Crosslinking Density Of Network Research Articles

Effect of limited hydrolysis on the structure and gel properties of soybean isolate proteins: A comparative study of papain or/and trypsin

Plant protein's gelation is crucial in various food applications, and hydrolysis may enhance their gelation properties. In this study, we prepared soybean protein isolate hydrolysates (SPIH) using trypsin and/or papain, and found significant improvement in the solubility and gelling properties. These proteases broken down the peptide bonds and caused the exposure of hydrophobic groups as well as the unfolding of protein. Low molecular weight (<35 kDa) SPIHs were generated by the two-step enzymatic hydrolysis, showing significant improvements in storage modulus (G′), loss modulus (G″), viscosity, strength, and water-holding capacity (WHC). Among, PT-10 exhibited the highest WHC (61.72 ± 0.36 %), gel strength (4.67 ± 0.12 g), and network cross-linking density (0.33 ± 0.01 mol/m3), while its solubility was also significantly increased up to 254 %. According to the results of gel molecular force interactions, disulfide bonds, hydrophobic interactions and hydrogen bonds involved in the gel network formation. These findings reveal that the appropriate hydrolysis modification may improve SPI gel's properties and expand its application in gel foods.

Triboelectric Nanogenerator Made with Stretchable, Antibacterial Hydrogel Electrodes for Biomechanical Sensing.

Triboelectric nanogenerators (TENGs) have attracted widespread attention as a promising candidate for energy harvesting due to their flexibility and high power density. To meet diverse application scenarios, a highly stretchable (349%), conductive (1.87 S m-1), and antibacterial electrode composed of carbon quantum dots/LiCl/agar-polyacrylamide (CQDs/LiCl/agar-PAAm) dual-network (DN) hydrogel is developed for wearable TENGs. Notably, the concentration of agar alters the pore spacing and pore size of the DN hydrogel, thereby impacting the network cross-linking density and the migration of conductive ions (Li+ and Cl-). This variation further affects the mechanical strength and conductivity of the hydrogel electrode, thus modulating the mechanical stability and electrical output performance of the TENGs. With the optimal agar content, the tensile strength and conductivity of the hydrogel electrode increase by 211 and 719%, respectively. This enhancement ensures the stable output of TENGs during continuous operation (6000 cycles), with open-circuit voltage, short-circuit current, and transferred charge increasing by 200, 530, and 155%, respectively. Additionally, doping with CQDs enables the hydrogel electrode to effectively inhibit the Gram-negative bacterium Escherichia coli. Finally, the TENGs are utilized as a self-power smart ring for efficient and concise information transmission via Morse code. Consequently, this study introduces a creative approach for designing and implementing multifunctional, flexible wearable devices.

Molecular simulation-guided and physics-informed constitutive modeling of highly stretchable hydrogels with dynamic ionic bonds

Adaptive polymers are being designed with dynamic molecular bonds or chain interactions to respond with external stimuli with unparalleled mechanical properties and multifunctionality. An elegant example is to substantially enhance the stretchability and toughness of hydrogels through the use of ionic bond interactions. To assist the materials design and applications, a predictive theory is in high demand. However, existing multi-scale mechanics models often rely on empirical assumptions and relationships derived from polymer chemistry or physics to describe the evolution of microscale details under external stimuli, which are challenging to be validated experimentally. This study introduces a new methodology to develop constitutive theories for stretchable hydrogels based on insights garnered from molecular dynamics (MD) simulations. The continuum-level viscoelastic theory establishes the thermodynamics framework for stress-strain relationships, while MD simulations inform the evolution mechanisms of microscale bond interactions and network rearrangements, such as the bond distance and network relaxation time. These insights are then properly formulated based on polymer physics principles and fed into the continuum-level model. The resulting constitutive theory closely captures the stress responses at various loading conditions observed in experiments, as well as the microscale system volume and bond distance uncovered in MD simulations. Parametric studies are conducted to investigate the influences of various loading and material parameters on the mechanical properties of the materials, including loading rates, network crosslinking density, maximum strain, and bonding strength. Overall, the study establishes the connection between microscale network structure and mechanical responses of stretchable hydrogels with dynamic ionic bonds. It also offers practical guidance for optimizing material structures and loading conditions to enhance energy absorption and dissipation capabilities. The modeling approach can be extended to the study of other adaptive polymers with different dynamic bonds to create more precise and physically meaningful constitutive models.

Network homogeneity on linear and nonlinear viscoelasticity of polyethylene terephthalate vitrimers

Designing network topology with tunable dynamics and rheology behaviors is the key for vitrimers applications. In this study, PET vitrimers with varying crosslinking density and network homogeneity were created by using different Mw of precursors and branching agents (catalysts). Our results show that the dynamic network formed by propane-type branching agent such as 1,3-bis[tris(hydroxymethyl) methylamino] propane (BIS-TRIS propane), is more uniform due to steric hindrance effect compared to 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol (BIS-TRIS). The thermal behavior of PET vitrimers was investigated by non-isothermal experiments, including glass transition and crystallization process. In particular, rheology behavior is sensitive to network structure and bond exchange process. The linear viscoelasticity (LVE) region of PET vitrimers is characterized by constructed pseudo-master curves that are guided by two distinct relaxation mechanisms: Rouse-type relaxation of strands and terminal relaxation of the network. Each relaxation mechanism is associated with a unique activation energy. The mechanical and processing properties of the PET vitrimers are reflected in their plateau modulus and characteristic relaxation time, which varies depending on the network topology. Based on the LVE analysis, we further investigated nonlinear rheology of PET vitrimers under extensional flow. Our results indicate that PET vitrimers exhibit significant strain hardening behavior, but display distinct stretching trends, corresponding to polymer melts' ductility. The ductility of materials decreases with a decrease in precursor's molecular weight (Mw), but improved with enhanced network homogeneity. Therefore, the crosslinking density and network homogeneity of dynamic network can be selectively tailored using appropriate precursors and branching agents to meet various industrial applications.

Zwitterionic Polymer Ionogel Electrolytes Supported by Coulombic Cross-Links: Impacts of Alkali Metal Cation Identity.

Zwitterionic (ZI) polymers enable the formation of noncovalent cross-links within ionic liquid electrolytes (ILEs) to create nonflammable, mechanically robust, and highly conductive ionogel electrolytes. In this study, ZI homopolymer poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] scaffolds are synthesized in situ within lithium and/or sodium salt-based ILEs to construct a series of ionogels that contain between 3 and 15 wt % poly(MPC). Room-temperature ionic conductivity values of these ionogels are found to vary between approximately 1.3 and 2.2 mS cm-1. For sodium only and 1:1 lithium/sodium equimolar mixed salt ionogels containing 6 wt % poly(MPC), the ionic conductivity is found to improve by 14% compared to the neat ILE due to the presence of the ZI scaffold. Moreover, comparing the elastic modulus values of lithium- versus sodium-containing ionogels revealed a difference of up to 1 order of magnitude [10.6 vs 111 kPa, respectively, for 3 wt % poly(MPC)]. Molecular dynamics simulations of ionogel precursor solutions corroborate the experimental results by demonstrating differences in the lithium/ZI monomer and sodium/ZI monomer cluster size distributions formed, which is hypothesized to influence the scaffold network cross-link density obtained upon photopolymerization. This work provides insights into why ZI polymer-supported ionogel properties that are relevant for the development of safer electrolytes for lithium-ion and sodium-ion batteries depend upon the chemical identity of the alkali metal cation.

Preparation and Characterization of Acrylic and Methacrylic Phospholipid-Mimetic Polymer Hydrogels and Their Applications in Optical Tissue Clearing.

The 2-methacryloyloxyethyl phosphorylcholine (MPC) polymers are mimetic to phospholipids, being widely used as biocompatible polymers. In our previous study, MPC polymer hydrogels proved more effective for optical tissue clearing compared to acrylamide (AAm) polymer hydrogels. In the present study, 2-acryloyloxyethyl phosphorylcholine (APC) was synthesized and employed to create hydrogels for a comparative analysis with methacrylic MPC-based hydrogels. APC, an acrylic monomer, was copolymerized with AAm in a similar reactivity. In contrast, MPC, as a methacrylic monomer, demonstrated higher copolymerization reactivity than AAm, leading to a spontaneously delayed two-step polymerization behavior. This suggests that the polymer sequences and network structures became heterogeneous when both methacrylic and acrylic monomers, as well as crosslinkers, were present in the copolymerization system. The molecular weight of the APC polymers was considerably smaller than that of the MPC polymers due to the formation of mid-chain radicals and subsequent β-scission during polymerization. The swelling ratios in water and strain sweep profiles of hydrogels prepared using acrylic and methacrylic compounds differed from those of hydrogels prepared using only acrylic compounds. This implies that copolymerization reactivity influences the polymer network structures and crosslinking density in addition to the copolymer composition. APC-based hydrogels are effective for the optical clearing of tumor tissues and are applicable to both passive and electrophoretic methods.

Thermally-induced phase fusion and color switching in ionogels for multilevel information encryption

The growing significance of data security has propelled the advancement of information encryption materials. Here, thermochromic poly(4-hydroxybutyl acrylate) (PHBA) ionogels with broad response range and excellent cyclic stability were successfully developed through photopolymerization. Due to the reversible phase diffusion between PHBA polymer networks and ionic liquids (ILs), the PHBA ionogels can switch between opaque and transparent states in response to changes in heating temperature. The enthalpic and entropic properties of the PHBA ionogels were modified by adjusting the crosslinking density (1.0%–2.5%) of polymer networks and concentration (30%-60%) of ILs, which in turn accurately controlled their phase fusion temperature (32 °C to over 68 °C). The size and optical properties of ionogels can be effectively maintained even after exposure to surpass daily ambient temperatures (−10 and 50 °C) or humidity (75%) levels for 12 h, as well as undergoing heating–cooling cycles or operating in ambient environments for 60 days. These findings demonstrate the exceptional stability of these ionogels, rendering them suitable for application as reversible information encryption devices. For the first time, proof-of-concept demonstrations of a thermochromic ionogel system for six-level information encryption and ionogel barcodes are presented here. This work is particularly significant for smart soft materials and information encryption fields.

Preparation and enhancement mechanisms of a novel modified nanographite hybrid polymer gel for profile control in deep reservoirs

This study presents the development of modified nanographite (MG) as a crosslinking agent to enhance the temperature and salt resistance of gel systems and enable their use in deep oil and gas reservoirs. The novel nanographite hybrid crosslinked gel was formed by combining polyacrylamide (PAM) as the polymer matrix with hexamethylenetetramine (HMTA), hydroquinone (HQ), and MG as the crosslinking agents. The effects of the MG concentration on the gelation time, gel strength, and thermal stability were investigated, and the plugging ability of the nanographite hybrid crosslinked gel system was evaluated. The results demonstrated that the gelation time of the hybrid gel system comprising 0.8 wt% PAM, 0.6 wt% HMTA, 0.6 wt% HQ, and 0.2 wt% MG was 4 h, and the maximum tolerance temperature was 154.9 °C. Furthermore, the addition of MG more than doubled the storage modulus (G') and loss modulus (G′') of the gel system. Compared to the conventional gel system without MG, the hybrid gel exhibited remarkable bound water contents as high as 21.14%, which represented a more than 5-fold improvement. Microstructural analyses revealed that the hybrid gel network contained numerous MG sheets, leading to a denser network structure compared to that of the conventional gel. The presence of the MG greatly increased the network strength and crosslinking density of the hybrid gel, thereby improving its thermal stability, temperature resistance, and salt resistance. Additionally, the hybrid gel exhibited excellent plugging performance, achieving a core plugging rate of 96.2%.

The Coordination Nanocages-Integrated Polymer Brush Networks for Flexible Microporous Membranes with Exceptional H2 /CO2 Separation Performance.

The emergence of polymers with intrinsic microporosity provides solutions for flexible gas separation membranes with both high gas permeability and selectivity. However, their applications are significantly hindered by the costly synthetic efforts, limited availability of chemical systems, and narrow window of microporosity sizes. Herein, flexible mixed matrix membranes with tunable intrinsic microporosity can be facilely fabricated from the coordination assembly of polymer brushes and coordination nanocages. Polymer brushes bearing isophthalic acid side groups can coordinate with Cu2+ to assemble into polymer networks crosslinked by 2nm nanocages. The semi-flexible feature of the polymer brush and the high crosslinking density of the network prevent the network from collapsing during solvent removal and the obtained aerogels demonstrate hierarchical structure with dual porosity from the crosslinked polymer network and coordination nanocage, respectively. The porosity can be facilely tuned via the amount of Cu2+ by regulating the network crosslinking density and nanocage loadings, and finally, optimized gas separation that surpasses Robeson upper bound for H2 /CO2 can be achieved. The coordination-driven assembly protocol paves a new avenue for the cost-effective synthesis of polymers with intrinsic microporosity and the fabrication of flexible gas separation membranes.

Dually crosslinked injectable alginate-based graft copolymer thermoresponsive hydrogels as 3D printing bioinks for cell spheroid growth and release

In this work a dual crosslinked network based on sodium alginate graft copolymer, bearing poly(N-isopropylacrylamide-co-N-tert-butylacrylamide) P(NIPAM-co-NtBAM) side chains was developed and examined as a shear thinning soft gelating bioink. The copolymer was found to undergo a two-step gelation mechanism; in the first step a three-dimensional (3D) network is formed through ionic interactions between the negatively ionized carboxylic groups of the alginate backbone and the positive charges of Ca2+ divalent cations, according to the “egg-box” mechanism. The second gelation step occurs upon heating which triggers the hydrophobic association of the thermoresponsive P(NIPAM-co-NtBAM) side chains, increasing the network crosslinking density in a highly cooperative manner. Interestingly, the dual crosslinking mechanism resulted in a five-to-eight-fold improvement of the storage modulus implying reinforced hydrophobic crosslinking above the critical thermo-gelation temperature which is further boosted by the ionic crosslinking of the alginate backbone. The proposed bioink could form arbitrary geometries under mild 3D printing conditions. Last, it is demonstrated that the proposed developed bioink can be further utilized as bioprinting ink and showcased its ability to promote human periosteum derived cells (hPDCs) growth in 3D and their capacity to form 3D spheroids. In conclusion, the bioink, owing its ability to reverse thermally the crosslinking of its polymer network, can be further utilized for the facile recovery of the cell spheroids, implying its promising potential use as cell spheroid-forming template bionk for applications in 3D biofabrication.

Using molecular straps to engineer conjugated porous polymer growth, chemical doping, and conductivity.

Controlling network growth and architecture of 3D-conjugated porous polymers (CPPs) is challenging and therefore has limited the ability to systematically tune the network architecture and study its impact on doping efficiency and conductivity. We have proposed that π-face masking straps mask the π-face of the polymer backbone and therefore help to control π-π interchain interactions in higher dimensional π-conjugated materials unlike the conventional linear alkyl pendant solubilizing chains that are incapable of masking the π-face. Herein, we used cycloaraliphane-based π-face masking strapped monomers and show that the strapped repeat units, unlike the conventional monomers, help to overcome the strong interchain π-π interactions, extend network residence time, tune network growth, and increase chemical doping and conductivity in 3D-conjugated porous polymers. The straps doubled the network crosslinking density, which resulted in 18 times higher chemical doping efficiency compared to the control non-strapped-CPP. The straps also provided synthetic tunability and generated CPPs of varying network size, crosslinking density, dispersibility limit, and chemical doping efficiency by changing the knot to strut ratio. For the first time, we have shown that the processability issue of CPPs can be overcome by blending them with insulating commodity polymers. The blending of CPPs with poly(methylmethacrylate) (PMMA) has enabled them to be processed into thin films for conductivity measurements. The conductivity of strapped-CPPs is three orders of magnitude higher than that of the poly(phenyleneethynylene) porous network.

The role of molecular architecture on the viscoelastic properties of thermoreversible polyurethane adhesives

New polyurethane (PUR) adhesives containing covalent Diels-Alder (DA) bonds that can break and form with temperature have been recently developed for sustainable multilayer packaging. The understanding of the mechanical properties and in particular of creep in terms of molecular architecture appears of outmost importance in view of their applications and potential reutilization. Oscillatory shear rheometry shows a modulus decrease with temperature associated to bond breakage and the enhancement found upon cooling can be associated with network reconstruction. Analysis of storage modulus values above the glass transition and below the retro-DA reaction suggests a lower network crosslinking density with increasing adduct content. Room temperature indentation and shear rheometry tests reveal that DA bonds improve the modulus and reduce the resistance to linear viscoelastic flow. The modulus improvement can be associated to the enhanced chain rigidity introduced by the DA moieties and the reduced creep resistance seems to be related to the decrease of crosslinking density.

Microtissue-Based Bioink as a Chondrocyte Microshelter for DLP Bioprinting.

Bioprinting specific tissues with robust viability is a great challenge, requiring a delicate balance between a densely cellular distribution and hydrogel network crosslinking density. Microtissues composed of tissue-specific mesenchymal stem cells and extra cellular matrix (ECM) particles provide an alternative scheme for realizing biomimetic cell density and microenvironment. Nevertheless, due to their instability during manufacturing, scarce efforts have been made to date to assemble them using rapid prototyping methods. Here, a novel microtissue bioink with good printability and cellular viability maintenance for digital light processing (DLP) bioprinting is introduced. Generally, the microtissue bioink is prepared by crosslinking acellular matrix microparticles and GelMA hydrogel with a specific proportion. The microtissue bioink exhibits the desired mechanical properties, swelling ratio, and has almost no influences on printability. For instance, a DLP bioprinted ear with a precise auricle structure using microtia chondrocytes microtissue boink is created. Additionally, the chondrocytes in the printed ears show obvious advantages in cell proliferation in vitro and auricular cartilage regeneration in vivo. The microtissue composite bioink for DLP printing not only enables accurate assembly of organ building blocks but also provides a 3D shelter to ensure printed cells' viability.

Exploring of the property of epoxy resins based on diselenide and disulfide dynamic linkers.

Over the last decade, there has been a lot of interest in incorporating dynamic covalent bonds (DCBs) into epoxy resins. Because diselenide and disulfide bonds have similar properties, they are frequently used as DCBs in self-healing epoxy networks. In this paper, we present diselenide and disulfide dynamic linkers containing epoxy networks by analyzing the effects of mechanical properties, thermal stability, activation energies, and self-healing properties. The glass transition temperature (T g) values, mechanical properties, crosslinking density (v e ), and thermal stability of disulfide linkers networks were higher than those of diselenide linkers networks, according to our research. The activation energies of disulfide linkers were higher than those of diselenide linkers (up to 14 kJ/mol), but their healing efficiency was lower than that of the diselenide network. These findings demonstrate the advantages of diselenide and disulfide dynamic linkers in epoxy networks systems, as well as a method for designing and preparing the appropriate diselenide dynamic linkers or disulfide dynamic linkers incorporated into epoxy networks for the appropriate application and processing technology.

Thiol-Based Three-Dimensional Printing of Fully Degradable Poly(propylene fumarate) Star Polymers.

Poly(propylene fumarate) star polymers photochemically 3D printed with degradable thiol cross-linkers yielded highly tunable biodegradable polymeric materials. Tailoring the alkene:thiol ratio (5:1, 10:1, 20:1 and 30:1) and thus the cross-link density within the PPF star systems yielded a wide variation of both the mechanical and degradation properties of the printed materials. Fundamental trends were established between the polymer network cross-link density, glass transition temperature, and tensile and thermomechanical properties of the materials. The tensile properties of the PPF star-based systems were compared to commercial state-of-the-art non-degradable polymer resins. The thiolene-cross-linked materials are fully degradable and possess properties over a wide range of mechanical properties relevant to regenerative medicine applications.

Ionic coordination strengthening of temperature-driven gradient hydrogel actuators with rapid responsiveness

Emerging applications of stimuli-responsive hydrogels as soft actuators and robotics have attracted great attention, but they face challenges in practical applications due to their poor mechanical properties, low driving force, and low actuation speed. Herein, we presented tough hydrogel actuators composed of a copolymer of N-isopropylacrylamide (NIPAM) and 3-sulfopropyl methacrylate potassium salt (SPA) monomers, and tunicate cellulose nanocrystals (TCNCs). The negatively charged TCNCs as nanofillers were gradient arranged by a direct current electric field (DC-EF) via electrophoresis. After in situ polymerization, TCNCs gradient distributed across the thickness of hydrogel, resulting in the formation of gradient crosslinking density of networks. Hydrogel actuators with high strength were obtained via Zr4+/−SO3- ionic coordination, whose tensile strength was about 200 times of hydrogel without ionic coordination. These hydrogel actuators exhibited rapid bending velocity, excellent stability, and good cycling performance in response to temperature. Importantly, these hydrogel actuators could be designed as soft robots to lift and transport objects by changing environment temperature. This work provided a facile yet efficient strategy to fabricate soft actuators with high strength and rapid responsiveness.

Influences of material and processing conditions on the depolymerization speed of anhydride-cured epoxy during the solvent-assisted recycling

Thermosetting polymers with permanent crosslinking networks have been intensively used in high-performance applications requiring thermal stability, chemical resistance, and structural integrity. However, they are extremely hard to be reprocessed and recycled using conventional techniques. The recently developed solvent-assisted recycling technique is shown to depolymerize and recycle thermoset wastes using low-toxic solvents and mild processing conditions. The macromolecular polymer chains can be cleaved at target covalent bonds on the chain backbone through bond exchange reactions with solvent molecules. In this study, the influences of various material and processing conditions on the network depolymerization speed are studied from both experimental and theoretical points of view. A diffusion-reaction chemomechanics modeling framework is defined to link the physical properties of organic solvent and microscale reaction kinetics to the overall depolymerization speed of thermosets at various material and processing parameters. The study reveals how the temperature, network crosslinking density, and physical properties of the solvent, in particular, the solvent diffusivity and solvent/polymer interactions would affect the depolymerization speed. It enhances our understanding of the underlying fundamentals of thermoset recycling using organic solvents, which provides valuable insights for industrials to optimize the recycling conditions and develop appropriate strategies for waste management. • Influencing mechanisms of various material and processing parameters are revealed. • A theory is defined to link solvent properties to the depolymerization speed. • There is an optical content of good solvent to maximize the depolymerization speed. • There are threshold values for solvent hydroxyl-hydrocarbon ratio and interaction parameters.

Sequential and selective shape memory by remote electrical control

Shape memory (SM) materials have been widely investigated for several years. Most polymers present SM behaviour based on their thermo-mechanical properties. However, they are usually stimulated by an external heating source, hindering their industrial application. The addition of carbon nanotubes (CNT) allows turning conventional SM polymers into electro-active actuators. In this regard, the resistive heating by the Joule effect is considerably fast with a low energy cost.The most used epoxy resins cured at high temperature are based on diglycidyl ether of bisphenol A (DGEBA) cured with aromatic amine hardeners, such as diaminodiohenylsulfone (DDS) and 4,4′diamine-diphenylmetane (DDM). In this work, they were synthesised with modification of the epoxy/amine ratio to vary the crosslinking density of networks so as to build up different viscoelastic properties in order to tailor their SM behaviour. Electrically conductive nanocomposites were manufactured by adding a CNT percentage above the percolation threshold.A comparison of SM behaviour stimulated by traditional convection and resistive heating was carried out, confirming the higher recovery ratio, speed, and applicability of the electrical stimuli. In addition, the configuration of electrodes allows the design of self-deployable materials with remote control. In this way, the most common dual-shape SM polymers (one permanent shape and one temporary shape) can easily develop several stable temporary shapes. Moreover, the electrical remote control provides sequential and selective actuators, enhancing their performance for developing smart structures with shape memory capability.

Synthesis of Biobased and Hybrid Polyurethane Xerogels from Bacterial Polyester for Potential Biomedical Applications.

Organic–inorganic xerogel networks were synthesized from bacterial poly (3-hydroxybutyrate) (PHB) for potential biomedical applications. Since silane-based networks usually demonstrate increased biocompatibility and mechanical properties, siloxane groups have been added onto polyurethane (PU) architectures. In this work, a diol oligomer (oligoPHB-diol) was first prepared from bacterial poly(3-hydroxybutyrate) (PHB) with an environmentally friendly method. Then, hexamethylene diisocyanate or biobased dimeryl diisocyanate was used as diisocyanate to react with the short oligoPHB-diol for the synthesis of different NCO-terminated PU systems in a bulk process and without catalyst. Various PU systems containing increasing NCO/OH molar ratios were prepared. Siloxane precursors were then obtained after reaction of the NCO-terminated PUs with (3-aminopropyl)triethoxysilane, resulting in silane-terminated polymers. These structures were confirmed by different analytical techniques. Finally, four series of xerogels were prepared via a sol–gel process from the siloxane precursors, and their properties were evaluated depending on varying parameters such as the inorganic network crosslinking density. The final xerogels exhibited adequate properties in connection with biomedical applications such as a high in vitro degradation up to 15 wt% after 12 weeks.

Smart actuation of liquid crystal elastomer elements: cross-link density-controlled response

Liquid crystal elastomers (LCEs) exhibit some remarkable physical properties, such as the reversible large mechanical deformation induced by proper environmental stimuli of different nature, such as the thermal stimulus, allowing their use as soft actuators. The unique features displayed by LCE are originated from their anisotropic microstructure characterized by the preferential orientation of the mesogen molecules embedded in the polymer network. An open issue in the design of LCEs is how to control their actuation effectiveness: the amount of mesogens molecules, how they are linked to the network, the nematic order degree, the cross-link density are some controllable parameters whose spatial distribution, in general, cannot be tuned except for the last one. In this paper, we develop a theoretical micromechanical-based framework to model and explore the effect of the network cross-link density on the mechanical actuation of LCE elements. In this context, the light-induced polymerization (photopolymerization) for obtaining the elastomers’ cross-linked network is of particular interest, being suitable for precisely tuning the cross-link density distribution within the material. This technology enables to obtain a molecular-scale architected LCEs, allowing the optimal design of the obtainable actuation. The possibility to properly set the cross-link density arrangement within the smart structural element (LCE microstructure design and optimization), represents an intriguing way to create molecular-scale engineered LCE elements having a material microstructure encoding the desired actuation capabilities.