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.

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.

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.

Facile preparation of cellulose nanocrystals/ZnO hybrids using acidified ZnCl 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.

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.

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.

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.

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

As a 3D topological insulator, bismuth selenide (BiSe) 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 BiSe thin films by time-resolved diffraction using an X-ray free-electron laser.

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.

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.

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

Novel magnetic Ag@RF@FeO 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 NaBH as the reducing agent. It was noteworthy that the MCS-3 was beneficial to obtain a superior reaction rate constant of 2.

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.

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 HO through a thermodynamically driven Ostwald ripening mechanism.

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 10 photons s 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.

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.

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.

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.

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{HB(pz)}(bipy)] polycrystalline films on AlO substrates have been studied, where pz  =  pyrazol-1-yl and bipy  =  2,2'-bipyridine. For [Fe{HB(pz)}(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{HB(pz)}(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{HB(pz)}(bipy)]/AlO interface.

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.

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.

X-ray and optical pulse interactions in GaAs.

Absorption of hard x-rays in GaAs creates excitations that can dramatically alter the propagation of optical laser pulses with photon energies near the bandgap. Measurements of optical transmission through a thin crystalline wafer of GaAs after absorption of an intense x-ray synchrotron pulse demonstrate how x-ray induced optical transparency depends on the recombination of excited conduction band electrons and valence band holes via Auger, spontaneous emission, and especially stimulated emission processes. The x-ray induced band fluorescence spectrum also reveals amplified spontaneous emission at the high x-ray fluences used, confirming the importance of stimulated emission.

Dynamic Optical Tuning of Interlayer Interactions in the Transition Metal Dichalcogenides.

Modulation of weak interlayer interactions between quasi-two-dimensional atomic planes in the transition metal dichalcogenides (TMDCs) provides avenues for tuning their functional properties. Here we show that above-gap optical excitation in the TMDCs leads to an unexpected large-amplitude, ultrafast compressive force between the two-dimensional layers, as probed by in situ measurements of the atomic layer spacing at femtosecond time resolution. We show that this compressive response arises from a dynamic modulation of the interlayer van der Waals interaction and that this represents the dominant light-induced stress at low excitation densities.