232 results on '"Chmelka, Bradley F."'
Search Results
202. Aluminum-27 double-rotation NMR investigations of SAPO-5 with variable silicon content
- Author
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Janicke, Michael, Chmelka, Bradley F., Demuth, Dirk, and Schüth, Ferdi
- Published
- 1995
- Full Text
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203. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores.
- Author
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Zhao, Dongyuan, Feng, Jianglin, Huo, Qisheng, Melosh, Nicholas, Fredrickson, Glenn H., Chmelka, Bradley F., and Stucky, Galen D.
- Subjects
- *
BLOCK copolymers , *SILICA , *CHEMICAL structure - Abstract
Presents research which used amphiphilic triblock copolymers for the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes. Synthesis of SBA-15; Calcination; Easy preparation of SBA-15; Recovery of block copolymer species; Product thermally stable in boiling water.
- Published
- 1998
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204. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly...
- Author
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Zhao, Dongyuan, Huo, Qisheng, Feng, Jianglin, Chmelka, Bradley F., and Stucky, Galen D.
- Subjects
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SILICA , *CHEMICAL structure - Abstract
Provides information on a study synthesizing a family of highly ordered mesoporous (20-300 ...) silica structures. Methodology used to conduct the study; Information on the formation of mesoporous silica; Oligomeric alkyl-ethylene oxide surfactants; Findings of the study.
- Published
- 1998
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205. Hierarchically Ordered Oxides.
- Author
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Yang, Peidong, Deng, Tao, Zhao, Dongyuan, Feng, Pingyun, Pine, David, Chmelka, Bradley F., Whitesides, George M., and Stucky, Galen D.
- Subjects
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POROUS materials , *OXIDES , *ORDER-disorder in alloys , *PHYSICAL metallurgy , *ANALYTICAL chemistry , *CHEMICAL structure - Abstract
Presents research which prepared porous silica, niobia, and titania with three-dimensional structures patterned over multiple length scales. Methods used to make the preparation; Materials showing hierarchical ordering over several scales; Modifying the ordered structures; Compositional and structural diversities possible with the method.
- Published
- 1998
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206. Unifying Energetic Disorder from Charge Transport and Band Bending in Organic Semiconductors.
- Author
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Karki, Akchheta, Wetzelaer, Gert‐Jan A. H., Reddy, Gollapalli Narayana Manjunatha, Nádaždy, Vojtech, Seifrid, Martin, Schauer, Franz, Bazan, Guillermo C., Chmelka, Bradley F., Blom, Paul W. M., and Nguyen, Thuc‐Quyen
- Subjects
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ORGANIC semiconductors , *CONJUGATED polymers , *SEMICONDUCTORS , *DENSITY of states , *THIN films , *NUCLEAR magnetic resonance spectroscopy , *SPECIFIC gravity - Abstract
Characterizing the density of states (DOS) width accurately is critical in understanding the charge‐transport properties of organic semiconducting materials as broader DOS distributions lead to an inferior transport. From a morphological standpoint, the relative densities of ordered and disordered regions are known to affect charge‐transport properties in films; however, a comparison between molecular structures showing quantifiable ordered and disordered regions at an atomic level and its impact on DOS widths and charge‐transport properties has yet to be made. In this work, for the first time, the DOS distribution widths of two model conjugated polymer systems are characterized using three different techniques. A quantitative correlation between energetic disorder from band‐bending measurements and charge transport is established, providing direct experimental evidence that charge‐carrier mobility in disordered materials is compromised due to the relaxation of carriers into the tail states of the DOS. Distinction and quantification of ordered and disordered regions of thin films at an atomic level is achieved using solid‐state NMR spectroscopy. An ability to compare solid‐state film morphologies of organic semiconducting polymers to energetic disorder, and in turn charge transport, can provide useful guidelines for applications of organic conjugated polymers in pertinent devices. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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207. Innenrücktitelbild: Preferential Siting of Aluminum Heteroatoms in the Zeolite Catalyst Al‐SSZ‐70 (Angew. Chem. 19/2019).
- Author
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Berkson, Zachariah J., Hsieh, Ming‐Feng, Smeets, Stef, Gajan, David, Lund, Alicia, Lesage, Anne, Xie, Dan, Zones, Stacey I., McCusker, Lynne B., Baerlocher, Christian, and Chmelka, Bradley F.
- Published
- 2019
- Full Text
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208. Inside Back Cover: Preferential Siting of Aluminum Heteroatoms in the Zeolite Catalyst Al‐SSZ‐70 (Angew. Chem. Int. Ed. 19/2019).
- Author
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Berkson, Zachariah J., Hsieh, Ming‐Feng, Smeets, Stef, Gajan, David, Lund, Alicia, Lesage, Anne, Xie, Dan, Zones, Stacey I., McCusker, Lynne B., Baerlocher, Christian, and Chmelka, Bradley F.
- Subjects
- *
ZEOLITE catalysts , *ALUMINUM , *NUCLEAR magnetic resonance spectroscopy - Published
- 2019
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209. ChemInform Abstract: Local Environments of Dilute Activator Ions in the Solid-State Lighting Phosphor Y3-xCexAl5O12.
- Author
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George, Nathan C., Pell, Andrew J., Dantelle, Geraldine, Page, Katharine, Llobet, Anna, Balasubramanian, M., Pintacuda, Guido, Chmelka, Bradley F., and Seshadri, Ram
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YTTRIUM aluminum garnet , *DILUTION , *ACTIVATORS (Chemistry) , *STOICHIOMETRY , *CERIUM , *DOPED semiconductors , *SOLID state chemistry , *PHOSPHORS , *FLUORESCENCE spectroscopy - Abstract
Ce-doped yttrium aluminum garnet (Ce:YAG), CexY3-xAl5O12 with x = 0-0.09, is prepared by solid state synthesis using stoichiometric amounts of Y2O3, Al2O3, and CeO2 plus an optimum of 5 wt% each of BaF2 and NH4F as sintering aids (alumina crucible, 1500 °C, 5 h, 5% H2/N2 atmosphere). [ABSTRACT FROM AUTHOR]
- Published
- 2014
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210. Observation of Transient Prenucleation Species of Calcium Carbonate by DNP-Enhanced NMR.
- Author
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Balodis M, Rao Y, Stevanato G, Kellner M, Meibom J, Negroni M, Chmelka BF, and Emsley L
- Abstract
Knowledge of the mechanism by which polymorphic inorganic species, such as carbonates, are formed is crucial to understand and guide the selective crystallization of end products. Recently it has been shown that a key step in the crystallization of calcium carbonate is the formation of intermediate species known as prenucleation clusters. However, the observation of these prenucleation clusters in solution is exceedingly challenging because of their short lifetime and low concentrations. Here, using dissolution DNP-enhanced NMR spectroscopy, we observe signals from prenucleation species of calcium carbonate from which the kinetics of formation and conversion are determined.
- Published
- 2024
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211. Reversible and size-controlled assembly of reflectin proteins using a charged azobenzene photoswitch.
- Author
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Tobin CM, Gordon R, Tochikura SK, Chmelka BF, Morse DE, and Read de Alaniz J
- Abstract
Disordered proteins often undergo a stimuli-responsive, disorder-to-order transition which facilitates dynamic processes that modulate the physiological activities and material properties of cells, such as strength, chemical composition, and reflectance. It remains challenging to gain rapid and spatiotemporal control over such disorder-to-order transitions, which limits the incorporation of these proteins into novel materials. The reflectin protein is a cationic, disordered protein whose assembly is responsible for dynamic color camouflage in cephalopods. Stimuli-responsive control of reflectin's assembly would enable the design of biophotonic materials with tunable color. Herein, a novel, multivalent azobenzene photoswitch is shown to be an effective and non-invasive strategy for co-assembling with reflectin molecules and reversibly controlling assembly size. Photoisomerization between the trans and cis ( E and Z ) photoisomers promotes or reduces Coulombic interactions, respectively, with reflectin proteins to repeatedly cycle the sizes of the photoswitch-reflectin assemblies between 70 nm and 40 nm. The protein assemblies formed with the trans and cis isomers show differences in interaction stoichiometry and secondary structure, which indicate that photoisomerization modulates the photoswitch-protein interactions to change assembly size. Our results highlight the utility of photoswitchable interactions to control reflectin assembly and provide a tunable synthetic platform that can be adapted to the structure, assembly, and function of other disordered proteins., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)
- Published
- 2024
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212. Dynamic Behavior of Platinum Atoms and Clusters in the Native Oxide Layer of Aluminum Nanocrystals.
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Robatjazi H, Battsengel T, Finzel J, Tieu P, Xu M, Hoffman AS, Qi J, Bare SR, Pan X, Chmelka BF, Halas NJ, and Christopher P
- Abstract
Strong metal-support interactions (SMSIs) are well-known in the field of heterogeneous catalysis to induce the encapsulation of platinum (Pt) group metals by oxide supports through high temperature H
2 reduction. However, demonstrations of SMSI overlayers have largely been limited to reducible oxides, such as TiO2 and Nb2 O5 . Here, we show that the amorphous native surface oxide of plasmonic aluminum nanocrystals (AlNCs) exhibits SMSI-induced encapsulation of Pt following reduction in H2 in a Pt structure dependent manner. Reductive treatment in H2 at 300 °C induces the formation of an AlOx SMSI overlayer on Pt clusters, leaving Pt single-atom sites (Ptiso ) exposed available for catalysis. The remaining exposed Ptiso species possess a more uniform local coordination environment than has been observed on other forms of Al2 O3 , suggesting that the AlOx native oxide of AlNCs presents well-defined anchoring sites for individual Pt atoms. This observation extends our understanding of SMSIs by providing evidence that H2 -induced encapsulation can occur for a wider variety of materials and should stimulate expanded studies of this effect to include nonreducible oxides with oxygen defects and the presence of disorder. It also suggests that the single-atom sites created in this manner, when combined with the plasmonic properties of the Al nanocrystal core, may allow for site-specific single-atom plasmonic photocatalysis, providing dynamic control over the light-driven reactivity in these systems.- Published
- 2024
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213. Mesostructured Materials with Controllable Long-Range Orientational Ordering and Anisotropic Properties.
- Author
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Jahnke JP, Kim D, Wildemuth DJ, Nolla J, Berkow MW, Gwak H, Neyshtadt S, Segal-Peretz T, Frey GL, and Chmelka BF
- Abstract
Inorganic-organic mesophase materials provide a wide range of tunable properties, which are often highly dependent on their nano-, micro-, or meso-scale compositions and structures. Among these are macroscopic orientational order and corresponding anisotropic material properties, the adjustability of which are difficult to achieve. This is due to the complicated transient and coupled transport, chemical reaction, and surface processes that occur during material syntheses. By understanding such processes, general criteria are established and used to prepare diverse mesostructured materials with highly aligned channels with uniform nanometer dimensions and controllable directionalities over macroscopic dimensions and thicknesses. This is achieved by using a micropatterned semipermeable poly(dimethylsiloxane) stamp to manage the rates, directions, and surfaces at which self-assembling phases nucleate and the directions that they grow. This enables mesostructured surfactant-directed silica and titania composites, including with functional guest species, and mesoporous carbons to be prepared with high degrees of hexagonal order, as well as controllable orthogonal macroscopic orientational order. The resulting materials exhibit novel anisotropic properties, as demonstrated by the example of direction-dependent photocurrent generation, and are promising for enhancing the functionality of inorganic-organic nanocomposite materials in separations, catalysis, and energy conversion applications., (© 2023 Wiley-VCH GmbH.)
- Published
- 2023
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214. Direct Detection of Paired Aluminum Heteroatoms in Chabazite Zeolite Catalysts and Their Significance for Methanol Dehydration Reactivity.
- Author
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Schmithorst MB, Prasad S, Moini A, and Chmelka BF
- Abstract
The distributions of heteroatoms within zeolite frameworks have important influences on the locations of exchangeable cations, which account for the diverse adsorption and reaction properties of zeolite catalysts. In particular for aluminosilicate zeolites, paired configurations of aluminum atoms separated by one or two tetrahedrally coordinated silicon atoms are important for charge-balancing pairs of H
+ cations, which are active for methanol dehydration, or divalent metal cations, such as Cu2+ , which selectively catalyze the reduction of NOx , both technologically important reactions. Such paired heteroatom configurations, however, are challenging to detect and probe, due to the typically nonstoichiometric compositions and nonperiodic distributions of aluminum atoms within aluminosilicate zeolite frameworks. Nevertheless, distinct configurations of paired framework aluminum atoms are unambiguously detected and resolved in solid-state 2D27 Al-29 Si and29 Si-29 Si NMR spectra, which are sensitive to the local environments of covalently bonded27 Al-O-29 Si and29 Si-O-29 Si moieties, respectively. Specifically, two H+ -chabazite zeolites with the same bulk framework aluminum contents are shown to have different types and populations of closely paired aluminum species, which correlate with higher activity for methanol dehydration. The methodologies and insights are expected to be broadly applicable to analyses of heteroatom sites, their distributions, and adsorption and reaction properties in other zeolite framework types.- Published
- 2023
- Full Text
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215. Lipid membrane mimetics and oligomerization tune functional properties of proteorhodopsin.
- Author
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Han CT, Nguyen KDQ, Berkow MW, Hussain S, Kiani A, Kinnebrew M, Idso MN, Baxter N, Chang E, Aye E, Winslow E, Rahman M, Seppälä S, O'Malley MA, Chmelka BF, Mertz B, and Han S
- Subjects
- Protons, Rhodopsins, Microbial chemistry, Lipids, Liposomes, Escherichia coli
- Abstract
The functional properties of proteorhodopsin (PR) have been found to be strongly modulated by oligomeric distributions and lipid membrane mimetics. This study aims to distinguish and explain their effects by investigating how oligomer formation impacts PR's function of proton transport in lipid-based membrane mimetic environments. We find that PR forms stable hexamers and pentamers in both E. coli membranes and synthetic liposomes. Compared with the monomers, the photocycle kinetics of PR oligomers is ∼2 and ∼4.5 times slower for transitions between the K and M and the M and N photointermediates, respectively, indicating that oligomerization significantly slows PR's rate of proton transport in liposomes. In contrast, the apparent pKa of the key proton acceptor residue D97 (pKa
D97 ) of liposome-embedded PR persists at 6.2-6.6, regardless of cross-protomer modulation of D97, suggesting that the liposome environment helps maintain PR's functional activity at neutral pH. By comparison, when extracted directly from E. coli membranes into styrene-maleic acid lipid particles, the pKaD97 of monomer-enriched E50Q PR drastically increases to 8.9, implying that there is a very low active PR population at neutral pH to engage in PR's photocycle. These findings demonstrate that oligomerization impacts PR's photocycle kinetics, while lipid-based membrane mimetics strongly affect PR's active population via different mechanisms., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2022 Biophysical Society. Published by Elsevier Inc. All rights reserved.)- Published
- 2023
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216. Synthesis and structural properties of a 2D Zn(II) dodecahydroxy- closo -dodecaborate coordination polymer.
- Author
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Ready AD, Becwar SM, Jung D, Kallistova A, Schueller E, Anderson KP, Kubena R, Seshadri R, Chmelka BF, and Spokoyny AM
- Abstract
In this work, we discuss the synthesis and characterization of a 2D coordination polymer composed of a dianionic perhydroxylated boron cluster, [B
12 (OH)12 2- ], coordinated to Zn(II)-the first example of a transition metal-coordinated [B12 (OH)12 ]2- compound. This material was synthesized via cation exchange from the starting cesium salt and then subjected to rigorous characterization prior to and after thermal activation. Numerous techniques, including XRD, FTIR, SEM, TGA, and solid-state NMR revealed a 2D coordination polymer composed of sheets of Zn(II) ions intercalated between planes of boron clusters. The as-synthesized material was then evacuated of solvent via thermal treatment, and atomic-level changes from this transformation were elucidated through a combination of 1D and 2D solid-state NMR analyses of11 B and1 H nuclei, suggesting the full removal of coordinated solvent molecules. Evidence also suggested that [B12 (OH)12 2- ] can adjust its coordination to Zn(II) in the solid-state through hemilability of its numerous -OH ligands.- Published
- 2022
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217. Scaling analyses for hyperpolarization transfer across a spin-diffusion barrier and into bulk solid media.
- Author
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Prisco NA, Pinon AC, Emsley L, and Chmelka BF
- Abstract
By analogy to heat and mass transfer film theory, a general approach is introduced for determining hyperpolarization transfer rates between dilute electron spins and a surrounding nuclear ensemble. These analyses provide new quantitative relationships for understanding, predicting, and optimizing the effectiveness of hyperpolarization protocols, such as Dynamic Nuclear Polarization (DNP) under magic-angle spinning conditions. An empirical DNP polarization-transfer coefficient is measured as a function of the bulk matrix 1H spin density and indicates the presence of two distinct kinetic regimes associated with different rate-limiting polarization transfer phenomena. Dimensional property relationships are derived and used to evaluate the competitive rates of spin polarization generation, propagation, and dissipation that govern hyperpolarization transfer between large coupled spin ensembles. The quantitative analyses agree closely with experimental measurements for the accumulation, propagation, and dissipation of hyperpolarization in solids and provide evidence for kinetically-limited transfer associated with a spin-diffusion barrier. The results and classical approach yield general design criteria for analyzing and optimizing polarization transfer processes involving complex interfaces and composite media for applications in materials science, physical chemistry and nuclear spintronics.
- Published
- 2021
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218. Crystallization of Mordenite Platelets using Cooperative Organic Structure-Directing Agents.
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Kumar M, Berkson ZJ, Clark RJ, Shen Y, Prisco NA, Zheng Q, Zeng Z, Zheng H, McCusker LB, Palmer JC, Chmelka BF, and Rimer JD
- Abstract
Organic structure-directing agents (OSDAs) are exploited in the crystallization of microporous materials to tailor the physicochemical properties of the resulting zeolite for applications ranging from separations to catalysis. The rational design of these OSDAs often entails the identification of molecules with a geometry that is commensurate with the channels and cages of the target zeolite structure. Syntheses tend to employ only a single OSDA, but there are a few examples where two or more organics operate synergistically to yield a desired product. Using a combination of state-of-the-art characterization techniques and molecular modeling, we show that the coupling of N , N , N -trimethyl-1,1-adamantammonium and 1,2-hexanediol, each yielding distinct zeolites when used alone, results in the cooperative direction of a third structure, HOU-4, with the mordenite framework type ( MOR ). Rietveld refinement using synchrotron X-ray diffraction data reveals the spatial arrangement of the organics in the HOU-4 crystals, with amines located in the large channels and alcohols oriented in the side pockets lining the one-dimensional pores. These results are in excellent agreement with molecular dynamics calculations, which predict similar spatial distributions of organics with an energetically favorable packing density that agrees with experimental measurements of OSDA loading, as well as with solid-state two-dimensional
27 Al{29 Si},27 Al{1 H}, and13 C{1 H} NMR correlation spectra, which establish the proximities and interactions of occluded OSDAs. A combination of high-resolution transmission electron microscopy and atomic force microscopy is used to quantify the size of the HOU-4 crystals, which exhibit a platelike morphology, and to index the crystal facets. Our findings reveal that the combined OSDAs work in tandem to produce ultrathin, nonfaulted HOU-4 crystals that exhibit improved catalytic activity for cumene cracking in comparison to mordenite crystals prepared via conventional syntheses. This novel demonstration of cooperativity highlights the potential possibilities for expanding the use of dual structure-directing agents in zeolite synthesis.- Published
- 2019
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219. Electrochemically Enhanced Dissolution of Silica and Alumina in Alkaline Environments.
- Author
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Dobbs HA, Degen GD, Berkson ZJ, Kristiansen K, Schrader AM, Oey T, Sant G, Chmelka BF, and Israelachvili JN
- Abstract
Dissolution of mineral surfaces at asymmetric solid-liquid-solid interfaces in aqueous solutions occurs in technologically relevant processes, such as chemical/mechanical polishing (CMP) for semiconductor fabrication, formation and corrosion of structural materials, and crystallization of materials relevant to heterogeneous catalysis or drug delivery. In some such processes, materials at confined interfaces exhibit dissolution rates that are orders of magnitude larger than dissolution rates of isolated surfaces. Here, the dissolution of silica and alumina in close proximity to a charged gold surface or mica in alkaline solutions of pH 10-11 is shown to depend on the difference in electrostatic potentials of the surfaces, as determined from measurements conducted using a custom-built electrochemical pressure cell and a surface forces apparatus (SFA). The enhanced dissolution is proposed to result from overlap of the electrostatic double layers between the dissimilar charged surfaces at small intersurface separation distances (<1 Debye length). A semiquantitative model shows that overlap of the electric double layers can change the magnitude and direction of the electric field at the surface with the less negative potential, which results in an increase in the rate of dissolution of that surface. When the surface electrochemical properties were changed, the dissolution rates of silica and alumina were increased by up to 2 orders of magnitude over the dissolution rates of isolated compositionally similar surfaces under otherwise identical conditions. The results provide new insights on dissolution processes that occur at solid-liquid-solid interfaces and yield design criteria for controlling dissolution through electrochemical modification, with relevance to diverse technologies.
- Published
- 2019
- Full Text
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220. Nanoscale Surface Compositions and Structures Influence Boron Adsorption Properties of Anion Exchange Resins.
- Author
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Manjunatha Reddy GN, Gerbec JA, Shimizu F, and Chmelka BF
- Abstract
Boron adsorption properties of poly(styrene- co -divinylbenzene) (PSDVB)-based anion-exchange resins with surface-grafted N -methyl-d-glucamine (NMDG) depend strongly on their local surface compositions, structures, and interfacial interactions. Distinct boron adsorption sites have been identified and quantified, and interactions between borate anions and hydroxyl groups of NMDG surface moieties have been established. A combination of X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR), and Fourier-transform infrared (FT-IR) spectroscopy were used to characterize the atomic-level compositions and structures that directly influence the adsorption of borate anions on the NMDG-functionalized resin surface. Surface-enhanced dynamic-nuclear-polarization (DNP)-NMR enabled dilute (3 atom % N) tertiary alkyl amines and quaternary ammonium ions of the NMDG groups to be detected and distinguished with unprecedented sensitivity and resolution at natural abundance
15 N (0.4%). Two-dimensional (2D) solid-state11 B{1 H},13 C{1 H}, and11 B{11 B} NMR analyses provide direct atomic-scale evidence for interactions of borate anions with the NMDG moieties on the resin surfaces, which form stable mono- and bischelate complexes. FT-IR spectra reveal displacements in the stretching vibrational frequencies associated with the O-H and N-H bonds of NMDG groups that corroborate the formation of chelate complexes on the resin surfaces. The atomic-level compositions and structures are related to boron adsorption properties of resin materials synthesized under different conditions, which have important remediation applications.- Published
- 2019
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221. Measurement of Proton Spin Diffusivity in Hydrated Cementitious Solids.
- Author
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Walder BJ, Prisco NA, Paruzzo FM, Yarava JR, Chmelka BF, and Emsley L
- Abstract
The study of hydration and crystallization processes involving inorganic oxides is often complicated by poor long-range order and the formation of heterogeneous domains or surface layers. In solid-state NMR,
1 H-1 H spin diffusion analyses can provide information on spatial composition distributions, domain sizes, or miscibility in both ordered and disordered solids. Such analyses have been implemented in organic solids but crucially rely on separate measurements of the1 H spin diffusion coefficients in closely related systems. We demonstrate that an experimental NMR method, in which "holes" of well-defined dimensions are created in proton magnetization, can be applied to determine spin diffusion coefficients in cementitious solids hydrated with17 O-enriched water. We determine proton spin diffusion coefficients of 240 ± 40 nm2 /s for hydrated tricalcium aluminate and 140 ± 20 nm2 /s for hydrated tricalcium silicate under quasistatic conditions.- Published
- 2019
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222. Materializing opportunities for NMR of solids.
- Author
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Chmelka BF
- Abstract
Advancements in sensitivity and resolution of NMR of solids are opening a bonanza of fundamental and technological opportunities in materials science. Many of these are at the boundaries of related disciplines that provide creative inputs to motivate the development of new methodologies and possibilities for new applications. As Boltzmann limitations are surmounted by dynamic-nuclear-polarization- and laser-enhanced hyperpolarization techniques, the correlative benefits of multidimensional NMR are becoming more and more impactful. Nevertheless, there are limits, and the atomic-level information provided by solid-state NMR will be most useful in combination with state-of-the-art diffraction, microscopy, computational, and materials synthesis methods. Collectively these can be expected to lead to design criteria that will promote discovery of new materials, lead to novel or improved material properties, catalyze new applications, and motivate further methodological advancements., (Copyright © 2019 Elsevier Inc. All rights reserved.)
- Published
- 2019
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223. Proteorhodopsin Function Is Primarily Mediated by Oligomerization in Different Micellar Surfactant Solutions.
- Author
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Idso MN, Baxter NR, Narayanan S, Chang E, Fisher J, Chmelka BF, and Han S
- Subjects
- Escherichia coli chemistry, Escherichia coli Proteins radiation effects, Kinetics, Protein Multimerization, Rhodopsins, Microbial radiation effects, Escherichia coli Proteins chemistry, Micelles, Rhodopsins, Microbial chemistry, Surface-Active Agents chemistry
- Abstract
The diverse functionalities of membrane proteins (MPs) have garnered much interest in leveraging these biomolecules for technological applications. One challenge of studying MPs in artificial micellar surfactant environments is that many factors modulate their structures and functionalities, including the surfactants that interact with the MP or their assembly into oligomers. As oligomerization offers a means by which MPs could selectively interact among the copious environmental factors in biological environments, we hypothesized that MP function is predominantly modified by oligomerization rather than interactions with local surfactants that, by comparison, largely interact with MPs nonspecifically. To test this, we study the light-activated proton pump proteorhodopsin (PR) in micellar surfactant solutions because it is functionally active in monomeric and oligomeric forms, the light-activated functionalities of which can be assessed in detail. The surfactant composition and oligomerization are correlated with PR function, as measured by the protonation behaviors of aspartic acid residue 97, which mediates light-activated proton transport, and the associated photocycle kinetics. The results demonstrate that oligomerization dominantly mediates PR function in different surfactant environments, whereas some surfactants can subtly modulate proton-pumping kinetics. This work underscores the importance of understanding and controlling oligomerization of MPs to study and exploit their function.
- Published
- 2019
- Full Text
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224. Direct Observation of the Relationship betweenMolecular Topology and Bulk Morphology for a π-Conjugated Material.
- Author
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Seifrid MT, Reddy GNM, Zhou C, Chmelka BF, and Bazan GC
- Subjects
- Density Functional Theory, Magnetic Resonance Spectroscopy, Molecular Structure, Semiconductors, Temperature, Organic Chemicals chemistry, Small Molecule Libraries chemistry
- Abstract
High-performance organic semiconducting materials are reliant upon subtle changes in structure across different length scales. These morphological features control relevant physical properties and ultimately device performance. By combining in situ NMR spectroscopy and theoretical calculations, the conjugated small molecule TT is shown to exhibit distinct temperature-dependent local structural features that are related to macroscopic properties. Specifically, lamellar and melt states are shown to exhibit different molecular topologies associated with planar and twisted conformations of TT, respectively. This topological transformation offers a novel avenue for molecular design and control of solid-state organization.
- Published
- 2019
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225. Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties.
- Author
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Gottschling K, Stegbauer L, Savasci G, Prisco NA, Berkson ZJ, Ochsenfeld C, Chmelka BF, and Lotsch BV
- Abstract
Tailorable sorption properties at the molecular level are key for efficient carbon capture and storage and a hallmark of covalent organic frameworks (COFs). Although amine functional groups are known to facilitate CO
2 uptake, atomistic insights into CO2 sorption by COFs modified with amine-bearing functional groups are scarce. Herein, we present a detailed study of the interactions of carbon dioxide and water with two isostructural hydrazone-linked COFs with different polarities based on the 2,5-diethoxyterephthalohydrazide linker. Varying amounts of tertiary amines were introduced in the COF backbones by means of a copolymerization approach using 2,5-bis(2-(dimethylamino)ethoxy)terephthalohydrazide in different amounts ranging from 25 to 100% substitution of the original DETH linker. The interactions of the frameworks with CO2 and H2 O were comprehensively studied by means of sorption analysis, solid-state NMR spectroscopy, and quantum-chemical calculations. We show that the addition of the tertiary amine linker increases the overall CO2 sorption capacity normalized by the surface area and of the heat of adsorption, whereas surface areas and pore size diameters decrease. The formation of ammonium bicarbonate species in the COF pores is shown to occur, revealing the contributing role of water for CO2 uptake by amine-modified porous frameworks., Competing Interests: The authors declare no competing financial interest.- Published
- 2019
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226. Highly Graphitic Mesoporous Fe,N-Doped Carbon Materials for Oxygen Reduction Electrochemical Catalysts.
- Author
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Kim D, Zussblatt NP, Chung HT, Becwar SM, Zelenay P, and Chmelka BF
- Abstract
The synthesis, characterization, and electrocatalytic properties of mesoporous carbon materials doped with nitrogen atoms and iron are reported and compared for the catalyzed reduction of oxygen gas at fuel cell cathodes. Mixtures of common and inexpensive organic precursors, melamine, and formaldehyde were pyrolyzed in the presence of transition-metal salts (e.g., nitrates) within a mesoporous silica template to yield mesoporous carbon materials with greater extents of graphitization than those of others prepared from small-molecule precursors. In particular, Fe,N-doped carbon materials possessed high surface areas (∼800 m
2 /g) and high electrical conductivities (∼19 S/cm), which make them attractive for electrocatalyst applications. The surface compositions of the mesoporous Fe,N-doped carbon materials were postsynthetically modified by acid washing and followed by high-temperature thermal treatments, which were shown by X-ray photoelectron spectroscopy to favor the formation of graphitic and pyridinic nitrogen moieties. Such surface-modified materials exhibited high electrocatalytic oxygen reduction activities under alkaline conditions, as established by their high onset and half-wave potentials (1.04 and 0.87 V, respectively vs reversible hydrogen electrode) and low Tafel slope (53 mV/decade). These values are superior to many similar transition-metal- and N-doped carbon materials and compare favorably with commercially available precious-metal catalysts, e.g., 20 wt % Pt supported on activated carbon. The analyses indicate that inexpensive mesoporous Fe,N-doped carbon materials are promising alternatives to precious metal-containing catalysts for electrochemical reduction of oxygen in polymer electrolyte fuel cells.- Published
- 2018
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227. Publisher Correction: A molecular cross-linking approach for hybrid metal oxides.
- Author
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Jung D, Saleh LMA, Berkson ZJ, El-Kady MF, Hwang JY, Mohamed N, Wixtrom AI, Titarenko E, Shao Y, McCarthy K, Guo J, Martini IB, Kraemer S, Wegener EC, Saint-Cricq P, Ruehle B, Langeslay RR, Delferro M, Brosmer JL, Hendon CH, Gallagher-Jones M, Rodriguez J, Chapman KW, Miller JT, Duan X, Kaner RB, Zink JI, Chmelka BF, and Spokoyny AM
- Abstract
In the version of this Article originally published, Liban M. A. Saleh was incorrectly listed as Liban A. M. Saleh due to a technical error. This has now been amended in all online versions of the Article.
- Published
- 2018
- Full Text
- View/download PDF
228. A molecular cross-linking approach for hybrid metal oxides.
- Author
-
Jung D, Saleh LMA, Berkson ZJ, El-Kady MF, Hwang JY, Mohamed N, Wixtrom AI, Titarenko E, Shao Y, McCarthy K, Guo J, Martini IB, Kraemer S, Wegener EC, Saint-Cricq P, Ruehle B, Langeslay RR, Delferro M, Brosmer JL, Hendon CH, Gallagher-Jones M, Rodriguez J, Chapman KW, Miller JT, Duan X, Kaner RB, Zink JI, Chmelka BF, and Spokoyny AM
- Abstract
There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO
2 , to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as 'molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12 (OH)12 ]2- . This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.- Published
- 2018
- Full Text
- View/download PDF
229. Erratum: Tuning underwater adhesion with cation-π interactions.
- Author
-
Gebbie MA, Wei W, Schrader AM, Cristiani TR, Dobbs HA, Idso M, Chmelka BF, Waite JH, and Israelachvili JN
- Published
- 2017
- Full Text
- View/download PDF
230. Tuning underwater adhesion with cation-π interactions.
- Author
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Gebbie MA, Wei W, Schrader AM, Cristiani TR, Dobbs HA, Idso M, Chmelka BF, Waite JH, and Israelachvili JN
- Subjects
- Adhesiveness, Adsorption, Aluminum Silicates chemistry, Animals, Bivalvia chemistry, Dihydroxyphenylalanine chemistry, Hydrogen Bonding, Lysine chemistry, Static Electricity, Adhesives chemistry, Biomimetic Materials chemistry, Cations chemistry, Peptides chemistry
- Abstract
Cation-π interactions drive the self-assembly and cohesion of many biological molecules, including the adhesion proteins of several marine organisms. Although the origin of cation-π bonds in isolated pairs has been extensively studied, the energetics of cation-π-driven self-assembly in molecular films remains uncharted. Here we use nanoscale force measurements in combination with solid-state NMR spectroscopy to show that the cohesive properties of simple aromatic- and lysine-rich peptides rival those of the strong reversible intermolecular cohesion exhibited by adhesion proteins of marine mussel. In particular, we show that peptides incorporating the amino acid phenylalanine, a functional group that is conspicuously sparing in the sequences of mussel proteins, exhibit reversible adhesion interactions significantly exceeding that of analogous mussel-mimetic peptides. More broadly, we demonstrate that interfacial confinement fundamentally alters the energetics of cation-π-mediated assembly: an insight that should prove relevant for diverse areas, which range from rationalizing biological assembly to engineering peptide-based biomaterials.
- Published
- 2017
- Full Text
- View/download PDF
231. Directing zeolite structures into hierarchically nanoporous architectures.
- Author
-
Na K, Jo C, Kim J, Cho K, Jung J, Seo Y, Messinger RJ, Chmelka BF, and Ryoo R
- Abstract
Crystalline mesoporous molecular sieves have long been sought as solid acid catalysts for organic reactions involving large molecules. We synthesized a series of mesoporous molecular sieves that possess crystalline microporous walls with zeolitelike frameworks, extending the application of zeolites to the mesoporous range of 2 to 50 nanometers. Hexagonally ordered or disordered mesopores are generated by surfactant aggregates, whereas multiple cationic moieties in the surfactant head groups direct the crystallization of microporous aluminosilicate frameworks. The wall thicknesses, framework topologies, and mesopore sizes can be controlled with different surfactants. The molecular sieves are highly active as catalysts for various acid-catalyzed reactions of bulky molecular substrates, compared with conventional zeolites and ordered mesoporous amorphous materials.
- Published
- 2011
- Full Text
- View/download PDF
232. Selective NMR measurements of homonuclear scalar couplings in isotopically enriched solids.
- Author
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Cadars S, Lesage A, Hedin N, Chmelka BF, and Emsley L
- Abstract
Scalar (J) couplings in solid-state NMR spectroscopy are sensitive to covalent through-bond interactions that make them informative structural probes for a wide range of complex materials. Until now, however, they have been generally unsuitable for use in isotopically enriched solids, such as proteins or many inorganic solids, because of the complications presented by multiple coupled but nonisolated spins. Such difficulties are overcome by incorporating a z-filter that results in a robust method for measuring pure J-coupling modulations between selected pairs of nuclei in an isotopically enriched spin system. The reliability of the new experimental approach is established by using numerical simulations and tested on fully (13)C-labeled polycrystalline L-alanine. It is furthermore shown to be applicable to partially enriched systems, when used in combination with a selective double-quantum (DQ) filter, as demonstrated for the measurement of (2)J((29)Si-O-(29)Si) couplings in a 50% (29)Si-enriched surfactant-templated layered silicate lacking long-range 3D crystallinity. J-coupling constants are obtained with sufficient accuracy to distinguish between different (29)Si-O-(29)Si pairs, shedding insight on the local structure of the silicate framework. The new experiment is appropriate for fully or partially enriched liquid or solid samples.
- Published
- 2006
- Full Text
- View/download PDF
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