5, which demonstrates the importance of clearly stating one's data fitting parameters so that accurate comparisons can be made within the literature.