Probing Viscoelastic Properties and Interfaces in High-Density Polyethylene Vitrimers at the Nanoscale Using Dynamic Mode Atomic Force Microscopy.

Vitrimers are a new class of heterogeneous polymers that combine the best features of thermosets with those of thermoplastics. The introduction of cross-links strongly changes the viscoelastic behavior of vitrimer materials. However, the characterization and understanding of the nanostructures and interfaces in vitrimers resulting from dynamic cross-linking formation remain a major challenge. Here, using dynamic modes of atomic force microscopy (AFM), namely intermodulation AFM (ImAFM) and AFM-based dynamic mechanical analysis (AFM-nDMA), local viscoelastic properties and interfaces at the nanoscale length of high-density polyethylene (HDPE) vitrimer materials are reported. ImAFM imaging in combination with the k-means clustering algorithm clearly reveals two distinct phases in the vitrimer system with highly different viscoelastic properties. AFM-nDMA further provides quantitative nanoviscoelastic properties at the nanoscale to confirm that there is a cross-linking-rich aggregation area forming a nanosize network structure in the cross-linking-poor matrix phase. The cross-linking-rich region shows a similar elastic modulus but much higher adhesion force measured by AFM compared to the cross-linking-poor HDPE matrix. Furthermore, the frequency influence on the local viscoelastic properties of HDPE vitrimer at the nanoscale was initially screened. The observed HDPE vitrimer nanostructures and viscoelastic properties at the nanoscale also provide explanations on the observed bulk HDPE vitrimer crystallinity decrease and dimensional stability increase compared to HDPE. Therefore, probing the viscoelastic properties and interfaces of HDPE vitrimer provides important insights into understanding of the correlations between the vitrimer nanostructure and the bulk mechanical and rheological behaviors.

iPP/HDPE blends compatibilized by a polyester: An unconventional concept to valuable products.

Polyolefins are the most widely used plastics accounting for a large fraction of the polymer waste stream. Although reusing polyolefins seems to be a logical choice, their recycling level remains disappointingly low. This is mainly due to the lack of large-scale availability of efficient and inexpensive compatibilizers for mixed polyolefin waste, typically consisting of high-density polyethylene (HDPE) and isotactic polypropylene (iPP) that, despite their similar chemical hydrocarbon structure, are immiscible. Here, we describe an unconventional approach of using polypentadecalactone, a straightforward and simple-to-produce aliphatic polyester, as a compatibilizer for iPP/HDPE blends, especially the brittle iPP-rich ones. The unexpectedly effective compatibilizer transforms brittle iPP/HDPE blends into unexpectedly tough materials that even outperform the reference HDPE and iPP materials. This simple approach creates opportunities for upcycling polymer waste into valuable products.

Ink-Deposited Transparent Electrochromic Structural Colored Foils.

Despite progress in the field of electrochromic devices, developing structural color-tunable photonic systems having both high transparency and flexibility remains challenging. Here, an ink-deposited transparent electrochromic structural colored foil displaying reflective colors, tuned by an integrated heater, is prepared in a single-substrate method. Efficient and homogeneous heating is induced by a gravure printed silver nanowire-based substrate, delivering an electrothermal response upon applying an electrical potential. On top of this flexible, transparent heater, a cholesteric liquid crystal ink is bar-coated and subsequently photopolymerized, yielding a structural colored film that exhibits temperature-responsive color changes. The transparent electrochromic foils appear colorless at room temperature but demonstrate structural color tuning with high optical quality when modifying the electrical potential. Both optical and electrothermal performances were preserved when deforming the foils. Applying the conductive and structural colored inks via the easy processable, continuous methods of gravure printing and bar-coating highlights the potential for scaling up to large-scale stimuli-responsive, transparent optical foils. These transparent structural colored foils can be potentially used for a wide range of photonic devices including smart windows, displays, and sensors and can be directly installed on top of curved, flexible surfaces.

Anisotropic Iridescence and Polarization Patterns in a Direct Ink Written Chiral Photonic Polymer.

The iridescence of structural color and its polarization characteristics originate from the nanoscale organization of materials. A major challenge in materials science is generating the bright, lustrous hues seen in nature through nanoscale engineering, while simultaneously controlling interaction of the material with different light polarizations. In this work, a suitable chiral nematic liquid crystal elastomer ink is synthesized for direct ink writing, which self-assembles into a chiral photonic structure. Tuning the writing direction and speed leads to the programmed formation of a slanted photonic axis, which exhibits atypical iridescence and polarization selectivity. After crosslinking, a freely programmable, chiroptical photonic polymer material is obtained. The strongly perspective-dependent appearance of the material can function as specialized anticounterfeit markers, as optical elements in decorative iridescent coatings, or, as demonstrated here, in optically based signaling features.

Wavelength-Selective Photopolymerization of Hybrid Acrylate-Oxetane Liquid Crystals.

We report on the wavelength-selective photopolymerization of a hybrid acrylate-oxetane cholesteric liquid crystal monomer mixture. By controlling the sequence and rate of the orthogonal free-radical and cationic photopolymerization reactions, it is possible to control the degree of phase separation in the resulting liquid crystal interpenetrating networks. We show that this can be used to tune the reflective color of the structurally colored coatings produced. Conversely, the structural color can be used to monitor the degree of phase separation. Our new photopolymerization procedure allows for structuring liquid crystal networks in three dimensions, which has great potential for fabricating liquid crystal polymer materials with programmable functional properties.

Reversible and oriented immobilization of ferrocene-modified proteins.

Adopting supramolecular chemistry for immobilization of proteins is an attractive strategy that entails reversibility and responsiveness to stimuli. The reversible and oriented immobilization and micropatterning of ferrocene-tagged yellow fluorescent proteins (Fc-YFPs) onto ß-cyclodextrin (ßCD) molecular printboards was characterized using surface plasmon resonance (SPR) spectroscopy and fluorescence microscopy in combination with electrochemistry. The proteins were assembled on the surface through the specific supramolecular host-guest interaction between ßCD and ferrocene. Application of a dynamic covalent disulfide lock between two YFP proteins resulted in a switch from monovalent to divalent ferrocene interactions with the ßCD surface, yielding a more stable protein immobilization. The SPR titration data for the protein immobilization were fitted to a 1:1 Langmuir-type model, yielding K(LM) = 2.5 × 10(5) M(-1) and K(i,s) = 1.2 × 10(3) M(-1), which compares favorably to the intrinsic binding constant presented in the literature for the monovalent interaction of ferrocene with ßCD self-assembled monolayers. In addition, the SPR binding experiments were qualitatively simulated, confirming the binding of Fc-YFP in both divalent and monovalent fashion to the ßCD monolayers. The Fc-YFPs could be patterned on ßCD surfaces in uniform monolayers, as revealed using fluorescence microscopy and atomic force microscopy measurements. Both fluorescence microscopy imaging and SPR measurements were carried out with the in situ capability to perform cyclic voltammetry and chronoamperometry. These studies emphasize the repetitive desorption and adsorption of the ferrocene-tagged proteins from the ßCD surface upon electrochemical oxidation and reduction, respectively.

Supramolecularly oriented immobilization of proteins using cucurbit[8]uril.

A supramolecular strategy is used for oriented positioning of proteins on surfaces. A viologen-based guest molecule is attached to the surface, while a naphthol guest moiety is chemoselectively ligated to a yellow fluorescent protein. Cucurbit[8]uril (CB[8]) is used to link the proteins onto surfaces through specific charge-transfer interactions between naphthol and viologen inside the CB cavity. The assembly process is characterized using fluorescence and atomic force microscopy, surface plasmon resonance, IR-reflective absorption, and X-ray photoelectron spectroscopy measurements. Two different immobilization routes are followed to form patterns of the protein ternary complexes on the surfaces. Each immobilization route consists of three steps: (i) attaching the viologen to the glass using microcontact chemistry, (ii) blocking, and (iii) either incubation or microcontact printing of CB[8] and naphthol guests. In both cases uniform and stable fluorescent patterns are fabricated with a high signal-to-noise ratio. Control experiments confirm that CB[8] serves as a selective linking unit to form stable and homogeneous ternary surface-bound complexes as envisioned. The attachment of the yellow fluorescent protein complexes is shown to be reversible and reusable for assembly as studied using fluorescence microscopy.

Microscale mechanical properties of single elastic fibers: the role of fibrillin-microfibrils.

Micromechanical properties of single elastic fibers and fibrillin-microfibrils, isolated from equine ligamentum nuchae using chemical and enzymatic methods, were determined with atomic force microscopy (AFM). Young's moduli of single elastic fibers immersed in water, devoid of or containing fibrillin-microfibrils, were determined using bending tests. Bending freely suspended elastic fibers on a micro-channeled substrate by a tip-less AFM cantilever generated a force versus displacement curve from which Young's moduli were calculated. For single elastic fibers, Young's moduli in the range of 0.3-1.5 MPa were determined, values not significantly affected by the presence of fibrillin-microfibrils. To further understand the role of fibrillin-microfibrils in vertebrate elastic fibers, layers of fibrillin-microfibrils were subjected to nano-indentation tests. From the slope of the force versus indentation curves, Young's moduli ranging between 0.56 and 0.74 MPa were calculated. The results suggest that fibrillin-microfibrils are not essential for the mechanical properties of single vertebrate elastic fibers.

Mechanical properties of single electrospun collagen type I fibers.

The mechanical properties of single electrospun collagen fibers were investigated using scanning mode bending tests performed with an AFM. Electrospun collagen fibers with diameters ranging from 100 to 600 nm were successfully produced by electrospinning of an 8% w/v solution of acid soluble collagen in 1,1,1,3,3,3-hexafluoro-2-propanol (HFP). Circular dichroism (CD) spectroscopy showed that 45% of the triple helical structure of collagen molecules was denatured in the electrospun fibers. The electrospun fibers were water soluble and became insoluble after cross-linking with glutaraldehyde vapor for 24h. The bending moduli and shear moduli of both non- and cross-linked single electrospun collagen fibers were determined by scanning mode bending tests after depositing the fibers on glass substrates containing micro-channels. The bending moduli of the electrospun fibers ranged from 1.3 to 7.8 GPa at ambient conditions and ranged from 0.07 to 0.26 MPa when immersed in PBS buffer. As the diameter of the fibrils increased, a decrease in bending modulus was measured clearly indicating mechanical anisotropy of the fiber. Cross-linking of the electrospun fibers with glutaraldehyde vapor increased the shear modulus of the fiber from approximately 30 to approximately 50 MPa at ambient conditions.

Mechanical properties of native and cross-linked type I collagen fibrils.

Micromechanical bending experiments using atomic force microscopy were performed to study the mechanical properties of native and carbodiimide-cross-linked single collagen fibrils. Fibrils obtained from a suspension of insoluble collagen type I isolated from bovine Achilles tendon were deposited on a glass substrate containing microchannels. Force-displacement curves recorded at multiple positions along the collagen fibril were used to assess the bending modulus. By fitting the slope of the force-displacement curves recorded at ambient conditions to a model describing the bending of a rod, bending moduli ranging from 1.0 GPa to 3.9 GPa were determined. From a model for anisotropic materials, the shear modulus of the fibril is calculated to be 33 +/- 2 MPa at ambient conditions. When fibrils are immersed in phosphate-buffered saline, their bending and shear modulus decrease to 0.07-0.17 GPa and 2.9 +/- 0.3 MPa, respectively. The two orders of magnitude lower shear modulus compared with the Young's modulus confirms the mechanical anisotropy of the collagen single fibrils. Cross-linking the collagen fibrils with a water-soluble carbodiimide did not significantly affect the bending modulus. The shear modulus of these fibrils, however, changed to 74 +/- 7 MPa at ambient conditions and to 3.4 +/- 0.2 MPa in phosphate-buffered saline.

Micromechanical bending of single collagen fibrils using atomic force microscopy.

A new micromechanical technique was developed to study the mechanical properties of single collagen fibrils. Single collagen fibrils, the basic components of the collagen fiber, have a characteristic highly organized structure. Fibrils were isolated from collagenous materials and their mechanical properties were studied with atomic force microscopy (AFM). In this study, we determined the Young's modulus of single collagen fibrils at ambient conditions from bending tests after depositing the fibrils on a poly(dimethyl siloxane) (PDMS) substrate containing micro-channels. Force-indentation relationships of freely suspended collagen fibrils were determined by loading them with a tip-less cantilever. From the deflection-piezo displacement curve, force-indentation curves could be deduced. With the assumption that the behavior of collagen fibrils can be described by the linear elastic theory of isotropic materials and that the fibrils are freely supported at the rims, a Young's modulus of 5.4 +/- 1.2 GPa was determined. After cross-linking with glutaraldehyde, the Young's modulus of a single fibril increases to 14.7 +/- 2.7 GPa. When it is assumed that the fibril would be fixed at the ends of the channel the Young's moduli of native and cross-linked collagen fibrils are calculated to be 1.4 +/- 0.3 GPa and 3.8 +/- 0.8 GPa, respectively. The minimum and maximum values determined for native and glutaraldehyde cross-linked collagen fibrils represent the boundaries of the Young's modulus.