Jamie M. Messman

Methanol Fractionation of Softwood Kraft Lignin: Impact on the Lignin Properties

The development of technologies to tune lignin properties for high-performance lignin-based materials is crucial for the utilization of lignin in various applications. Here, the effect of methanol (MeOH) fractionation on the molecular weight, molecular weight distribution, glass transition temperature (Tg ), thermal decomposition, and chemical structure of lignin were investigated. Repeated MeOH fractionation of softwood Kraft lignin successfully removed the low-molecular-weight fraction. The separated high-molecular-weight lignin showed a Tg of 211 °C and a char yield of 47 %, much higher than those of as-received lignin (Tg 153 °C, char yield 41 %). The MeOH-soluble fraction of lignin showed an increased low-molecular-weight fraction and a lower Tg (117 °C) and char yield (32%). The amount of low-molecular-weight fraction showed a quantitative correlation with both 1/Tg and char yield in a linear regression. This study demonstrated the efficient purification or fractionation technology for lignin; it also established a theoretical and empirical correlation between the physical characteristics of fractionated lignins.

Ternary behavior and systematic nanoscale manipulation of domain structures in P3HT/PCBM/P3HT-b-PEO films

Nanophase separation plays a critical role in the performance of donor–acceptor based organic photovoltaic (OPV) devices. Although post-fabrication annealing is often used to enhance OPV efficiency, the ability to exert precise control over phase separated domains and connectivity remains elusive. In this work, we use a diblock copolymer to systematically manipulate the domain sizes of an organic solar cell active layer at the nanoscale. More specifically, a poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-b-PEO) diblock copolymer with a low polydispersity index (PDI = 1.3) is added to a binary blend of P3HT and 6,6-phenyl C61-butyric acid methyl ester (PCBM) at different concentrations (0–20 wt%). Energy-filtered TEM (EFTEM) results suggest systematic changes of P3HT distribution as a function of block copolymer compatibilizer concentration and thermal annealing. X-ray scattering and microscopy techniques are used to show that prior to annealing, active layer domain sizes do not change substantially as compatibilizer is added; however after thermal annealing, the domain sizes are significantly reduced as the amount of P3HT-b-PEO compatibilizer increases. The impact of compatibilizer is further rationalized through quantum density functional theory calculations. Overall, this work demonstrates the possibility of block copolymers to systematically manipulate the nanoscale domain-structure of blends used for organic photovoltaic devices. If coupled with efficient charge transport and collection (through judicious choice of block copolymer type and composition), this approach may contribute to further optimization of OPV devices.

Immobilization of biomolecules on poly(vinyldimethylazlactone)-containing surface scaffolds.

We describe the successful development of a procedure for the step-by-step formation of a reactive, multilayer polymer scaffold incorporating polymers based on 2-vinyl-4,4-dimethylazlactone (VDMA) on a silicon wafer and the characterization of these materials. Also discussed is the development of a procedure for the nonsite specific attachment of a biomolecule to a modified silicon wafer, including scaffolds modified via drop-on-demand (DOD) inkjet printing. VDMA-based polymers were used because of their hydrolytic stability and ability of the pendant azlactone rings to form stable covalent bonds with primary amines without byproducts via nucleophilic addition. This reaction proceeds without a catalyst and at room temperature, yielding a stable amide linkage, which adds to the ease of construction expected when using VDMA-based polymers. DOD inkjet printing was explored as an interesting method for creating surfaces with one or more patterns of biomolecules because of the flexibility and ease of pattern design.

Nonfunctionalized Polydimethyl Siloxane Superhydrophobic Surfaces Based on Hydrophobic−Hydrophilic Interactions

Superhydrophobic surfaces based on polydimethyl siloxane (PDMS) were fabricated using a 50:50 PDMS-poly(ethylene glycol) (PEG) blend. PDMS was mixed with PEG, and incomplete phase separation yielded a hierarchic structure. The phase-separated mixture was annealed at a temperature close to the crystallization temperature of the PEG. The PEG crystals were formed isothermally at the PDMS/PEG interface, leading to an engineered surface with PDMS spherulites. The resulting roughness of the surface was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The PDMS spherulites, a few micrometers in diameter observed from SEM images, were found to have an undulated (rippled) surface with nanometer-sized features. The combination of micrometer- and nanometer-sized surface features created a fractal surface and increased the water contact angle (WCA) of PDMS more than 60°, resulting in a superhydrophobic PDMS surface with WCA of >160°. The active surface layer for the superhydrophobicity was approximately 100 μm thick, illustrating that the material had bulk superhydrophobicity compared to conventional fluorocarbon or fluorinated coated rough surfaces. Theoretical analysis of the fractal surface indicates that the constructed surface has a fractal dimension of 2.5, which corresponds to the Apollonian sphere packing.

Lectin-functionalized poly(glycidyl methacrylate)-block-poly(vinyldimethyl azlactone) surface scaffolds for high avidity microbial capture.

Microbial exopolysaccharides (EPS) play a critical and dynamic role in shaping the interactions between microbial community members and their local environment. The capture of targeted microbes using surface immobilized lectins that recognize specific extracellular oligosaccharide moieties offers a nondestructive method for functional characterization of EPS content. In this report, we evaluate the use of the block copolymer, poly(glycidyl methacrylate)-block-4,4-dimethyl-2-vinylazlactone (PGMA-b-PVDMA), as a surface scaffold for lectin-specific microbial capture. Three-dimensional polymer films were patterned on silicon substrates to provide discrete, covalent coupling sites for Triticum vulgare and Lens culinaris lectins. This material increased the number of Pseudomonas fluorescens microbes captured by up to 43% compared to control scaffolds that did not contain the copolymer. These results demonstrate that PGMA-b-PVDMA scaffolds provide a platform for improved microbe capture and screening of EPS content by combining high avidity lectin surfaces with three-dimensional surface topography.

Tunable morphologies from charged block copolymers

The bulk morphologies formed by a new class of charged block copolymers, 75 vol % fluorinated polyisoprene (FPI) – 25 vol% sulfonated polystyrene (PSS) with 50% sulfonation, are characterized, and the fundamental underlying forces that promote the self-assembly processes are elucidated. The results show how the bulk morphologies are substantially different from their uncharged diblock counterparts (PS-PI) and also how morphology can be tuned with volume fraction of the charged block and the casting solvent. A physical understanding based on the underlying strong electrostatic interactions between the charged block and counterions is obtained using Monte Carlo (MC) and Molecular Dynamics (MD) simulations. The 75/25 FPI-PSS shows hexagonal morphologies with the minority blocks (PSS) forming the continuous phase due to charge percolation and the FPI blocks arranged in hexagonal cylinders. Some long-range order can be sustained even if lipophobicity is increased (addition of water), albeit with lower dimensional structures. However, thermal annealing provides sufficient energy to disrupt the percolated charges and promotes aggregation of ionic sites which leads to a disordered system. Diverse and atypical morphologies are readily accessible by simply changing the number distribution of the charges on the PSS block.

Polypeptide Grafted Hyaluronan: Synthesis and Characterization

Poly(l-leucine) grafted hyaluronan (HA-g-PLeu) has been synthesized via a Michael addition reaction between primary amine terminated poly(l-leucine) and acrylate-functionalized HA (TBAHA-acrylate). The precursor hyaluronan was first functionalized with acrylate groups by reaction with acryloyl chloride in the presence of triethylamine in N,N-dimethylformamide. (1)H NMR analysis of the resulting product indicated that an increase in the concentration of acryloylchoride with respect to hydroxyl groups on HA has only a moderate effect on functionalization efficiency, f. A precise control of stoichiometry was not achieved, which could be attributed to partial solubility of intermolecular aggregates and the hygroscopic nature of HA. Michael addition at high [PLeu-NH(2)]/[acrylate](TBAHA) ratios gave a molar grafting ratio of only 0.20 with respect to the repeat unit of HA, indicating grafting limitation due to insolubility of the grafted HA-g-PLeu. Soluble HA-g-PLeu graft copolymers were obtained for low grafting ratios (<0.039) with <8.6% by mass of PLeu and were characterized thoroughly using light scattering, (1)H NMR, FT-IR, and AFM techniques. Light scattering experiments showed a strong hydrophobic interaction between PLeu chains, resulting in aggregates with segregated nongrafted HA segments. This yields local networks of aggregates, as demonstrated by atomic force microscopy. Circular dichroism spectroscopy showed a β-sheet conformation for aggregates of poly(l-leucine).

Spontaneous wrinkling in azlactone-based functional polymer thin films in 2D and 3D geometries for guided nanopatterning

We report a simple, one step process for developing wrinkling patterns in azlactone-based polymer thin films and brushes in 2D and 3D surfaces. The polymer used in this work wrinkles spontaneously upon deposition and solidification on a substrate without applying any external strain to the substrate, with the mode of deposition defining the direction of the wrinkles. Wrinkle formation is shown to occur on a variety of substrates over large areas. We also find that a very thin brush-like layer of an azlactone-containing block copolymer also exhibits wrinkled topology. Given the spontaneity and versatility of wrinkle formation, we further demonstrate two proofs-of-concept, (i) that these periodic wrinkled structures are not limited to planar surfaces, but are also developed in complex geometries including tubes, cones and other 3D structures; and (ii) that this one step wrinkling process can be used to guide the deposition of metal nanoparticles and quantum dots, creating a periodic, nanopatterned film.

Resolving transitions in the mesoscale domain configuration in VO2 using laser speckle pattern analysis

The configuration and evolution of coexisting mesoscopic domains with contrasting material properties are critical in creating novel functionality through emergent physical properties. However, current approaches that map the domain structure involve either spatially resolved but protracted scanning probe experiments without real time information on the domain evolution, or time resolved spectroscopic experiments lacking domain-scale spatial resolution. We demonstrate an elegant experimental technique that bridges these local and global methods, giving access to mesoscale information on domain formation and evolution at time scales orders of magnitude faster than current spatially resolved approaches. Our straightforward analysis of laser speckle patterns across the first order phase transition of VO2 can be generalized to other systems with large scale phase separation and has potential as a powerful method with both spatial and temporal resolution to study phase separation in complex materials.

Grafting density effects, optoelectrical properties and nano-patterning of poly(para-phenylene) brushes

Well-defined conjugated polymers in confined geometries are challenging to synthesize and characterize, yet they are potentially useful in a broad range of organic optoelectronic devices such as transistors, light emitting diodes, solar cells, sensors, and nanocircuits. Herein we report a systematic study of optoelectrical properties, grafting density effects, and nanopatterning of a model, end-tethered conjugated polymer system. Specifically, poly(para-phenylene) (PPP) brushes of various grafting density are created in situ by aromatizing well-defined, end-tethered poly(1,3-cyclohexadiene) (PCHD) “precursor brushes”. This novel precursor brush approach provides a convenient way to make and systematically control the grafting density of high molecular weight conjugated polymer brushes that would otherwise be insoluble. This allows us to examine how grafting density impacts the effective conjugation length of the conjugated PPP brushes and to adapt the fabrication method to develop spatially patterned conjugated brush systems, which is important for practical applications of conjugated polymer brushes.