Using Rheology and Image Processing to Study the Effects of Cellulose Nanocrystal Sedimentation.

The effect of sedimentation on lyotropic liquid crystalline dispersions is both an interesting subject in colloidal science and is of practical importance for understanding changes that can occur during dispersion storage. This research explored how the seemingly subtle changes in average length resulting from a single sedimentation step affected the rheological properties and self-assembly of aqueous dispersions of sulfated cellulose nanocrystals. Sedimentation of a primarily isotropic aqueous cellulose nanocrystal dispersion for 1 month at ambient conditions resulted in an isotropic top phase and a biphasic bottom phase, which were separated for further study.

Properties of APTES-Modified CNC Films.

Sulfated cellulose nanocrystals' (CNCs') facile aqueous dispersibility enables producing films, fibers, and other materials using only water as a solvent but prevents using sulfated CNCs in applications that require water immersion. We report that modifying CNCs with 3-aminopropyl-triethoxysilane (APTES) via a simple, single-pot reaction scheme dramatically improves the hydrolytic stability of CNC films. The effects of APTES modification on CNCs' properties were studied using attenuated total reflectance Fourier transform infrared spectroscopy, atomic force and optical microscopy, thermogravimetric analysis, dynamic light scattering, and ultimate analysis.

Phase Behavior and Rheological Properties of Size-Fractionated MXene (TiCT) Dispersions.

Understanding the dispersion behavior of MXenes is interesting from a fundamental colloid science perspective and critical to enabling the fluid-phase manufacturing of MXene devices with controlled microstructures and properties. However, the polydispersity, irregular shape, and charged surfaces of MXenes result in a complex phase behavior that is difficult to predict through theoretical calculations. As two-dimensional (2D) nanomaterials, MXenes can form lyotropic liquid crystal phases, gels, and aggregates.

Anisotropic Nanomaterial Liquid Crystals: From Fiber Spinning to Additive Manufacturing.

There have long been synergistic relationships among the discovery of new anisotropic materials, advancements in liquid crystal science, and the production of manufactured goods with exciting new properties. Ongoing progress in understanding the phase behavior and shear response of lyotropic liquid crystals comprised of one-dimensional and two-dimensional nanomaterials, coupled with advancements in extrusion-based manufacturing methods, promises to enable the scalable production of solid materials with outstanding properties and controlled order across multiple length scales. This Perspective highlights progress in using anisotropic nanomaterial liquid crystals in two extrusion-based manufacturing methods: solution spinning and direct ink writing.

Antibody Immobilization on Sulfated Cellulose Nanocrystals.

Exploiting cellulose nanocrystals' high aspect ratio and tailorable surface for immunological biosensors has been hindered by the relatively limited research on using commonly available sulfated cellulose nanocrystals (CNCs) for antibody immobilization and by the low hydrolytic stability of dried assemblies produced from sulfated CNCs. Herein, we report a reaction scheme that enables both hydrolytic stability and antibody immobilization through 3-aminopropyl-triethoxysilane and glutaric anhydride chemistry. Immobilization was demonstrated using three model antibodies used in the detection of the cancer biomarkers: alpha-fetoprotein, prostate-specific antigen, and carcinoembryonic antigen.

Additive Manufacturing of Viscoelastic Polyacrylamide Substrates for Mechanosensing Studies.

Polymerized polyacrylamide (PAA) substrates are linearly elastic hydrogels that are widely used in mechanosensing studies due to their biocompatibility, wide range of functionalization capability, and tunable mechanical properties. However, such cellular response on purely elastic substrates, which do not mimic the viscoelastic living tissues, may not be physiologically relevant. Because the cellular response on 2D viscoelastic PAA substrates remains largely unknown, we used stereolithography (SLA)-based additive manufacturing technique to create viscoelastic PAA substrates with tunable mechanical properties that allow us to identify physiologically relevant cellular behaviors.

Microstructure and electrochemical properties of high performance graphene/manganese oxide hybrid electrodes.

Hybrids consisting of 2D ultra-large reduced graphene oxide (RGO) sheets (∼30 μm long) and 1D α-phase manganese oxide (MnO) nanowires were fabricated through a versatile synthesis technique that results in electrostatic binding of the nanowires and sheets. Two different hybrid (RGO/MnO) compositions had remarkable features and performance: 3 : 1 MnO/RGO (75/25 wt%) denoted as 3H and 10 : 1 MnO/RGO (90/10 wt%) denoted as 10H. Characterization using spectroscopy, microscopy, and thermal analysis provided insights into the microstructure and behavior of the individual components and hybrids.

Dispersant Effects on Single-Walled Carbon Nanotube Antibacterial Activity.

There is significant interest in understanding whether nanomaterials with outstanding mechanical or electrical properties also possess antibacterial properties. However, assessment of antibacterial activity is a complex problem at the interface of chemistry and microbiology. Results can be affected by many factors including nanomaterial size, surface chemistry, concentration, and the dispersion media.

Effects of Non-covalent Functionalization and Initial Mixing Methods on SWNT/PP and SWNT/EVOH Composites.

We report that a simple, low-cost type of spray-freeze drying (SFD) significantly improves the dispersion of single-walled carbon nanotubes (SWNTs) in thermoplastic polymers. Conventional SFD requires costly specialized equipment and large amounts of material, both of which are impediments to laboratory research on nanomaterial composites. Our method uses more readily available equipment and can be adapted to use milligrams to grams of material.

Getting Everyone to the Fair: Supporting Teachers in Broadening Participation in Science and Engineering Fairs.

Science and Engineering (S&E) fairs are a valuable educational activity and are believed to increase students' engagement and learning in science and engineering. However, due to differences in resources, many schools do not implement fairs to achieve these benefits for their students. This study reports the findings of a program intended to increase the participation of students from low-achieving and under-resourced schools in a regional fair program that feeds into the international fair competition.

Substrate properties as controlling parameters in attached algal cultivation.

There is growing interest in attached algae cultivation systems because they could provide a more cost- and energy-efficient alternative to planktonic (suspended algae) cultivation systems for many applications. However, attached growth systems have been far less studied than planktonic systems and have largely emphasized algae strains of most interest for biofuels. New algal biorefinery pathways have assessed the commercial potentials of algal biomass beyond biofuel production and placed more emphasis on value-added products from that biomass.

Chiral Structure Formation during Casting of Cellulose Nanocrystalline Films.

A Landau-de Gennes formulation coupled with a mass-transfer equation was used to track the evaporation front and the development of chiral microstructures during the casting of sulfuric acid-hydrolyzed cellulose nanocrystal (CNC) films. These simulations are compared to thin-film casting experiments that used analogous processing parameters and environments. The results show that the initial concentration, chiral strength, surface anchoring, speed of drying, and the influence of initial shear alignment all affect the uniformity of the microstructure and the orientation of the chiral director.

Comparison of Attachment and Antibacterial Activity of Covalent and Noncovalent Lysozyme-Functionalized Single-Walled Carbon Nanotubes.

Carbon nanotube-lysozyme (LSZ) conjugates provide an attractive combination of high strength and antimicrobial activity. However, there has not been a direct comparison of the covalent and noncovalent methods for creating them. In this work, single-walled carbon nanotubes (SWNT) were functionalized with LSZ using both noncovalent adsorption and covalent attachment via -ethyl--(3-dimethylamino-propyl) carbodiimide hydrochloride--hydroxysuccinimide (EDC-NHS) chemistry.

3D Printing of Additive-Free 2D TiCT (MXene) Ink for Fabrication of Micro-Supercapacitors with Ultra-High Energy Densities.

Recent advances in the development of self-powered devices and miniaturized electronics have increased the demand for on-chip energy storage devices that can deliver high power and energy densities in a limited footprint area. Here, we report the fabrication of all-solid-state micro-supercapacitors (MSCs) through a three-dimensional (3D) printing of additive-free and water-based MXene ink. The fabricated MSCs benefit from the high electrical conductivity and excellent electrochemical properties of two-dimensional (2D) TiCT MXene and a 3D interdigital electrode architecture to deliver high areal and volumetric energy densities.

Transparent and Homogenous Cellulose Nanocrystal/Lignin UV-Protection Films.

In the context of valorization of lignin produced from the pulp and paper industries, biodegradable UV-protection films were prepared using lignin and cellulose nanocrystals (CNCs). Initially, CNC films were optimized for improving their transparency by studying the effect of various sodium hydroxide (NaOH) concentrations. Maximum (%) transmittance of CNC film was obtained for NaOH addition between 3 and 4 wt %.

Microelectromechanical Systems from Aligned Cellulose Nanocrystal Films.

Microelectromechanical systems (MEMS) have become a ubiquitous part of a multitude of industries including transportation, communication, medical, and consumer products. The majority of commercial MEMS devices are produced from silicon using energy-intensive and harsh chemical processing. We report that actuatable standard MEMS devices such as cantilever beam arrays, doubly clamped beams, residual strain testers, and mechanical strength testers can be produced via low-temperature fabrication of shear-aligned cellulose nanocrystal (CNC) films.

Single-Walled Carbon Nanotube Dispersion in Tryptic Soy Broth.

There has been little research on the dispersion of carbon nanotubes in dispersions of standard microbiological media. We report that tryptic soy broth (TSB) containing casein digest disperses single-walled carbon nanotubes (SWNT) at concentrations similar to those achieved in lysozyme (LSZ), one of the best known biomolecular SWNT dispersants. Similar to LSZ, the proposed mechanism for SWNT dispersion in TSB is favorable π-π stacking interactions with l-tryptophan.

New insights into the flow and microstructural relaxation behavior of biphasic cellulose nanocrystal dispersions from RheoSANS.

Cellulose nanocrystals (CNC) have been studied as nanostructured building blocks for functional materials and function as a model nanomaterial mesogen for cholesteric (chiral nematic) liquid crystalline phases. In this study, both rheology and small angle neutron scattering (RheoSANS) were used to measure changes in flow-oriented order parameter and viscosity as a function of shear rate for isotropic, biphasic, liquid crystalline, and gel dispersions of CNC in deuterium oxide (DO). In contrast to plots of viscosity versus shear rate, the order parameter trends showed three distinct rheological regions over a range of concentrations.

Concentration of lysozyme/single-walled carbon nanotube dispersions.

The dispersion of single-walled carbon nanotubes (SWNT) in aqueous solutions of biological materials enables the production of bulk films and fibers that combine natural biological activity with SWNT's intrinsic mechanical, thermal, and electrical properties. In this work, we report the rheology and phase behavior of concentrated lysozyme (LSZ)/SWNT dispersions. Even at low concentration, the LSZ's globular structure causes a deviation from the rheological behavior expected of rigid rods such as SWNT.

A Potential Role for Acrolein in Neutrophil-Mediated Chronic Inflammation.

Neutrophils (PMNs) are key mediators of inflammatory processes throughout the body. In this study, we investigated the role of acrolein, a highly reactive aldehyde that is ubiquitously present in the environment and produced endogenously at sites of inflammation, in mediating PMN-mediated degradation of collagen facilitating proline-glycine-proline (PGP) production. We treated peripheral blood neutrophils with acrolein and analyzed cell supernatants and lysates for matrix metalloproteinase-9 (MMP-9) and prolyl endopeptidase (PE), assessed their ability to break down collagen and release PGP, and assayed for the presence of leukotriene A4 hydrolase (LTA4H) and its ability to degrade PGP.

Liquid crystalline phase behavior of silica nanorods in dimethyl sulfoxide and water.

We report lyotropic smectic liquid crystalline phase behavior of silica nanorods dispersed in binary mixtures of dimethyl sulfoxide (DMSO) and water (H2O). The phase behavior is affected by nanorod size polydispersity and DMSO concentration in the binary solvent. The isotropic to biphasic transition is strongly affected by the relative amount of DMSO in the solvent, but the solvent has little effect on the biphasic to liquid crystal transition above 40/60 DMSO/H2O by volume.

Free-Standing Films from Aqueous Dispersions of Lysozyme, Single-Walled Carbon Nanotubes, and Polyvinyl Alcohol.

Transparent antibacterial films were produced by casting concentrated dispersions of lysozyme (LSZ), single-walled carbon nanotubes (SWNTs), and polyvinyl alcohol (PVA). The initial SWNT dispersion state had a significant influence on the films' mechanical properties. Films containing 9 wt % bundled SWNTs had six times higher Young's modulus than control films produced without SWNTs.

A novel nano-nonwoven fabric with three-dimensionally dispersed nanofibers: entrapment of carbon nanofibers within nonwovens using the wet-lay process.

This study demonstrates, for the first time, the manufacturing of novel nano-nonwovens that are comprised of three-dimensionally distributed carbon nanofibers within the matrices of traditional wet-laid nonwovens. The preparation of these nano-nonwovens involves dispersing and flocking carbon nanofibers, and optimizing colloidal chemistry during wet-lay formation. The distribution of nanofibers within the nano-nonwoven was verified using polydispersed aerosol filtration testing, air permeability, low surface tension liquid capillary porometry, SEM and cyclic voltammetry.