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Controlling the interfaces and interactions of colloidal nanoparticles (NPs) via tethered molecular moieties is crucial for NP applications in engineered nanomaterials, optics, catalysis, and nanomedicine. Despite a broad range of molecular types explored, there is a need for a flexible approach to rationally vary the chemistry and structure of these interfacial molecules for controlling NP stability in diverse environments, while maintaining a small size of the NP molecular shell. Here, we demonstrate that low-molecular-weight, bifunctional comb-shaped, and sequence-defined peptoids can effectively stabilize gold NPs (AuNPs). The generality of this robust functionalization strategy was also demonstrated by coating of silver, platinum, and iron oxide NPs with designed peptoids. Each peptoid (PE) is designed with varied arrangements of a multivalent AuNP-binding domain and a solvation domain consisting of oligo-ethylene glycol (EG) branches. Among designs, a peptoid (PE5) with a diblock structure is demonstrated to provide a superior nanocolloidal stability in diverse aqueous solutions while forming a compact shell (∼1.5 nm) on the AuNP surface. We demonstrate by experiments and molecular dynamics simulations that PE5-coated AuNPs (PE5/AuNPs) are stable in select organic solvents owing to the strong PE5 (amine)-Au binding and solubility of the oligo-EG motifs. At the vapor-aqueous interface, we show that PE5/AuNPs remain stable and can self-assemble into ordered 2D lattices. The NP films exhibit strong near-field plasmonic coupling when transferred to solid substrates.

Here, we report a series of two-dimensional lanthanide metal-organic frameworks Ln-DBTPA (where DBTPA = 2,5-dibromoterephthalic acid and Ln = Tb (

All radical S-adenosylmethionine (radical-SAM) enzymes, including the noncanonical radical-SAM enzyme diphthamide biosynthetic enzyme Dph1–Dph2, require at least one [4Fe–4S](Cys)3 cluster for activity. It is well-known in the radical-SAM enzyme community that the [4Fe–4S](Cys)3 cluster is extremely air-sensitive and requires strict anaerobic conditions to reconstitute activity in vitro. Thus, how such enzymes function in vivo in the presence of oxygen in aerobic organisms is an interesting question. Working on yeast Dph1–Dph2, we found that consistent with the known oxygen sensitivity, the [4Fe–4S] cluster is easily degraded into a [3Fe–4S] cluster. Remarkably, the small iron-containing protein Dph3 donates one Fe atom to convert the [3Fe–4S] cluster in Dph1–Dph2 to a functional [4Fe–4S] cluster during the radical-SAM enzyme catalytic cycle. This mechanism to maintain radical-SAM enzyme activity in aerobic environments is likely general, and Dph3-like proteins may exist to keep other radical-SAM enzymes functional in aerobic environments.

We report the synthesis, single-crystal structure, solid-state ultraviolet-visible-near-infrared spectroscopy, and theoretical calculations on the first trivalent plutonium crown ether inclusion complex, [(H3O)(18-crown-6)][Pu(H2O)4(18-crown-6)](ClO4)4·2(H2O) (denoted as PuIII-18C6). Single-crystal X-ray diffraction reveals that PuIII-18C6 crystallizes in the orthorhombic space group of Pccn, which is assembled by independent ionic pairs including [Pu(H2O)4(18-crown-6)]3+, [(H3O)(18-crown-6)]+, and perchlorate anions. The plutonium atom is fully encapsulated within the cavity of the 18-crown-6, generating a distorted bicapped square antiprism geometry. The theoretical evaluation confirms that weak Pu-O dative bond is involved between PuIII ions with 18-crown-6. This work may deepen the understanding of the host-guest interactions between trivalent transuranic and macrocyclic ligands.

X-ray photon correlation spectroscopy (XPCS) microrheology and conventional bulk rheology were performed on silica nanoparticle dispersions associated with battery electrolyte applications to probe the properties of these specific complex materials and to explore the utility of XPCS microrheology in characterizing nanoparticle dispersions. Sterically stabilized shear-thickening electrolytes were synthesized by grafting poly(methyl methacrylate) chains onto silica nanoparticles. Coated silica dispersions containing 5-30 wt % nanoparticles dispersed in propylene carbonate were studied. In general, both XPCS microrheology and conventional rheology showed that coated silica dispersions were more viscous at higher concentrations, as expected. The complex viscosity of coated silica dispersions showed shear-thinning behavior over the frequency range probed by XPCS measurements. However, measurements using conventional mechanical rheometry yielded a shear viscosity with weak shear-thickening behavior for dispersions with the highest concentration of 30% particles. Our results indicate that there is a critical concentration needed for shear-thickening behavior, as well as appropriate particle size and surface polymer chain length, for this class of nanoparticle-based electrolytes. The results of this study can provide insights for comparing XPCS microrheology and bulk rheology for related complex fluids and whether XPCS microrheology can capture expected macroscopic rheological properties by probing small-scale particle dynamics.

We use computer simulations and experiments to study the interactions between nanoparticles (NPs) grafted with self-complementary DNA strands. Each strand ends with a sticky palindromic single-stranded sequence, allowing it to associate equally favorably with strands grafted on the same particle or on different NPs. Surprisingly we find an attractive interaction between a pair of NPs, and we demonstrate that at low temperature it arises purely from a combinatorial-entropy contribution. We evaluate theoretically and verify numerically this entropic contribution originating from the number of distinct bonding patterns associated with intra- and interparticle binding. This entropic attraction becomes more favorable with decreasing inter-NP distance because more sticky ends can participate in making this choice.

A uranyl–europium heterobimetallic compound, (TEA)3[(UO2)6Eu(H2O)4(PPA)6] (H3PPA = phosphonoacetic acid, TEA = tetraethylammonium cation), was synthesized under mild hydrothermal conditions. The em...

The semicrystalline protein structure and impressive mechanical properties of major ampullate (MA) spider silk make it a promising natural alternative to polyacrylonitrile (PAN) fibers for carbon fiber manufacture. However, when annealed using a similar procedure to carbon fiber production, the tensile strength and Young’s modulus of MA silk decrease. Despite this, MA silk fibers annealed at 600 °C remain stronger and tougher than similarly annealed PAN but have a lower Young’s modulus. Although MA silk and PAN graphitize to similar extents, annealing disrupts the hydrogen bonding that controls crystal alignment within MA silk. Consequently, unaligned graphite crystals form in annealed MA silk, causing it to weaken, while graphite crystals in PAN maintain alignment along the fiber axis, strengthening the fibers. These shortcomings of spider silk when annealed provide insights into the selection and design of future alternative carbon fiber precursors.

Aldehyde dehydrogenases (ALDHs) are a large family of enzymes that oxidize aldehydes into carboxylic acids. All ALDHs have a conserved catalytic cysteine residue but different cofactor preferences for NAD+ or NADP+. We discovered a CC motif composed of the catalytic and an adjacent cysteine, which are prone to disulfide bond formation under oxidative stress. This facilitates rapid detection of and response to oxidants, as well as protects the catalytic cysteine from overoxidation into irreversible products. In ALDHs, the CC motif only exists in NAD+-dependent ones, which leads to selective inhibition of NAD+-dependent ALDHs under oxidative stress, diverting carbon sources to the NADPH producing ALDHs. This alleviates the oxidative stress and promotes cell survival. Our findings revealed a novel regulatory mechanism for ALDHs that functions in the oxidative stress response. Many enzymes with catalytic cysteine residues have proximal cysteine, suggesting that such a regulatory mechanism may be general.

Searching for new green phosphors featured with a narrow band, small Stokes-shift, high thermal stability, and decent chemical resistance is critical for white light emitting diodes (LEDs) in liqui...

We here report that adsorbed chains composed of one of the constituent blocks can be used as a new surface modification approach to induce perpendicularly oriented lamellar microdomains in block copolymer thin films. A nearly symmetric polystyrene-block-poly(methyl methacrylate) (PS-block-PMMA) diblock copolymer was used as a model. Densely packed PS- or PMMA-adsorbed chains of about 2–3 nm in thickness (“polymer nanocoatings”) were deposited on silicon (Si) substrates using a solvent-rinsing approach. Spin-cast films of 40 or 60 nm-thick PS-block-PMMA (equivalent to two or three interdomain spacings) were subsequently deposited onto the PS or PMMA nanocoatings. Grazing incidence small-angle X-ray scattering experiments revealed the formation of perpendicularly oriented lamellar microdomains within the entire films at 200 °C, where balanced interfacial interactions at the polymer–air interface were achieved. Additionally, X-ray photon correlation spectroscopy studies demonstrated the dynamics of the fully...

TiF3 exhibits a rhombohedral to ReO3-type cubic phase transformation at ∼340 K. Here we report that, by introducing ZrF4 into TiF3, the cubic phase is stabilized at least down to 123 K in the Ti1- xZr xF3+ x compounds. All compounds exhibit low thermal expansion (LTE) between 123 and 623 K, and a nearly zero thermal expansion (ZTE) was obtained in Ti0.7Zr0.3F3.3 (αL = 0.91 ppm/K). The analysis of pair distribution function reveals that the cation-centered octahedra are partially changed to pentagonal bipyramids in Ti1- xZr xF3+ x due to the excess fluorines relative to the case of TiF3. Therefore, the cooperative rotation of the polyhedra tends to be restricted, and the cubic phase is thus stabilized. The restrained polyhedral rotations compete against the lattice softening caused by the introduction of Zr4+, giving rise to the LTE. Our present strategy is applicable to other rhombohedral metal trifluorides for the design of new isotropic ZTE materials.

Isozymes are enzymes with similar sequences that catalyze the same reaction in a given species. In Saccharomyces cerevisiae, most isozymes have major isoforms with high expression levels and minor isoforms with little expression in normal growth conditions. In a proteomic study aimed to identify yeast protein regulated by rapamycin, we found an interesting phenomenon that for several metabolic enzymes, the major isozymes are downregulated while the minor isozymes are upregulated. Through enzymological and biochemical studies, we demonstrate that a rapamycin-upregulated enolase isozyme (ENO1) favors gluconeogenesis and a rapamycin-upregulated alcohol dehydrogenase isozyme (ALD4) promotes the reduction of NAD(+) to NADH (instead of NADP(+) to NADPH). Gene deletion study in yeast showed that the ENO1 and ALD4 are important for yeast survival in less favorable growth conditions. Our study thus highlights the different metabolic needs of cells under different conditions and how nature chooses different isozymes to fit the metabolic needs.

The control of phonon propagation in nanoparticle arrays is one of the new frontiers of nanotechnology, potentially enabling the discovery of materials with unknown functionalities for potential innovative applications. The exploration of the terahertz window appears quite promising as phonons in this range are the leading carriers of heat transport in insulators and their control is the key to implement devices for heat flow management. Unfortunately, this scientific field is still in its infancy and even a basic topic such as the influence of floating nanoparticles on the terahertz phonon propagation of a colloidal suspension still eludes a firm answer. Shedding some light on this topic is the main motivation of the present work, which focuses an Inelastic X-Ray Scattering (IXS) measurements on a dilute suspension of Au nano-spheres in water. Measured spectra showed a non-trivial and unexpected shape displaying multiple inelastic features that, based on a Bayesian inference analysis, we assign to phonon modes propagating throughout the nanoparticle interior. Surprisingly, the spectra bear no evidence of propagating modes, which are known to dominate the spectrum of pure water, owing to the scattering that these modes suffer from the sparse nanoparticles in suspension. In perspective, this finding may inspire simple routes to manipulate high-frequency acoustic propagation in hybrid - liquid and solid- materials.

One challenge in studying high-temperature superconductivity (HTSC) stems from a lack of direct experimental evidence linking lattice inhomogeneity and superconductivity. Here, we apply synchrotron hard X-ray nanoimaging and small-angle scattering to reveal a novel micron-scaled ribbon phase in optimally doped Bi2Sr2CaCu2O8+δ (Bi-2212, with δ = 0.1). The morphology of the ribbon-like phase evolves simultaneously with the dome-shaped TC behavior under pressure. X-ray absorption studies show that the increasing of TC is associated with oxygen-hole redistribution in the CuO2 plan, while TC starts to decrease with pressure when oxygen holes become immobile. Additional X-ray irradiation experiments reveal that nanoscaled short-range ordering of oxygen vacancies could further lower TC, which indicates that the optimal TC is affected not only by an optimal morphology of the ribbon phase, but also an optimal distribution of oxygen vacancies. Our studies thereby provide for the first time compelling experimental e...

Radical S-adenosylmethionine (SAM) enzymes are a superfamily of enzymes that use SAM and reduced [4Fe-4S] cluster to generate a 5'-deoxyadenosyl radical to catalyze numerous challenging reactions. We have reported a type of noncanonical radical SAM enzymes in the diphthamide biosynthesis pathway. These enzymes also use SAM and reduced [4Fe-4S] clusters, but generate a 3-amino-3-carboxypropyl (ACP) radical to modify the substrate protein, translation elongation factor 2. The regioselective cleavage of a different C-S bond of the sulfonium center of SAM in these enzymes comparing to canonical radical SAM enzymes is intriguing. Here, we highlight some recent findings in the mechanism of these types of enzymes, showing that the diphthamide biosynthetic radial SAM enzymes bound SAM with a distinct geometry. In this way, the unique iron of the [4Fe-4S] cluster in the enzyme can only attack the carbon on the ACP group to form an organometallic intermediate. The homolysis of the organometallic intermediate releases the ACP radical and generates the EF2 radial.

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film–substrate interface and form an “immobile interfacial layer”, which is believed to be the mechanism behind dewetting suppression. We here report a new mechanism of dewetting suppression from the structural aspect of polymer chains accommodated at the film–substrate interface. Dodecanethiol-functionalized gold (Au) nanoparticles embedded in relatively low molecular weight PS thin films prepared on silicon (Si) substrates were used as a model. We mimicked the previously reported conditions, where the nanoparticles preferentially migrate to the substrate, and successfully stabilized the PS thin films via thermal annealing. A suite of surface-sensitive techniques including atomic force microscopy, grazing incidence small-angle X-ray scattering, X-ray/neutron reflectivity, and sum frequency generation spectroscopy in conjunction with the established solvent leaching process enabled us to unveil the polymer chain...

Colloidal quantum dots can be stabilized in either a polar solvent or a nonpolar solvent depending on their surface chemistry. The former is typically achieved by charge stabilization while the latter by steric hindrance. This allows reversible tuning of their surface polarity for targeted application by engineering their ligand profile. Here we developed a hybrid stabilization approach that leveraged a combination of steric hindrance and charge stabilization simultaneously. We demonstrated this mechanism in a phase transfer process where hexane dispersed and hydrophobic CdSe/CdS core/shell quantum dots were exchanged into the hydrophilic dimethylformamide (DMF) phase. This was achieved by employing both Z-type cadmium acetate and X-type halide ligands. The results suggested only by using this hybrid stabilization strategy were we able to achieve good colloidal stability while preserving their photoluminescence quantum yield. This hybrid ligand strategy may promise new opportunities for the application of QDs in optoelectronic areas.

Incorporation of shape-shifting building blocks into self-assembled systems has emerged as a promising concept for dynamic structural control. The computational work by Nguyen et al. reported in this issue of ACS Nano examines the phase reconfigurations and kinetic pathways for systems built from shape-shifting building blocks. The studies illustrate several unique properties of such systems, including more efficient packings, novel structures that are distinctive from those obtained through conventional self-assembly, and reversible multistep shape-shifting pathways. The proposed assembly strategy is potentially applicable to a diverse range of systems because it relies on a change of geometrical constraints, which are common across all length scales. Recent developments in the areas of responsive materials and self-assembly methods provide feasible platforms for experimental realizations of shape-shifting reconfigurations; such systems might enable the next generation of dynamically switchable materials and reconfigurable devices.

We report a facile, seed-mediated method to synthesize nanoscale gold truncated ditetragonal nanoprisms (TDPs) enclosed by 12 high-index {310} facets. The method leads to the formation of nanoparticles with high size and shape monodispersity and allows for easy surfactant removal. The dependence of particle shape on the synergetic contribution of metallic ions, halide ions, and surfactant adsorbates during synthesis is described. The resulting high-index nanoparticle facets were demonstrated as efficient activators of a supported catalytic material (platinum). A Pt monolayer deposited onto the Au TDP nanofacets with sharp electrochemical signatures exhibits an enhanced catalytic activity.

Hierarchical nanostructures are of particular interest to researchers for their promising applications in functional materials. This work focused on the large-scale construction of 2-fold-symmetrical hierarchical ZnO nanostructure through wet-chemical route on preformed caky Zn substrate via the electroplating method. The result suggested that the preferential layer-by-layer dissolution of Zn plating, the in situ growth of ZnO nanowire arrays, and the gradual dissolution of the Zn substrate with the ongoing synthetic reaction jointly led to the growth of the hierarchical ZnO nanostructure. Meanwhile, the formation of the caky Zn substrate can be attributed to the spiral dislocation growth behavior of Zn plating and the existence of the precipitated H2 bubbles serving as the template. Multiple morphologies of such hierarchical ZnO nanostructure could be readily obtained not only by changing the synthetic conditions, but also by well-designing the structural parameters of the caky Zn substrate through contr...

Photoluminescence quenching of colloidal CdSe core/shell quantum dots (QDs) with CdS, ZnS and CdS/CdZnS/ZnS shells in the presence of hole-transporting materials (HTMs) is studied by means of steady-state and time-resolved photoluminescence spectroscopy. Static quenching is surprisingly found to play an even more important role in the PL quenching process than the dynamic one originating from a hole transfer from QDs to HTMs. The static quenching efficiency of the QDs with single CdS shells of 3 and 6 monolayers is much larger than that of the QDs with a multilayer CdS/CdZnS/ZnS shell. The experimental results are important for understanding the control of the static quenching pathways in QDs by using multishell structures.

Large-scale, well-aligned, and oriented wurtzite ZnS nanobelt arrays have been synthesized by a simple template-free solvothermal reaction and subsequent heat-treatment process. The ZnS nanobelts grow along the [0001] direction perpendicularly on a zinc substrate, which have a thickness of about 30 nm, widths of several hundreds of nanometers, and uniform length up to 4 μm. The selection of Zn foil as the substrate is crucial for the formation of ZnS nanostructured arrays. The concentration of Zn ions, the pH value in the initial precursor solution, and the reaction temperature also have an important influence on the morphology of the final arrays. The formation of the nanobelt arrays are attributed to the structural compatibility of the substrate with ZnS and the growth-rate-dependence of morphology. Importantly, such nanostructured arrays show good field-emission properties with low turn-on fields (3.8 Vμm-1) and high field-enhancement factors (1839). This is attributed to the top edges and corners of t...

Tower-like ZnS nanostructures are facilely synthesized via a ZnS nanoparticle-assisted vapor deposition route. Scanning electron microscopy and transmission microscopy observations show that the tower-like structures are likely to be made up in a layer-by-layer fashion and consist of quasi-hexagonal plates. The growth of nanotowers is initiated by the preferred nucleation on the ZnS nanoparticles precoated on Si substrate, followed by alternate two-dimensional growth of hexagonal plates/layers inside nanotowers and one-dimensional stacking in the direction perpendicular to the plates/layers via vapor-solid growth processes. Such nanotowers, due to the existence of many interfacial defects, display distinct photoluminescence and Raman spectra from nanoplates prepared without the assistance of ZnS nanoparticles. The photoluminescence spectra of the nanotowers show two strong emission bands located at 394 and 592 nm. In Raman spectra, two anomalous modes at 233 and 488 cm-1 are observed.

Highly oriented and densely packed ZnO films of nanorod arrays are formed free of substrate via a chemical vapor deposition (CVD) route. The resulting films are composed of single-crystal ZnO nanorods, which grow along their c-axis paralleling each other. The ZnO nanoclusters form first in the highly saturated vapor environment, followed by preferential growth along their [0001] directions to produce nanorods via a vapor-solid (VS) growth process. During transferring, the nanorods aggregate into films by oriented attachment with assistance of ZnCO 3 . Raman scattering studies confirm that the ZnO nanorods are c-axis oriented and well-aligned as well as being of high-crystal quality. Room-temperature photoluminescence spectrum of such ZnO films exhibit a strong and narrow ultraviolet emission, which facilitates their potential applications in the future photoelectric nanodevices.

In situ neutron reflectivity was used to investigate the effects of density fluctuations on the solubility of supercritical carbon dioxide (scCO2) in polymer thin films. Deuterated polystyrene, deuterated polybutadiene, and the corresponding random copolymer, deuterated styrene-random- butadiene copolymer, as well as deuterated poly(methyl methacrylate) were investigated. Data were obtained as a function of pressure under two isothermal conditions (T ) 36 and 50 °C). All the polymer films used showed anomalous swelling and CO2 sorption on the density fluctuation ridge in the P-T phase diagram of CO2. We found that the magnitude of the swelling was a function of the elasticity of the films rather than the bulk solubility of CO2. The enhanced miscibility of the rubber/CO2 systems, which are very poor in bulk, was found to be almost identical to that of the silicon rubber/CO2 mixture, which is one of the highly miscible polymeric materials under moderate CO2 conditions.