An Intrinsically Disordered Peptide from Ebola Virus VP35 Controls Viral RNA Synthesis by Modulating Nucleoprotein-RNA Interactions
Abstract not provided
Leung, Daisy W.↗
SEARCH · Engineering Papers
Results for “Synthesis”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Synthesis of oxy-hydroxyfluorinated anatase nanoparticles grown on carbon nanotubes [Synthesis of oxy-hydroxyfluorinated anatase grown on carbon nanotubes]
The synthesis of composite materials containing carbon nanotubes (CNTs) and inorganic nanocrystals is of interest to combine the specific properties of each components. While literature provides broad studies on the growth of anatase TiO 2 onto CNTs, it has never been reported how the presence of aqueous HF could affect the chemical composition of CNTs. Here, we demonstrated that CNTs are inactive toward fluorination during the solvothermal synthesis of an oxy-hydroxyfluorinated compound featuring the anatase-type structure. We further showed that functionalized CNTs offer nucleation sites that favor nanocrystals growth. As a result, the prepared composite features CNTs that are decorated by anatase nanocrystals. The results also showed that, in this condition, titanium alkoxide readily react with HF via a fluorolysis reaction allowing stabilizing high content of fluorine within the anatase network.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
New Synthesis Strategies to Improve Co-Free LiNi0.5Mn0.5O2 Cathodes: Early Transition Metal d0 Dopants and Manganese Pyrophosphate Coating
In this work, we report solution-based doping and coating strategies to improve the electrochemical performance of the Co-free layered oxide cathode LiNi0.5Mn0.5O2 (LNMO). Small amounts of d0 dopants (e.g., Mo6+and Ti4+, 0.5-1 at. %) increase the cathode’s specific capacity, cycling stability, and rate capability. More specifically, a Mo-doped cathode with the nominal composition LiNi0.495Mn0.495Mo0.01O2 achieves a high reversible capacity of 180 mAh/g at 20 mA/g with good retention at higher rates (e.g., 120 mAh/g at 100 mA/g). Effects of 1 at.% Mo dopant on the cathode structure were studied using a suite of characterization tools including X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). These measurements demonstrate that Mo6+ reduces Li+/Ni2+cation mixing and mitigates undesirable phase transformations near the cathode surface during cycling. This work also reports the use of an inorganic Mn2P2O7 coating which enhances cycling stability, presumably through formation of a stable cathode electrolyte interphase (CEI) layer. Overall, the synthesis approaches reported herein are quite general and can potentially be expanded to other high voltage LIB cathodes.
Co-free cathodes, d0 cation, pyrophosphate coating↗
Synthesis-dependent properties of barlowite and Zn-substituted barlowite
The mineral barlowite, Cu4(OH)6FBr, has been the focus of recent attention due to the possibility of substituting the interlayer Cu2+ site with non-magnetic ions to develop new quantum spin liquid materials. We re-examine previous methods of synthesizing barlowite and describe a novel hydrothermal synthesis method that produces large single crystals of barlowite and Zn-substituted barlowite (Cu3ZnxCu1–x(OH)6FBr). The two synthesis techniques yield barlowite with indistinguishable crystal structures and spectroscopic properties at room temperature; however, the magnetic ordering temperatures differ by 4 K, and the thermodynamic properties are clearly different. The dependence of properties upon synthetic conditions implies that the defect chemistry of barlowite and related materials is complex and significant. Zn-substituted barlowite exhibits a lack of magnetic order down to T = 2 K, characteristic of a quantum spin liquid, and we provide a synthetic route towards producing large crystals suitable for neutron scattering.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Predictive Synthesis
Current solid state synthesis intrinsically involves a multidimensional space which is challenging to parametrize and predict. The diversity of extended structures comes from the diversity of basic properties of elements of the Periodic system which may exhibit a variety of bonding modes. The fundamental challenges of prediction of the preparative outcome are further complicated by practical synthetic issues. Current development in computational and experimental methods calls for collaborative efforts to make solid state synthesis more predictable. Overall, this Perspective discusses several steps in this direction, including integration of predictions of synthetic conditions with new structure predictions, widespread in situ studies to obtain a panoramic view of the reaction mechanism, and the creation of a synthetic database to properly document all synthetic efforts, including the unsuccessful ones.
36 MATERIALS SCIENCE↗
Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La 2 MnNiO 6
Over the past decades a confluence of advanced synthesis techniques, data-driven characterization, and rapid increases in computing power has sparked a renaissance in materials engineering. The emerging “materials-by-design” approach, while radically transforming the development of multicomponent systems, has tended to overlook the complex kinetic pathways that define materials synthesis. Although we are able to envision almost limitless materials combinations, we are unable to synthesize all of them in practice, since existing characterization and modeling approaches often fail to capture the inherent complexity of such systems. There is currently a disconnect between highly local structural characterization and macroscale properties measurements, resulting in oversimplified or incomplete structure-property models. Here we describe a multi-technique approach that combines aberration-corrected transmission electron microscopy with emerging oxide atom probe tomography to measure chemical ordering and extended defects in the model complex oxide, La2MnNiO6. We visualize cation ordering, as well as a three-dimensional network of secondary phases, which we describe in terms of ab initio structure calculations. We propose a defect model in which these phases alter their surrounding octahedral environment, severely disrupting cation superexchange. Through this array of experimental and theoretical techniques, we uncover fundamental structure-property relationships and illustrate a new approach to engineer complex, multicomponent systems.
atom probe tomography↗
Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides
Abstract not provided
White, Miles A.↗
Synthesis and Characterization of MgCr 2 S 4 Thiospinel as a Potential Magnesium Cathode
Magnesium-ion batteries are a promising energy storage technology because of their higher theoretical energy density and lower cost of raw materials. Among the major challenges has been the identification of cathode materials that demonstrate capacities and voltages similar to lithium-ion systems. Thiospinels represent an attractive choice for new Mg-ion cathode materials owing to their interconnected diffusion pathways and demonstrated high cation mobility in numerous systems. Reported magnesium thiospinels, however, contain redox inactive metals such as scandium or indium, or have low voltages, such as MgTi 2 S 4 . This article describes the direct synthesis and structural and electrochemical characterization of MgCr 2 S 4 , a new thiospinel containing the redox active metal chromium and discusses its physical properties and potential as a magnesium battery cathode. However, as chromium(III) is quite stable against oxidation in sulfides, removing magnesium from the material remains a significant challenge. Finally, early attempts at both chemical and electrochemical demagnesiation are discussed.
25 ENERGY STORAGE↗
Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope
Abstract not provided
Abellan, Patricia↗
Synthesis of Acid Hydrazides from Carboxylic Acids in Continuous Flow
A concise methodology for the synthesis of acid hydrazides from carboxylic acids via a continuous flow process in yields ranging from 65 to 91% is described. Using short residence times of between 13 and 25 mins, the conditions proved amenable to a variety of mono- and diacids, including aliphatic, aromatic, and heteroaromatic functionalities. Furthermore, to demonstrate scalability, a large-scale (200 g) synthesis of azelaic dihydrazide was conducted over a continuous run of 9 h with an 86% overall yield, equating to a 22 g/h output.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sequential Infiltration Synthesis for the Design of Low Refractive Index Surface Coatings with Controllable Thickness
Control over refractive index and thickness of surface coatings is central to the design of low refraction films used in applications ranging from optical computing to antireflective coatings. Here, we introduce gas-phase sequential infiltration synthesis (SIS) as a robust, powerful, and efficient approach to deposit conformal coatings with very low refractive indices. We demonstrate that the refractive indices of inorganic coatings can be efficiently tuned by the number of cycles used in the SIS process, composition, and selective swelling of the of the polymer template. We show that the refractive index of Al2O3 can be lowered from 1.76 down to 1.1 using this method. The thickness of the Al2O3 coating can be efficiently controlled by the swelling of the block copolymer template in ethanol at elevated temperature, thereby enabling deposition of both single-layer and graded-index broadband antireflective coatings. Using this technique, Fresnel reflections of glass can be reduced to as low as 0.1% under normal illumination over a broad spectral range.
Berman, Diana↗
Direct Aqueous-Phase Synthesis of Sub-10 nm “Luminous Pearls” with Enhanced in vivo Renewable Near-Infrared persistent luminescence
Near-infrared persistent luminescence nanoparticles (PLNPs) possess unique near-infrared persistent luminescence properties. They have recently been emerging as important materials for a wide variety of applications in chemistry and biology. Yet, they must endure high-temperature solid-state annealing reactions and subsequent complicated physical post-treatments. Herein, we report on a first direct aqueous-phase chemical synthesis route of NIR PLNPs and present their enhanced in vivo renewable near-infrared persistent luminescence. Our method leads to monodisperse PL nanoparticles as small as ca. 8 nm. More importantly, such sub-10 nm nanocrystals are readily dispersed, functionalized as well as form stable colloidal solutions in aqueous solution and cell culture medium for biological applications. Under bio-tissue penetrable red-light excitation, we found that such nanocrystals possess superior renewable PL photoluminescence in vitro and in vivo than current larger counterparts made by existing methods. We believe that this solid-state-reaction-free chemical approach overcomes the current key roadblock in regard to PLNP development, and thus will pave the way to broad use of these advanced miniature “luminous pearls” in photonics and biophotonics.
Luminous Pearls, Near-Infrared persistent luminesc↗
Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production
The reaction of ozone with isoprene, one of the most abundant volatile organic compounds in the atmosphere, produces three distinct carbonyl oxide species (RR'COO) known as Criegee intermediates: formaldehyde oxide (CH 2 OO), methyl vinyl ketone oxide (MVK-OO), and methacrolein oxide (MACR-OO). The nature of the substituents (R,R' = H, CH 3 , CH＝CH 2 ) and conformations of the Criegee intermediates control their subsequent chemistry in the atmosphere. In particular, unimolecular decay of MVK-OO is predicted to be the major source of hydroxyl radicals (OH) in isoprene ozonolysis. Our study reports the initial laboratory synthesis and direct detection of MVK-OO through reaction of a photolytically generated, resonance-stabilized monoiodoalkene radical with O 2 . MVK-OO is characterized utilizing infrared (IR) action spectroscopy, in which IR activation of MVK-OO with two quanta of CH stretch at ca. 6000 cm –1 is coupled with ultraviolet detection of the resultant OH products. MVK-OO is identified by comparison of the experimentally observed IR spectral features with theoretically predicted IR absorption spectra. For syn -MVK-OO, the rate of appearance of OH products agrees with the unimolecular decay rate predicted using statistical theory with tunneling. This validates the hydrogen atom transfer mechanism and computed transition-state barrier (18.0 kcal mol –1 ) leading to OH products. Theoretical calculations display a further roaming pathway between the separating radical fragments, which results in other products. Master equation modeling yields a thermal unimolecular decay rate for syn -MVK-OO of 33 s –1 (298 K, 1 atm). For anti -MVK-OO, theoretical exploration of several unimolecular decay pathways predicts that isomerization to dioxole is the most likely initial step to products.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis
Correlations between the energies of elementary steps limit the rates of thermally catalysed reactions at surfaces. Here, we show how these limitations can be circumvented in ammonia synthesis by coupling catalysts to a non-thermal plasma. We postulate that plasma-induced vibrational excitations in N 2 decrease dissociation barriers without influencing subsequent reaction steps. We develop a density-functional-theory-based microkinetic model to incorporate this effect, and parameterize the model using N 2 vibrational excitations observed in a dielectric-barrier-discharge plasma. We predict plasma enhancement to be particularly great on metals that bind nitrogen too weakly to be active thermally. Ammonia synthesis rates observed in a dielectric-barrier-discharge plasma reactor are consistent with predicted enhancements and predicted changes in the optimal metal catalyst. The results provide guidance for optimizing catalysts for application with plasmas.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
An efficient synthesis strategy for metal-organic frameworks: Dry-gel synthesis of MOF-74 framework with high yield and improved performance
Here, vapor-assisted dry-gel synthesis of MOF-74 structure, specifically NiMOF-74 from its synthetic precursors, was conducted with high yield and improved performance showing promise for gas (CO 2 ) and water adsorption applications. Unlike conventional synthesis, which takes 72 h, this kinetic study showed that NiMOF-74 forms within 12 h under dry-gel conditions with similar performance characteristics and exhibits the best performance characteristics after 48 h of heating.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Magnetic gold nanotriangles by microwave-assisted polyol synthesis
Simple approaches to synthesize hybrid nanoparticles with magnetic and plasmonic functionalities, with high control of their shape and avoiding cytotoxic reactants, to target biomedical applications remain a huge challenge. Here, we report a facile, fast and bio-friendly microwave-assisted polyol route for the synthesis of a complex multi-material consisting of monodisperse gold nanotriangles around 280 nm in size uniformly decorated by superparamagnetic iron oxide nanoparticles of 5 nm. These nanotriangles are readily dispersible in water, display a strong magnetic response (10 wt% magnetic fraction) and exhibit a localized surface plasmon resonance band in the NIR region (800 nm). Moreover, these hybrid particles can be easily self-assembled at the liquid–air interfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Crucial breakthrough of second near-infrared biological window fluorophores: design and synthesis toward multimodal imaging and theranostics
Recent advances in the chemical design and synthesis of fluorophores in the second near-infrared biological window (NIR-II) for multimodal imaging and theranostics are summarized and highlighted in this review article.
Chemistry↗