Water Content of Polyelectrolyte Multilayer Films Measured by Quartz Crystal Microbalance and Deuterium Oxide Exchange.

Water content of natural and synthetic, thin, polymer films is of considerable interest to a variety of fields because it governs properties such as ion conductivity, rigidity, porosity, and mechanical strength. Measuring thin film water content typically requires either complicated and expensive instrumentation or use of multiple instrumental techniques. However, because a quartz crystal microbalance (QCM) is sensitive to changes in mass and viscosity, deuterated solvent exchange has emerged as a simple, single-instrument, in situ method to quantify thin film water content. Relatively few studies, though, have employed this technique to measure water content of polyelectrolyte multilayers formed by layer-by-layer (LbL) assembly. In this work, poly (allyl amine) (PAH) and poly (styrene sulfonate) (PSS) films of up to nine layers were formed and the water content for each layer was measured via QCM with deuterium oxide exchange. The well-characterized nature of PAH/PSS films facilitated comparisons of the technique used in this work to other instrumental methods. Water content results showed good agreement with the literature and good precision for hydrated films thicker than 20 nm. Collectively, this work highlights the utility, repeatability, and limitations of this deuterated exchange technique in measuring the solvent content of thin films.

Vapor Selectivity of a Natural Photonic Crystal to Binary and Tertiary Mixtures Containing Chemical Warfare Agent Simulants.

Vapor sensing via light reflected from photonic crystals has been increasingly studied as a means to rapidly identify analytes, though few studies have characterized vapor mixtures or chemical warfare agent simulants via this technique. In this work, light reflected from the natural photonic crystals found within the wing scales of the Morpho didius butterfly was analyzed after exposure to binary and tertiary mixtures containing dimethyl methylphosphonate, a nerve agent simulant, and dichloropentane, a mustard gas simulant. Distinguishable spectra were generated with concentrations tested as low as 30 ppm and 60 ppm for dimethyl methylphosphonate and dichloropentane, respectively. Individual vapors, as well as mixtures, yielded unique responses over a range of concentrations, though the response of binary and tertiary mixtures was not always found to be additive. Thus, while selective and sensitive to vapor mixtures containing chemical warfare agent simulants, this technique presents challenges to identifying these simulants at a sensitivity level appropriate for their toxicity.

Cyclophilin 20-3 relays a 12-oxo-phytodienoic acid signal during stress responsive regulation of cellular redox homeostasis.

The jasmonate family of phytohormones plays central roles in plant development and stress acclimation. However, the architecture of their signaling circuits remains largely unknown. Here we describe a jasmonate family binding protein, cyclophilin 20-3 (CYP20-3), which regulates stress-responsive cellular redox homeostasis. (+)-12-Oxo-phytodienoic acid (OPDA) binding promotes CYP20-3 to form a complex with serine acetyltransferase 1, which triggers the formation of a hetero-oligomeric cysteine synthase complex with O-acetylserine(thiol)lyase B in chloroplasts. The cysteine synthase complex formation then activates sulfur assimilation that leads to increased levels of thiol metabolites and the buildup of cellular reduction potential. The enhanced redox capacity in turn coordinates the expression of a subset of OPDA-responsive genes. Thus, we conclude that CYP20-3 is a key effector protein that links OPDA signaling to amino acid biosynthesis and cellular redox homeostasis in stress responses.

Effects of sulfate groups on the adsorption and activity of cellulases on cellulose substrates.

Pretreatment of lignocellulosic biomass with sulfuric acid may leave sulfate groups on its surface that may hinder its biochemical conversion. This study investigates the effects of sulfate groups on cellulase adsorption onto cellulose substrates and the enzymatic hydrolysis of these substrates. Substrates with different sulfate group densities were prepared from H2SO4- and HCl-hydrolyzed and partially and fully desulfated cellulose nanocrystals. Adsorption onto and hydrolysis of the substrates was analyzed by quartz crystal microbalance with dissipation monitoring (QCM-D). The surface roughness of the substrates, measured by atomic force microscopy, increased with decreasing sulfate group density, but their surface accessibilities, measured by QCM-D H2O/D2O exchange experiments, were similar. The adsorption of cellulose binding domains onto sulfated substrates decreased with increasing sulfate group density, but the adsorption of cellulases increased. The rate of hydrolysis of sulfated substrates decreased with increasing sulfate group density. The results indicated an inhibitory effect of sulfate groups on the enzymatic hydrolysis of cellulose, possibly due to nonproductive binding of the cellulases onto the substrates through electrostatic interactions instead of their cellulose binding domains.

Chitinase activity on amorphous chitin thin films: a quartz crystal microbalance with dissipation monitoring and atomic force microscopy study.

Chitinases are widely distributed in nature and have wide-ranging pharmaceutical and biotechnological applications. This work highlights a real-time and label-free method to assay Chitinase activity via a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). The chitin substrate was prepared by spincoating a trimethylsilyl chitin solution onto a silica substrate, followed by regeneration to amorphous chitin (RChi). The QCM-D and AFM results clearly showed that the hydrolysis rate of RChi films increased as Chitinase (from Streptomyces griseus) concentrations increased, and the optimal temperature and pH for Chitinase activity were around 37 °C and 6-8, respectively. The Chitinase showed greater activity on chitin substrates, having a high degree of acetylation, than on chitosan substrates, having a low degree of acetylation.

Enhanced dewatering of polyelectrolyte nanocomposites by hydrophobic polyelectrolytes.

We demonstrate that increasing the hydrophobic environment around the charge center of a polyelectrolyte (PE) not only decreases the water content of an adsorbed PE layer but can even dewater up to ~50% of an initially hydrated substrate. The results of this work are expected to yield new stratagies to dewater PE systems and have potential applications in mineral recovery, paper manufacturing, and biomedical materials. Adsorption of a series of cationically derivatized dextran polyelectrolytes onto sulfated nanocrystalline cellulose (SNC) has been studied using quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR). Synthesized samples of (N,N-dimethylamino)ethyldextran (DMAE-Dex), (N,N-diethylamino)ethyldextran (DEAE-Dex), and (N,N-diisopropylamino)ethyldextran (DIAE-Dex) had degrees of substitution (DS) ranging from 0.05 to 0.82. DMAE-Dex, DEAE-Dex, and DIAE-Dex all showed decreasing adsorption onto SNC and decreasing water content of the adsorbed film with increasing DS. Additionally, DEAE-Dex and DIAE-Dex films adsorbed onto SNC contained less water than DMAE-Dex films with the same DS. Interestingly, QCM-D results for high DS DIAE-Dex adsorbed onto SNC revealed mass loss, whereas SPR results clearly showed DIAE-Dex adsorbed. These observations were consistent with dehydration of the SNC substrate. This study indicates that the water content of the substrate could be tailored by controlling the DS and hydrophobic character of the adsorbed polyelectrolytes.

Ultrathin chitin films for nanocomposites and biosensors.

Chitin is the second most abundant biopolymer and insight into its natural synthesis, enzymatic degradation, and chemical interactions with other biopolymers is important for bioengineering with this renewable resource. This work is the first report of smooth, homogeneous, ultrathin chitin films, opening the door to surface studies of binding interactions, adsorption kinetics, and enzymatic degradation. The chitin films were formed by spincoating trimethylsilyl chitin onto gold or silica substrates, followed by regeneration to a chitin film. Infrared and X-ray photoelectron spectroscopy, X-ray diffraction, ellipsometry, and atomic force microscopy were used to confirm the formation of smooth, homogeneous, and amorphous chitin thin films. Quartz crystal microbalance with dissipation monitoring (QCM-D) solvent exchange experiments showed these films swelled with 49% water by mass. The utility of these chitin films as biosensors was evident from QCM-D and surface plasmon resonance studies that revealed the adsorption of a bovine serum albumin monolayer.

Supervised dimension reduction for optical vapor sensing.

Detecting and identifying vapors at low concentrations is important for air quality assessment, food quality assurance, and homeland security. Optical vapor sensing using photonic crystals has shown promise for rapid vapor detection and identification. Despite the recent advances of optical sensing using photonic crystals, the data analysis method commonly used in this field has been limited to an unsupervised method called principal component analysis (PCA). In this study, we applied four different supervised dimension reduction methods on differential reflectance spectra data from optical vapor sensing experiments. We found that two of the supervised methods, linear discriminant analysis and least-squares regression PCA, yielded better interclass separation, vapor identification and improved classification accuracy compared to PCA.

Vapor Sorption-Desorption Phenomena of HD and GB Simulants from Polyurethane Thin Films on Aluminum Oxide via a Quartz Crystal Microbalance.

Protection and decontamination of surfaces after exposure to chemical warfare agents (CWAs) are of considerable interest to the homeland defense and battlespace operation communities. In this work, polyurethane was spin-coated onto aluminum oxide quartz crystal microbalance (QCM) sensors. Polyurethane film thickness was varied by altering the concentration of the polymer/chloroform solution used for spin-coating. Atomic force microscopy confirmed the formation of smooth, homogeneous films on the QCM sensor surface. Aluminum oxide QCM sensors coated with polyurethane were exposed to saturated vapors of dichloropentane (DCP), a mustard gas (HD) simulant, and dimethyl methylphosphonate (DMMP), a sarin gas (GB) simulant, and the mass uptake, diffusion coefficient, volume fraction, and partition coefficient of the simulant in the film were determined from QCM data. Results showed that both DCP and DMMP readily sorbed into the films although the mass uptake of DCP was greater than that of DMMP owing to DCP's higher vapor pressure. Additionally, the CWA simulant uptake increased with polyurethane film thickness. Sorption diffusion coefficients were 1 × 10-13 cm2/s and 1 × 10-12 cm2/s for DCP and DMMP vapor, respectively. Simulant desorption was also measured and showed that some DMMP remained in the film/substrate system, while DCP sorption was fully reversible. Reversible desorption for both CWA simulants was relatively quick and independent over the range of film thicknesses studied, with average desorption diffusion coefficients of 2 × 10-9 cm2/s and 1 × 10-11 cm2/s for DCP and DMMP, respectively. Collectively, this study is expected to inform protection and decontamination strategies of equipment and structures upon exposure to CWAs.

Equilibrium water contents of cellulose films determined via solvent exchange and quartz crystal microbalance with dissipation monitoring.

Model cellulose surfaces have attracted increasing attention for studying interactions with cell wall matrix polymers and as substrates for enzymatic degradation studies. Quartz crystal microbalance with dissipation monitoring (QCM-D) solvent exchange studies showed that the water content of regenerated cellulose (RC) films was proportional to the film thickness (d) and was consistent with about five water molecules per anhydroglucose unit. Sulfated nanocrystalline cellulose (SNC) and desulfated nanocrystalline cellulose (DNC) films had comparable water contents and contained about five times more water than RC films. A cellulase mixture served as a probe for studies of substrate accessibility and degradation. Cellulase adsorption onto RC films was independent of d, whereas degradation times increased with d. However, adsorption onto SNC and DNC films increased with d, whereas cellulase degradation times for DNC films were independent of studied d. Enhanced access to guest molecules for SNC and DNC films revealed they are more porous than RC films.

Additive Combination of Spectra Reflected from Porous Silicon and Carbon/Porous Silicon Rugate Filters to Improve Vapor Selectivity.

Selectivity remains a challenge for rapid optical vapor sensing via light reflected from porous silicon photonic crystals. This work highlights a method to increase optical vapor selectivity of porous silicon rugate filters by analyzing additive spectra from two rugate filter substrates with different functionalities, an oxidized and carbonized surface. Individually, both porous silicon rugate filters demonstrated sensitivity but not selectivity toward the vapor analytes. However, differences in peak shift trends between the two substrates suggested differences in vapor affinities for the surfaces. By adding the two spectra, improvements to selectivity relative to the individual surfaces were observed even at low vapor pressures and for analytes of similar polarity, refractive index, and concentration. These results are expected to contribute toward optical vapor selectivity improvements in one-dimensional porous silicon photonic crystals.

Adsorption of Xyloglucan onto Thin Films of Cellulose Nanocrystals and Amorphous Cellulose: Film Thickness Effects.

The interaction between cellulose and hemicelluloses is of fundamental importance for understanding the molecular architecture of plant cell walls. Adsorption of xyloglucan (XG) onto regenerated cellulose (RC), sulfated cellulose nanocrystal (s-CNC), and desulfated cellulose nanocrystal (d-CNC) films was studied by quartz crystal microbalance with dissipation monitoring, surface plasmon resonance, and atomic force microscopy. The amount of XG adsorbed onto different cellulose substrates increased in the order RC < s-CNC < d-CNC. The adsorption of XG onto RC films was independent of film thickness (d), whereas XG adsorption was weakly dependent on d for s-CNC films and strongly dependent on d for d-CNC films. However, approximately the same amount of XG adsorbed onto "monolayer-thin" films of RC, s-CNC, and d-CNC. These results suggest that the morphology and surface charge of the cellulose substrate played a limited role in XG adsorption and highlight the importance of film thickness of cellulose nanocrystalline films to XG adsorption.

Sensing Chemical Warfare Agent Simulants via Photonic Crystals of the Morpho didius Butterfly.

The rapid and portable detection of trace chemical warfare agents (CWAs) remains a challenge for the international security and monitoring community. This work reports the first use of natural photonic crystals (PhCs) as vapor sensors for CWA simulants. Dimethyl methylphosphonate, a nerve agent simulant, and dichloropentane, a mustard gas simulant, were successfully detected at the parts per million level by processing visible light reflected from the PhC inherent to the wing scales of the Morpho didius butterfly. Additionally, modeling of this natural system suggested several parameters for enhancing the sensitivity of a synthetic PhC toward CWA simulants, including materials selection, structure, and spacing of the PhC, and partial functionalization of the PhC toward the analyte of interest. Collectively, this study provides strategies for designing a sensitive, selective, rapid, and affordable means for CWA detection.