Liquid crystalline elastomers (LCEs) are materials that reveal unusual mechanical, optical and thermal properties due to their molecular orientability characteristic of low molar mass liquid crystals while maintaining the mechanical elasticity distinctive of rubbers. As such, they are considered smart shape-changing responsive systems. In this work, we report on the preparation of magnetic sensitized nematic LCEs using iron oxide nanoparticles with loadings of up to 0.7 wt%. The resultant thermal and mechanical properties were characterized by differential scanning calorimetry, expansion/contraction experiments and extensional tests. The magnetic actuation ability was also evaluated for the neat elastomer and the composite with 0.5 wt% magnetic content, finding reversible contractions of up to 23% with the application of alternating magnetic fields (AMFs) of up to 48 kA/m at 300 kHz. Thus, we were able to demonstrate that the inclusion of magnetic nanoparticles yields LCEs with adjustable properties that can be tailored by changing the amount of particles embedded in the elastomeric matrix, which can be suitable for applications in actuation, sensing, or as smart substrates.

Functionalization of gelatin with desaminotyrosine (DAT) and desamino tyrosyl tyrosine (DATT) has been demonstrated to allow network formation based on non-covalent interactions of the aromatic moieties. Based on the observation that the DAT(T) groups furthermore could interact with hydroxyapatite fillers, here it was investigated whether such interactions of DAT(T) could also be employed to stabilize composites formed by functionalized gelatins and bioactive glass (BG) particles. Because of sedimentation of the BG microparticles during the gelification, anisotropic composites with two distinct layers were formed. The characterization of mechanical properties by tensile tests and rheology showed that all composites of non-functionalized and DAT(T) functionalized gelatins with BG microparticles showed an increased Young’s modulus (E) up to 3 MPa, an increased storage modulus (G’) up to 100 kPa, increased tensile strength (σmax) up to 3.4 MPa, and increased loss modulus (G’’) compared to the pure matrices. As the observed effects were more pronounced in the DAT(T) functionalized gelatins compared to non-functionalized gelatins, and a much increased thermal stability of these composites was found, it is likely that there are binding interactions between the aromatic moieties and the BG microparticles. This effect open opportunities for the further development of this type of gelatin-based composites for bone regeneration applications.

We investigated the effects of varying the multiwalled carbon nanotube (MWCNT) contents, as well as the additional use of drawing and poling on the polymorphic behavior and electroactive (piezoelectric) properties of the cast poly(vinylidene fluoride) (PVDF)/MWCNT membranes. Dramatic changes occurred in the polar β-phase crystal contents with the MWCNT loading. An optimum concentration of MWCNT exists for PVDF film polarization. On the other hand, films prepared by electrospinning process exhibited almost constant amount of β-phase with the MWCNT concentration. In this process, polymer fibers with diameters down to the nanometer range, or nanofibers, are formed by subjecting a fluid jet to a high electric field. The remanent polarization and piezoelectric response increased with the β-phase crystals. Cell adhesion and proliferation measured with MTT (Methylthiazolyl diphenyl-tetrazolium bromide) assay coincidentally responded to the polarized PVDF films (β-phase amount).

In situ temperature-resolved Near-edge X-ray Absorption Fine Structure (NEXAFS) measurements were performed on thermo-active ethylene-vinyl acetate (EVA) – multiwall carbon nanotube (MWCNT) composites 12 months following synthesis, and compared with spectra acquired shortly after synthesis to examine aging effects on non-covalent interactions. Room temperature spectra revealed no difference between unstrained and strained composites, suggesting relaxation. Further, energy shifts in π* C=C resonances indicated a change in π–π interactions between MWCNT walls and chemical dispersant, supported also by AFM phase imaging. Temperature-resolved NEXAFS analysis showed a lack of interaction between nanotubes and polymeric chains, suggesting the chemical dispersant unlatched from MWCNT walls. The extent of this effect is finally quantified through a comparative study of spectral trends.

In this study, thiol-epoxy polymer composites are explored as candidates for high-temperature die attach applications. We present a polymer composite processing technique for die attach adhesives with low cure-stress. Lap shear samples of both a polymer adhesive and current industry adhesives were subjected to tensile testing and die shear strength was compared. At 260 °C, the candidate polymer adhesive exhibited a die shear strength of 0.500 MPa in comparison with 1.35 MPa and 0.258 MPa for two control adhesives. While samples showed less variation in properties in die shear strength between room temperature and 260 °C, the absolute die shear strength values were inferior to commercial adhesives at both room and elevated temperatures. We hypothesize that low cure stress networks, such as the thiol-epoxies presented, provide a compelling choice to engineer new die attach adhesives, but realize that further network refining is needed including the addition of adhesion promoters and other additives, a task better suited to industrial research with a focus in properties optimization.

In this work, a systematic study on the factors that influence the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAM) solutions during remote radiofrequency (RF) heating, using Fe3O4 magnetic nanoparticles (MNPs) is reported. A series of PNIPAM solutions with varying concentrations of Fe3O4 MNPs were prepared and characterized using transmission electron microscopy and Raman spectroscopy. Preliminary studies showed the highest specific absorption rate (SAR) for 15 nm sized Fe3O4 MNPs, which monotonically decreased as the MNP sizes increased to 20-30 nm. In-situ transmission measurements were used to determine the LCST of PNIPAM under various aqueous concentrations with dispersed Fe3O4 MNPs. A systematic decrease in the LCST from 34 °C to 31 °C was observed as the concentration of PNIPAM was increased from 0.3 wt. % to 1.0 wt. %, keeping the concentration of Fe3O4 MNPs constant. On the other hand, varying the concentrations of the MNPs did not drastically affect the LCSTs of PNIPAM solutions. However, varying the ion concentration of the PNIPAM solutions by adding adjusted KOH pellets, showed a pronounced lowering of the LCST by 2-3 °C at all PNIPAM concentrations. The remote triggering of phase transitions in PNIPAM solutions by raising the temperature above the LCST using Fe3O4 MNPs as reported here is important in targeted drug-delivery applications using thermo-responsive polymers.

Temperature-memory effects in polymers under stress-free conditions are typically limited to one way effects. Recently, crosslinked polymer networks comprising crystallizable domains, which were capable of a reversible temperature-memory effect (rTME) under stress-free conditions, were introduced. The utilization of crystallizable actuator domains (AD) and shape determining domains (SD) where related to two different temperature ranges of a single broad melting temperature transition in case of rTME. In this study we investigated the nanostructure of crosslinked poly[ethylene-co-(vinyl acetate)] cPEVA capable of rTME in situ during actuation cycles utilizing X-ray scattering techniques and related the changes on the nanoscale to effects on the macroscopic scale. It was observed that 23% of SD obtained at a separation temperature of 75 °C gave the highest reversible strain and when exceeding 80 °C only isotropic crystallization occurred and no rTME was observed. Furthermore, distances between oriented crystalline lamellae correlated to the macroscopic actuation during heating-cooling cycles, exhibiting long-periods from 14 to 17 nm as function of temperature.

Photoswitchable polymeric materials comprise moieties that undergo light-induced chemical reactions or conformational alteration. The reversibility of photo-responsive molecular switches has an influence on material functions observed on the macroscopic level such as reversibility of shape switching, especially with regard to the number of cycles. Cinnamylidene acetic acid (CAA) has received attention due to its reversible dimerization by [2+2] cycloaddition reactions. In the present study, possible side-reactions during photo-scission of the CAA dimers as netpoints in poly(ε-caprolactone) based materials were studied by fluorescence spectroscopy, HPLC and 1H,1H-COSY. Liberation of fluorescent fragments, which have their origin in the various dimer structures, could only be found in small amounts, while a non-identified species seems to be generated during dimerization and photo-scission. The results furthermore suggest that CAA-based switches in PCL-networks do not provide full reversibility of netpoint formation under the examined conditions, due to non-selective side-reactions, which could lead to an attenuation of the macroscopic effect in multiple photo-cycles. In perspective, the design of CAA derivatives with enhanced photo-reversibility should be targeted.

2-, 4-, 6- and 8-arm star amphiphilic block copolymers were prepared with the branching point located in the hydrophobic core composed of poly(propylene sulfide) (PPS); poly(ethylene glycol) (PEG) pendant chains completed the macromolecular structure. The level of branching influenced the rigidity of the PPS core and of the overall macromolecule, with the Mark-Houwink parameter a gradually approaching the value typical of globules for 6 and 8 arms. A binary behavior (linear vs. branched) was noticed for the kinetics of oxidation by H2O2 and the stability of the colloidal aggregates formed in water: irrespective of the number of arms, all branched polymers showed a slower response (to oxidation) and a more stable hydrophobic domains (a critical micellar concentration < 0.01 mg/mL).

Photo-actuating structures inspired by the chemical sensing and signal transmission observed in sun-tracking leaves have recently been proposed by Dicker et al. The proposed light tracking structures are complex, multicomponent material systems, principally composed of a reversible photoacid or base, combined with a pH responsive hydrogel actuator. New modelling and characterization approaches for pH responsive hydrogels are presented in order to facilitate the development of the proposed structures. The model employs Donnan equilibrium for the prediction of hydrogel swelling in systems where the pH change is a variable resulting from the equilibrium interaction of all free and fixed (hydrogel) species. The model allows for the fast analysis of a variety of combinations of material parameters, allowing for the design space for the proposed photo-actuating structures to be quickly established. In addition, experimental examination of the swelling of a polyether-based polyurethane and poly(acrylic acid) interpenetrating network hydrogel is presented. The experiment involves simultaneously performing a titration of the hydrogel, and undertaking digital image correlation (DIC) to determine the hydrogel’s state of swelling. DIC allows for the recording of the hydrogel’s state of swelling with previously unattained levels of resolution. Experimental results provide both model material properties, and a means for model validation.

Covalent integration of inorganic nanoparticles into polymer matrices leads to a homogenization of their distribution and enhances the structural properties. Here, we report on a thermally-controlled reversible shape-memory effect (R-SME) of magnetic nanocomposites under stress-controlled conditions. The magnetic nanocomposites consisted of an oligo(ω-pentadecalactone) (OPDL) matrix with covalently integrated or physically added magnetic nanoparticles (MNP). The R-SME of these materials was based on crystallization-induced elongation (CIE) and melting-induced contraction (MIC) under a constant stress in thermomechanical experiments. Furthermore, the adjustability of the recovery stress in magnetic nanocomposites as a function of MNP content was investigated. A slight increase in the recovery stress from 0.9 MPa for pure OPDL network to 1.2 MPa for H-NC containing 9 wt% of covalently integrated MNP was observed.

Tubular grafts were fabricated from blends of polycaprolactone (PCL) and poly(glycolide-co-caprolactone) (PGC) polymers and coated with an extracellular matrix containing collagens, laminin, and proteoglycans, but not growth factors (HuBiogel™). Multifunctional scaffolds from polymer blends and membrane proteins provide the necessary biomechanics and biological functions for tissue regeneration. Two crosslinking agents, a natural crosslinker namely genipin (Gp) and a carbodiimide reagent namely 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), were used for further stabilizing the protein matrix and the effect of crosslinking was evaluated for structural, morphological, mechanical properties using SEM, DSC and DMA. SEM images and fiber diameter distribution showed fiber-size between 0.2 μm to 1 μm with the majority of fiber diameters being under 500 nm, indicating upper range of protein fiber-sizes (for example, collagen fibers in extracellular matrix are in 50 to 500 nm diameter range). HB coating did not affect the mechanical properties, but increased its hydrophilicity of the graft. Overall data showed that PCL/PGC blends with 3:1 mass ratio exhibited mechanical properties comparable to those of human native arteries (tensile strength of 1-2 MPa and Young’s modulus of <10 MPa). Additionally, the effect of crosslinking on coating stability was investigated to assure the retention of proteins on scaffold for effective cell-matrix interactions.

The formation of injectable implants in the presence of cells or solutes has previously been conceptualized to be based on the selectivity of bioorthogonal chemical reactions. As an alternative approach, hydrogel network synthesis by enzymatic reactions with a typically high inherent substrate specificity and low toxicity have been repeatedly proposed, e.g. using commercial mushroom tyrosinase (MTyr), which specifically catalyzes phenol oxidation. In this study, it should be explored whether MTyr is compatible with therapeutic peptides that may be delivered from such hydrogels in the future. Based on the specificity of MTyr to phenol residues, no modification of peptides lacking the amino acid tyrosine would be expected. One example of such peptides is gramicidin S (GS), a potent antimicrobial peptide. However, when GS was incubated with commercial MTyr, peptide degradation occurred as observed by HPLC analysis. Several fragments of the peptide were detected by MALDI-TOF. Contamination of MTyr with peptidases was proven as the source of undesired peptide cleavage, which needs to be considered when preparing enzymatically crosslinked hydrogels for biomedical applications.

Cellulose nanocrystals (CNCs) have emerged as a new class of renewable material for various applications due to their remarkable properties and commercialization prospect. The relative low density, expected low cost, non-toxic character, uniform nanosize distribution, high aspect ratios, high surface area, thermal properties and high modulus of elasticity make CNCs attractive nanomaterials that recently prompted the industrial production of CNCs in North America. Surface functionalization of CNCs continues to be an exciting area of research for the design of novel CNC-based materials. In this work, we report the synthesis, characterization and cytotoxicity studies of novel cationic surface modified CNC derivatives. The negative surface of CNC was rendered positive after grafting with cationic polymers via surface-initiated living radical polymerization method. The modified CNCs were characterized by both spectroscopic and microscopic techniques. Their cytotoxicity effects were evaluated using MTT assay in two cell lines such as mouse macrophages (J774.A1) and human breast cancer (MCF7). Preliminary studies indicated that only one of the modified CNCs caused significant decrease in J774.A1 cell viability (50%), at the highest concentration tested (100 µg/mL). However this concentration is well above of what would be applicable for biomedical purposes. MCF7 cells were not affected by any of the cationic CNCs at any concentration. A detailed cytotoxicity study is currently underway to fully understand the interaction of these cationic CNCs with the biological systems for possible bio-inspired applications.

Polymer-based therapeutic strategies require biomaterials with properties and functions tailored to the demands of specific applications leading to an increasing number of newly designed polymers. For the evaluation of those new materials, comprehensive biocompatibility studies including cyto-, tissue-, and immunocompatibility are essential. Recently, it could be demonstrated that star-shaped amino oligo(ethylene glycol)s (sOEG) with a number average molecular weight of 5 kDa and functionalized with the phenol-derived moieties desaminotyrosine (DAT) or desaminotyrosyl tyrosine (DATT) behave in aqueous solution like surfactants without inducing a substantial cytotoxicity, which may qualify them as solubilizer for hydrophobic drugs in aqueous solution. However, for biomedical applications the polymer solutions need to be free of immunogenic contaminations, which could result from inadequate laboratory environment or contaminated starting material. Furthermore, the materials should not induce uncontrolled or undesired immunological effects arising from material intrinsic properties. Therefore, a comprehensive immunological evaluation as perquisite for application of each biomaterial batch is required. This study investigated the immunological properties of sOEG-DAT(T) solutions, which were prepared using sOEG with number average molecular weights of 5 kDa, 10 kDa, and 20 kDa allowing analyzing the influence of the sOEG chain lengths on innate immune mechanisms. A macrophage-based assay was used to first demonstrate that all DAT(T)-sOEG solutions are free of endotoxins and other microbial contaminations such as fungal products. In the next step, the capacity of the different DAT(T)-functionalized sOEG solutions to induce cytokine secretion and generation of reactive oxygen species (ROS) was investigated using whole human blood. It was observed that low levels of the pro-inflammatory cytokines interleukin(IL)-1β and IL-6 were detected for all sOEG solutions but only when used at concentrations above 250 µg·mL-1. Furthermore, only the 20 kDa sOEG-DAT induced low amounts of ROS-producing monocytes. Conclusively, the data indicate that the materials were not contaminated with microbial products and do not induce substantial immunological adverse effects in vitro, which is a prerequisite for future biological applications.

Gelatin functionalized with glycidyl methacrylate (GMA) has been shown to allow crosslinking by photopolymerization and metathesis reaction. However, side chain functionalization of gelatin might reduce triple helicalization, which influences mechanical properties of gelatin-based polymer networks. Here, the influence of glycidylmethycrylation of gelatin on the chain organization, swelling, and mechanical properties is investigated by comparing among each other physical gels prepared from GMA-gelatin solutions of different concentrations (5-20 wt.-%) by drying and rehydration. An increase of GMA-gelatin concentration from 5 wt.-% to 20 wt.-% led to an increased density of produced gelatin films and a decreasing water uptake of the films from 1160 wt.-% to 730 wt.-%, while the storage modulus was increasing about one order of magnitude from 440 Pa to 4090 Pa. The relative single and triple helix content was not influenced by the variation of polymer concentration.

Dihydroxy telechelics are precursors for the synthesis of multiblock copolymers. In order to synthesize high molecular weight polymers with good elastic properties it is necessary to gain detailed knowledge of the reaction behavior of these precursors. Therefore it was explored whether the polyaddition reaction of polyester-diols can be established in a robotic synthesizer platform to facilitate the elucidation of reaction characteristics. A series of 16 reactions was performed using a telechelic polyester and trimethylhexamethylene diisocyanate. The chain extension behavior of the building block was compared with respect to the Carothers equation. It was found, that the chain extension behavior follows the expected trend. The molecular weight of the polymers increased when the optimal ratio of reactive groups was approached.

The advantage of magnetic resonance imaging (MRI) is mainly the direct visualization of the physico-chemical processes occurring during the polymer dissolution in real time. Nowadays, polymeric matrices as a means to control the release of the active pharmaceutical ingredient (API) are widely used. Hence it seems necessary to describe the polymer swelling and find the relationship between the type of used polymer and the dissolution profile of API.

The aim of our research was to monitor the dissolution kinetics of polymeric matrices with the different ratio of hydrophilic and lipophilic components utilizing MRI technology. For this purpose, six different matrices were prepared. For the dissolution experiments in MRI magnet, plastic flow through cell and tablet holder were designed and manufactured using a 3-D printer. The experiments were performed under specific conditions i.e. phosphate buffer saline pH 6 as a medium, medium temperature - 37°C, the flow rate of medium - 4 ml/min, the time of experiment - 8 hours. To improve the visibility of the erosion front, composite magnetic nanoparticles SiO2/FeOx as a MRI contrast agent were used. Each matrix was measured three times and the thickness of gel layer was evaluated in three different regions. Results from MRI experiments were compared to the results obtained by utilizing the texture analyzer, and then the relationship between polymer swelling and drug release was evaluated.

To sum up, MRI turned out to be a suitable imaging method for polymer swelling quantification. For the future measurements, the effect of different additives on the polymer swelling kinetics will be evaluated. The results from the whole research should lead to the database of matrix components and conditions of technological processes and their effects on the dissolution profile of API, thus simplifying the formulation of dosage forms with the desired drug release.

Crosslinked poly[ethylene-co-(vinyl acetate)] (cPEVA) has been recently introduced as a polymer material, which can be functionalized with various shape-memory effects by solely altering the thermomechanical treatment called programming.

In this study two series of cPEVAs with different vinyl acetate contents of 18 wt% (cPEVA18) and 28 wt% (cPEVA28) comprising different crosslink densities were investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) in the temperature range of -130 °C to 120 °C. DMTA tests were performed in torsion mode, because such movements are highly relevant in the context of complex shape changes in shape-memory polymer based devices. Finally, the obtained DMTA results were compared with DMTA conducted in tension mode. Swelling experiments revealed a gel content in the range from 81% to 90% for cPEVA18 samples while for cPEVA28s a complete conversion was observed. The degree of swelling was found to decrease substantially with increasing crosslink density for both cPEVA series.

The influence of VA content and extent of crosslinking on the appearance of the respective melting (Tm) and glass transition (Tg) as well as the thermomechanical properties of cPEVA systems could be demonstrated by discussing both DSC and DMTA results. The temperature range of mechanical stability correlates with the VA content and is determined by decreasing Tm values. The cross links do barely alter the stiffness of a PEVA up to the Tm rang, but lead to constant mechanical rigidity in the rubbery range above Tm.

Adenosine triphosphate (ATP) has numerous biological functions both intra- and extracellularly, including effects on the directed migration of cells with a regenerative potential in brain tissue. Therefore, carrier systems would be of interest that would be capable to be loaded with ATP and release it in a controlled manner. In the present study, poly(n-butylcyanoacrylate) (PBCA) nanoparticles as a potential carrier system were prepared by anionic polymerization using different polymerization media, which resulted in different zeta potential values and in some cases aggregation of nanoparticles. By decorating the particle surface with positively charged diethylaminoethyl dextran, multivalent ionic interaction allowed to load ATP to the nanoparticles by adsorption. In release experiments, an ATP release over 6 hours was observed. ATP-loaded nanoparticles may thus be suitable to explore biological effects of short-term ATP delivery for biomedical applications.