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At least 415 records · Page 23

Correlation of nanoparticle size distribution features to spatiotemporal flame luminosity in gasoline direct injection engines

Particle size distribution measured by mobility instruments is a common diagnostic used to characterize ultrafine and nanoparticle emissions in engine exhaust; however, some features of particle size distribution data are poorly correlated to in-cylinder combustion phenomena. In this work, in-cylinder spatiotemporal flame luminosity is quantitatively correlated to features in the solid particle size distribution measured in the exhaust of a gasoline direct injection engine operating in lean and stoichiometric combustion modes. A multi-channel optical sensor was used to measure diffusion flame light intensity in different areas of the combustion chamber. Furthermore, total solid particle number and particle size distribution in the exhaust were measured using a scanning mobility particle sizer after a catalytic stripper that removed semi-volatile compounds. Results of the experiments showed that different flame phenomenon resulted in distinct particle size distribution characteristics. A large accumulation mode (particles with diameter of 50–100 nm) in the particle size distribution from stoichiometric engine operation with early injection resulted from anomalous diffusion flames like piston-top pool fires. In lean operation incorporating a secondary fuel injection, particle emissions were dominated by flame propagation through fuel-rich regions of the combustion chamber resulting in a comparatively broad particle size distribution. More generally, this work illustrates how particle size distribution data can be more accurately used to diagnose soot formation in gasoline direct injection engines.

33 ADVANCED PROPULSION SYSTEMS↗

Quantitative Reflectance Spectra of Solid Powders as a Function of Particle Size

We have recently developed vetted methods for obtaining quantitative infrared directional-hemispherical reflectance spectra using a commercial integrating sphere. In this paper, the effects of particle size on the spectral properties are analyzed for several samples such as ammonium sulfate, calcium carbonate, and sodium sulfate as well as one organic compound, lactose. We prepared multiple size fractions for each sample and confirmed the mean sizes using optical microscopy. Most species displayed a wide range of spectral behavior depending on the mean particle size. General trends of reflectance vs. particle size are observed such as increased albedo for smaller particles: for most wavelengths, the reflectivity drops with increased size, sometimes displaying a factor of 4 or more drop in reflectivity along with a loss of spectral contrast. In the longwave infrared, several species with symmetric anions or cations exhibited reststrahlen features whose amplitude was nearly invariant with particle size, at least for intermediate- and large-sized sample fractions; that is, > ~150 microns. Trends of other types of bands (Christiansen minima, transparency features) are also investigated as well as quantitative analysis of the observed relationship between reflectance vs. particle diameter.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Sample Size Effects on Petrophysical Characterization and Fluid-to-Pore Accessibility of Natural Rocks

Laboratory-scale analysis of natural rocks provides petrophysical properties such as density, porosity, pore diameter/pore-throat diameter distribution, and fluid accessibility, in addition to the size and shape of framework grains and their contact relationship with the rock matrix. Different types of laboratory approaches for petrophysical characterization involve the use of a range of sample sizes. While the sample sizes selected should aim to be representative of the rock body, there are inherent limitations imposed by the analytical principles and holding capacities of the different experimental apparatuses, with many instruments only able to accept samples at the μm–mm scale. Therefore, a total of nine (three limestones, three shales, two sandstones, and one dolomite) samples were collected from Texas to fill the knowledge gap of the sample size effect on the resultant petrophysical characteristics. The sample sizes ranged from 3 cm cubes to <75 μm particles. Using a combination of petrographic microscopy, helium expansion pycnometry, water immersion porosimetry, mercury intrusion porosimetry, and (ultra-) small-angle X-ray scattering, the impact of sample size on the petrophysical properties of these samples was systematically investigated here. The results suggest that the sample size effect is influenced by both pore structure changes during crushing and sample size-dependent fluid-to-pore connectivity.

36 MATERIALS SCIENCE↗

Lower molar shape and size in prosimian and platyrrhine primates

Abstract The goal of this research is to evaluate the relative strength of the influences of diet, size, and phylogenetic signal on dental geometric shape. Accurate comprehension of these factors and their interaction is important for reconstructing diet and deriving characters for a cladistic analysis in fossil primates. Geometric morphometric analysis is used to identify axes of shape variation in the lower second molars of (a) prosimian primates and (b) platyrrhines. Landmarks were placed on µCT‐generated surface renderings. Landmark configurations were aligned using generalized Procrustes analysis. Principal components analysis and phylogenetic principal components analysis (pPCA) were performed on species average landmark co‐ordinates. pPCs were examined with phylogenetic generalized least squares analysis for association with size and with diet. PCs from both phylogenetic and non‐phylogenetic analyses were sufficient to separate species by broad dietary categories, including insectivores and folivores. In neither analysis was pPC1 correlated with tooth size, but some other pPCs were significantly correlated with size. The pattern of association between pPCs and size altered when centroid size and dietary variables were combined in the model; effects of diet factors typically exceeded effects of size. These results indicate a dominant phylogenetic and dietary signal in molar shape but also show some shape change correlated with size in the absence of obvious dietary associations. Geometric morphometric analysis appears to be useful for tracking functional traits in molars, particularly in tracking differences between folivorous and insectivorous species.

St. Clair, Elizabeth M.↗

Protein adsorption onto nanoparticles induces conformational changes: Particle size dependency, kinetics, and mechanisms

The use of nanomaterials in bioapplications demands a detailed understanding of protein–nanoparticle interactions. Proteins can undergo conformational changes while adsorbing onto nanoparticles, but studies on the impact of particle size on conformational changes are scarce. We have shown that conformational changes happening upon adsorption of myoglobin and BSA are dependent on the size of the nanoparticle they are adsorbing to. Out of eight initially investigated model proteins, two (BSA and myoglobin) showed conformational changes, and in both cases this conformational change was dependent on the size of the nanoparticle. Nanoparticle sizes ranged from 30 to 1000 nm and, in contrast to previous studies, we attempted to use a continuous progression of sizes in the range found in live viruses, which is an interesting size of nanoparticles for the potential use as drug delivery vehicles. Conformational changes were only visible for particles of 200 nm and bigger. Using an optimized circular dichroism protocol allowed us to follow this conformational change with regard to the nanoparticle size and, thanks to the excellent temporal resolution also in time. We uncovered significant differences between the unfolding kinetics of myoglobin and BSA. In this study, we also evaluated the plausibility of commonly used explanations for the phenomenon of nanoparticle size-dependent conformational change. Currently proposed mechanisms are mostly based on studies done with relatively small particles, and fall short in explaining the behavior seen in our studies.

Biotechnology & Applied Microbiology↗

Size Selectivity of Sampling Gears Used to Sample Kokanee

Abstract Kokanee Oncorhynchus nerka provide valued recreational fisheries and also serve as a prey resource for economically, socially, and ecologically important fishes. As such, management of kokanee is a major focus of natural resource agencies. Kokanee are typically monitored using midwater trawls, but the interpretation of data collected using midwater trawls is difficult due to the unknown size selectivity of the gear. We sought to assess the length selectivity of midwater trawls by comparing estimates obtained from midwater trawls with estimates obtained from gill nets adjusted for size selectivity. Experimental curtain gill nets and midwater trawls were used in conjunction to sample kokanee in seven lentic systems in Idaho. The size selectivity of gill nets was estimated by accounting for the probability of encounter and the probability of retention. Estimates of size selectivity were then used to adjust the length distribution of fish sampled in gill nets. The adjusted length distribution of fish sampled in gill nets was compared with estimates obtained from midwater trawls to identify potential size selectivity of midwater trawls. A pattern of size selectivity was apparent for both sampling techniques. The average length of kokanee sampled with midwater trawls was 111 mm; whereas, kokanee sampled with gill nets had a mean length of 235 mm. Our results suggest experimental gill nets are useful for common sampling of kokanee (e.g., trend monitoring) because the gear is less size selective than midwater trawls and is adjustable for size selectivity. However, midwater trawls are likely the best gear for addressing questions associated with early life history. Overall, our results provide a better understanding of gill-net and midwater trawl selectivity and ultimately improve the ability to sample and manage the species.

Klein, Zachary B.↗

Contradictory Feature Size Effects in the Tensile Yield Strength of Cu Sheets Produced Using Different Sequences Involving Annealing, Rolling, and Grinding

The feature size effect is significant research interest in the field of microforming. It is assumed that the size effect is influenced by the material preparation process. To verify this, the feature size effects associated with the tensile yield strength of Cu sheets with thicknesses ranging from 100 to 200 μm, produced using different sequences involving annealing, rolling, and grinding, were studied. Differing feature size effects were observed in the Cu specimens, and it was confirmed that the size effect was indeed influenced by the specimen preparation sequence. The tensile yield strengths of the annealed–ground–rolled and annealed–rolled specimens increased as the specimen thicknesses decreased. However, an opposing size effect was observed in the case of the annealed–rolled–annealed, annealed–ground, and annealed–rolled–ground specimens. The reduction ratio did not alter the trend associated with the size effect, but influenced the intensity of the size effect. It is believed that the reinforcement and erosion of the surface-hardened layer introduced during rolling resulted in the contradictory results.

36 MATERIALS SCIENCE↗

Phase-field simulation of domain size effect on dielectric and piezoelectric responses in K 0.5 Na 0.5 NbO 3 epitaxial thin films with superdomain structures

Size effects of mesoscale ferroelectric domains on the macroscopic dielectric and piezoelectric responses in domain-engineered bulk piezocrystals have been extensively studied for more than two decades. However, less is known about the domain size effects in ferroelectric epitaxial thin films, especially for films consisting of low-symmetry ferroelectric phases and exhibits hierarchical superdomain structures. Herein, using phase-field simulations, we systemically evaluate the effective out-of-plane dielectric and piezoelectric coefficients, κ$^{*}_{33}$ and d$^{*}_{33}$, as a function of the domain periods for two types of superdomain structures in ferroelectric K 0.5 Na 0.5 NbO 3 epitaxial thin films. In one type of the superdomain structures, we find that more than 70% increase of κ$^{*}_{33}$ and nearly 20% increase of d$^{*}_{33}$ can be achieved by tuning the domain period by a few tens of nanometers. Dissimilar behaviors are found when the domain period varies along different lateral directions, suggesting anisotropic domain size effects in thin films. By analyzing the local dielectric and piezoelectric responses from each domain variants and domain walls, we reveal that the domain size effect is governed by the variation of out-of-plane polarization inside the domains. Moreover, we also demonstrate enhanced domain size effects by modulating the misfit strains and temperature to approach the polymorphic phase boundaries, suggesting tunability of the size effect by doping and strain engineering. Furthermore, our results reveal multimodal domain size dependence of dielectric and piezoelectric responses in low-symmetry ferroelectric epitaxial thin films, implying that domain size engineering can be used to tune macroscopic properties of thin-film ferroelectrics, similar to their bulk counterparts.

36 MATERIALS SCIENCE↗

Combining disdrometer, microscopic photography, and cloud radar to study distributions of hydrometeor types, size and fall velocity

Addressing solid precipitation poses additional challenges compared to warm rain due to complex hydrometeor shapes involved, including the dependence of fall velocity on hydrometeor sizes, hydrometeor size distributions, and hydrometeor classification. This study is an extension of our previous work (Niu et al., 2010) to address these challenges by combining measurements from a PARSIVEL disdrometer, microscope photography, and millimeter wavelength cloud radar. The combined measurements are analyzed to classify the precipitation hydrometeor types, examine the dependence of fall velocity on hydrometeor sizes for different hydrometeor types, and determine the best distributions to describe the hydrometeor size distributions of different hydrometeor types. The results show: (1) Hydrometeors can be classified to four main types of raindrop, graupel, snowflake and mixed-phase according to the dependence of terminal velocity on particle sizes, corresponding microscope photos and cloud radar observations; (2) There are significant scatters in fall velocity for a given hydrometer size velocities, and the fall velocity spread for the solid hydrometeors appear wider than that for raindrops across hydrometeor sizes, with that for the mixed-phase precipitation being largest, suggesting that the effects of hydrometeor shape on hydrometeor fall velocities; (3) Hydrometeor size distributions for the four types can all be well described by the Gamma or Weibull distribution; Weibull (Gamma) distribution performs better when skewness is less (larger) than 2.

54 ENVIRONMENTAL SCIENCES↗

Effect of sample size on the maximum value distribution of fatigue driving forces in metals and alloys

An analytical framework is presented to predict the effects of sample size on the maximum value distribution (MVD) of the driving forces for fatigue crack formation in metals and alloys. The distribution of the maximum driving force for fatigue crack formation over the domain follows the generalized extreme value theory in the limit as the domain size increases to infinity. Here, a simulation-based analysis of microstructure influences on fatigue resistance for polycrystalline metals and alloys is very costly, and reaching those limits is intractable. This work models the MVD of Fatigue Indicator Parameters (FIPs), which serve as surrogate measures for the driving force for fatigue crack formation, at finite sample sizes prior to their convergence to a limiting extreme value distribution. Large-scale crystal plasticity finite element (CPFE) simulations of FCC Al 7075-T6 with microstructure realizations of various sizes are incorporated to calibrate and evaluate the developed framework, and a total of ∼6.5 million grains of Al 7075-T6 are examined. The calibrated analytical solution agrees well with the brute force Monte Carlo simulation results extracted from the CPFE simulations. Furthermore, the developed formulation can predict the MVD of FIPs for different sample sizes using a size-dependent parameter, and it is capable of accurately extrapolating the MVD of FIPs for much larger microstructure sample sizes than the size used for its calibration.

Crystal plasticity↗

The Impact of the Size of Nodal Metastases on Recurrence Risk in Breast Cancer Patients With 1-3 Positive Axillary Nodes After Mastectomy

Purpose: Use of postmastectomy radiation therapy (PMRT) in breast cancer patients with 1-3 positive nodes is controversial. The objective of this study was to determine whether the size of nodal metastases in this subset could predict who would benefit from PMRT. Methods and Materials: We analyzed 250 breast cancer patients with 1-3 positive nodes after mastectomy treated with contemporary surgery and systemic therapy at our institution. Of these patients, 204 did not receive PMRT and 46 did receive PMRT. Local and regional recurrence risks were stratified by the size of the largest nodal metastasis measured as less than or equal to 5 mm or greater than 5 mm. Results: The median follow-up was 65.6 months. In the whole group, regional recurrences occurred in 2% of patients in whom the largest nodal metastasis measured 5 mm or less vs 6% for those with metastases measuring greater than 5 mm. For non-irradiated patients only, regional recurrence rates were 2% and 9%, respectively. Those with a maximal nodal size greater than 5 mm had a significantly higher cumulative incidence of regional recurrence (P=.013). The 5-year cumulative incidence of a regional recurrence in the non-irradiated group was 2.7% (95% confidence interval [CI], 0.7%-7.2%) for maximal metastasis size of 5 mm or less, 6.9% (95% CI, 1.7%-17.3%) for metastasis size greater than 5 mm, and 16% (95% CI, 3.4%-36.8%) for metastasis size greater than 10 mm. The impact of the maximal nodal size on regional recurrences became insignificant in the multivariable model. Conclusions: In patients with 1-3 positive lymph nodes undergoing mastectomy without radiation, nodal metastasis greater than 5 mm was associated with regional recurrence after mastectomy, but its effect was modified by other factors (such as tumor stage). The size of the largest nodal metastasis may be useful to identify high-risk patients who may benefit from radiation therapy after mastectomy.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Motion Interplay as a Function of Patient Parameters and Spot Size in Spot Scanning Proton Therapy for Lung Cancer

Purpose: To quantify the impact of respiratory motion on the treatment of lung tumors with spot scanning proton therapy. Methods and Materials: Four-dimensional Monte Carlo simulations were used to assess the interplay effect, which results from relative motion of the tumor and the proton beam, on the dose distribution in the patient. Ten patients with varying tumor sizes (2.6-82.3 cc) and motion amplitudes (3-30 mm) were included in the study. We investigated the impact of the spot size, which varies between proton facilities, and studied single fractions and conventionally fractionated treatments. The following metrics were used in the analysis: minimum/maximum/mean dose, target dose homogeneity, and 2-year local control rate (2y-LC). Results: Respiratory motion reduces the target dose homogeneity, with the largest effects observed for the highest motion amplitudes. Smaller spot sizes (σ ≈ 3 mm) are inherently more sensitive to motion, decreasing target dose homogeneity on average by a factor 2.8 compared with a larger spot size (σ ≈ 13 mm). Using a smaller spot size to treat a tumor with 30-mm motion amplitude reduces the minimum dose to 44.7% of the prescribed dose, decreasing modeled 2y-LC from 87.0% to 2.7%, assuming a single fraction. Conventional fractionation partly mitigates this reduction, yielding a 2y-LC of 71.6%. For the large spot size, conventional fractionation increases target dose homogeneity and prevents a deterioration of 2y-LC for all patients. No correlation with tumor volume is observed. The effect on the normal lung dose distribution is minimal: observed changes in mean lung dose and lung V{sub 20} are <0.6 Gy(RBE) and <1.7%, respectively. Conclusions: For the patients in this study, 2y-LC could be preserved in the presence of interplay using a large spot size and conventional fractionation. For treatments using smaller spot sizes and/or in the delivery of single fractions, interplay effects can lead to significant deterioration of the dose distribution and lower 2y-LC.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

The nature of nano-sized precipitates in ferritic/martensitic steel P92 produced by thermomechanical treatment

Thermomechanical treatment (TMT) can effectively improve the mechanical properties of high-Cr ferritic/martensitic (F/M) steels, which has been mainly attributed to a dense dispersion of nano-sized precipitates. Precipitate phases in high-Cr F/M steels produced by TMT require further investigations. Precipitates in commercial F/M steel P92 produced by a TMT process, warm-rolled at 650 °C plus tempered at 650 °C for 1 h, were investigated by transmission electron microscopy. Nano-sized precipitates with a high number density in the steel after the TMT were found to be Cr-rich M{sub 2}(C,N) carbonitride, rather than MX or M{sub 23}C{sub 6} phase. The M{sub 2}(C,N) carbonitride has a hexagonal lattice with the lattice parameters about a/c = 0.299/0.463 nm. These M{sub 2}(C,N) carbonitrides with a typical composition of (Cr{sub 0.85}V{sub 0.06}Fe{sub 0.06}Mo{sub 0.03}){sub 2}(C,N) have an average diameter smaller than 30 nm, and mainly distribute on dislocations and at the boundaries of equiaxed ferrite grains in the TMT steel. The TMT process inhibits the precipitation of M{sub 23}C{sub 6} and M{sub 5}C{sub 2} phases. Enhanced creep properties of the P92 steel after the TMT, as reported previously, were considered to be mainly attributed to plenty of nano-sized Cr-rich M{sub 2}(C,N) carbonitrides produced by the TMT rather than to MX and M{sub 23}C{sub 6} precipitates. - Graphical abstract: TEM micrographs of precipitates on extraction carbon replicas prepared from ferritic/martensitic (F/M) steel P92. (a) After conventional heat treatment, normalized at 1050 °C for 30 min plus tempered at 765 °C for 1 h. (b) After a thermomechanical treatment (TMT), warm-rolled at 650 °C plus tempered at 650 °C for 1 h. Nano-sized precipitates with a high number density in the steel produced by the TMT were found to be Cr-rich M{sub 2}(C,N) carbonitride, rather than MX or M{sub 23}C{sub 6} phase. The TMT process inhibits the precipitation of M{sub 23}C{sub 6} and M{sub 5}C{sub 2} phases. Enhanced creep properties of the steel by the TMT are mainly attributed to plenty of nano-sized Cr-rich M{sub 2}(C,N) carbonitrides, rather than to MX and M{sub 23}C{sub 6} precipitates. It is suggested that plenty of nano-sized Cr-rich M{sub 2}(C,N) carbonitrides produced by the TMT are more helpful to improve the creep properties of the steel than M{sub 23}C{sub 6} plus MX precipitates obtained by the conventional heat treatment. - Highlights: •Carbon replicas were used for precisely identifying nano-sized phases in steel produced by TMT. •Densely nano-sized precipitates in P92 steel after TMT were found to be Cr-rich M{sub 2}(C,N) phase. •Fine precipitates produced by TMT can be M{sub 2}X phase instead of MX and/or M{sub 23}C{sub 6} phase. •Enhanced creep properties of P92 steel by TMT is attributed to fine M{sub 2}X, rather than to MX and M{sub 23}C{sub 6}. •TMT involving a tempering at 650 °C inhibits the formation of M{sub 23}C{sub 6}/M{sub 5}C{sub 2} phases in high-Cr steels.

36 MATERIALS SCIENCE↗

Cryo-electron microscopy and single molecule fluorescent microscopy detect CD4 receptor induced HIV size expansion prior to cell entry

Viruses are often thought to have static structure, and they only remodel after the viruses have entered target cells. Here, we detected a size expansion of virus particles prior to viral entry using cryo-electron microscopy (cryo-EM) and single molecule fluorescence imaging. HIV expanded both under cell-free conditions with soluble receptor CD4 (sCD4) targeting the CD4 binding site on the HIV-1 envelope protein (Env) and when HIV binds to receptor on cellular membrane. We have shown that the HIV Env is needed to facilitate receptor induced virus size expansions, showing that the ‘lynchpin’ for size expansion is highly specific. We demonstrate that the size expansion required maturation of HIV and an internal capsid core with wild type stability, suggesting that different HIV compartments are linked and are involved in remodelling. Our work reveals a previously unknown event in HIV entry, and we propose that this pre-entry priming process enables HIV particles to facilitate the subsequent steps in infection. - Highlights: • Cell free viruses are able to receive external trigger that leads to apparent size expansion. • Virus envelope and CD4 receptor engagement is the lynchpin of virus size expansion. • Internal capsid organisation can influence receptor mediated virus size expansion. • Pre-existing virus-associated lipid membrane in cell free virus can accommodate the receptor mediated virus size expansion.

60 APPLIED LIFE SCIENCES↗

Combination of Cation Exchange and Quantized Ostwald Ripening for Controlling Size Distribution of Lead Chalcogenide Quantum Dots

A new strategy for narrowing the size distribution of colloidal quantum dots (QDs) was developed by combining cation exchange and quantized Ostwald ripening. Medium-sized reactant CdS(e) QDs were subjected to cation exchange to form the target PbS(e) QDs, and then small reactant CdS(e) QDs were added which were converted to small PbS(e) dots via cation exchange. The small-sized ensemble of PbS(e) QDs dissolved completely rapidly and released a large amount of monomers, promoting the growth and size-focusing of the medium-sized ensemble of PbS(e) QDs. The addition of small reactant QDs can be repeated to continuously reduce the size distribution. The new method was applied to synthesize PbSe and PbS QDs with extremely narrow size distributions and as a bonus they have hybrid surface passivation. In conclusion, the size distribution of prepared PbSe and PbS QDs are as low as 3.6% and 4.3%, respectively, leading to hexagonal close packing in monolayer and highly ordered three-dimensional superlattice.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Tuning Precursor Reactivity toward Nanometer-Size Control in Palladium Nanoparticles Studied by in Situ Small Angle X-ray Scattering

Synthesis of monodisperse nanoparticles (NPs) with precisely controlled size is critical for understanding their size-dependent properties. Although significant synthetic developments have been achieved, it is still challenging to synthesize well-defined NPs in a predictive way due to a lack of in-depth mechanistic understanding of reaction kinetics. Here we use synchrotron-based small-angle X-ray scattering (SAXS) to monitor in situ the formation of palladium (Pd) NPs through thermal decomposition of Pd–TOP (TOP: trioctylphosphine) complex via the “heat-up” method. We systematically study the effects of different ligands, including oleylamine, TOP, and oleic acid, on the formation kinetics of Pd NPs. Through quantitative analysis of the real-time SAXS data, we are able to obtain a detailed picture of the size, size distribution, and concentration of Pd NPs during the syntheses, and these results show that different ligands strongly affect the precursor reactivity. We find that oleylamine does not change the reactivity of the Pd–TOP complex but promote the formation of nuclei due to strong ligand–NP binding. On the other hand, TOP and oleic acid substantially change the precursor reactivity over more than an order of magnitude, which controls the nucleation kinetics and determines the final particle size. A theoretical model is used to demonstrate that the nucleation and growth kinetics are dependent on both precursor reactivity and ligand–NP binding affinity, thus providing a framework to explain the synthesis process and the effect of the reaction conditions. Quantitative understanding of the impacts of different ligands enables the successful synthesis of a series of monodisperse Pd NPs in the broad size range from 3 to 11 nm with nanometer-size control, which serve as a model system to study their size-dependent catalytic properties. Furthermore, the in situ SAXS probing can be readily extended to other functional NPs to greatly advance their synthetic design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystallographic Evidence of Size-Dependent Bond Flexibility in Metal–Organic Framework Nanocrystals

Size-dependent electronic, magnetic, and optical behavior suggests that metal–organic frameworks become softer materials as their particle sizes decrease, but direct evidence is lacking. Here, we report variable-temperature powder X-ray diffraction data of Fe(1,2,3-triazolate)2 particles that offer crystallographic insight into size-dependent bond flexibility. Rietveld refinement reveals size-dependent positive thermal expansion upon downsizing the crystalline domains from 178 to 9 nm, with a 6-fold increase from 16 MK –1 to 96 MK –1 . Here, this behavior occurs in tandem with size-dependent elongation of metal–ligand bonds and increasing thermal displacement parameters, consistent with pronounced metal-linker bond lability. We propose that these effects, as well as size-dependent annealing of crystallite sizes, originate from the high charge density and surface stress of smaller particles. Taken together, these results provide structural evidence that size reduction serves as a synthetic route to controlling the dynamic response of materials to external stimuli.

Crystals↗

SALT LONG-SLIT SPECTROSCOPY OF LUMINOUS OBSCURED QUASARS: AN UPPER LIMIT ON THE SIZE OF THE NARROW-LINE REGION?

We present spatially resolved long-slit spectroscopy from the Southern African Large Telescope to examine the spatial extent of the narrow-line regions (NLRs) of a sample of eight luminous obscured quasars at 0.10 < z < 0.43. Our results are consistent with an observed shallow slope in the relationship between NLR size and L{sub [OIII]}, which has been interpreted to indicate that NLR size is limited by the density and ionization state of the NLR gas rather than the availability of ionizing photons. We also explore how the NLR size scales with a more direct measure of instantaneous active galactic nucleus power using mid-IR photometry from the Wide Field Infrared Explorer, which probes warm to hot dust near the central black hole and so, unlike [O III], does not depend on the properties of the NLR. Using our results as well as samples from the literature, we obtain a power-law relationship between NLR size and L{sub 8{mu}m} that is significantly steeper than that observed for NLR size and L{sub [OIII]}. We find that the size of the NLR goes approximately as L{sup 1/2}{sub 8{mu}m}, as expected from the simple scenario of constant-density clouds illuminated by a central ionizing source. We further see tentative evidence for a flattening of the relationship between NLR size and L{sub 8{mu}m} at the high-luminosity end, and propose that we are seeing a limiting NLR size of 10-20 kpc, beyond which the availability of gas to ionize becomes too low. We find that L{sub [OIII]}{approx}L{sub 8{mu}m}{sup 1.4}, consistent with a picture in which the L{sub [OIII]} is dependent on the volume of the NLR. These results indicate that high-luminosity quasars have a strong effect in ionizing the available gas in a galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗