Ultrafast Near‐Infrared Light‐Triggered Intracellular Uncaging to Probe Cell Signaling

The possibility of regulating cell signaling with high spatial and temporal resolution within individual cells and complex cellular networks has important implications in biomedicine. This article demonstrates a general strategy that uses near‐infrared tissue‐penetrating laser pulses to uncage biomolecules from plasmonic gold‐coated liposomes, i.e., plasmonic liposomes, to activate cell signaling in a nonthermal, ultrafast, and highly controllable fashion. Near‐infrared picosecond laser pulse induces transient nanobubbles around plasmonic liposomes. The mechanical force generated from the collapse of nanobubbles rapidly ejects encapsulated compound within 0.1 ms. This article shows that single pulse irradiation triggers the rapid intracellular uncaging of calcein from plasmonic liposomes inside endolysosomes. The uncaged calcein then evenly distributes over the entire cytosol and nucleus. Furthermore, this article demonstrates the ability to trigger calcium signaling in both an immortalized cell line and primary dorsal root ganglion neurons by intracellular uncaging of inositol triphosphate (IP₃), an endogenous cell calcium signaling second messenger. Compared with other uncaging techniques, this ultrafast near‐infrared light‐driven molecular uncaging method is easily adaptable to deliver a wide range of bioactive molecules with an ultrafast optical switch, enabling new possibilities to investigate signaling pathways within individual cells and cellular networks.     

Sensing polarization with variable coherence tomography

Variable coherence tomography (VCT) was recently developed by Baleine and Dogariu for the purpose of directly sensing the second-order statistical properties of a randomly scattering volume [J. Opt. Soc. Am. A21, 1917 (2004)]. In this paper we generalize the theory of VCT to include polarized inputs and anisotropic scatterers. In general the measurement of the scattered coherency matrix or Stokes vector is not adequate to describe the scattering, as these quantities depend on the coherence state of the incident beam. However, by controlling the polarized coherence properties of the source beam, VCT can be generalized to probe the polarimetric scattering properties of objects from a single-point Stokes vector or coherency matrix measurements. With polarized VCT, we are able to design a method that can measure analogous information to the polarimetric bidirectional reflection distribution function (BRDF), but do it from monostatic data. This capability would allow the BRDF to be measured remotely without having to adjust either the incident or observation angle with respect to the target.     

Thermodynamic assessment of the pseudoternary Na2O–Al2O3–SiO2 system

Vitrified high‐level radioactive waste that contains high concentrations of Na₂O and Al₂O₃, such as the waste stored at the Hanford site, can cause nepheline to precipitate in the glass upon cooling in the canisters. Nepheline formation removes oxides such as Al₂O₃ and SiO₂ from the host glass, which can reduce its chemical durability. Uncertainty in the extent of precipitated nepheline necessitates operating at an enhanced waste loading margin, which increases operational costs by extending the vitrification mission as well as increasing waste storage requirements. A thermodynamic evaluation of the Na₂O–Al₂O₃–SiO₂ system that forms nepheline was conducted by utilizing the compound energy formalism and ionic liquid model to represent the solid solution and liquid phases, respectively. These were optimized with experimental data and used to extrapolate phase boundaries into regions of temperature and composition where measurements are unavailable. The intent is to import the determined Gibbs energies into a phase field model to more accurately predict nepheline phase formation and morphology evolution in waste glasses to allow for the design of formulations with maximum loading.     

Subcritical crack growth models for static fatigue of Hi-NicalonTM-S SiC fiber in air and steam

Three subcritical crack growth (SCG) laws were used to model strain-rates and failure times for static fatigue of Hi-Nicalon^TM-S SiC fiber tows in air and Si(OH)₄(g)-saturated steam. Models were fit to tow failure times ( t_f ) and steady-state strain rates ( ἑ ) for brittle creep measured at 700 to 1100°C under initial applied stresses ( σ_A ) of 260 to 1260 MPa. A power law, a reaction-rate law, and a bond-energy law were used to describe SCG that caused sequential filament failure, and ultimately tow failure. Two versions of each model were developed. One allowed access of chemisorbed species to flaws throughout the fiber (mode 1) and another only allowed access to flaws at the SiC-SiO₂ interface (mode 2). The stress increase on intact filaments as others fractured and as filaments oxidized, and the increase in stress intensity geometric factors ( Y ) as crack size increased were incorporated in the models. The fits to data were compared for the different models by using both simple regression analysis and orthogonal distance regression (ODR) analysis. Faster convergence and more consistent results were achieved using ODR analysis. Regression analyses found parameters for all models with similar error in data fits, so validity of a model could not be distinguished by regression analysis alone. For all models, the stress dependence of SCG rates was much stronger in steam than in air, and for most models activation energies were between 300 and 420 kJ/mol, regardless of environment. For the steam environment, the bond-length parameter ( δ ) for the bond-energy model was very close to the lattice parameter of β-SiC (.436 nm), but in air it was significantly lower at 0.25-0.26 nm, but still larger than the Si-C bond length of 0.189 nm. Other factors suggest that either a bond-energy based law or a modified version of a reaction-rate law are the best choices for a SCG law. Filament strength distributions initially described by Weibull distributions could not be described by such distributions after application of the models. SCG mechanisms are discussed.     

Esterification of ethanol with sulfuric acid: A kinetic study

Experiments were conducted in a stirred batch reactor under isothermal conditions for obtaining kinetics of the esterification reaction between ethanol and sulfuric acid. Reactive adsorption technique was employed to enhance the conversion. Anhydrous sodium sulfate was used as an adsorbing agent to remove the water formed during the reaction. The variables include the mole ratio of ethanol to sulfuric acid, reaction temperature, purity of the reactants, and the amount of adsorbing agent. The reaction was found to be reversible and second order at low mole ratios, and irreversible and first order at high mole ratios. The kinetic parameters of the rate law were estimated. A possible reaction mechanism was proposed and validated with the experimental data. The effect of the mole ratio of reactants, anhydrous sodium sulfate loading, and purity of the reactants on the yield of ethyl hydrogen sulfate was studied, using full‐factorial search and optimized conditions were obtained by the method of steepest ascent. More precise optimum conditions were obtained using the Box‐Wilson composite method.     

Prediction of just suspended speed for mixed slurries at high solids loadings

One design heuristic used to determine the just suspended speed, N_js, for mixed slurries assumes that the mixture N_js is dominated by the particle phase with the maximum N_js. This approach does not incorporate the effect of the second solid phase. Two new models are proposed to predict the mixture N_js: the power model and the momentum model. These models determine the mixture N_js using the sum of the power or the sum of the momentum required to suspend the individual solid phases. The models were tested using experimental data for two impellers, a Lightnin A310 impeller and a 45° pitched-blade turbine. A range of off-bottom clearances, and six mixtures of solids up to 27 wt% solids loading completed the data set. The power model accurately predicts mixture N_js for both impellers over the full range of clearances and up to 27 wt% mixtures.     

Inhibition of CCL2 Signaling in Combination with Docetaxel Treatment Has Profound Inhibitory Effects on Prostate Cancer Growth in Bone

The C-C chemokine ligand 2 (CCL2) stimulates migration, proliferation, and invasion of prostate cancer (PCa) cells, and its signaling also plays a role in the activation of osteoclasts. Therefore targeting CCL2 signaling in regulation of tumor progression in bone metastases is an area of intense research. The objective of our study was to investigate the efficacy of CCL2 blockade by neutralizing antibodies to inhibit the growth of PCa in bone. We used a preclinical model of cancer growth in the bone in which PCa C4-2B cells were injected directly into murine tibiae. Animals were treated for ten weeks with neutralizing anti-CCL2 antibodies, docetaxel, or a combination of both, and then followed an additional nine weeks. CCL2 blockade inhibited the growth of PCa in bone, with even more pronounced inhibition in combination with docetaxel. CCL2 blockade also resulted in increases in bone mineral density. Furthermore, our results showed that the tumor inhibition lasted even after discontinuation of the treatment. Our data provide compelling evidence that CCL2 blockade slows PCa growth in bone, both alone and in combination with docetaxel. These results support the continued investigations of CCL2 blockade as a treatment for advanced metastatic PCa.     

Design aspects of the cyclic hybrid adsorbent-membrane reactor (HAMR) system for hydrogen production

As a result of stricter environmental regulations worldwide, hydrogen is becoming an important clean energy source. For it to replace fossil fuels in mobile applications, however, it will require the creation of a production and delivery infrastructure equivalent to the one that currently exists for fossil fuels, which is an immense task. As an alternative and interim step towards the new hydrogen economy, various groups are currently studying steam reforming of methane (SRM) for the on-board generation of hydrogen, or for on site production, in order to alleviate the need for compressed or liquid hydrogen storage. One such technology is the hybrid adsorbent-membrane reactor (HAMR) system, which couples reaction and membrane separation steps with adsorption on the reactor and/or membrane permeate side. Our early studies involved the development of a mathematical model for the HAMR system applied to hydrogen production through SRM. Recently, experimental investigations with the water-gas shift reaction, using microporous membranes and hydrotalcite-type CO₂ adsorbents, were carried out in order to validate the HAMR design model. In this paper, we focus on the practical process design aspects of the HAMR hydrogen production process. A continuous, four-bed HAMR process scheme is proposed and investigated both experimentally and through modeling studies.     

Durable Cr-substituted (Ba,Cs)1.33(Cr,Ti)8O16 hollandite waste forms with high Cs loading

A series of Cr-substituted hollandite solid solution Ba_xCs_yCr_2x+yTi_8−2x−yO₁₆ over a broad range of Cs content (x + y = 1.33, 0 ≤ x and y ≤ 1.33) were systematically investigated. A monoclinic-to-tetragonal phase transition was induced by increasing Cs content in the tunnel sites of the hollandite structure, and all members of the series show structure modulations related to the ordering of the Ba/Cs and vacancies along the tunnels. The thermodynamic stability of the Cr-substituted hollandite samples was measured via high-temperature oxide melt solution calorimetry, which included making the first measurements of the enthalpies of drop solution for Cs₂O and BaO in sodium molybdate solvent at 800°C. Thermodynamic stability increased with increasing Cs content for the series of Cr-substituted hollandite, which also exhibited a greater thermodynamic stability compared to other substituted hollandite analogs including Zn, Ga, Fe, and Al variants. The leaching performance, also known as aqueous durability, demonstrated that the fractional Cs release in the Cr hollandite samples is much lower than in other hollandite systems. After 7 days of leaching at 90°C, the lowest Cs release was observed in the sample with the highest Cs content, approximately 22 wt.% Cs. The Cs release could be further suppressed, by approximately 3× if the sample was further densified and sintered. The Cs release results correlated inversely to the thermodynamic stability, suggesting that the thermodynamic stability may be used in future materials design for nuclear waste immobilization.     

Preferential Nucleation of Metallic Clusters on a Nanotemplate: Co on Oxygen-Faceted Re(12 \overline{3} 1)

Preferential nucleation of cobalt nanoclusters at specific sites on oxidized faceted Re(12 $ \overline{3} $ 1) is investigated by means of Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM). An oxygen terminated nanofaceted Re surface containing ridges and valleys is used as the nanotemplate in this study. Deposition of cobalt onto this surface, followed by annealing to ~800 K, results in preferential cobalt nanocluster nucleation and growth within the valleys of the nanofaceted surface. Decreasing the nanofacet width, cobalt coverage, and annealing temperature lead to the same preferential cobalt nanocluster self assembly, an increase in nanocluster density, and a decrease in nanocluster volume. The preferential nucleation and growth observed for Co nanoclusters on faceted Re makes this a model system for future studies of different substrates and metallic overlayers more relevant to catalytic reactions.