Origin of micro-scale heterogeneity in polymerisation of photo-activated resin composites.

Photo-activated resin composites are widely used in industry and medicine. Despite extensive chemical characterisation, the micro-scale pattern of resin matrix reactive group conversion between filler particles is not fully understood. Using an advanced synchrotron-based wide-field IR imaging system and state-of-the-art Mie scattering corrections, we observe how the presence of monodispersed silica filler particles in a methacrylate based resin reduces local conversion and chemical bond strain in the polymer phase. Here we show that heterogeneity originates from a lower converted and reduced bond strain boundary layer encapsulating each particle, whilst at larger inter-particulate distances light attenuation and monomer mobility predominantly influence conversion. Increased conversion corresponds to greater bond strain, however, strain generation appears sensitive to differences in conversion rate and implies subtle distinctions in the final polymer structure. We expect these findings to inform current predictive models of mechanical behaviour in polymer-composite materials, particularly at the resin-filler interface.

Selective Growth of Interface Layers from Reactions of Sc(MeCp)2(Me2pz) with Oxide Substrates.

The transformation of an oxide substrate by its reaction with a chemical precursor during atomic layer deposition (ALD) has not attracted much attention, as films are typically deposited on top of the oxide substrate. However, any modification to the substrate surface can impact the electrical and optical properties of the device. We demonstrate herein the ability of a precursor to react deep within an oxide substrate to form an interfacial layer that is distinct from both the substrate and deposited film. This phenomenon is studied using a scandium precursor, Sc(MeCp)2(Me2pz) (1, MeCp = methylcyclopentadienyl, Me2pz = 3,5-dimethylpyrazolate), and five oxide substrates (SiO2, ZnO, Al2O3, TiO2, and HfO2). In situ Fourier transform infrared (FTIR) spectroscopy shows that at moderate temperatures (∼150 °C) the pyrazolate group of 1 reacts with the surface hydroxyl groups of OH-terminated SiO2 substrates. However, at slightly higher temperatures (≥225 °C) typically used for the ALD of Sc2O3, there is a direct reaction between 1 and the SiO2 layer, in addition to chemisorption at the surface hydroxyl groups. This reaction is sustained by sequential exposures of 1 until an ∼2 nm thick passivating interface layer is formed, indicating that 1 reacts with oxygen derived from SiO2. A shift of the Si 2p core level position, measured by ex situ X-ray photoelectron spectroscopy, is consistent with the formation of a ScSi xO y layer. Similar observations are made following the exposure of a ZnO substrate to 1 at 275 °C. In contrast, Al2O3, TiO2, and HfO2 substrates remain resistant to reaction with 1 under similar conditions, except for a surface reaction occurring in the case of TiO2. These striking observations are attributed to the differences in the electrochemical potentials of the elements comprising the oxide substrates to that of scandium. Precursor 1 can react with SiO2 or ZnO substrates, since the constituent elements of these oxides have less-negative electrochemical potentials than do aluminum, titanium, and hafnium. Additionally, Sc2O3 and surface carbonates are deposited on all substrates by gas-phase reactions between 1 and residual water vapor in the reactor. The extent of gas-phase reactions contributing to film growth is governed by the relative pressure of water vapor in the presence of 1. These results suggest caution when using very reactive, oxophilic precursors such as 1 to avoid misinterpreting unconventional film deposition as that resulting from a standard ALD process.

Thermal Atomic Layer Etching of Silica and Alumina Thin Films Using Trimethylaluminum with Hydrogen Fluoride or Fluoroform.

Thermal atomic layer etching (ALE) is an emerging technique that involves the sequential removal of monolayers of a film by alternating self-limiting reactions, some of which generate volatile products. Although traditional ALE processes rely on the use of plasma, several thermal ALE processes have recently been developed using hydrogen fluoride (HF) with precursors such as trimethylaluminum (TMA) or tin acetylacetonate. While HF is currently the most effective reagent for ALE, its potential hazards and corrosive nature have motivated searches for alternative chemicals. Herein, we investigate the feasibility of using fluoroform (CHF3) with TMA for the thermal ALE of SiO2 and Al2O3 surfaces and compare it to the established TMA/HF process. A fundamental mechanistic understanding is derived by combining in situ Fourier transform infrared spectroscopy, ex situ X-ray photoemission spectroscopy, ex situ low-energy ion scattering, and ex situ spectroscopic ellipsometry. Specifically, we determine the role of TMA, the dependence of the etch rate on precursor gas pressure, and the formation of a residual fluoride layer. Although CHF3 reacts with TMA-treated oxide surfaces, etching is hindered by the concurrent deposition of a fluorine-containing layer, which makes it unfavorable for etching. Moreover, since fluorine contamination can be deleterious to device performance and its presence in thin films is an inherent problem for established ALE processes using HF, we present a novel method to remove the residual fluorine accumulated during the ALE process by exposure to water vapor. XPS analysis herein reveals that an Al2O3 film etched using TMA/HF at 325 °C contains 25.4 at. % fluorine in the surface region. In situ exposure of this film to water vapor at 325 °C results in ∼90% removal of the fluorine. This simple approach for fluorine removal can easily be applied to ALE-treated films to mitigate contamination and retain surface stoichiometry.

In Situ Infrared Absorption Study of Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride.

Despite the success of plasma-enhanced atomic layer deposition (PEALD) in depositing quality silicon nitride films, a fundamental understanding of the growth mechanism has been difficult to obtain because of lack of in situ characterization to probe the surface reactions noninvasively and the complexity of reactions induced/enhanced by the plasma. These challenges have hindered the direct observation of intermediate species formed during the reactions. We address this challenge by examining the interaction of Ar plasma using atomically flat, monohydride-terminated Si(111) as a well-defined model surface and focusing on the initial PEALD with aminosilanes. In situ infrared and X-ray photoelectron spectroscopy reveals that an Ar plasma induces desorption of H atoms from H-Si(111) surfaces, leaving Si dangling bonds, and that the reaction of di-sec-butylaminosilane (DSBAS) with Ar plasma-treated surfaces requires the presence of both active sites (Si dangling bonds) and Si-H; there is no reaction on fully H-terminated or activated surfaces. By contrast, high-quality hydrofluoric acid-etched Si3N4 surfaces readily react with DSBAS, resulting in the formation of O-SiH3. However, the presence of back-bonded oxygen in O-SiH3 inhibits H desorption by Ar or N2 plasma, presumably because of stabilization of H against ion-induced desorption. Consequently, there is no reaction of adsorbed aminosilanes even after extensive Ar or N2 plasma treatments; a thermal process is necessary to partially remove H, thereby promoting the formation of active sites. These observations are consistent with a mechanism requiring the presence of both undercoordinated nitrogen and/or dangling bonds and unreacted surface hydrogen. Because active sites are involved, the PEALD process is found to be sensitive to the duration of the plasma exposure treatment and the purge time, during which passivation of these sites can occur.

Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer.

The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk-as is typically done to enhance adsorption-here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO2, SO2, C2H4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained by ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. These findings may provide alternative strategies for gas storage, delivery and separation.

Correction: Cold shock induces apoptosis of dorsal root ganglion neurons plated on infrared windows.

Correction for 'Cold shock induces apoptosis of dorsal root ganglion neurons plated on infrared windows' by Ebrahim Aboualizadeh et al., Analyst, 2015, 140, 4046-4056.

Cold shock induces apoptosis of dorsal root ganglion neurons plated on infrared windows.

The chemical status of live sensory neurons is accessible with infrared microspectroscopy of appropriately prepared cells. In this paper, individual dorsal root ganglion (DRG) neurons have been prepared with two different protocols, and plated on glass cover slips, BaF2 and CaF2 substrates. The first protocol exposes the intact DRGs to 4 °C for between 20-30 minutes before dissociating individual neurons and plating 2 hours later. The second protocol maintains the neurons at 23 °C for the entire duration of the sample preparation. The visual appearance of the neurons is similar. The viability was assessed by means of trypan blue exclusion method to determine the viability of the neurons. The neurons prepared under the first protocol (cold exposure) and plated on BaF2 reveal a distinct chemical signature and chemical distribution that is different from the other sample preparations described in the paper. Importantly, results for other sample preparation methods, using various substrates and temperature protocols, when compared across the overlapping spectral bandwidth, present normal chemical distribution within the neurons. The unusual chemically specific spatial variation is dominated by a lack of protein and carbohydrates in the center of the neurons and signatures of unraveling DNA are detected. We suggest that cold shock leads to apoptosis of DRGs, followed by osmotic stress originating from ion gradients across the cell membrane leading to cell lysis.

Chemical structure and morphology of dorsal root ganglion neurons from naive and inflamed mice.

Fourier transform infrared spectromicroscopy provides label-free imaging to detect the spatial distribution of the characteristic functional groups in proteins, lipids, phosphates, and carbohydrates simultaneously in individual DRG neurons. We have identified ring-shaped distributions of lipid and/or carbohydrate enrichment in subpopulations of neurons which has never before been reported. These distributions are ring-shaped within the cytoplasm and are likely representative of the endoplasmic reticulum. The prevalence of chemical ring subtypes differs between large- and small-diameter neurons. Peripheral inflammation increased the relative lipid content specifically in small-diameter neurons, many of which are nociceptive. Because many small-diameter neurons express an ion channel involved in inflammatory pain, transient receptor potential ankyrin 1 (TRPA1), we asked whether this increase in lipid content occurs in TRPA1-deficient (knock-out) neurons. No statistically significant change in lipid content occurred in TRPA1-deficient neurons, indicating that the inflammation-mediated increase in lipid content is largely dependent on TRPA1. Because TRPA1 is known to mediate mechanical and cold sensitization that accompanies peripheral inflammation, our findings may have important implications for a potential role of lipids in inflammatory pain.

Ultrasensitive chemical sensing through facile tuning defects and functional groups in reduced graphene oxide.

Herein, we report on a facile, low-cost, and efficient method to tune the structure and properties of chemically reduced graphene oxide (rGO) by applying a transient voltage across the rGO for ultrasensitive gas sensors. A large number of defects, including pits, are formed in the rGO upon the voltage activation. More interestingly, the number of epoxide and ether functional groups in the rGO increased after the voltage activation. The voltage-activated rGO was highly sensitive to NO2 with a sensitivity 500% higher than that of the original rGO. The lower detection limit can reach an unprecedented ultralow concentration of 50 ppb for NO2 sensing. Density functional theory (DFT) calculations revealed that the high sensitivity to NO2 is attributed to the efficient charge transfer from ether groups to NO2, which is the dominant sensing mechanism. This study points to a promising method to tune the properties of graphene-based materials through the creation of additional defects and functional groups for high-performance gas sensors.

Opportunities for live cell FT-infrared imaging: macromolecule identification with 2D and 3D localization.

Infrared (IR) spectromicroscopy, or chemical imaging, is an evolving technique that is poised to make significant contributions in the fields of biology and medicine. Recent developments in sources, detectors, measurement techniques and speciman holders have now made diffraction-limited Fourier transform infrared (FTIR) imaging of cellular chemistry in living cells a reality. The availability of bright, broadband IR sources and large area, pixelated detectors facilitate live cell imaging, which requires rapid measurements using non-destructive probes. In this work, we review advances in the field of FTIR spectromicroscopy that have contributed to live-cell two and three-dimensional IR imaging, and discuss several key examples that highlight the utility of this technique for studying the structure and chemistry of living cells.

Toward optimal spatial and spectral quality in widefield infrared spectromicroscopy of IR labelled single cells.

Advancements in widefield infrared spectromicroscopy have recently been demonstrated following the commissioning of IRENI (InfraRed ENvironmental Imaging), a Fourier Transform infrared (FTIR) chemical imaging beamline at the Synchrotron Radiation Center. The present study demonstrates the effects of magnification, spatial oversampling, spectral pre-processing and deconvolution, focusing on the intracellular detection and distribution of an exogenous metal tris-carbonyl derivative 1 in a single MDA-MB-231 breast cancer cell. We demonstrate here that spatial oversampling for synchrotron-based infrared imaging is critical to obtain accurate diffraction-limited images at all wavelengths simultaneously. Resolution criteria and results from raw and deconvoluted images for two Schwarzschild objectives (36×, NA 0.5 and 74×, NA 0.65) are compared to each other and to prior reports for raster-scanned, confocal microscopes. The resolution of the imaging data can be improved by deconvolving the instrumental broadening that is determined with the measured PSFs, which is implemented with GPU programming architecture for fast hyperspectral processing. High definition, rapidly acquired, FTIR chemical images of respective spectral signatures of the cell 1 and shows that 1 is localized next to the phosphate- and Amide-rich regions, in agreement with previous infrared and luminescence studies. The infrared image contrast, localization and definition are improved after applying proven spectral pre-processing (principal component analysis based noise reduction and RMie scattering correction algorithms) to individual pixel spectra in the hyperspectral cube.

Multiple morphologies of gold-magnetite heterostructure nanoparticles are effectively functionalized with protein for cell targeting.

Nanoparticles composed of a magnetic iron oxide core surrounded by a metal shell have utility in a broad range of biomedical applications. However, the presence of surface energy differences between the two components makes wetting of oxide with metal unfavorable, precluding a "core-shell" structure of an oxide core completely surrounded by a thin metal shell. Three-dimensional island growth followed by island coalescence into thick shells is favored over the two-dimensional layer-by-layer growth of a thin, continuous metal coating of a true core-shell. Aqueous synthesis of gold-coated magnetite nanoparticles with analysis by infrared, energy-dispersive X-ray, and electron energy loss spectroscopies; high-resolution transmission electron microscopy; selected area electron diffraction; and high-angle annular dark-field scanning transmission electron microscopy showed two distinct morphologies that are inconsistent with an idealized core-shell. The majority were isolated ~16-22-nm-diameter nanoparticles consisting of ~7-nm-diameter magnetite and a thick deposition of gold, most often discontinuous, with some potentially "sandwiched" morphologies. A minority were aggregates of agglomerated magnetite decorated with gold but displaying significant bare magnetite. Both populations were successfully conjugated to fibrinogen and targeted to surface-activated platelets, demonstrating that iron oxide-gold nanoparticles produced by aqueous synthesis do not require an ideal core-shell structure for biological activity in cell labeling and targeting applications.

Ag nanocrystal as a promoter for carbon nanotube-based room-temperature gas sensors.

We have investigated the room-temperature sensing enhancement of Ag nanoparticles (NPs) for multiwalled carbon nanotube (MWCNT)-based gas sensors using electrical measurements, in situ infrared (IR) microspectroscopy, and density functional theory (DFT) calculations. Multiple hybrid nanosensors with structures of MWCNTs/SnO(2)/Ag and MWCNTs/Ag have been synthesized using a process that combines a simple mini-arc plasma with electrostatic force directed assembly, and characterized by electron microscopy techniques. Ag NPs were found to enhance the sensing behavior through the "electronic sensitization" mechanism. In contrast to sensors based on bare MWCNTs and MWCNTs/SnO(2), sensors with Ag NPs show not only higher sensitivity and faster response to NO(2) but also significantly enhanced sensitivity to NH(3). Our DFT calculations indicate that the increased sensitivity to NO(2) is attributed to the formation of a NO(3) complex with oxygen on the Ag surface accompanying a charge rearrangement and a net electron transfer from the hybrid to NO(2). The significant response to NH(3) is predicted to arise because NH(3) is attracted to hollow sites on the oxidized Ag surface with the H atoms pointing towards Ag atoms and electron donation from H to the hybrid sensor.

Fast and selective room-temperature ammonia sensors using silver nanocrystal-functionalized carbon nanotubes.

We report a selective, room-temperature NH(3) gas-sensing platform with enhanced sensitivity, superfast response and recovery, and good stability, using Ag nanocrystal-functionalized multiwalled carbon nanotubes (Ag NC-MWCNTs). Ag NCs were synthesized by a simple mini-arc plasma method and directly assembled on MWCNTs using an electrostatic force-directed assembly process. The nanotubes were assembled onto gold electrodes with both ends in Ohmic contact. The addition of Ag NCs on MWCNTs resulted in dramatically improved sensitivity toward NH(3). Upon exposure to 1% NH(3) at room temperature, Ag NC-MWCNTs showed enhanced sensitivity (~9%), very fast response (~7 s), and full recovery within several minutes in air. Through density functional theory calculations, we found that the fully oxidized Ag surface plays a critical role in the sensor response. Ammonia molecules are adsorbed at Ag hollow sites on the AgO surface with H pointing toward Ag. A net charge transfer from NH(3) to the Ag NC-MWCNTs hybrid leads to the conductance change in the hybrid.

Restoration and spectral recovery of mid-infrared chemical images.

Fourier transform infrared (FTIR) microspectroscopy is a powerful technique for label-free chemical imaging that has supplied important chemical information about heterogeneous samples for many problems across a variety of disciplines. State-of-the-art synchrotron based infrared (IR) microspectrometers can yield high-resolution images, but are truly diffraction limited for only a small spectral range. Furthermore, a fundamental trade-off exists between the number of pixels, acquisition time and the signal-to-noise ratio, limiting the applicability of the technique. The recently commissioned infrared synchrotron beamline, infrared environmental imaging (IRENI), overcomes this trade off and delivers 4096-pixel diffraction limited IR images with high signal-to-noise ratio in under a minute. The spatial oversampling for all mid-IR wavelengths makes the IRENI data ideal for spatial image restoration techniques. Here, we measured and fitted wavelength-dependent point-spread-functions (PSFs) at IRENI for a 74× objective between the sample plane and detector. Noise-free wavelength-dependent theoretical PSFs are deconvoluted from images generated from narrow bandwidths (4 cm(-1)) over the entire mid-infrared range (4000-900 cm(-1)). The stack of restored images is used to reconstruct the spectra. Restored images of metallic test samples with features that are 2.5 µm and smaller are clearly improved in comparison to the raw data images for frequencies above 2000 cm(-1). Importantly, these spatial image restoration methods also work for samples with vibrational bands in the recorded mid-IR fingerprint region (900-1800 cm(-1)). Improved signal-to-noise spectra are reconstructed from the restored images as demonstrated for a mixture of spherical polystyrene beads in a polyurethane matrix. Finally, a freshly thawed retina tissue section is used to demonstrate the success of deconvolution achievable with a heterogeneous, irregularly shaped, biologically relevant sample with distinguishing spectroscopic features across the entire mid-IR spectral range.

Evidence of nanocrystalline semiconducting graphene monoxide during thermal reduction of graphene oxide in vacuum.

As silicon-based electronics are reaching the nanosize limits of the semiconductor roadmap, carbon-based nanoelectronics has become a rapidly growing field, with great interest in tuning the properties of carbon-based materials. Chemical functionalization is a proposed route, but syntheses of graphene oxide (G-O) produce disordered, nonstoichiometric materials with poor electronic properties. We report synthesis of an ordered, stoichiometric, solid-state carbon oxide that has never been observed in nature and coexists with graphene. Formation of this material, graphene monoxide (GMO), is achieved by annealing multilayered G-O. Our results indicate that the resulting thermally reduced G-O (TRG-O) consists of a two-dimensional nanocrystalline phase segregation: unoxidized graphitic regions are separated from highly oxidized regions of GMO. GMO has a quasi-hexagonal unit cell, an unusually high 1:1 O:C ratio, and a calculated direct band gap of ∼0.9 eV.

High-resolution Fourier-transform infrared chemical imaging with multiple synchrotron beams.

Conventional Fourier-transform infrared (FTIR) microspectroscopic systems are limited by an inevitable trade-off between spatial resolution, acquisition time, signal-to-noise ratio (SNR) and sample coverage. We present an FTIR imaging approach that substantially extends current capabilities by combining multiple synchrotron beams with wide-field detection. This advance allows truly diffraction-limited high-resolution imaging over the entire mid-infrared spectrum with high chemical sensitivity and fast acquisition speed while maintaining high-quality SNR.