Sonochemical synthesis of lignin nanoparticles and their applications in poly (vinyl) alcohol composites.

Lignin is a common and abundant byproduct of the pulp and paper industry and is generally burned to produce steam. Opportunities exist to acquire greater value from lignin by leveraging the properties of this highly conjugated biomacromolecule for applications in UV absorption and polymer reinforcement. These applications can be commercialized by producing value-added lignin nanoparticles (LNPs) using a scalable sonochemical process. In the present research, monodisperse LNPs have been synthesized by subjecting aqueous dispersions of alkali lignin to acoustic irradiation. The resulting particle size distribution and colloidal stability, as determined by dynamic light scattering, transmission electron microscopy and zeta potential analysis, of LNPs can be adjusted by varying the solution pH and ultrasonication energy. As-synthesized LNPs with a mean diameter of 204 nm were incorporated into poly (vinyl) alcohol (PVA) to prepare thin and flexible nanocomposite films using a simple solvent casting method. The addition of 2.5 wt% LNP increased the material's Sun Protection Factor up to 26 compared to 0 for neat PVA, while maintaining light transmission above 75 % in the visible spectra. In addition, the tensile strength and elastic modulus of the PVA nanocomposites improved by 47 % and 36 %, respectively. The presence of LNP also enhanced the thermal stability of the materials. Significantly, the proposed sonochemical process may be generally applicable to the synthesis of a range of naturally-derived LNPs for a variety of value-added applications.

Dynamic Assembly of Strong and Conductive Carbon Nanotube/Nanocellulose Composite Filaments and Their Application in Resistive Liquid Sensing.

The continuous flow assembly of colloidal nanoparticles from aqueous suspensions into macroscopic materials in a field-assisted double flow focusing system offers an attractive way to bridge the outstanding nanoscale characteristics of renewable cellulose nanofibrils (CNFs) at scales most common to human technologies. By incorporating single-walled carbon nanotubes (SWNTs) during the fabrication process, high-performance functional filament nanocomposites were produced. CNFs and SWNTs were first dispersed in water without any external surfactants or binding agents, and the resulting nanocolloids were aligned by means of an alternating electric field combined with extensional sheath flows. The nanoscale orientational anisotropy was then locked by a liquid-gel transition during the materials assembly into macroscopic filaments, which greatly improved their mechanical, electrical, and liquid sensing properties. Significantly, these findings pave the way toward the environmentally friendly and scalable manufacturing of a variety of multifunctional fibers for diverse applications.

A Robust Process to Produce Lignocellulosic Nanofibers from Corn Stover, Reed Canary Grass, and Industrial Hemp.

The use of agricultural waste biomass for nanocellulose production has gained interest due to its environmental and economic benefits compared to conventional bleached pulp feedstock. However, there is still a need to establish robust process technologies that can accommodate the variability of waste feedstocks and to understand the effects of feedstock characteristics on the final nanofiber properties. Here, lignocellulosic nanofibers with unique properties are produced from various waste biomass based on a simple and low-cost process using mild operating conditions. The process robustness is demonstrated by diversifying the feedstock, ranging from food crop waste (corn stover) to invasive grass species (reed canary grass) and industrial lignocellulosic residues (industrial hemp). This comprehensive study provides a thorough examination of the influence of the feedstocks' physico-chemical characteristics on the conversion treatment, including process yield, degree of delignification, effectiveness of nanofibrillation, fiber morphology, surface charge, and density. Results show that nanofibers have been successfully produced from all feedstocks, with minor to no adjustments to process conditions. This work provides a framework for future studies to engineer nanocellulose with specific properties by taking advantage of biomass feedstocks' intrinsic characteristics to enable versatile applications.

Facile preparation of cellulose nanocrystals/ZnO hybrids using acidified ZnCl2 as cellulose hydrolytic media and ZnO precursor.

Hybridization of nanocellulose with zinc oxide nanoparticles can improve the dispersibility of the zinc oxide and bring new functions to the bio-based products. In this study, cellulose nanocrystal/zinc oxide (CNC/ZnO) nanohybrids with reinforcing and antibacterial properties were prepared via a facile one-pot route. Microcrystalline cellulose (MCC) was first treated with acidified zinc chloride and hydrolyzed into CNCs, which then served as a stabilizing and supporting agent for the in-situ growth of ZnO nanoparticles during subsequent chemical precipitation. The acidified ZnCl2 solution played a dual role, acting both as cellulose hydrolytic media and as ZnO precursor. By adjusting the pH of the zinc precursor solution (pH = 9-12), well-dispersed rod-like (length: 137.0-468.0 nm, width: 54.1-154.1 nm) and flower-like (average diameter: 179.6 nm) ZnO nanoparticles with hexagonal wurtzite structure were obtained. CNC/ZnO nanohybrids were incorporated into waterborne polyurethane (WPU) films. The Young's modulus and tensile strength of the nanocomposite films increased gradually from 154.8 to 509.0 MPa and from 16.5 to 29.9 MPa, respectively, with increasing CNC/ZnO nanofiller content up to 10 wt%. The 10 % CNC/ZnO composites showed inhibition rates to both E. coli and S. aureus above 88.8 %.

Lignocellulosic nanomaterials production from wheat straw via peracetic acid pretreatment and their application in plastic composites.

Cellulose nanofibrils are typically prepared from high-purity bleached pulp through harsh chemical treatments (e.g., TEMPO oxidation), resulting in high costs and environmental impact. In this work, we utilize inexpensive wheat straw feedstock and alkaline peroxide pulping followed by mild peracetic acid (PAA) pretreatment to produce lignocellulosic nanomaterials (nano and microfibrils) with potential bioplastics applications. PAA was chosen due to its biodegradability, non-toxicity, and high reaction selectivity. As-synthesized lignocellulosic nanomaterials were thoroughly characterized and compared to nanofibrils produced via TEMPO oxidation pretreatment and then applied as reinforcing agents in plastic composites. A remarkable case of simultaneous strengthening and toughening of the polymer nanocomposite was achieved with high specific tensile strength (up to 59.5 MPa g-1 cm3), elastic modulus (up to 2.6 GPa g-1 cm3), and fracture strain (up to 138 %). This work is a comprehensive investigation of all process steps involved in lignocellulosic nanomaterials production, from original residue feedstock to final product application.

X-ray nanodiffraction imaging reveals distinct nanoscopic dynamics of an ultrafast phase transition.

SignificancePhase transitions, the changes between states of matter with distinct electronic, magnetic, or structural properties, are at the center of condensed matter physics and underlie valuable technologies. First-order phase transitions are intrinsically heterogeneous. When driven by ultrashort excitation, nanoscale phase regions evolve rapidly, which has posed a significant experimental challenge to characterize. The newly developed laser-pumped X-ray nanodiffraction imaging technique reported here has simultaneous 100-ps temporal and 25-nm spatial resolutions. This approach reveals pathways of the nanoscale structural rearrangement upon ultrafast optical excitation, different from those transitions under slowly varying parameters. The spatiotemporally resolved structural characterization provides crucial nanoscopic insights into ultrafast phase transitions and opens opportunities for controlling nanoscale phases on ultrafast time scales.

Simultaneous multiparameter whole blood hemostasis assessment using a carbon nanotube-paper composite capacitance sensor.

Rapid and accurate clinical assessment of hemostasis is essential for managing patients who undergo invasive procedures, experience hemorrhages, or receive antithrombotic therapies. Hemostasis encompasses an ensemble of interactions between the cellular and non-cellular blood components, but current devices assess only partial aspects of this complex process. In this work, we describe the development of a new approach to simultaneously evaluate coagulation function, platelet count or function, and hematocrit using a carbon nanotube-paper composite (CPC) capacitance sensor. CPC capacitance response to blood clotting at 1.3 MHz provided three sensing parameters with distinctive sensitivities towards multiple clotting elements. Whole blood-based hemostasis assessments were conducted to demonstrate the potential utility of the developed sensor for various hemostatic conditions, including pathological conditions, such as hemophilia and thrombocytopenia. Results showed good agreements when compared to a conventional thromboelastography. Overall, the presented CPC capacitance sensor is a promising new biomedical device for convenient non-contact whole-blood based comprehensive hemostasis evaluation.

Ultrafast Carrier-Lattice Interactions and Interlayer Modulations of Bi2Se3 by X-ray Free-Electron Laser Diffraction.

As a 3D topological insulator, bismuth selenide (Bi2Se3) has potential applications for electrically and optically controllable magnetic and optoelectronic devices. Understanding the coupling with its topological phase requires studying the interactions of carriers with the lattice on time scales down to the subpicosecond regime. Here, we investigate the ultrafast carrier-induced lattice contractions and interlayer modulations in Bi2Se3 thin films by time-resolved diffraction using an X-ray free-electron laser. The lattice contraction depends on the carrier concentration and is followed by an interlayer expansion accompanied by oscillations. Using density functional theory and the Lifshitz model, the initial contraction can be explained by van der Waals force modulation of the confined free carrier layers. Our theoretical calculations suggest that the band inversion, related to a topological phase transition, is modulated by the expansion of the interlayer distance. These results provide insights into the topological phase control by light-induced structural change on ultrafast time scales.

Dynamic Tilting of Ferroelectric Domain Walls Caused by Optically Induced Electronic Screening.

Optical excitation perturbs the balance of phenomena selecting the tilt orientation of domain walls within ferroelectric thin films. The high carrier density induced in a low-strain BaTiO_{3} thin film by an above-band-gap ultrafast optical pulse changes the tilt angle that 90° a/c domain walls form with respect to the substrate-film interface. The dynamics of the changes are apparent in time-resolved synchrotron x-ray scattering studies of the domain diffuse scattering. Tilting occurs at 298 K, a temperature at which the a/b and a/c domain phases coexist but is absent at 343 K in the better ordered single-phase a/c regime. Phase coexistence at 298 K leads to increased domain-wall charge density, and thus a larger screening effect than in the single-phase regime. The screening mechanism points to new directions for the manipulation of nanoscale ferroelectricity.

In situ immobilization of ultra-fine Ag NPs onto magnetic Ag@RF@Fe3O4 core-satellite nanocomposites for the rapid catalytic reduction of nitrophenols.

Novel magnetic Ag@RF@Fe3O4 core-satellite (MCS) nanocomposites were prepared through in situ photoreduction upon bridging Fe(III) and Ag+ via hydroxyl groups in resorcinol formaldehyde (RF) resin by virtue of the coordination effect. The catalytic activity of MCS nanocomposites was evaluated based on catalytic 4-nitrophenol (4-NP) reduction with NaBH4 as the reducing agent. It was noteworthy that the MCS-3 was beneficial to obtain a superior reaction rate constant of 2.27 min-1 and a TOF up to 72.7 h-1. Moreover, the MCS could be easily recovered by applying an external magnetic field and was reused for five times without significantly decrease in catalytic activity. Kinetic and thermodynamic study revealed that catalytic 4-NP reduction using MCS nanocatalysts obeyed the Langmuir-Hinshelwood mechanism and was controlled by the diffusion rate of substrates. Overall, the immobilization of ultra-fine Ag nanoparticles and the extremely negative potentials around MCS nanocomposites, which were effective for the diffusion of reactants, synergistically accelerated the catalytic reduction reactions.

Field-Assisted Alignment of Cellulose Nanofibrils in a Continuous Flow-Focusing System.

The continuous production of macroscale filaments of 17 µm in diameter comprising aligned TEMPO-oxidized cellulose nanofibrils (CNFs) is conducted using a field-assisted flow-focusing process. The effect of an AC external field on the material's structure becomes significant at a certain voltage, beyond which augmentations of the CNF orientation factor up to 16% are obtained. Results indicate that the electric field significantly contributes to improve the CNF ordering in the bulk, while the CNF alignment on the filament surface is only slightly affected by the applied voltage. X-ray diffraction shows that CNFs are densely packed anisotropically in the plane parallel to the filament axis without any preferential out of plane orientation. The improved nanoscale ordering combined with the tight CNF packing yields impressive enhancements in mechanical properties, with stiffness up to 25 GPa and more than 63% (up to 260 MPa), 46% (up to 2.8%), and 120% (up to 4.7 kJ/m3) increase in tensile strength, strain-to-failure, and toughness, respectively. This study demonstrates for the first time the control over the structural ordering of anisotropic nanoparticles in a dynamic system using an electric field, which can have important implications for the development of sustainable alternatives to synthetic textiles.

Cellulose Nanofibril/Carbon Nanomaterial Hybrid Aerogels for Adsorption Removal of Cationic and Anionic Organic Dyes.

Advances in nanoscale science and engineering are providing new opportunities to develop promising adsorbents for environmental remediation. Here, hybrid aerogels are assembled from cellulose nanofibrils (CNFs) and carbon nanomaterials to remove cationic dye methylene blue (MB) and anionic dye Congo red (CR) in single and binary systems. Two classes of carbon nanomaterials, carbon nanotubes (CNTs) and graphene nanoplates (GnPs), are incorporated into CNFs with various amounts, respectively. The adsorption, mechanics and structure properties of the hybrid aerogels are investigated and compared among different combinations. The results demonstrate CNF-GnP 3:1 hybrid exhibits the best performance among all composites. Regarding a single dye system, both dye adsorptions follow a pseudo-second-order adsorption kinetic and monolayer Langmuir adsorption isotherm. The maximal adsorption capacities of CNF-GnP aerogels for MB and CR are 1178.5 mg g-1 and 585.3 mg g-1, respectively. CNF-GnP hybrid show a superior binary dye adsorption capacity than pristine CNF or GnP. Furthermore, nearly 80% of MB or CR can be desorbed from CNF-GNP using ethanol as the desorption agent, indicating the reusability of this hybrid material. Hence, the CNF-GnP aerogels show great promise as adsorption materials for wastewater treatment.

High temperature and fire behavior of hydrothermally modified wood impregnated with carbon nanomaterials.

Wood is one of the most widely used construction materials but it is thermally degradable and combustible, which poses serious safety concerns. In this research, the high temperature and fire behavior of hydrothermally modified western hemlock, impregnated with carbon nanomaterials pre-adsorbed with alkali lignin, was examined by cone calorimetry, scanning electron microscopy, thermal gravimetric analysis, and Fourier transform infrared spectroscopy. The hydrothermal treatment made the wood less hydrophilic, allowing the formation of a dense protective layer of carbon-rich additives on the external wood surface at low loading (5 wt%) after aqueous-phase vacuum impregnation. Results revealed that the unique combination of these two processes reduced the total heat release by up to 32%, diminished flame spread by 31%, decreased the average carbon dioxide yield by 12%, lowered the total mass loss by 10%, and significantly slowed the pyrolytic reactions of wood. This research has important implications for the development of valued-added wood products with superior fire safety from relatively low cost timbers, such as western hemlock.

Hybridization between cellulose nanofibrils and faceted silver nanoparticles used with surface enhanced Raman scattering for trace dye detection.

This research studies the surface enhanced Raman scattering (SERS) activity of cellulose nanofibrils (CNFs) hybridized with faceted silver nanoparticles (AgFNPs) for the detection of organic dyes in aqueous media. Faceted AgNPs were synthesized under environmentally benign conditions using TEMPO-oxidized CNFs as both shape-regulating, reducing and stabilizing agents. Small, zero valent, spherical AgNPs first formed on the CNF surface and transformed into larger and faceted AgNPs when reacting with H2O2 through a thermodynamically driven Ostwald ripening mechanism. The as-synthesized hybrids exhibited strong analytical enhancement in the Raman signal of methylene blue, up to 6.8 × 103 at 448 cm-1 with less than 32% spatial variations and 10% sample-to-sample variability, enabling the detection of dyes in water at the sub part-per million level. The origin of the SERS enhancement came from discrete hotspots of high silver content on the substrate, as characterized by spatially resolved laser ablation inductively coupled plasma mass spectrometry.

Micro-focused MHz pink beam for time-resolved X-ray emission spectroscopy.

The full radiation from the first harmonic of a synchrotron undulator (between 5 and 12 keV) at the Advanced Photon Source is microfocused using a stack of beryllium compound refractive lenses onto a fast-moving liquid jet and overlapped with a high-repetition-rate optical laser. This micro-focused geometry is used to perform efficient nonresonant X-ray emission spectroscopy on transient species using a dispersive spectrometer geometry. The overall usable flux achieved on target is above 1015 photons s-1 at 8 keV, enabling photoexcited systems in the liquid phase to be tracked with time resolutions from tens of picoseconds to microseconds, and using the full emission spectrum, including the weak valence-to-core signal that is sensitive to chemically relevant electronic properties.

Nanosecond Optically Induced Phase Transformation in Compressively Strained BiFeO_{3} on LaAlO_{3}.

Above-band-gap optical illumination of compressively strained BiFeO_{3} induces a transient reversible transformation from a state of coexisting tilted tetragonal-like and rhombohedral-like phases to an untilted tetragonal-like phase. Time-resolved synchrotron x-ray diffraction reveals that the transformation is induced by an ultrafast optically induced lattice expansion that shifts the relative free energies of the tetragonal-like and rhombohedral-like phases. The transformation proceeds at interfaces between regions of the tetragonal-like phase and regions of a mixture of tilted phases, consistent with the motion of a phase boundary. The optically induced transformation demonstrates that there are new optically driven routes towards nanosecond-scale control of phase transformations in ferroelectrics and multiferroics.

Simultaneous scanning near-field optical and X-ray diffraction microscopy for correlative nanoscale structure-property characterization.

A multimodal imaging instrument has been developed that integrates scanning near-field optical microscopy with nanofocused synchrotron X-ray diffraction imaging. The instrument allows for the simultaneous nanoscale characterization of electronic/near-field optical properties of materials together with their crystallographic structure, facilitating the investigation of local structure-property relationships. The design, implementation and operating procedures of this instrument are reported. The scientific capabilities are demonstrated in a proof-of-principle study of the insulator-metal phase transition in samarium sulfide (SmS) single crystals induced by applying mechanical pressure via a scanning tip. The multimodal imaging of an in situ tip-written region shows that the near-field optical reflectivity can be correlated with the heterogeneously transformed structure of the near-surface region of the crystal.

Tunable spin-state bistability in a spin crossover molecular complex.

The spin crossover (SCO) transitions at both the surface and over the entire volume of the [Fe{H2B(pz)2}2(bipy)] polycrystalline films on Al2O3 substrates have been studied, where pz = pyrazol-1-yl and bipy = 2,2'-bipyridine. For [Fe{H2B(pz)2}2(bipy)] films of hundreds of nm thick, magnetometry and x-ray absorption spectroscopy measurements show thermal hysteresis in the SCO transition with temperature, although the transition in bulk [Fe{H2B(pz)2}2(bipy)] occurs in a non-hysteretic fashion at 157 K. While the size of the crystallites in those films are similar, the hysteresis becomes more prominent in thinner films, indicating a significant effect of the [Fe{H2B(pz)2}2(bipy)]/Al2O3 interface. Bistability of spin states, which can be inferred from the thermal hysteresis, was directly observed using temperature-dependent x-ray diffraction; the crystallites behave as spin-state domains that coexist during the transition. The difference between the spin state of molecules at the surface of the [Fe{H2B(pz)2}2(bipy)] films and that of the molecules within the films, during the thermal cycle, indicates that both cooperative (intermolecular) effects and coordination are implicated in perturbations to the SCO transition.

Dynamics of Quaternary Structure Transitions in R-State Carbonmonoxyhemoglobin Unveiled in Time-Resolved X-ray Scattering Patterns Following a Temperature Jump.

It is well-known that tetrameric hemoglobin binds ligands cooperatively by undergoing a ligand-induced T → R quaternary structure transition, a structure-function relationship that has long served as a model system for understanding allostery in proteins. However, kinetic studies of the reverse, R → T quaternary structure transition following photolysis of carbonmonoxyhemoglobin (HbCO) reveal complex behavior that may be better explained by the presence of two different R quaternary structures coexisting in thermal equilibrium. Indeed, we report here time-resolved small- and wide-angle X-ray scattering (SAXS/WAXS) patterns of HbCO following a temperature jump that not only provide unambiguous evidence for more than one R state, but also unveil the time scale for interconversion between them. Since the time scale for the photolysis-induced R → T transition is likely different for different R-states, this structural heterogeneity must be accounted for to properly explain the kinetic heterogeneity observed in time-resolved spectroscopic studies following photolysis of HbCO.

A color x-ray camera for 2-6 keV using a mass produced back illuminated complementary metal oxide semiconductor sensor.

There are several reports in the scientific literature of the use of mass-produced charge coupled device or complementary metal oxide semiconductor (CMOS) sensors as x-ray detectors that combine high spatial resolution with significant energy resolution. Exploiting a relatively new especially favorable ambient-temperature back-illuminated CMOS sensor, we report the development of a spectroscopic x-ray camera having particularly impressive performance for 2-6 keV photons. This instrument has several beneficial characteristics for advanced x-ray spectroscopy studies in the laboratory, at synchrotron light sources, at x-ray free electron lasers, or when using pulsed x-ray sources such as for laser plasma physics research. These characteristics include fine position and energy resolution for individual photon events, high saturation rates, frame rates above 100 Hz, easy user maintenance for damaged sensors, and software for real-time processing. We evaluate this camera as an alternative to traditional energy-dispersive solid-state detectors, such as silicon drift detectors, and also illustrate its use in a very high resolution wavelength-dispersive x-ray fluorescence spectrometer (i.e., x-ray emission spectrometer) that has recently been reported elsewhere [W. M. Holden et al., Rev. Sci. Instrum. 88(7), 073904 (2017)].