Microbial green synthesis of luminescent terbium sulfide nanoparticles using E. Coli: a rare earth element detoxification mechanism.

BACKGROUND: Rare-earth sulfide nanoparticles (NPs) could harness the optical and magnetic features of rare-earth ions for applications in nanotechnology. However, reports of their synthesis are scarce and typically require high temperatures and long synthesis times. RESULTS: Here we present a biosynthesis of terbium sulfide (TbS) NPs using microorganisms, identifying conditions that allow Escherichia coli to extracellularly produce TbS NPs in aqueous media at 37 °C by controlling cellular sulfur metabolism to produce a high concentration of sulfide ions. Electron microscopy revealed ultrasmall spherical NPs with a mean diameter of 4.1 ± 1.3 nm. Electron diffraction indicated a high degree of crystallinity, while elemental mapping confirmed colocalization of terbium and sulfur. The NPs exhibit characteristic absorbance and luminescence of terbium, with downshifting quantum yield (QY) reaching 28.3% and an emission lifetime of ~ 2 ms. CONCLUSIONS: This high QY and long emission lifetime is unusual in a neat rare-earth compound; it is typically associated with rare-earth ions doped into another crystalline lattice to avoid non-radiative cross relaxation. This suggests a reduced role of nonradiative processes in these terbium-based NPs. This is, to our knowledge, the first report revealing the advantage of biosynthesis over chemical synthesis for Rare Earth Element (REE) based NPs, opening routes to new REE-based nanocrystals.

Intramolecular Catalytic Hydrogen Atom Transfer (CHAT).

Intramolecular catalysis (IntraCat) is the acceleration of a process at one site of a molecule catalyzed by a functional group in the same molecule; an external agent such as a solvent typically facilitates it. Here, we report a general first-principles-based IntraCat mechanism, which strictly occurs within a single molecule with no coreagent being involved─we call it intramolecular catalytic transfer of hydrogen atoms (CHAT). A reactive part of a molecule (chat catalyst moiety or chat agent, represented by -OOH, -COOH, -SH, -CH2OH, -HPO4, or another bifunctional H-donor/acceptor group) catalyzes an interconversion process, such as keto-enol or amino-imino tautomerization, and cyclization in the same molecule, while being regenerated in the process. It can thus be regarded as an intramolecular version of the intermolecular H atom transfer processes mediated by an external molecular catalyst, e.g., dihydrogen, water, or a carboxylic acid. Earlier, we proposed a general mechanistic systematization of intermolecular processes, illustrated in the simplest case of the H2-mediated reactions classified as dihydrogen catalysis [Asatryan, R.; et al. Catal. Rev.: Sci. Eng., 2014, 56, 403-475]. Following this systematization, the CHAT catalysis belongs to the category of relay transfer of H atoms, albeit in an intramolecular manner. A broader class of intramolecular processes includes all types of H-transfer reactions stimulated by an H-migration, which we call self-catalyzed H atom transfer (SC-HAT). The CHAT mechanism comprises a subset of SC-HAT in which the catalytic moiety is regenerated (i.e., acts as a true catalyst and not a reagent). We provide several characteristic examples of CHAT mechanism based on detailed analysis of the corresponding potential energy surfaces. All such cases showed a dramatically reduced activation barrier relative to the corresponding uncatalyzed H-transfer reactions. For example, we show that CHAT can facilitate long-range H-migration in larger molecules and can occur multiple times in one molecule with multiple interconverting groups. It also facilitates amino-imino tautomerization of unsaturated GABA-analogues and peptides, as well as intramolecular cyclization processes to form heterocycles, e.g., oxygenated rings. CHAT pathways may also explain the pH-dependent increase of mutarotation rate of glucose-6-phosphate demonstrated in pioneering experiments that introduced the classical IntraCat concept. In addition, we identify a ground electronic state CHAT pathway as an alternative to the UV-promoted long-range molecular crane keto-enol conversion with a remarkably low activation energy. To initially assess the possible impact of the new keto-enol conversion pathway on combustion of n-alkanes, we present a detailed kinetic analysis of isomerization and decomposition of pentane-2,4-ketohydroperoxide (2,4-KHP). The results are compared with key alternative reactions, including direct dissociation and Korcek channels (for which a new alkyl group migration channel is also identified), revealing the competitiveness of the CHAT pathway across a range of conditions. Taken together, this work provides insight into a general class of reaction pathways that has not previously being systematically considered and that may occur in a broad range of contexts from combustion to atmospheric chemistry to biochemistry.

Challenging thermodynamics: combining immiscible elements in a single-phase nano-ceramic.

The Hume-Rothery rules governing solid-state miscibility limit the compositional space for new inorganic material discovery. Here, we report a non-equilibrium, one-step, and scalable flame synthesis method to overcome thermodynamic limits and incorporate immiscible elements into single phase ceramic nanoshells. Starting from prototype examples including (NiMg)O, (NiAl)Ox, and (NiZr)Ox, we then extend this method to a broad range of Ni-containing ceramic solid solutions, and finally to general binary combinations of elements. Furthermore, we report an "encapsulated exsolution" phenomenon observed upon reducing the metastable porous (Ni0.07Al0.93)Ox to create ultra-stable Ni nanoparticles embedded within the walls of porous Al2O3 nanoshells. This nanoconfined structure demonstrated high sintering resistance during 640 h of catalysis of CO2 reforming of methane, maintaining constant 96% CH4 and CO2 conversion at 800 °C and dramatically outperforming conventional catalysts. Our findings could greatly expand opportunities to develop novel inorganic energy, structural, and functional materials.

Plasticizer-Induced Enhancement of Mesoscale Dissymmetry in Thin Films of Chiral Polymers with Variable Chain Length.

Conjugated polymers with chiral side chains are of interest in areas including chiral photonics, optoelectronics, and chemical and biological sensing. However, the low dissymmetry factors of most neat polymer thin films have limited their practical application. Here, a robust method to increase the absorption dissymmetry factor in a poly-fluorene-thiophene (PF8TS series) system is demonstrated by varying molecular weight and introducing an achiral plasticizer, polyethylene mono alcohol (PEM-OH). Extending chain length within the optimal range and adding this long-chain alcohol significantly enhance the chiroptical properties of spin-coated and annealed thin films. Mueller matrix spectroscopic ellipsometry (MMSE) analysis shows good agreement with the steady-state transmission measurements confirming a strong chiral response (circular dichroism (CD) and circular birefringence (CB)), ruling out linear dichroism, birefringence, and specific reflection effects. Solid-state NMR studies of annealed hybrid chiral polymer systems show enhancement of signals associated with aromatic π-stacked backbone and the ordered side-chain conformations. Further studies using Raman spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry (DSC), atomic force microscopy (AFM), and polarized optical microscopy (POM) indicate that PEM-OH facilitates mesoscopic crystal domain ordering upon annealing. This provides new insights into routes for tuning optical activity in conjugated polymers.

Palladium-Percolated Networks Enabled by Low Loadings of Branched Nanorods for Enhanced H2 Separations.

Nanoparticles (NPs) at high loadings are often used in mixed matrix membranes (MMMs) to improve gas separation properties, but they can lead to defects and poor processability that impede membrane fabrication. Herein, it is demonstrated that branched nanorods (NRs) with controlled aspect ratios can significantly reduce the required loading to achieve superior gas separation properties while maintaining excellent processability, as demonstrated by the dispersion of palladium (Pd) NRs in polybenzimidazole for H2 /CO2 separation. Increasing the aspect ratio from 1 for NPs to 40 for NRs decreases the percolation threshold volume fraction by a factor of 30, from 0.35 to 0.011. An MMM with percolated networks formed by Pd NRs at a volume fraction of 0.039 exhibits H2 permeability of 110 Barrer and H2 /CO2 selectivity of 31 when challenged with simulated syngas at 200 °C, surpassing Robeson's upper bound. This work highlights the advantage of NRs over NPs and nanowires and shows that right-sizing nanofillers in MMMs is critical to construct highly sieving pathways at minimal loadings. This work paves the way for this general feature to be applied across materials systems for a variety of chemical separations.

Branching phenomena in nanostructure synthesis illuminated by the study of Ni-based nanocomposites.

Branching phenomena are ubiquitous in both natural and artificial crystallization processes. The branched nanostructures' emergent properties depend upon their structures, but their structural tunability is limited by an inadequate understanding of their formation mechanisms. Here we developed an ensemble of Nickel-Based nano-Composites (NBCs) to investigate branching phenomena in solution-phase synthesis with precision and in depth. NBCs of 24 morphologies, including dots, core@shell dots, hollow shells, clusters, polyhedra, platelets, dendrites, urchins, and dandelions, were synthesized through systematic adjustment of multiple synthesis parameters. Relationships between the synthesis parameters and the resultant morphologies were analyzed. Classical or non-classical models of nucleation, nascent growth, 1D growth, 2D growth, 3D reconstruction, aggregation, and carburization were defined individually and then integrated to provide a holistic view of the formation mechanism of branched NBCs. Finally, guidelines were extracted and verified to guide the rational solution-phase syntheses of branched nanomaterials with emergent biological, chemical, and physical properties for potential applications in immunology, catalysis, energy storage, and optics. Demonstrating a systematic approach for deconvoluting the formation mechanism and enhancing the synthesis tunability, this work is intended to benefit the conception, development, and improvement of analogous artificial branched nanostructures. Moreover, the progress on this front of synthesis science would, hopefully, deepen our understanding of branching phenomena in nature.

Ultrasensitive Room-Temperature NO2 Detection Using SnS2/MWCNT Composites and Accelerated Recovery Kinetics by UV Activation.

High performance with lower power consumption is one among the essential features of a sensing device. Minute traces of hazardous gases such as NO2 are difficult to detect. Tin disulfide (SnS2) nanosheets have emerged as a promising NO2 sensor. However, their poor room-temperature conductivity gives rise to inferior sensitivity and sluggish recovery rates, thereby hindering their applications. To mitigate this problem, we present a low-cost ultrasensitive NO2 gas sensor with tin disulfide/multiwalled carbon nanotube (SnS2/MWCNT) nanocomposites, prepared using a single-step hydrothermal method, as sensing elements. Relative to pure SnS2, the conductivity of nanocomposites improved significantly. The sensor displayed a decrease in resistance when exposed to NO2, an oxidizing gas, and exhibited p-type conduction, also confirmed in separate Mott-Schottky measurements. At a temperature of 20 °C, the sensor device has a relative response of about ≈5% (3%) for 25 ppb (1 ppb) of NO2 with complete recovery in air (10 min) and excellent recovery rates with UV activation (0.3 min). A theoretical lower limit of detection (LOD) of 7 ppt implies greater sensitivity than all previously reported SnS2-based gas sensors, to the best of our knowledge. The improved sensing characteristics were attributed to the formation of nano p-n heterojunctions, which enhances the charge transport and gives rise to faster response. The composite sensor also demonstrated good NO2 selectivity against a variety of oxidizing and reducing gases, as well as excellent stability and long-term durability. This work will provide a fresh perspective on SnS2-based composite materials for practical gas sensors.

Paper-Based Hydrogen Sensors Using Ultrathin Palladium Nanowires.

Hydrogen (H2), as a chemical energy carrier, is a cleaner alternative to conventional fossil fuels with zero carbon emission and high energy density. The development of fast, low-cost, and sensitive H2 detection systems is important for the widespread adoption of H2 technologies. Paper is an environment-friendly, porous, and flexible material with great potential for use in sustainable electronics. Here, we report a paper-based sensor for room-temperature H2 detection using ultrathin palladium nanowires (PdNWs). To elucidate the sensing mechanism, we compare the performance of polycrystalline and quasi-single-crystalline PdNWs. The polycrystalline PdNWs showed a response of 4.3% to 1 vol % H2 with response and recovery times of 4.9 and 10.6 s, while quasi-single-crystalline PdNWs showed a response of 8% to 1 vol % H2 with response and recovery times of 9.3 and 13.0 s, respectively. The polycrystalline PdNWs show excellent selectivity, stability, and sensitivity, with a limit of detection of 10 ppm H2 in air. The fast response of ultrathin polycrystalline PdNW paper-based sensors arises from the synergistic effects of their ultrasmall diameter, high-index surface facets, strain-coupled grain boundaries, and porous paper substrate. This paper-based sensor is one of the fastest chemiresistive H2 sensors reported and is potentially orders of magnitude less expensive than current state-of-the-art H2-sensing solutions. This brings low-cost, room-temperature chemiresistive H2 sensing closer to the performance of ultrafast optical sensors and high-temperature metal oxide-based sensors.

Strontium-loaded hydrogel scaffolds to promote gingival fibroblast function.

Dental implant clinical success is dependent on effective peri-implant tissue attachment to the trans-mucosal portion following placement. Modification of transmucosal implant surfaces can improve cellular adhesion and function leading to formation of an effective soft-tissue seal during healing, of which gingival fibroblasts are prominent cells to migrate to repair wounds and crucial for the development of a collagen rich connective tissue. Biocompatible loaded scaffold materials have been developed to allow local release of molecules with effective biological activity. Our previous studies indicate that strontium can promote gingival fibroblast metabolism, decrease apoptosis and support adhesion to titanium healing abutments. In this study, we developed a strontium-loaded alginate hydrogel scaffold which can be easily personalized to fit over any size and shape of implant transmucosal collar or healing abutment. Results indicate that biologically active strontium ions are effectively released from loaded alginate hydrogel material to promote fibroblast viability and migration to repair in vitro wounds similar to that of strontium citrate solution. Overall, this novel strontium-loaded alginate scaffold device displays good biocompatibility and functionality, demonstrating high potential as a system to provide local delivery of strontium to improve peri-implant mucosal healing following implant placement and clinical success.

Automated Generation of a Compact Chemical Kinetic Model for n-Pentane Combustion.

We have employed automated mechanism generation tools to construct a detailed chemical kinetic model for combustion of n-pentane, as a step toward the generation of compact kinetic models for larger alkanes. Pentane is of particular interest as a prototype for combustion of alkanes and as the smallest paraffin employed as a hybrid rocket fuel, albeit at cryogenic conditions. A reaction mechanism for pentane combustion thus provides a foundation for modeling combustion of extra-large alkanes (paraffins) that are of more practical interest as hybrid rocket fuels, for which manual construction becomes infeasible. Here, an n-pentane combustion kinetic model is developed using the open-source software package Reaction Mechanism Generator (RMG). The model was generated and tested across a range of temperatures (650 to 1350 K) and equivalence ratios (0.5, 1.0, 2.0) at pressures of 1 and 10 atm. Available thermodynamic and kinetic databases were incorporated wherever possible. Predictions using the mechanism were validated against the published laminar burning velocities (Su) and ignition delay times (IDT) of n-pentane. To improve the model performance, a comprehensive analysis, including reaction path and sensitivity analyses of n-pentane oxidation, was performed, leading us to modify the thermochemistry and rate parameters for a few key species and reactions. These were combined as a separate data set, an RMG library, that was then used during mechanism generation. The resulting model predicted IDTs as accurately as the best manually constructed mechanisms, while remaining much more compact. It predicted flame speeds to within 10% of published experimental results. The degree of success of automated mechanism generation for this case suggests that it can be extended to construct reliable and compact models for combustion of larger n-alkanes, particularly when using this mechanism as a seed submodel.

Modulating the Chiroptical Response of Chiral Polymers with Extended Conjugation within the Structural Building Blocks.

Advancing the emerging area of chiral photonics requires modeling-guided concepts of chiral material design to enhance optical activity and associated optical rotatory dispersion. Herein, we introduce conformational engineering achieved by tuning polymer backbone conjugation through introduction of thiophene structural units in a chiral fluorene polymer backbone. Our theoretical calculations reveal a relationship between the structural conformation and the resultant rotational strength. We further synthesize a series of chiral fluorene-based polymers copolymerized with thiophene whose optical chirality trend is in qualitative agreement with predictions of our quantum chemical calculations. Varying the number of thiophene units in the monomer building block allows us to modulate the rotational strength by tuning the intrafibril helicity of single-stranded polymer chains, whereby the monomer conjugation is retained throughout the whole length of the polymer backbone. Our design concept delineates an underexamined approach: the concept of tuning backbone conjugation and helicity within the main chain to enhance the optical activity of chiral polymer systems.

In Situ Imaging of Ion Motion in a Single Nanoparticle: Structural Transformations in Selenium Nanoparticles.

Intraparticle ion motions are critical to the structure and properties of nanomaterials, but rarely disclosed. Herein, in situ visualization of ion motions in a single nanoparticle is presented by dark-field microscopy imaging, which shows HgCl2 -induced structural transformation of amorphous selenium nanoparticles (SeNPs) with the main composition of Se8 . Owing to the high binding affinity with selenium and coulomb interactions, Hg2+ ions can permeate into the interior of SeNPs, making the amorphous Se8 turn to polycrystalline Hg3 Se2 Cl2 . As a proof of concept, SeNPs then serve as a highly effective scavenger for selective removal of Hg2+ ions from solution. This new finding offers visual proof for the photophysical process involving intraparticle ion motion, demonstrating that tracking the ion motions is a novel strategy to comprehend the formation mechanism with the purpose of developing new nanostructures like nanoalloys and nano metal compounds.

Humidity-Tolerant Room-Temperature Selective Dual Sensing and Discrimination of NH3 and NO Using a WS2/MWCNT Composite.

Continuous detection of toxic and hazardous gases like nitric oxide (NO) and ammonia (NH3) is needed for environmental management and noninvasive diagnosis of various diseases. However, to the best of our knowledge, dual detection of these two gases has not been previously reported. To address the challenge, we demonstrate the design and fabrication of low-cost NH3 and NO dual gas sensors using tungsten disulfide/multiwall carbon nanotube (WS2/MWCNT) nanocomposites as sensing channels which maintained their performance in a humid environment. The composite-based device has shown successful dual detection at temperatures down to 18 °C and relative humidity of 90%. For 0.1 ppm ammonia, it exhibited a p-type conduction with response and recovery times of 102 and 261 s, respectively; on the other hand, with NO (10 ppb, n-type), these times were 285 and 198 s, respectively. The device with 5 mg MWCNTs possesses a superior selectivity along with a relative response of ≈7% (5 ppb) and ≈5% (0.1 ppm) for NO and NH3, respectively, at 18 °C. The response is less affected by relative humidity, and this is attributed to the presence of MWCNTs that are hydrophobic in nature. Upon simultaneous exposure to NO (5-10 ppb) and NH3 (0.1-5 ppm), the response was dominated by NO, implying clear discrimination to the simultaneous presence of these two gases. We propose a sensing mechanism based on adsorption/desportion and accompanied charge transfer between the adsorbed gas molecules and sensing surface. The results suggest that an optimized weight ratio of WS2 and MWCNTs could govern favorable sensing conditions for a particular gas molecule.

A General Route to Flame Aerosol Synthesis and In Situ Functionalization of Mesoporous Silica.

Mesoporous silica is a versatile material for energy, environmental, and medical applications. Here, for the first time, we report a flame aerosol synthesis method for a class of mesoporous silica with hollow structure and specific surface area exceeding 1000 m2 g-1 . We show its superior performance in water purification, as a drug carrier, and in thermal insulation. Moreover, we propose a general route to produce mesoporous nanoshell-supported nanocatalysts by in situ decoration with active nanoclusters, including noble metal (Pt/SiO2 ), transition metal (Ni/SiO2 ), metal oxide (CrO3 /SiO2 ), and alumina support (Co/Al2 O3 ). As a prototypical application, we perform dry reforming of methane using Ni/SiO2 , achieving constant 97 % CH4 and CO2 conversions for more than 200 hours, dramatically outperforming an MCM-41 supported Ni catalyst. This work provides a scalable strategy to produce mesoporous nanoshells and proposes an in situ functionalization mechanism to design and produce flexible catalysts for many reactions.

Mechanical characterization and adhesive properties of a dental adhesive modified with a polymer antibiotic conjugate.

This study is a follow up investigation on recent work by our group demonstrating synthesis, release and strong antibacterial character of resins modified with penicillin V (PV)-based polymer-antibiotic conjugates (PACs). Here, we aimed to evaluate the mechanical, bonding, and other relevant biomedical properties of a commercial adhesive resin modified with PV-PAC. Single Bond Plus (SB+) was modified with PAC containing 1.8 wt% conjugated PV. Adhesive resins were bonded to dentin from extracted human molars and restorative resin added. Beams of cross-sectional area of 0.9 ± 0.1 mm (Kutsch and Young, 2011) (n = 20) were obtained from the molars and tested for micro-tensile bond strength (µTBS) at 24 h and 4 months. For cohesive strength, hourglass beams (10 × 2 × 1 mm; n = 10) were assessed for ultimate tensile strength (UTS), beam-shaped specimens (25x2x2 mm; n = 10) evaluated for flexural strength and modulus (FS/FM) via three-point bending, and cylindrical specimens (3 × 2 mm; n = 10) assessed for ultimate compressive strength (UCS). For surface micro-hardness (MH), cylindrical specimens (3 × 2 mm; n = 6) were assessed before and after an EtOH challenge. The degree of conversion (DC) (5 × 1 mm; n = 6) was determined based on changes in absorbance ratio between peaks at ∼1637 cm-1 and ∼1608 cm-1 before and after curing of adhesive resins using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. To monitor water uptake and diffusion kinetics over a 28-day period, specimens (5 × 1mm) were desiccated, weighed and stored in deionized water. Control and PV-PAC modified adhesive resins demonstrated similar µTBS at 24 h and 4 months; both showing decrease in values after 4 months (p = 0.001 and 0.004). No significant differences between adhesive resins were shown in UTS, FS/FM or UCS (p<0.05). MH of PV-PAC adhesive resin was significantly reduced relative to the control (p<0.001). The DC values of the adhesive resins were not significantly different. While sorption and solubility were no different between materials, the diffusion coefficient of PV-PAC modified adhesive resin was higher than the control (p<0.001). We conclude that incorporation of PV-PAC with 1.8 wt% PV into an adhesive resin does not adversely affect its mechanical, bonding, and physical properties, thus providing a promising option for materials with long-term antibacterial character and on-demand release.

Palladium Nanosheet-Based Dual Gas Sensors for Sensitive Room-Temperature Hydrogen and Carbon Monoxide Detection.

Palladium has long been explored for use in gas sensors because of its excellent catalytic properties and its unique property of forming hydrides in the presence of H2. However, pure Pd-based sensors usually suffer from low response and a relatively high limit of detection. Palladium nanosheets (PdNS) are of particular interest for gas sensing applications due to their high surface area and excellent electrical conductivity. Here, we demonstrate the design and fabrication of low-cost PdNS-based dual gas sensors for room-temperature detection of H2 and CO over a wide concentration range. We fabricated sensors using multiwalled carbon nanotube@PdNS (MWCNT@PdNS) composites and compared their performance against pure PdNS devices for hydrogen sensing based on electrical resistive response. Devices using PdNS alone had a response and response time of 0.4% and 50 s, respectively, to 1% H2 in air. MWCNT@PdNS (1:5 mass ratio) showed enhanced performance at a lower hydrogen concentration with a limit of detection (LODH2) of 5 ppm. Nearly an order of magnitude increase in response was observed on increasing the amount of MWCNT to 50 mass % in the nanocomposite, but the response fell off at low H2 concentration. Overall, these PdNS-based sensors were found to show good repeatability, stability, and performance under humid conditions. Their response was selective for H2versus CH4, CO2, and NH3; the response to CO was comparable in magnitude but opposite in sign to the response to H2. Upon simultaneous exposure to equal concentrations (10 ppm each) of H2 and CO, the response to CO was dominant. The PdNS showed high sensitivity to CO, detecting as little as 1 ppm CO in air at room temperature. The sensitivity to CO could be used either in a stand-alone room-temperature CO detector, where H2 is known not to be present, or in combination with CO and combustible gas detectors to distinguish H2 from other combustible gases.

Magnetically Controllable Flowerlike, Polyhedral Ag-Cu-Co3O4 for Surface-Enhanced Raman Scattering.

Syntheses of Cu-, Ag-, and Ag-Cu-Co3O4 nanomaterials are of interest for a wide range of applications including electrochemistry, thermal catalysis, energy storage, and electronics. However, Co3O4-based nanomaterials have not been explored for surface-enhanced Raman scattering (SERS). Here, we present Cu-, Ag-, and Ag-Cu-Co3O4 nanomaterials of a hierarchical flower shape comprising two separate phases: a pure Cu or Ag core and multiple Co3O4 branches, in which the optical properties of the core and the magnetic properties of the branches are integrated. In addition, a series of nonmagnetic Cu-dominant Cu-Co-O polyhedra without Co3O4 branches were derived from Cu-Co3O4. The polyhedron morphology can be controlled and transformed among cubes, cuboctahedra, and truncated octahedra by tuning the amounts of ligands and additives to vary the potential energy and growth rate of specific crystal facets. The flowerlike Cu-, Ag-, and Ag-Cu-Co3O4 were characterized for SERS enhancement, showing that Ag-Cu-Co3O4 does not enhance SERS from 4-mercaptobenzoic acid (4-MBA) but dramatically and selectively does so for adsorbed rhodamine 6G. Obviously, the synergy of Ag and Cu within the Co3O4 flower constraint promotes the SERS activity. This type of spinel with not only excellent SERS activity but also ferromagnetism could be of great potential in tandem SERS detection/magnetic separation and related applications.

Tuning Materials-Binding Peptide Sequences toward Gold- and Silver-Binding Selectivity with Bayesian Optimization.

Peptide sequence engineering can potentially deliver materials-selective binding capabilities, which would be highly attractive in numerous biotic and abiotic nanomaterials applications. However, the number of known materials-selective peptide sequences is small, and identification of new sequences is laborious and haphazard. Previous attempts have sought to use machine learning and other informatics approaches that rely on existing data sets to accelerate the discovery of materials-selective peptides, but too few materials-selective sequences are known to enable reliable prediction. Moreover, this knowledge base is expensive to expand. Here, we combine a comprehensive and integrated experimental and modeling effort and introduce a Bayesian Effective Search for Optimal Sequences (BESOS) approach to address this challenge. Through this combined approach, we significantly expand the data set of Au-selective peptide sequences and identify an additional Ag-selective peptide sequence. Analysis of the binding motifs for the Ag-binders offers a roadmap for future prediction with machine learning, which should guide identification of further Ag-selective sequences. These discoveries will enable wider and more versatile integration of Ag nanoparticles in biological platforms.

Scalable Polymeric Few-Nanometer Organosilica Membranes with Hydrothermal Stability for Selective Hydrogen Separation.

Nanoporous silica membranes exhibit excellent H2/CO2 separation properties for sustainable H2 production and CO2 capture but are prepared via complicated thermal processes above 400 °C, which prevent their scalable production at a low cost. Here, we demonstrate the rapid fabrication (within 2 min) of ultrathin silica-like membranes (∼3 nm) via an oxygen plasma treatment of polydimethylsiloxane-based thin-film composite membranes at 20 °C. The resulting organosilica membranes unexpectedly exhibit H2 permeance of 280-930 GPU (1 GPU = 3.347 × 10-10 mol m-2 s-1 Pa-1) and H2/CO2 selectivity of 93-32 at 200 °C, far surpassing state-of-the-art membranes and Robeson's upper bound for H2/CO2 separation. When challenged with a 3 d simulated syngas test containing water vapor at 200 °C and a 340 d stability test, the membrane shows durable separation performance and excellent hydrothermal stability. The robust H2/CO2 separation properties coupled with excellent scalability demonstrate the great potential of these organosilica membranes for economic H2 production with minimal carbon emissions.

Vapor-phase production of nanomaterials.

The synthesis of nanomaterials, with characteristic dimensions of 1 to 100 nm, is a key component of nanotechnology. Vapor-phase synthesis of nanomaterials has numerous advantages such as high product purity, high-throughput continuous operation, and scalability that have made it the dominant approach for the commercial synthesis of nanomaterials. At the same time, this class of methods has great potential for expanded use in research and development. Here, we present a broad review of progress in vapor-phase nanomaterial synthesis. We describe physically-based vapor-phase synthesis methods including inert gas condensation, spark discharge generation, and pulsed laser ablation; plasma processing methods including thermal- and non-thermal plasma processing; and chemically-based vapor-phase synthesis methods including chemical vapor condensation, flame-based aerosol synthesis, spray pyrolysis, and laser pyrolysis. In addition, we summarize the nanomaterials produced by each method, along with representative applications, and describe the synthesis of the most important materials produced by each method in greater detail.