Coordination Assembly of Discoid Nanoparticles

Supramolecular chemistry utilizes coordination bonds to assemble molecular building blocks into a variety of sophisticated constructs. However, traditional coordination assemblies are based on organic compounds that have limited ability to transport charge. Herein, we describe coordination assembly of anisotropic FeS2 pyrite nanoparticles (NPs) that can facilitate charge transport. Zn2+ ions form supramolecular complexes with carboxylate end‐groups on NP surface, leading to multiparticle sheets with liquid‐crystal‐like organization. Conductivity and Hall carrier mobility of the p‐type layered semiconductor films with Zn2+ coordination bridging exceed those known for coordination compounds, some by several orders of magnitude. The nanoscale porosity of the assembled sheets combined with fast hole transport leads to high electrocatalytic activity of the NP films. The coordination assembly of NPs embraces the versatility of several types of building blocks and opens a new design space for self‐organized materials combining nanoscale and supramolecular structural motifs.Zinc ions are the “glue”: FeS2 nanoparticles (NPs) spontaneously assemble into sheets because of coordination bridging between Zn2+ and carboxylate groups on the NP surface. Conductivity and Hall carrier mobility of the p‐type semiconductor films exceed those known for coordination compounds and MOFs. The nanoscale porosity and fast hole transport of assembled sheets leads to high electrocatalytic activity of the NP films.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/112281/1/8966_ftp.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/112281/2/anie_201502057_sm_miscellaneous_information.pd

Coordination Assembly of Discoid Nanoparticles

Supramolecular chemistry utilizes coordination bonds to assemble molecular building blocks into a variety of sophisticated constructs. However, traditional coordination assemblies are based on organic compounds that have limited ability to transport charge. Herein, we describe coordination assembly of anisotropic FeS2 pyrite nanoparticles (NPs) that can facilitate charge transport. Zn2+ ions form supramolecular complexes with carboxylate end‐groups on NP surface, leading to multiparticle sheets with liquid‐crystal‐like organization. Conductivity and Hall carrier mobility of the p‐type layered semiconductor films with Zn2+ coordination bridging exceed those known for coordination compounds, some by several orders of magnitude. The nanoscale porosity of the assembled sheets combined with fast hole transport leads to high electrocatalytic activity of the NP films. The coordination assembly of NPs embraces the versatility of several types of building blocks and opens a new design space for self‐organized materials combining nanoscale and supramolecular structural motifs.Schichtleiter: FeS2‐Nanopartikel (NPs) lagern sich durch koordinative Bindung zwischen Zn2+ und Carboxylatgruppen an der NP‐Oberfläche spontan zu Schichten zusammen. Die Leitfähigkeit und Hall‐Trägerbeweglichkeit der p‐Halbleiterfilme übertreffen die Werte bekannter Koordinationsverbindungen und MOFs. Die nanoskalige Porosität und der schnelle Lochtransport der Schichten führen zu einer hohen elektrokatalytischen Aktivität der NP‐Filme.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/112255/1/9094_ftp.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/112255/2/ange_201502057_sm_miscellaneous_information.pd

Enhancement of Local Piezoresponse in Polymer Ferroelectrics via Nanoscale Control of Microstructure

Polymer ferroelectrics are flexible and lightweight electromechanical materials that are widely studied due to their potential application as sensors, actuators, and energy harvesters. However, one of the biggest challenges is their low piezoelectric coefficient. Here, we report a mechanical annealing effect based on local pressure induced by a nanoscale tip that enhances the local piezoresponse. This process can control the nanoscale material properties over a microscale area at room temperature. We attribute this improvement to the formation and growth of β-phase extended chain crystals via sliding diffusion and crystal alignment along the scan axis under high mechanical stress. We believe that this technique can be useful for local enhancement of piezoresponse in ferroelectric polymer thin films

Structural Characterization Using the Multiple Scattering Effects in Grazing-Incidence Small-Angle X-Ray Scattering

The multiple scattering effects present in grazing-incidence small-angle X-ray scattering (GISAXS) data and interference between them are addressed theoretically as well as experimentally with measurement of a series of patterns at different incident angles, referred to as `incident-angle-resolved GISAXS\u27 (IAR-GISAXS). X-ray reflectivity (XR), GISAXS and IAR-GISAXS of virus particles on Si-substrate supported-polystyrene films have been measured and all the data have been analyzed with appropriate formalisms. It was found that under certain conditions it is possible to extract the correct structural features of the materials from the GISAXS/IAR-GISAXS data using the kinematic SAXS formalisms, without the need to use the distorted-wave Born approximation. Furthermore, the Kiessig fringes in GISAXS enable the measurement of the average distance between the particle and the substrate, similar to the measurement of film thickness using the fringes in the XR data. It is believed that the methods developed here will expand the application of GISAXS as they enable the application of model-independent and kinematic SAXS theories to nanostructured two-dimensional ordered films

Synchrotron X-ray reflectivity studies of nanoporous organosilicate thin films with low dielectric constants

Quantitative, non-destructive X-ray reflectivity analysis using synchrotron radiation sources was successfully performed on nanoporous dielectric thin films prepared by thermal processing of blend films of a thermally curable polymethylsilsesquioxane dielectric precursor and a thermally labile triethoxy-silyl-terminated six-arm poly(epsilon-caprolactone) porogen in various compositions. In addition, thermogravimetric analysis and transmission electron microscopy analysis were carried out. These measurements provided important structural information about the nanoporous films. The thermal process used in this study was found to cause the porogen molecules to undergo efficiently sacrificial thermal degradation, generating closed, spherical nanopores in the dielectric film. The resultant nanoporous films exhibited a homogeneous, well defined structure with a thin skin layer and low surface roughness. In particular, no skin layer was formed in the porous film imprinted using a porogen loading of 30 wt%. The film porosities ranged from 0 to 33.8% over the porogen loading range of 0-30 wt%open131

Detection of an intermediate during the unfolding process of the dimeric ketosteroid isomerase

AbstractFailure to detect the intermediate in spite of its existence often leads to the conclusion that two-state transition in the unfolding process of the protein can be justified. In contrast to the previous equilibrium unfolding experiment fitted to a two-state model by circular dichroism and fluorescence spectroscopies, an equilibrium unfolding intermediate of a dimeric ketosteroid isomerase (KSI) could be detected by small angle X-ray scattering (SAXS) and analytical ultracentrifugation. The sizes of KSI were determined to be 18.7Å in 0M urea, 17.3Å in 5.2M urea, and 25.1Å in 7M urea by SAXS. The size of KSI in 5.2M urea was significantly decreased compared with those in 0M and 7M urea, suggesting the existence of a compact intermediate. Sedimentation velocity as obtained by ultracentrifugation confirmed that KSI in 5.2M urea is distinctly different from native and fully-unfolded forms. The sizes measured by pulse field gradient nuclear magnetic resonance (NMR) spectroscopy were consistent with those obtained by SAXS. Discrepancy of equilibrium unfolding studies between size measurement methods and optical spectroscopies might be due to the failure in detecting the intermediate by optical spectroscopic methods. Further characterization of the intermediate using 1H NMR spectroscopy and Kratky plot supported the existence of a partially-folded form of KSI which is distinct from those of native and fully-unfolded KSIs. Taken together, our results suggest that the formation of a compact intermediate should precede the association of monomers prior to the dimerization process during the folding of KSI

Epitaxy: Programmable Atom Equivalents

The programmability of DNA makes it an attractive structure-directing ligand for the assembly of nanoparticle (NP) superlattices in a manner that mimics many aspects of atomic crystallization. However, the synthesis of multilayer single crystals of defined size remains a challenge. Though previous studies considered lattice mismatch as the major limiting factor for multilayer assembly, thin film growth depends on many interlinked variables. Here, a more comprehensive approach is taken to study fundamental elements, such as the growth temperature and the thermodynamics of interfacial energetics, to achieve epitaxial growth of NP thin films. Both surface morphology and internal thin film structure are examined to provide an understanding of particle attachment and reorganization during growth. Under equilibrium conditions, single crystalline, multilayer thin films can be synthesized over 500 × 500 μm² areas on lithographically patterned templates, whereas deposition under kinetic conditions leads to the rapid growth of glassy films. Importantly, these superlattices follow the same patterns of crystal growth demonstrated in atomic thin film deposition, allowing these processes to be understood in the context of well-studied atomic epitaxy and enabling a nanoscale model to study fundamental crystallization processes. Through understanding the role of epitaxy as a driving force for NP assembly, we are able to realize 3D architectures of arbitrary domain geometry and size.United States. Air Force Office of Scientific Research (AFOSR FA9550-11-1-0275)United States. Air Force Office of Scientific Research (FA9550-12-1-0280)United States. Department of Defense (N00014-15-1-0043)United States. Department of Energy (Grant DE-SC0000989-0002)National Science Foundation (U.S.) (Award DMR-1121262

Manipulating the ABCs of self-assembly via low-χ block polymer design

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ_ij). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ_(AC) ≲ 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAM_P. Transmission electron microscopy indicates that LAM_P exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM_3) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAM_P is thermodynamically stable below a critical χ_(AC), above which LAM_3 emerges. Both experiments and theory expose close analogies to ABA′ triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials

A Directional Entropic Force Approach to Assemble Anisotropic Nanoparticles into Superlattices

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/102143/1/14230_ftp.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/102143/2/ange_201306009_sm_miscellaneous_information.pd

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.Fil: Kwon, Soon Gu. Argonne National Laboratory; Estados UnidosFil: Chattopadhyay, Soma. Argonne National Laboratory; Estados Unidos. Illinois Institute of Technology; Estados UnidosFil: Koo, Bonil. Argonne National Laboratory; Estados UnidosFil: Dos Santos Claro, Paula Cecilia. Argonne National Laboratory; Estados UnidosFil: Shibata, Tomohiro. Argonne National Laboratory; Estados UnidosFil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Giovanetti, Lisandro Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Liu, Yuzi. Argonne National Laboratory; Estados UnidosFil: Johnson, Christopher. Argonne National Laboratory; Estados UnidosFil: Prakapenka, Vitali. University of Chicago; Estados UnidosFil: Lee, Byeongdu. Argonne National Laboratory; Estados UnidosFil: Shevchenko, Elena V.. Argonne National Laboratory; Estados Unido