The morphological change of silicon macropore arrays formed by metal-assisted chemical etching using shape-controlled Au thin film arrays was investigated during anisotropic chemical etching in tetramethylammonium hydroxide (TMAH) aqueous solution. After the deposition of Au as the etching catalyst on (111) silicon through a honeycomb mask prepared by sphere lithography, the specimens were etched in a mixed solution of HF and H2O2 at room temperature, resulting in the formation of ordered macropores in silicon along the  direction, which is not achievable by conventional chemical etching without a catalyst. In the anisotropic etching in TMAH, the macropores changed from being circular to being hexagonal and finally to being triangular, owing to the difference in etching rate between the crystal planes.
BACKGROUND: Cigarette smoking is a cause of a variety of serious diseases, and to understand the toxicological impact of tobacco smoke in vitro, whole smoke exposure systems can be used. One of the main challenges of the different whole smoke exposure systems that are commercially available is that they dilute and deliver smoke in different ways, limiting/restricting the cross-comparison of biological responses. This is where dosimetry – dose quantification – can play a key role in data comparison. Quartz crystal microbalance (QCM) technology has been put forward as one such tool to quantify smoke particle deposition in vitro, in real-time. RESULTS: Using four identical QCMs, installed into the Vitrocell® mammalian 6/4 CF Stainless exposure module, we were able to quantify deposited smoke particle deposition, generated and diluted by a Vitrocell® VC 10 Smoking Robot. At diluting airflows 0.5-4.0 L/min and vacuum flow rate 5 ml/min/well through the exposure module, mean particle deposition was in the range 8.65 +/- 1.51 mug/cm2-0.72 +/- 0.13 mug/cm2. Additionally, the effect of varying vacuum flow rate on particle deposition was assessed from 5 ml/min/well - 100 ml/min/well. Mean deposited mass for all four airflows tested per vacuum decreased as vacuum rate was increased: mean deposition was 3.79, 2.75, 1.56 and 1.09 mug/cm2 at vacuum rates of 5, 10, 50 and 100 ml/min/well respectively. CONCLUSIONS: QCMs within the Vitrocell® exposure module have demonstrated applicability at defining particle dose ranges at various experimental conditions. This tool will prove useful for users of the Vitrocell® system for dose–response determination and QC purposes.
- Proceedings of the National Academy of Sciences of the United States of America
- Published over 2 years ago
Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin’s tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.
Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ(18)O values. Overall, Toba quartz crystals exhibit comparatively high δ(18)O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ(18)O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆core-rim = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ(18)O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ(18)O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems.
In various shocked meteorites, low-pressure silica polymorph α-cristobalite is commonly found in close spatial relation with the densest known SiO2 polymorph seifertite, which is stable above ∼80 GPa. We demonstrate that under hydrostatic pressure α-cristobalite remains untransformed up to at least 15 GPa. In quasi-hydrostatic experiments, above 11 GPa cristobalite X-I forms-a monoclinic polymorph built out of silicon octahedra; the phase is not quenchable and back-transforms to α-cristobalite on decompression. There are no other known silica polymorphs, which transform to an octahedra-based structure at such low pressures upon compression at room temperature. Further compression in non-hydrostatic conditions of cristobalite X-I eventually leads to the formation of quenchable seifertite-like phase. Our results demonstrate that the presence of α-cristobalite in shocked meteorites or rocks does not exclude that materials experienced high pressure, nor is the presence of seifertite necessarily indicative of extremely high peak shock pressures.
Aquaporins (AQPs) feature highly selective water transport through cell membranes, where the dipolar orientation of structured water wires spanning the AQP pore is of considerable importance for the selective translocation of water over ions. We recently discovered that water permeability through artificial water channels formed by stacked imidazole I-quartet superstructures increases when the channel water molecules are highly organized. Correlating water structure with molecular transport is essential for understanding the underlying mechanisms of (fast) water translocation and channel selectivity. Chirality adds another factor enabling unique dipolar oriented water structures. We show that water molecules exhibit a dipolar oriented wire structure within chiral I-quartet water channels both in the solid state and embedded in supported lipid bilayer membranes (SLBs). X-ray single-crystal structures show that crystallographic water wires exhibit dipolar orientation, which is unique for chiral I-quartets. The integration of I-quartets into SLBs was monitored with a quartz crystal microbalance with dissipation, quantizing the amount of channel water molecules. Nonlinear sum-frequency generation vibrational spectroscopy demonstrates the first experimental observation of dipolar oriented water structures within artificial water channels inserted in bilayer membranes. Confirmation of the ordered confined water is obtained via molecular simulations, which provide quantitative measures of hydrogen bond strength, connectivity, and the stability of their dipolar alignment in a membrane environment. Together, uncovering the interplay between the dipolar aligned water structure and water transport through the self-assembled I-quartets is critical to understanding the behavior of natural membrane channels and will accelerate the systematic discovery for developing artificial water channels for water desalting.
The influence of shape on nanomaterial aggregation and deposition was systematically studied with poly-acrylic acid (PAA) coated uniform-sized gold nanospheres (AuNSs) and nanorods (AuNRs). Time resolved dynamic light scattering was employed to study their aggregation kinetics in a wide range of mono- and di-valent electrolyte conditions. Results indicated that PAA coated AuNSs have higher aggregation propensity compared to anisotropic PAA coated AuNRs, as observed through critical coagulation concentration (CCC). The CCC values were estimated as 50mM NaCl and 1.8mM CaCl(2) for AuNS, which showed substantial increase to 250mM NaCl and 7mM CaCl(2) for anisotropic AuNRs. Though electrokinetic behavior showed similar surface potential for the spherical and rod-shaped materials, the geometric differences between the samples have likely resulted in unique conformation of the PAA coatings, leading to different magnitudes of steric hindrances and hence yielding the observed aggregation behavior. The deposition kinetics was monitored using the quartz crystal microbalance with dissipation technique. AuNRs showed relatively slower deposition compared to AuNSs for low electrolytes concentrations. With the increase in electrolyte concentration, the differences in deposition rates between spheres and rods diminished. The results from this study showed that the shape of nanomaterials can influence interfacial properties and result in unique aggregation and deposition behavior under typical aquatic conditions.
Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye, “N3,” to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by SEM, EDX, and XPS. We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption, and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.
125I-radiolabeling, Surface Plasmon Resonance and Quartz Crystal Microbalance with Dissipation: Three Tools to Compare Protein Adsorption on Surfaces of Different Wettability
- Langmuir : the ACS journal of surfaces and colloids
- Published over 4 years ago
The extent of protein adsorption is an important consideration for the biocompatibility of biomaterials. Various experimental methods can be used to determine the quantity of protein adsorbed, but the results usually differ. In the present work, self-assembled monolayers (SAMs) were used to prepare a series of model gold surfaces varying systematically in water wettability, from hydrophilic to hydrophobic. Three commonly used methods, namely, surface plasmon resonance (SPR), quartz crystal microbalance with dissipation (QCM-D) and 125I-radiolabeling, were employed to quantify fibrinogen (Fg) adsorption on these surfaces. This approach allows a direct comparison of the mass of Fg adsorbed using these three techniques. The results from all three methods showed that protein adsorption increases with increasing surface hydrophobicity. The increase in the mass of Fg adsorbed with increasing surface hydrophobicity in the SPR data was parallel to that from 125I-radiolabeling, but the absolute values were different, and there does not seem to be a “universal congruent” relationship between the two methods for surfaces with varying wettability. For QCM-D, the variation in protein adsorption with wettability was different from that for SPR and radiolabeling. On the more hydrophobic surfaces, QCM-D gave adsorbed mass much higher than the two other methods, possibly because QCM-D measures both the adsorbed Fg and its associated water. However, on the more hydrophilic surfaces, the adsorbed mass from QCM-D was slightly greater than from SPR, and both were smaller than from 125I-radiolabeling; this was true whether the Sauerbrey equation or the Voigt model was used to convert QCM-D data to adsorbed mass.
A facile route to phosphorus-functionalized polyurethane dispersions (P-PUDs) with improved adhesion properties is presented. (Bis)phosphonic acid moieties serve as adhesion promoting sites that are covalently attached via an endcapping reaction to isocyanate-reactive polyurethane particles under aqueous conditions. The synthetic approach circumvents solubility issues, offers great flexibility in terms of polyurethane composition, and allows for the synthesis of semi-crystalline systems with thermomechanical response due to reversible physical crosslinking. Differential Scanning Calorimetry (DSC) is used to investigate the effect of functionalization on the semi-crystallinity. The endcapping conversion was determined via Inductively-Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and was surprisingly found to be almost independent of the stoichiometry of reaction, suggesting an adsorption-dominated process. Particle Charge Detection (PCD) experiments reveal that a dense surface coverage of phosphonic acid groups can be attained, and that at high functionalization degrees, the phosphonic adhesion moieties are partially dragged inside the colloidal P-PUD particle. Quartz Crystal Microbalance with Dissipation (QCMD) investigations conducted with hydroxyapatite (HAP) sensors as model surfaces show a greatly enhanced affinity of the aqueous P PUDs and furthermore indicate polymer chain rearrangements and autonomous film formation under wet conditions. Due to their facile synthesis, significantly improved adhesion, and variable film properties, P-PUD systems such as the one described here are believed to be of great interest for multiple applications, e.g. adhesives, paints, anti-corrosion, or dentistry.