Search

Ionically crosslinked alginate hydrogels have been widely studied for application in tissue engineering. Crosslinking of alginates is routinely done by ionic interaction of the carboxyl groups with multivalent anions such as Ca2+ and Fe3+. In more complex hydrogel designs, such as interpenetrating network hydrogels and double network hydrogels, alginates have been combined with other synthetic polymers to benefit from the advantages of both worlds. The effect of different ions on the properties of single network alginate hydrogels and double network poly(acrylamide)/alginate hydrogels have been studied extensively. However, past reports offer less in terms of comparing different crosslinking methods or different salt precursors. Here, we explore the influence of ionic crosslinking strategies used for crosslinking alginate in double network P(AAm)/Alginate hybrid hydrogels. A comparison is made between different calcium-based crosslinking methods, including a two-step method using CaCl 2 , a one-step method using CaSO 4, and a one-step method using the combination of CaCO 3 with glucono-δ-lactone (GDL). Furthermore, the effect of different metal ions is investigated, including Fe3+, Al3+, Ba2+, Sr2+, and Ca2+. Mechanical properties of the resulting gels are analyzed by tensile and compression testing, revealing a strong correlation between preparation protocol, counter-ion identity, and mechanical response. [Display omitted] • The form of ions introduced in hybrid hydrogels containing alginate has a strong impact on mechanical performance. • The efficiency of crosslinking is primarily linked to the solubility of the ion source. • Different multivalent ions allow fine-tuning of the physical properties in alginate-hybrid hydrogels. [ABSTRACT FROM AUTHOR]

A library of Y-shaped poly(dimethylsiloxane) (PDMS)-b-poly(d,l-lactide) (PLA) diblock copolymers and their corresponding linear counterparts were synthesized, and their morphologies and feature sizes in bulk and thin films were compared using small-angle X-ray scattering (SAXS), scanning force microscopy (SFM), and grazing incidence small-angle X-ray scattering (GI-SAXS). For macromolecular isomers with approximately the same molecular weights and volume fractions (PLA fL: 0.20 and 0.35), different thin film morphologies were obtained for the Y-shaped PDMS-b-PLA derivatives when compared to the corresponding linear derivatives. These data also gave us the option to determine some of the key parameters of these block copolymers. A relatively high χ value of 0.24 was found for these PDMS-b-PLA systems and was shown to be influenced by architecture. [ABSTRACT FROM AUTHOR]

A dilute (30 mM) dichloromethane solution of the copper(I) complex 1·Cu+ of a [2]-catenane composed of two identical 28-membered macrocyclic alkenes featuring a phenanthroline moiety in the backbone was subjected to ring-opening metathesis polymerization (ROMP) with second-generation Grubbs catalyst. Shortly after mixing of reactants, the dark red solution transformed into a gel. The bis(phenanthroline)copper(I) units were effectively preserved during ROMP, as evinced by spectroscopic analysis. This implies that the putative metal alkylidene pseudorotaxane intermediates did not undergo dethreading processes but were involved in ring-chain equilibria strongly biased toward the ring products at the low monomer concentration employed in the ROMP reactions. MALDI-TOF mass spectra of the reaction mixtures obtained at an early stage of the reaction revealed a distribution of interlocked oligomers (1·Cu+)n(PF6-)n-1 with n up to 7, with no traces of peaks ascribable to open chain species. Rheological and mechanical analyses of the gel products provided independent evidence in support of the conclusion that the fraction of linear species in the polymer is negligible. Indications were obtained that the major portion of the polymeric material is composed of fully interlocked species. [ABSTRACT FROM AUTHOR]

Hydrogels were prepared with physical crosslinks comprising 2-ureido-4[1H]-pyrimidinone (UPy) hydrogen bonding units within the backbone of segmented amphiphilic macromolecules having hydrophihc poly(ethylene glycol) (PEG). The bulk materials adopt nanoscopic physical cross-links composed of UPy-UPy dimers embedded in segregated hydrophobic domains dispersed within the PEG matrix as comfirmed by cryo-electron microscopy. The amphiphilic network was swollen with high weight fractions of water (wH2≈0 0.8) owing to the high PEG weight fraction within the pristine polymers (wPEG 0.9). Two different PEG chain lengths were investigated and illustrate the corresponding consequences of cross link density on mechanical properties. The resulting hydrogels exhibited high strength and resilience upon deformation, consistent with a microphase separated network, in which the UPy-UPy interactions were adequately shielded within hydrophobic nanoscale pockets that maintain the network despite extensive water content. The cumulative result is a series of tough hydrogels with tunable mechanical properties and tractable synthetic preparation and processing. Furthermore, the melting transition of PEG in the dry polymer was shown to be an effective stimulus for shape memory behavior. [ABSTRACT FROM AUTHOR]

AB diblock copolymers were prepared by sequential ring-opening metathesis polymerization of cyclooctenes catalyzed by a Ru-based Grubbs catalyst. The relatively slow polymerization of cis-3-phenylcyclooct-1-ene (3PC) or cis-cyclooct-2-en-1-yl acetate (3AC) was first carried out and then followed by the faster polymerization of unsubstituted cis-cyclooctene (COE) from the active Ru-alkylidene chain ends. In contrast, simultaneous polymerization of the two monomers provides copolymers with a statistical monomer distribution owing to extensive chain transfer. The resulting poly(3PC-b-COE) and poly(3AC-b-COE) diblock copolymers were subjected to hydrogenation to selectively saturate the backbone alkenes. The consequences of architectural variance between the materials from simultaneous vs. sequential polymerizations are reflected by the contrasting thermal characteristics. [ABSTRACT FROM AUTHOR]

3-Substituted cis-cyclooctenes (3RCOEs, R = methyl, ethyl, hexyl, and phenyl) were synthesized and polymerized, and the polymers therefrom were hydrogenated to prepare model linear low density polyethylene (LLDPE) samples. The ring-opening metathesis polymerization (ROMP) of the 3RCOEs using Grubbs' catalyst proceeded in a regio- and stereoselective manner to afford polyoctenamers [poly(3RCOE)] exhibiting remarkably high head-to-tail regioregularity and high trans-stereoregularity. The overall selectivity increases with the increasing size of the R substituent. Hydrogenation of poly(3RCOE)s afforded precision LLDPEs with R substituents on every eighth backbone carbon. [ABSTRACT FROM AUTHOR]

The article discusses the development of nanoporous membranes generated from linear polyethylene (LPE)-polylactide (PLA) triblock copolymers. Researchers use polymerization mechanisms to prepare LPE block polymers containing a sacrificial block and employ a selective etching protocol to develop nanoporous LPE. By analyzing the PLA-LPE-PLA (LEL) triblocks, researchers observe that nanoporous membranes shows the chemical and thermal stability of LPE materials.

[Display omitted] • Mechanical performance is linked to network architecture in tough PEG-based hydrogels. • Entanglements dominate the hydrogel mechanics below a certain crosslinking density threshold. • Modeling of stretching experiments highlights the role of crosslinks and entanglements on mechanical performance. • Photocrosslinking using thiol-ene chemistry lends itself to digital light processing (3D printing). Hydrogels have been widely investigated for applications in the human body due to their tunability and biocompatibility. Nevertheless, their application is still limited by their relatively low mechanical strength relative to load-bearing tissue scaffolds like articular cartilage. In this work, we synthesized hydrogels by combining linear poly(ethylene glycol) dimethacrylate (PEGDMA) with a 3-arm-PEG end-functionalized with thiol. We demonstrate that the combination of thiol-ene click chemistry with a multifunctional crosslinker reduces the crosslink and entanglement density in comparison with the otherwise statistically crosslinked/polymerized PEGDMA, whereby the only viable mode of gelation is through radical propagation or termination at the double bond. The corresponding minimization of topological heterogeneities that arises during thiol-ene crosslinking results in hydrogels with compressive strength in the range of tens of MPa. The molar mass of the linear PEGDMA precursor is readily tunable, unlocking access to a wider range of mechanical properties. We employed photo-mediated crosslinking protocol, which is amenable to advanced processing technologies such as light-based 3D printing techniques. Such advanced fabrication processes offer high precision and control during the generation of customizable macroscopic objects. Simple prototypes were generated using digital light processing (DLP) equipment. We demonstrate that integrating a simple co-macromonomer into a widely employed hydrogel platform can unlock new mechanical regimes and mitigate the inherent brittleness associated with these materials. The simplicity of this approach, coupled with its easy tunability and adaptability to light-based techniques, holds promise for broadening hydrogel applications in tissue engineering. Our findings contribute to advancing materials and methodologies, facilitating enhanced design and fabrication of functional constructs. [ABSTRACT FROM AUTHOR]

Most of the theoretical and computational descriptions of the phase behavior of block copolymers describe the chain ensembles of perfect and uniform polymers. In contrast, experimental studies on block copolymers always employ materials with disperse molecular makeup. Although most polymers are so-called monodisperse, they still have a molecular weight dispersity. Here, we describe the synthesis and properties of a series of discrete length diblock co-oligomers, based on oligo-dimethylsiloxane (oDMS) and oligo-lactic acid (oLA), diblock co-oligomers with highly noncompatible blocks. By utilizing an iterative synthetic protocol, co-oligomers with molar masses up to 6901 Da, ultralow molar mass dispersities (Đ ≤ 1.00002), and unique control over the co-oligomer composition are synthesized and characterized. This specific block co-oligomer required the development of a new divergent strategy for the oDMS structures by which both bis- and monosubstituted oDMS derivatives up to 59 Si-atoms became available. The incompatibility of the two blocks makes the final coupling more demanding the longer the blocks become. These optimized synthetic procedures granted access to multigram quantities of most of the block co-oligomers, useful to study the lower limits of block copolymer phase segregation in detail. Cylindrical, gyroid, and lamellar nanostructures, as revealed by DSC, SAXS, and AFM, were generated. The small oligomeric size of the block co-oligomers resulted in exceptionally small feature sizes (down to 3.4 nm) and long-range organization. [ABSTRACT FROM AUTHOR]