Block co-polyMOFs: morphology control of polymer-MOF hybrid materials.

The hybridization of block copolymers and metal-organic frameworks (MOFs) to create novel materials (block co-polyMOFs, BCPMOFs) with controlled morphologies is reported. In this study, block copolymers containing poly(1,4-benzenedicarboxylic acid, H2bdc) and morphology directing poly(ethylene glycol) (PEG) or poly(cyclooctadiene) (poly(COD)) blocks were synthesized for the preparation of BCPMOFs. Block copolymer architecture and weight fractions were found to have a significant impact on the resulting morphology, mediated through the assembly of polymer precursors prior to MOF formation, as determined through dynamic light scattering. Simple modification of block copolymer weight fraction allowed for tuning of particle size and morphology with either faceted and spherical features. Modification of polymer block architecture represents a simple and powerful method to direct morphology in highly crystalline polyMOF materials. Furthermore, the BCPMOFs could be prepared from both Zr4+ and Zn2+ MOFs, yielding hybrid materials with appreciable surface areas and tuneable porosities. The resulting Zn2+ BCPMOF yielded materials with very narrow size distributions and uniform cubic morphologies. The use of topology in BCPMOFs to direct morphology in block copolymer assemblies may open new methodologies to access complex materials far from thermodynamic equilibrium

Multicomponent metal-organic framework membranes for advanced functional composites.

The diverse chemical and structural properties of metal-organic frameworks (MOFs) make them attractive for myriad applications, but their native powder form is limiting for industrial implementation. Composite materials of MOFs hold promise as a means of exploiting MOF properties in engineered forms for real-world applications. While interest in MOF composites is growing, research to date has largely focused on utilization of single MOF systems. The vast number of different MOF structures provides ample opportunity to mix and match distinct MOF species in a single composite to prepare multifunctional systems. In this work, we describe the preparation of three types of multi-MOF composites with poly(vinylidene fluoride) (PVDF): (1) co-cast MOF MMMs, (2) mixed MOF MMMs, and (3) multilayer MOF MMMs. Finally, MOF MMMs are explored as catalytic membrane reactors for chemical transformations

The Lick AGN Monitoring Project: Broad-Line Region Radii and Black Hole Masses from Reverberation Mapping of Hbeta

We have recently completed a 64-night spectroscopic monitoring campaign at the Lick Observatory 3-m Shane telescope with the aim of measuring the masses of the black holes in 12 nearby (z < 0.05) Seyfert 1 galaxies with expected masses in the range ~10^6-10^7 M_sun and also the well-studied nearby active galactic nucleus (AGN) NGC 5548. Nine of the objects in the sample (including NGC 5548) showed optical variability of sufficient strength during the monitoring campaign to allow for a time lag to be measured between the continuum fluctuations and the response to these fluctuations in the broad Hbeta emission. We present here the light curves for the objects in this sample and the subsequent Hbeta time lags for the nine objects where these measurements were possible. The Hbeta lag time is directly related to the size of the broad-line region, and by combining the lag time with the measured width of the Hbeta emission line in the variable part of the spectrum, we determine the virial mass of the central supermassive black hole in these nine AGNs. The absolute calibration of the black hole masses is based on the normalization derived by Onken et al. We also examine the time lag response as a function of velocity across the Hbeta line profile for six of the AGNs. The analysis of four leads to ambiguous results with relatively flat time lags as a function of velocity. However, SBS 1116+583A exhibits a symmetric time lag response around the line center reminiscent of simple models for circularly orbiting broad-line region (BLR) clouds, and Arp 151 shows an asymmetric profile that is most easily explained by a simple gravitational infall model. Further investigation will be necessary to fully understand the constraints placed on physical models of the BLR by the velocity-resolved response in these objects.Comment: 24 pages, 16 figures and 13 tables, submitted to Ap

The Lick AGN Monitoring Project: Reverberation Mapping of Optical Hydrogen and Helium Recombination Lines

We have recently completed a 64-night spectroscopic monitoring campaign at the Lick Observatory 3-m Shane telescope with the aim of measuring the masses of the black holes in 12 nearby (z < 0.05) Seyfert 1 galaxies with expected masses in the range ~10^6-10^7M_sun and also the well-studied nearby active galactic nucleus (AGN) NGC 5548. Nine of the objects in the sample (including NGC 5548) showed optical variability of sufficient strength during the monitoring campaign to allow for a time lag to be measured between the continuum fluctuations and the response to these fluctuations in the broad Hbeta emission, which we have previously reported. We present here the light curves for the Halpha, Hgamma, HeII 4686, and HeI 5876 emission lines and the time lags for the emission-line responses relative to changes in the continuum flux. Combining each emission-line time lag with the measured width of the line in the variable part of the spectrum, we determine a virial mass of the central supermassive black hole from several independent emission lines. We find that the masses are generally consistent within the uncertainties. The time-lag response as a function of velocity across the Balmer line profiles is examined for six of the AGNs. Finally we compare several trends seen in the dataset against the predictions from photoionization calculations as presented by Korista & Goad. We confirm several of their predictions, including an increase in responsivity and a decrease in the mean time lag as the excitation and ionization level for the species increases. Further confirmation of photoionization predictions for broad-line gas behavior will require additional monitoring programs for these AGNs while they are in different luminosity states. [abridged]Comment: 37 pages, 18 figures and 15 tables, accepted for publication in the Astrophysical Journa

The Lick AGN Monitoring Project 2011: Dynamical Modeling of the Broad Line Region in Mrk 50

We present dynamical modeling of the broad line region (BLR) in the Seyfert 1 galaxy Mrk 50 using reverberation mapping data taken as part of the Lick AGN Monitoring Project (LAMP) 2011. We model the reverberation mapping data directly, constraining the geometry and kinematics of the BLR, as well as deriving a black hole mass estimate that does not depend on a normalizing factor or virial coefficient. We find that the geometry of the BLR in Mrk 50 is a nearly face-on thick disk, with a mean radius of 9.6(+1.2,-0.9) light days, a width of the BLR of 6.9(+1.2,-1.1) light days, and a disk opening angle of 25\pm10 degrees above the plane. We also constrain the inclination angle to be 9(+7,-5) degrees, close to face-on. Finally, the black hole mass of Mrk 50 is inferred to be log10(M(BH)/Msun) = 7.57(+0.44,-0.27). By comparison to the virial black hole mass estimate from traditional reverberation mapping analysis, we find the normalizing constant (virial coefficient) to be log10(f) = 0.78(+0.44,-0.27), consistent with the commonly adopted mean value of 0.74 based on aligning the M(BH)-{\sigma}* relation for AGN and quiescent galaxies. While our dynamical model includes the possibility of a net inflow or outflow in the BLR, we cannot distinguish between these two scenarios.Comment: Accepted for publication in ApJ. 8 pages, 6 figure

First Results from the Lick AGN Monitoring Project: The Mass of the Black Hole in Arp 151

We have recently completed a 64-night spectroscopic monitoring campaign at the Lick Observatory 3-m Shane telescope with the aim of measuring the masses of the black holes in 13 nearby (z < 0.05) Seyfert 1 galaxies with expected masses in the range ~10^6-10^7 M_sun. We present here the first results from this project -- the mass of the central black hole in Arp 151. Strong variability throughout the campaign led to an exceptionally clean Hbeta lag measurement in this object of 4.25(+0.68/-0.66) days in the observed frame. Coupled with the width of the Hbeta emission line in the variable spectrum, we determine a black hole mass of (7.1 +/- 1.2)x10^6 M_sun, assuming the Onken et al. normalization for reverberation-based virial masses. We also find velocity-resolved lag information within the Hbeta emission line which clearly shows infalling gas in the Hbeta-emitting region. Further detailed analysis may lead to a full model of the geometry and kinematics of broad line region gas around the central black hole in Arp 151.Comment: 4 pages, 4 figures and 2 tables, accepted for publication in ApJ Letter

Synthesis and Characterization of Linear and Branched Polylactic Acid for Use in Food Packaging Applications

Polylactic acid (PLA) resins of various molecular weights and molecular weight distributions were synthesized. Linear, narrow molecular weight distribution (MWD) PLA resins were synthesized, as well as resins containing both high molecular weight branched structures and low molecular weight chains and oligomers. Narrow MWD resins were synthesized for use as adhesives for corrugated paperboard and broad MWD resins were synthesized for use as a waterborne coating. PLA resins were dispersed for use as a waterborne coating. Success has been made at forming films utilizing various plasticizers and surfactants as well as polyvinyl alcohol as dispersing agents. A cold dispersion procedure realized the most success, as a 15% PLA waterborne formulation was achieved. Standard test methods show a high degree of grease resistance for the formulated coatings. A hot melt adhesive was also formulated utilizing blends of narrow MWD resins of various molecular weights. The hot melt adhesive showed a high degree of success as failure occurred at the substrate for the materials tested

Block co-polyMOFs: morphology control of polymer-MOF hybrid materials.

The hybridization of block copolymers and metal-organic frameworks (MOFs) to create novel materials (block co-polyMOFs, BCPMOFs) with controlled morphologies is reported. In this study, block copolymers containing poly(1,4-benzenedicarboxylic acid, H2bdc) and morphology directing poly(ethylene glycol) (PEG) or poly(cyclooctadiene) (poly(COD)) blocks were synthesized for the preparation of BCPMOFs. Block copolymer architecture and weight fractions were found to have a significant impact on the resulting morphology, mediated through the assembly of polymer precursors prior to MOF formation, as determined through dynamic light scattering. Simple modification of block copolymer weight fraction allowed for tuning of particle size and morphology with either faceted and spherical features. Modification of polymer block architecture represents a simple and powerful method to direct morphology in highly crystalline polyMOF materials. Furthermore, the BCPMOFs could be prepared from both Zr4+ and Zn2+ MOFs, yielding hybrid materials with appreciable surface areas and tuneable porosities. The resulting Zn2+ BCPMOF yielded materials with very narrow size distributions and uniform cubic morphologies. The use of topology in BCPMOFs to direct morphology in block copolymer assemblies may open new methodologies to access complex materials far from thermodynamic equilibrium

Solvent Effects on Modulus of Poly(propylene oxide)-based Organogels as Measured by Cavitation Rheology

A series of novel organogels were synthesized from poly(propylene oxide) (PPO) functionalized with main chain urea moieties which provided rapid gelation and high moduli in a variety of solvents. Three different molecular weight PPOs were used in this study: 430, 2000, and 4000 g mol(-1), each with alpha,omega-amino-end groups. Four urea groups were introduced into the main chain by reaction with hexamethylene diisocyanate followed by subsequent reaction with a monofunctional alkyl or aromatic amine. This PPO/urea gelator was found to form gels in carbon tetrachloride, chloroform, dichloromethane, toluene, ethyl acetate, and tetrahydrofuran. Among these, carbon tetrachloride and toluene were found to be the best solvents for this system, resulting in perfectly clear gels with high moduli at low mass fraction for PPO-2000 systems. Flory-Huggins polymer-solvent interaction parameter, chi, was found to be a useful indicator of gel quality for these systems, with chi(CCl4)/(PPO-2000) \u3c 0.5 and chi(toluene)/PPO-2000 approximate to 0.5. Systems with chi parameters \u3e0.5 were found to form low moduli gels, indicating that for these systems, polymer-solvent interaction parameters can be a useful predictor of gel quality in different solvent systems

Chain Dispersity Effects on Brush Properties of Surface-Grafted Polycaprolactone-Modified Silica Nanoparticles: Unique Scaling Behavior in the Concentrated Polymer Brush Regime

Silica nanoparticles (<i>R</i>_h = 70 nm) were functionalized with high dispersity (<i>Đ</i> > 2.3) polycaprolactone at various grafting densities, and the brush properties were investigated using dynamic light scattering. Owing to recent advances in controlled polymerization techniques, low dispersity brushes are easily grafted from nanoparticle surfaces, and these systems have been well studied. However, the effect of high dispersity brushes on nanoparticle surfaces is largely unexplored. Here we discuss the brush properties of high dispersity polycaprolactone-grafted silica nanoparticles. Because of the polymerization conditions used, transesterification events are induced during the polymerization to give brushes with increasing dispersity both as brush length increases and as grafting density is increased (e.g., <i>Đ</i> from 1.32 to 2.39 for σ from 0.21 to 0.61 chains/nm²). All grafting densities showed extended chains in the concentrated polymer brush regime, with brush length, <i>l</i>_b, scaling with degree of polymerization, <i>l</i>_b ∼ <i>N</i>^<i>a</i>, where <i>a</i> = 1.39, 1.47, and 1.84 for the high, mid, and low grafting density sets. This study provides the first experimental insight into the effects of increasing chain dispersity on brush properties of nanoparticle systems. Furthermore, this system offers a facile method to tune dispersity of grafted brushes concurrent with the grafting polymerization. We expect this work to be of significant interest to the ongoing study of fundamental properties of polymer brushes as well as these materials finding use in polymer composite applications and provide enhanced mechanical properties compared to their monodisperse analogues